JP2021155596A - Film - Google Patents

Abstract

To provide a film that has a high dielectric breakdown strength at high temperatures and a low shrinkage rate at high temperatures so that it can maintain sufficient quality even when used in harsh high temperature environments, and does not easily tear during film processing steps such as slitting and capacitor manufacturing steps.SOLUTION: The film of the present invention is a film having MD tensile breaking strength/TD tensile breaking strength of 0.5 to 3.0, which is obtained by biaxially stretching a film comprising 90 to 5 pts.mass of a 4-methyl-1-pentene copolymer (A) satisfying a particular requirement and 10 to 95 pts.mass of a 4-methyl-1-pentene copolymer (B) satisfying a particular requirement.SELECTED DRAWING: None

Description

The present invention relates to films.

The 4-methyl-1-pentene polymer is superior to polyethylene and polypropylene in properties such as heat resistance and electrical properties, and is widely used in various applications (see, for example, Patent Document 1). Specifically, a film for a capacitor made of a 4-methyl-1-pentene copolymer is known (see, for example, Patent Document 2).

In recent years, from the viewpoint of energy saving and high efficiency, metallized film capacitors having high withstand voltage and low loss electrical characteristics have been attracting attention. In the conventional metallized film capacitor, a polypropylene (PP) film is generally used as the dielectric film. The heat-resistant temperature of PP film is as low as about 110 ° C, and the melting point has been improved to about 170 ° C by studying to improve heat resistance. However, even PP film with improved melting point is required for automobiles. It could not be used satisfactorily under the harsh conditions of continuous use at a heat resistant temperature of 130 ° C. (see Patent Document 2 and the like). Further, if the rigidity of the film is increased in order to increase the heat resistance, there is a problem that the film is easily torn due to a trade-off with flexibility. This leads to a decrease in product yield.

International Publication No. 2014/050817 Japanese Unexamined Patent Publication No. 2014-11182

The subject of the present invention is to have high dielectric breakdown strength at high temperature and low shrinkage rate at high temperature so that sufficient quality can be maintained even when used in a harsh high temperature environment, and a film such as a slit. The purpose of the present invention is to provide a film in which film tearing is unlikely to occur in the processing process and the capacitor manufacturing process.

The present inventors have made diligent studies to solve the above problems. As a result, they have found that the films described below can solve the above problems, and have completed the present invention.
The present invention relates to, for example, the following [1] to [8].

[1]
90 to 5 parts by mass of 4-methyl-1-pentene copolymer (A) satisfying the following requirements (Aa) to (Ad), and the following requirements (Ba) to (Bd) and ( 10 to 95 parts by mass of the 4-methyl-1-pentene copolymer (B) satisfying B-a1) (however, the total of the copolymer (A) and the copolymer (B) is 100 parts by mass). The ratio of the tensile breaking strength of MD (polymer direction) to the tensile breaking strength of TD (transverse direction) (tensile breaking strength of MD / tensile breaking strength of TD) obtained by biaxially stretching the containing film (α) is A film (β) in the range of 0.5 to 3.0.

(A-a) The amount (U3) of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the number of carbon atoms other than 4-methyl-1-pentene is 5 to 20. The amount (U4) of the building blocks derived from the α-olefin is 80.0 to 2.0 mol%. (However, the total of the U3 and the U4 is 100 mol%).
(A-b) The ultimate viscosity [η] _A measured in decalin at 135 ° C. is 1.7 to 8.0 dL / g.
(Ac) When the copolymer (A) is measured by a cross-separation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the amount of eluted components is in the range of 0 ° C. or higher and lower than 100 ° C. There is at least one peak of.
(Ad) When the copolymer (A) is measured with a cross fractionation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the elution components in the range of 0 ° C. or higher and lower than 100 ° C. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 1.0 to 7.0.

(BA) The amount (U5) of the structural unit derived from 4-methyl-1-pentene is 80.0 to 99.9 mol%, and has 2 to 20 carbon atoms other than 4-methyl-1-pentene. The amount (U6) of the structural unit derived from the α-olefin is 20.0 to 0.1 mol%. (However, the total of the U5 and the U6 is 100 mol%).
(B-b) The ultimate viscosity [η] _B measured in decalin at 135 ° C. is 0.5 to 5.0 dL / g.
(B-c) When the copolymer (B) is measured by a cross-separation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the amount of eluted components is in the range of 100 ° C. or higher and lower than 140 ° C. There is at least one peak of.
(B-d) When the copolymer (B) is measured with a cross fractionation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the elution components in the range of 100 ° C. or higher and lower than 140 ° C. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 1.0 to 3.5.
(B-a1) The ratio (U4 / U6) of U4 (mol%) described in the requirement (A-a) to U6 (mol%) described in the requirement (B-a) is 1.0. Exceeded and less than 50.0.

[2]
The film (β) according to [1], wherein the film (β) is a film obtained by sequentially biaxially stretching the film (α).

[3]
The film (β) according to [1] or [2], wherein the α-olefin in the copolymer (B) is an α-olefin having 5 to 20 carbon atoms other than 4-methyl-1-pentene.

[4]
The film according to any one of [1] to [3], wherein the α-olefins in the copolymer (A) and the copolymer (B) are independently α-olefins having 10 to 20 carbon atoms. β).

[5]
The film (β) according to any one of [1] to [4], wherein the stretch ratio in the biaxial stretching is 1.1 to 100 times in terms of area.

[6]
The film (β) according to any one of [1] to [5], which has a thickness of 1 to 100 μm.
[7]
The film (β) according to any one of [1] to [6], which is a film for a capacitor.

[8]
The film (β) according to any one of [1] to [7], which is a film for a dielectric of a film capacitor.

According to the present invention, it is possible to provide a film obtained by biaxial stretching, which has high heat resistance capable of maintaining quality even when used in a high temperature environment, and is less likely to cause film tearing.

Next, the present invention will be specifically described.
In the present specification, the numerical ranges n1 to n2 mean a numerical range of n1 or more and n2 or less when n1 <n2, and a numerical range of n2 or more and n1 or less when n1> n2.

As used herein, the term "capacitor" is used interchangeably with a capacitor.
In addition, although various physical properties are described in the following description, the details of the measurement conditions of the various physical properties are described in the Example column.

[Film (β)]
The film (β) of the present invention contains two films (α) containing a specific amount of the 4-methyl-1-pentene copolymer (A) and the 4-methyl-1-pentene copolymer (B) described below. Obtained by axial stretching.

In the present invention, "film" is a general term for molded articles on a flat surface, and is a concept including sheets, membranes, tapes, and the like.
The application of the film (β) of the present invention is not particularly limited, but is preferably a film for a capacitor such as a film for a dielectric of a film capacitor. Since the film (α) contains the 4-methyl-1-pentene copolymer (A) and the 4-methyl-1-pentene copolymer (B), the film (α) is excellent in film stretchability. Further, the film (β) of the present invention has high heat resistance that can maintain the quality even when used in a high temperature environment. When the film (β) of the present invention is a film for a capacitor, the decrease in dielectric breakdown voltage is small even when used in a high temperature environment, the film has high heat resistance that can maintain quality, and the dielectric loss characteristic at high temperature is good. Therefore, it has excellent electrical characteristics from the viewpoint of long-term life.

<4-Methyl-1-pentene copolymer (A)>
The 4-methyl-1-pentene copolymer (A) is a copolymer having a structural unit derived from 4-methyl-1-pentene, and meets the following requirements (Aa) to (Ad). Fulfill.

The 4-methyl-1-pentene copolymer (A) may be one kind of 4-methyl-1-pentene copolymer satisfying the following requirements (Aa) to (Ad), and may be the following. Two or more kinds of 4-methyl-1-pentene copolymers satisfying the requirements (Aa) to (Ad) may be used.

<< Requirements (A-a) >>
In the copolymer (A), the amount (U3) of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the number of carbon atoms other than 4-methyl-1-pentene is 5 The amount (U4) of the building blocks derived from ~ 20 α-olefins is 80.0 to 2.0 mol%. U3 is preferably 20.0 to 97.0 mol%, more preferably 25.0 to 97.0 mol%. U4 is preferably 80.0 to 3.0 mol%, more preferably 75.0 to 3.0 mol%. However, the total of the U3 and the U4 is 100 mol%. The 100 mol% means the total of the U3 and the U4, and does not mean 100 mol% of all the constituent units constituting the copolymer (A).

When the amount of each structural unit is within the above range, the stretchability of the film (α) becomes good, and as a result, the withstand voltage characteristics of the film (β) tend to improve. For example, the dielectric breakdown voltage decreases in a high temperature environment. Tends to be smaller.

When an α-olefin having 5 to 20 carbon atoms is used as the comonomer, the stretchability of the film (α) and the withstand voltage characteristics of the film (β) tend to be excellent. Examples of the α-olefin having 5 to 20 carbon atoms include 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and the like. 1-Eikosen is mentioned. Among these, α-olefins having 6 to 20 carbon atoms are preferable, α-olefins having 10 to 20 carbon atoms are more preferable, and 1-decene and 1-tetradecene are preferable from the viewpoint that the film (α) is more excellent in stretchability. , 1-Hexadecene and 1-Octadecene are more preferred.

The copolymer (A) may have only one type of structural unit derived from an α-olefin having 5 to 20 carbon atoms other than 4-methyl-1-pentene, or may have two or more types.
The copolymer (A) can further have a structural unit derived from another polymerizable compound as long as the object of the present invention is not impaired. Other polymerizable compounds include, for example, vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, vinylnorbornene; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; butadiene. , Isoprene, pentadiene, conjugated diene such as 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadien, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7- Methyl-1,6-octadien, dicyclopentadiene, cyclohexadiene, dicyclooctadien, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2 -Norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2- Examples include non-conjugated polyenes such as norbornene.

In the copolymer (A), the content ratio of the structural unit derived from the other polymerizable compound is usually 10 mol% or less, preferably 5 mol%, out of 100 mol% of all the structural units constituting the (A). Hereinafter, it is more preferably 3 mol% or less.

<< Requirements (A-b) >>
_{The ultimate viscosity [η] A} of the copolymer (A) measured in decalin at 135 ° C. is 1.7 to 8.0 dL / g. The [η] _A is preferably 2.0 to 7.7 dL / g, more preferably 2.5 to 7.5 dL / g, still more preferably 2.7 to 7.3 dL / g, and particularly preferably 2. It is 9 to 7.0 dL / g.

The copolymer (A) in which [η] _A is in the above range exhibits good fluidity during molding, and is stretchable when combined with the 4-methyl-1-pentene copolymer (B). It is thought to contribute to improvement.

<< Requirements (Ac) >>
When the copolymer (A) is measured by a cross-separation chromatograph (CFC) device using an infrared spectrophotometer as a detection unit, at least one peak of the amount of eluted components is in the range of 0 ° C. or higher and lower than 100 ° C. exist. The peak of the amount of the eluted component preferably exists in the range of 0 to 80 ° C. The position of the peak of the amount of the eluted component is determined at the position of the peak top.

In one embodiment, the copolymer (A) preferably has no peak in the amount of eluted components in the range of 100 ° C. or higher and lower than 140 ° C. That is, it is preferable that the peak top of the amount of the eluted component is not in the range of 100 ° C. or higher and lower than 140 ° C.
The copolymer (A) satisfying the requirement (A-c) contains a component having lower crystallinity than the copolymer (B) described later, and the obtained film (β) tends to show high flexibility. be.

<< Requirements (Ad) >>
When the copolymer (A) is measured by a cross fractionation chromatograph (CFC) device using an infrared spectrophotometer as a detection unit, the weight average molecular weight (Mw) of the eluted components in the range of 0 ° C. or higher and lower than 100 ° C. ) And the number average molecular weight (Mn), the molecular weight distribution (Mw / Mn) is 1.0 to 7.0. The Mw / Mn is preferably 1.0 to 6.5, more preferably 1.2 to 6.0. Each of the average molecular weights is measured by a gel permeation chromatography (GPC) method and is a polystyrene-equivalent value.

By using the copolymer (A) having Mw / Mn in the above range, the stretchability of the film (α) is improved, and as a result, the withstand voltage characteristics of the film (β) tend to be improved. For example, in a high temperature environment. Underneath, the decrease in dielectric breakdown voltage tends to be small, and the stable electrical characteristics required for capacitor films are likely to be exhibited.
The copolymer (A) having Mw / Mn in the above range can be obtained, for example, by using a metallocene catalyst described later.

<4-Methyl-1-pentene copolymer (B)>
The 4-methyl-1-pentene copolymer (B) is a copolymer having a structural unit derived from 4-methyl-1-pentene, and has the following requirements (B-a) to (B-d) and ( B-a1) is satisfied.

The 4-methyl-1-pentene copolymer (B) is a type of 4-methyl-1-pentene copolymer that satisfies the following requirements (B-a) to (B-d) and (B-a1). It may be two or more kinds of 4-methyl-1-pentene copolymers satisfying the following requirements (B-a) to (B-d) and (B-a1).

<< Requirements (BA) >>
In the copolymer (B), the amount (U5) of the structural unit derived from 4-methyl-1-pentene is 80.0 to 99.9 mol%, and the number of carbon atoms other than 4-methyl-1-pentene is 2. The amount (U6) of the building blocks derived from ~ 20 α-olefins is 20.0 to 0.1 mol%. U5 is preferably 85.0 to 99.9 mol%, more preferably 90.0 to 99.9 mol%. U6 is preferably 15.0 to 0.1 mol%, more preferably 10.0 to 0.1 mol%. However, the total of the U5 and the U6 is 100 mol%. The 100 mol% means the total of the U5 and the U6, and does not mean 100 mol% of all the constituent units constituting the copolymer (B).

When the amount of each structural unit is within the above range, the crystallinity of the film (β) increases and the elastic modulus of the film increases, and as a result, the withstand voltage characteristics of the film (β) tend to improve, for example, high temperature. The decrease in dielectric breakdown voltage tends to be small in the environment.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. Examples thereof include 1-heptadecene, 1-octadecene, and 1-eikosen. In the present specification, ethylene is included in α-olefin. Among these, α-olefins having 5 to 20 carbon atoms are preferable, and α-olefins having 6 to 20 carbon atoms are more preferable, from the viewpoint of excellent stretchability of the film (α) and withstand voltage characteristics of the film (β). , Alpha-olefins having 10 to 20 carbon atoms are more preferable, and 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are particularly preferable.

The copolymer (B) may have only one type of structural unit derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene, or may have two or more types.
The copolymer (B) further has a structural unit derived from a polymerizable compound other than 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms, as long as the object of the present invention is not impaired. be able to. Specific examples of other polymerizable compounds are described in the description of the copolymer (A).

In the copolymer (B), the content ratio of the structural unit derived from the other polymerizable compound is usually 10 mol% or less, preferably 5 mol%, out of 100 mol% of all the structural units constituting the (B). Hereinafter, it is more preferably 3 mol% or less.

<< Requirements (B-b) >>
_{The ultimate viscosity [η] B} of the copolymer (B) measured in decalin at 135 ° C. is 0.5 to 5.0 dL / g. The [η] _B is preferably 0.5 to 4.5 dL / g, more preferably 0.5 to 4.0 dL / g.

The copolymer (B) in which [η] _B is in the above range exhibits good fluidity during preparation and molding of the raw material (α) described later, and is also a 4-methyl-1-pentene copolymer (4-methyl-1-pentene copolymer). When combined with A), it is considered to contribute to the improvement of stretchability. As a result, the withstand voltage characteristics of the film (β) tend to improve.

<< Requirements (BC) >>
When the copolymer (B) is measured by a cross-separation chromatograph (CFC) device using an infrared spectrophotometer as a detection unit, at least one peak of the amount of eluted components is in the range of 100 ° C. or higher and lower than 140 ° C. exist. The peak of the amount of the eluted component preferably exists in the range of 100 to 135 ° C. The position of the peak of the amount of the eluted component is determined at the position of the peak top.

In one embodiment, the copolymer (B) preferably has no peak in the amount of eluted components in the range of 0 ° C. or higher and lower than 100 ° C. That is, it is preferable that the peak top of the amount of the eluted component is not in the range of 0 ° C. or higher and lower than 100 ° C.
The copolymer (B) satisfying the requirement (B-c) contains a highly crystalline component, and the obtained film (β) tends to exhibit high heat resistance.

<< Requirements (B-d) >>
When the copolymer (B) was measured with a cross fractionation chromatograph (CFC) device using an infrared spectrophotometer as the detection unit, the weight average molecular weight (Mw) of the eluted components in the range of 100 ° C. or higher and lower than 140 ° C. ) And the number average molecular weight (Mn), the molecular weight distribution (Mw / Mn) is 1.0 to 3.5. The Mw / Mn is preferably 1.0 to 3.0, more preferably 1.5 to 2.8. Each of the average molecular weights is measured by a gel permeation chromatography (GPC) method and is a polystyrene-equivalent value.

By using the copolymer (B) having Mw / Mn in the above range, the stretchability of the film (α) is improved, and as a result, the withstand voltage characteristics of the film (β) tend to be improved. For example, in a high temperature environment. Underneath, the decrease in dielectric breakdown voltage tends to be small, and the stable electrical characteristics required for capacitor films are likely to be exhibited.
The copolymer (B) having Mw / Mn in the above range can be obtained, for example, by using a metallocene catalyst described later.

<< Requirements (B-a1) >>
The ratio (U4 / U6) of U4 (mol%) described in the requirement (Aa) to U6 (mol%) described in the requirement (BA) exceeds 1.0 and 50. It is less than 0. The ratio (U4 / U6) is preferably 2.0 to 40.0, more preferably 3.0 to 35.0.

U4 is a structural unit derived from an α-olefin having 5 to 20 carbon atoms other than 4-methyl-1-pentene, when the total of U3 and U4 described in (A) above is 100 mol%. Amount (mol%). U6 is a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene, when the total of U5 and U6 described in (BA) above is 100 mol%. Amount (mol%).

The requirement (B-a1) is that the copolymer (A) contains a constituent unit derived from the α-olefin, which is a comonomer with respect to 4-methyl-1-pentene, more than the copolymer (B). Means that there are many. By using the copolymer (A) and the copolymer (B) that satisfy the requirement (B-a1), the stretchability of the film (α) is improved, and the breakdown voltage of the film (β) in a high temperature environment is increased. There is a tendency that the decrease is small and the effect of improving heat resistance can be obtained.

<< Requirements (B-b1) >>
It is preferable that the copolymer (B) further satisfies the requirement (B-b1).
_{Requirement (B-b1) The ratio of [η] A} described in the requirement (A-b) to _{[η] B} described in the requirement (B-b) ([η] _A / [η] _B ). Is more than 1.0 and 6.0 or less.
[Η] _A / [η] _B ) is more preferably more than 1.0 and 5.0 or less, still more preferably 1.1 to 4.0.

The film (α) containing the copolymer (A) and the copolymer (B) is excellent in stretchability while maintaining the heat resistance derived from the 4-methyl-1-pentene copolymer. Therefore, the copolymer (A) and the copolymer (B) are suitable for producing a film for a capacitor, which requires heat resistance and stretchability. In one embodiment, the copolymer (B) is a hard component having a relatively low ultimate viscosity [η] with respect to the copolymer (A).

<Amount ratio of copolymer (A) and copolymer (B)>
The content of the copolymer (A) in the film (α) is 90 to 5 parts by mass, preferably 90 to 15 parts by mass, more preferably 85 to 20 parts by mass; the content of the copolymer (B). Is 10 to 95 parts by mass, preferably 10 to 85 parts by mass, and more preferably 15 to 80 parts by mass. However, the total of the copolymer (A) and the copolymer (B) is 100 parts by mass. In such an embodiment, the stretchability of the film (α) is improved, and as a result, the withstand voltage characteristics of the film (β) tend to be improved.

It is considered that the copolymer (A) and the copolymer (B) have good compatibility. Due to the good compatibility, the obtained film (α) tends to have a good balance between rigidity and extensibility.
The film (α) can contain one or more copolymers (A). Further, the film (α) can contain one kind or two or more kinds of copolymers (B).

The film (α) contains the copolymer (A) and the copolymer (B), but may be produced from a raw material containing components other than the copolymer (A) and the copolymer (B). .. The total amount of the copolymer (A) and the copolymer (B) in 100% by mass of the raw material of the film (α) is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass. That is all. The raw material of the film (α) is also hereinafter referred to as “raw material (α)”. The upper limit of the total amount of the copolymer (A) and the copolymer (B) in 100% by mass of the raw material (α) is 100% by mass. That is, the film (α) may be formed only from the copolymer (A) and the copolymer (B).

<Other ingredients>
As the raw material of the film (α), components other than the above-mentioned copolymer (A) and copolymer (B) may be used. Examples of the components other than the copolymer (A) and the copolymer (B) include polymers other than the copolymer (A) and the copolymer (B) (hereinafter, also referred to as “other polymers”). Can be used. Examples of other polymers include α-olefin polymer (C), which will be described later, and elastomers other than these.

Further, various additives can be used as the components other than the copolymer (A) and the copolymer (B). Additives include, for example, secondary antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. Examples include fillers and hydrochloric acid absorbers. The amount of the additive used is not particularly limited, but the amount of the components other than the copolymer (A) and the copolymer (B) in 100% by mass of the raw material (α) is usually 50% by mass or less, preferably 50% by mass or less. Is 30% by mass or less, more preferably 10% by mass or less. The lower limit of the amount of the components other than the copolymer (A) and the copolymer (B) in 100% by mass of the raw material (α) is 0% by mass.

<Method for producing copolymer (A) and copolymer (B)>
The method for producing the copolymer (A) and the copolymer (B) is not particularly limited. The copolymer (A) and the copolymer (B) are one of the preferred embodiments obtained as a mixture. Examples of the method for producing the copolymer (A) and the copolymer (B) include a method in which the copolymer (A) and the copolymer (B) are separately produced and then mixed, or a copolymer ( Examples thereof include a method of producing A) and the copolymer (B) by a multi-stage polymerization method. In the case of multi-stage polymerization, the copolymer (B) may be polymerized after the copolymer (A) is polymerized, and the copolymer (A) may be polymerized after the copolymer (B) is polymerized. Although it may be polymerized, it is preferable to polymerize the copolymer (B) first as described later.

The copolymer (A) and the copolymer (B) are each polymerized with, for example, 4-methyl-1-pentene, the above-mentioned α-olefin, and the above-mentioned other polymerizable compound, if necessary. Can be obtained by By carrying out the polymerization in the presence of a metallocene catalyst, the copolymer (A) and the copolymer (B) satisfying the above-mentioned requirements can be preferably obtained.

Examples of the metallocene catalyst include International Publication No. 01/53369, International Publication No. 01/27124, Japanese Patent Application Laid-Open No. 3-193996, Japanese Patent Application Laid-Open No. 02-41303, International Publication No. 06/025540, International Publication No. Examples include the metallocene catalysts described in 2013/099876 and WO 2014/050817.

<< Metallocene compound (a) >>
The metallocene catalyst preferably contains the metallocene compound (a).
The metallocene compound (a) is represented by, for example, the general formula (1) or (2).

The meaning of each symbol in the general formula (1) or (2) is as follows.
R ^{1 to} R ¹⁴ are independently hydrogen atoms, hydrocarbon groups, substituted hydrocarbon groups or silicon-containing groups, respectively. Adjacent substituents from R ¹ to R ⁴ may combine with each other to form a ring. Adjacent substituents from R ⁵ to R ¹² may combine with each other to form a ring.

Y is a carbon atom or a silicon atom.
A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring. A may include two or more ring structures, including a ring formed with Y.

M is a transition metal selected from Group 4 of the periodic table, and examples thereof include titanium, zirconium, and hafnium.
Q is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. When j is 2 or more, each Q may be the same or different.

j is an integer of 1 to 4, preferably 2.
Examples of the hydrocarbon group in R ^{1 to} R ¹⁴ include a hydrocarbon group having 1 to 20 carbon atoms, and specifically, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms. , An arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylaryl group having 7 to 20 carbon atoms.

In the ^{substituted hydrocarbon groups (excluding silicon-containing groups) in R 1 to} R ¹⁴ , some or all of the hydrogen atoms contained in the hydrocarbon groups are halogen atoms (fluorine, chlorine, bromine, iodine) and hydroxyl groups. And a group substituted with a functional group such as an amino group.

Examples of the silicon-containing group in R ^{1 to} R ¹⁴ include an alkylsilyl group or an arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl and tert-butyl. Examples thereof include dimethylsilyl and triphenylsilyl.

^{Adjacent substituents R 5} to R ¹² on the fluorene ring may combine with each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl.

^{Substituents of R 5} to R ¹² on the fluorene ring are symmetrical for ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , R ⁸ = R ^9. Is preferable. The fluorene ring moiety is preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-4-substituted fluorene. The 3rd, 6th, 2nd, and 7th positions on the fluorene ring ^{correspond to R 7} , R ¹⁰ , R ⁶ , and R ¹¹ , respectively.

It is preferable that R ¹³ and R ¹⁴ are independently hydrogen atoms, hydrocarbon groups or substituted hydrocarbon groups, respectively.
In the case of the general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a crosslinked portion. Specific examples of the substituted methylene group and the substituted silylene group include, for example, dialkylmethylene, dicycloalkylmethylene, alkylcycloalkylmethylene, alkylarylmethylene, diarylmethylene, dialkylsilylene, dicycloalkylsilylene, alkylcycloalkylsilylene, and alkylaryl. Examples thereof include silylene, diallyl silylene, and groups obtained by halogenating these.

In the case of the general formula (2), Y is bonded to the divalent hydrocarbon group A to form a cycloalkylidene group, a cyclomethylenecilylene group, or the like. Specific examples of the cycloalkylidene group and the cyclomethylenecilylene group include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptilidene, bicyclo [3.3.1] nonylidene, norbornylidene, and adaman. Examples thereof include chiliden, tetrahydronaphthylidene, dihydroindanylidene, cyclodimethylene silylene, cyclotrimethylene silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene and cycloheptamethylene silylene.

In Q, the halogen atom includes fluorine, chlorine, bromine and iodine; the hydrocarbon group having 1 to 20 carbon atoms includes a ^{group similar to the hydrocarbon group of R 1 to} R ¹⁴ ; an anion arrangement. Examples of the position include an alkoxy group, an aryloxy group, a carboxylate group, a sulfonate group and the like; and examples of a neutral ligand capable of coordinating with an isolated electron pair include trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethyl. Examples thereof include organic phosphorus compounds such as phosphine, ethers such as tetrahydrofuran, diethyl ether, dioxane and 1,2-dimethoxyethane. At least one of Q is preferably a halogen atom or an alkyl group having 1 to 20 carbon atoms.

Specific examples of the metallocene compound (a) include the compounds exemplified in International Publication No. 01/27124, International Publication No. 2006/025540 or International Publication No. 2007/308607.

As the metallocene compound (a), the compound represented by the general formula [A2] described in International Publication No. 2014/050817 and the like is particularly preferable.

In the formula [A2], R ^1b is a hydrocarbon group, a silicon-containing group or a halogen-containing hydrocarbon group, and R ^{2b to} R ^12b are a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group. They may be the same or different from each other, and the respective substituents may be bonded to each other to form a ring. M is a Group 4 transition metal of the periodic table, n is an integer of 1 to 3, Q is synonymous with Q in the general formula (1) or (2), and j is an integer of 1 to 4. be.

Examples of the hydrocarbon group in R ^1b to R ^12b include a linear hydrocarbon group such as a linear alkyl group and a linear alkenyl group; a branched hydrocarbon group such as a branched alkyl group; and a cycloalkyl group. Cyclic saturated hydrocarbon groups such as norbornyl group and adamantyl group; cyclic unsaturated hydrocarbon groups such as aryl group and cycloalkenyl group; cyclic unsaturated hydrocarbons having one or more hydrogen atoms of saturated hydrocarbon groups such as aralkyl group. Examples thereof include groups formed by substituting a hydrocarbon group. The hydrocarbon group usually has 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

Examples of the silicon-containing group in R ^1b to R ^12b _{include a group represented by the formula −SiR 3} (in the formula, each of the plurality of Rs is independently an alkyl group or a phenyl group having 1 to 15 carbon atoms). Can be mentioned.

Examples of the halogen-containing hydrocarbon group in R ^1b to R ^12b include a group formed by substituting one or more hydrogen atoms of the above-mentioned hydrogen atom with a halogen atom, such as a trifluoromethyl group.

Examples of the halogen atom in R ^2b to R ^12b include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the ring (spiro ring, additional ring) formed by bonding two substituents to each other in the formula [A2] include an alicyclic ring and an aromatic ring. Specific examples thereof include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring and a cyclopentene ring, and preferably a cyclohexane ring, a benzene ring and a hydrogenated benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

It is particularly preferable that R ^1b is a substituent in which the carbon having a free valence (carbon bonded to the cyclopentadienyl ring) is a tertiary carbon. Specifically, R ^1b is a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group.

The fluorene ring moiety is not particularly limited as long as it has a structure obtained from a known fluorene derivative, but R ^4b and R ^5b are preferably hydrogen atoms from the viewpoint of molecular weight.
R ^2b , R ^3b , R ^6b and R ^7b are preferably hydrocarbon groups having 1 to 20 carbon atoms. Further, R ^2b and R ^3b may be bonded to each other to form a ring, and R ^6b and R ^7b may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2. , 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl-2,3, 6,7,8,10-Hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1', 1', 3', 6', 8', 8'-hexamethyl-1'H, 8'H-dicyclopenta [B, h] Examples include the fluorenyl group.

R ^8b is preferably a hydrogen atom. R ^9b is preferably an alkyl group having 2 or more carbon atoms. From a synthetic point of view, it is also preferable that ^{R 10b} and R ^{11b are hydrogen atoms.}

Alternatively, when n = 1, ^{it is more preferable that R 9b} and R ^10b are bonded to each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring. In this case, R ^11b is preferably a hydrogen atom.

R ^12b is preferably an alkyl group.
M is a Group 4 transition metal of the periodic table, for example Ti, Zr or Hf, preferably Zr or Hf, and particularly preferably Zr.

n is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. When n is the above value, it is preferable from the viewpoint of efficiently obtaining the polymer to be produced.
j is an integer of 1 to 4, preferably 2.

Examples of the compound represented by the general formula [A2] include (8-octamethylfluorene-12'-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6, 7,7a,8-octahydrocyclopenta [a] indene)) zirconium dichloride or (8- (2,3,6,7-tetramethylfluorene) -12'-yl- (2- (adamantan-1-yl)) )-8-Methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta [a] indene)) Zyroxide dichloride is particularly preferred. Here, the above-mentioned octamethylfluorene is 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b]. , h] Fluorene.

<Co-catalyst (b)>
The metallocene catalyst is at least one selected from an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and a compound (b-3) that reacts with an organometallic compound (a) to form an ion pair. It is preferable that the compound of (co-catalyst (b)) is further contained.

Organometallic compound (b-1) (where an organoaluminum oxy-compound (excluding b-2)) include, for example, an organoaluminum compound may be mentioned, specifically, the general formula R ^a _m Al (OR _{b) n} H _p X _q (In the formula, R ^a and R ^b may be the same or different from each other, and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and X is a halogen atom. m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Examples include compounds. Specific examples thereof include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum and trinormaloctylaluminum, dialkylaluminum hydride such as diisobutylaluminum hydride, and tricycloalkylaluminum such as tricyclohexylaluminum.

The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Specific examples thereof include methylaluminoxane. Further, it is exemplified in organoaluminum oxy compounds containing a boron atom, aluminoxane containing halogens as exemplified in International Publication No. 2005/066191 and International Publication No. 2007/131010, and International Publication No. 2003/082879. Ionic aluminoxane as well can be mentioned.

As the aluminoxane, solid aluminoxane is also preferably used, and for example, solid aluminoxane disclosed in International Publication No. 2010/055652, International Publication No. 2013/146337, or International Publication No. 2014/123212 is particularly preferable. Used for.

By "solid state" is meant that the aluminoxane remains substantially in a solid state in a reaction environment in which the solid aluminoxane is used. More specifically, for example, when each component constituting a metallocene catalyst is brought into contact with each other to prepare a solid catalyst component, the solid catalyst component is prepared in an inert hydrocarbon medium such as hexane or toluene used in the reaction under a specific temperature and pressure environment. Indicates that the aluminoxane is in a solid state.

The solid aluminoxane preferably contains an aluminoxane having at least one structural unit selected from the structural unit represented by the formula (1) and the structural unit represented by the formula (2), and more preferably the structural unit represented by the formula (1). ) Is contained, and more preferably, polymethylaluminoxane having only the structural unit represented by the formula (1) is contained.

In formula (1), Me is a methyl group.
In the formula (2), R ¹ is a hydrocarbon group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 2 to 15 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aryl group.

The structure of the solid aluminoxane has not always been clarified, and it is presumed that the solid aluminoxane usually has a structure in which the structural units represented by the formulas (1) and / or the formula (2) are repeated by about 2 to 50. However, the configuration is not limited to this. In addition, the binding mode of the constituent units varies from linear, cyclic or clustered, for example, and aluminoxane is usually composed of one of these or presumed to be a mixture thereof. .. Further, the aluminoxane may consist of only the structural unit represented by the formula (1) or the formula (2).

As the solid aluminoxane, a solid polymethylaluminoxane is preferable, and a solid polymethylaluminoxane composed of only the structural unit represented by the formula (1) is more preferable.
The solid aluminoxane is usually in the form of particles, and the D50 in the volume statistical value is preferably 1 to 500 μm, more preferably 2 to 200 μm, and further preferably 5 to 50 μm. The D50 in the volume statistical value can be obtained by a laser diffraction / scattering method using, for example, MT3300EX II manufactured by Microtrac.

Solid aluminoxane has a specific surface area of preferably 100~1000m ² / g, more preferably 300~800m ² / g. The specific surface area can be determined by using the BET adsorption isotherm method and utilizing the gas adsorption and desorption phenomenon on the solid surface.

The solid aluminoxane also functions as a carrier (c). Therefore, when solid aluminoxane is used, for example, it is not necessary to use a solid inorganic carrier such as silica, alumina, silica-alumina, magnesium chloride, or a solid organic carrier such as polystyrene beads.

The solid aluminoxane can be prepared, for example, by the methods described in WO 2010/055652 and WO 2014/123212.
Examples of the compound (b-3) that reacts with the metallocene compound (a) to form an ion pair include Japanese Patent Application Laid-Open No. 1-501950, Japanese Patent Application Laid-Open No. 1-502036, Japanese Patent Application Laid-Open No. 3-179005, and Japanese Patent Application Laid-Open No. Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in Kaihei 3-179006, JP-A-3-207703, JP-A-3-207704, and US5321106. Further, heteropoly compounds and isopoly compounds can also be mentioned. For example, trialkylammonium tetraarylborates, trialkylammonium tetra (aryl halides) borates, dioctadecylmethylammonium tetraarylborates, dioctadecylmethylammonium tetra (aryl halides) borates, N, N-dialkylanilinium tetraarylborates. , N, N-dialkylanilinium tetra (aryl halide) borate and other organoboron compounds.

<Carrier (c)>
The metallocene catalyst preferably further contains the carrier (c).
The carrier (c) is preferably in the form of particles, and the metallocene catalyst is formed by immobilizing the metallocene compound (a) on the surface and / or inside thereof, for example.

The carrier (c) usually consists of an inorganic or organic compound. Examples of the solid inorganic carrier include carriers composed of inorganic compounds such as porous oxides, inorganic halides, clays, clay minerals, and ion-exchange layered compounds. Examples of the solid organic carrier include carriers such as polystyrene beads.

Further, as the carrier (c), the above-mentioned solid aluminoxane can also be mentioned. As the carrier (c), a carrier containing an aluminum atom is preferable from the viewpoint of high activity and further suppressing the amount of solvent-soluble parts. The content of aluminum atoms in the carrier (c) is preferably 20% by mass or more, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and particularly preferably 35 to 47% by mass.

Examples of the porous oxide include oxides such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or a composite containing these. Examples include mixtures. For example, natural or synthetic zeolite, SiO _2- MgO, SiO _2- Al ₂ O ₃ , SiO _2- TiO ₂ , SiO _2- V ₂ O ₅ , SiO _2- Cr ₂ O ₃ , SiO _2- TiO _2- MgO Can be mentioned.

Examples of the inorganic halide include MgCl ₂ , MgBr ₂ , MnCl ₂ , and MnBr ₂ . The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitant.

Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Examples of clay, clay mineral or ion-exchangeable layered compound include clay, clay mineral, or an ionic crystalline compound having a layered crystal structure such as _{hexagonal closest packing type, antimony type, CdCl 2} type and CdI _{2 type.} Can be mentioned.

It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment and the like.

The D50 of the carrier (c) in terms of volume statistics is preferably 1 to 500 μm, more preferably 2 to 200 μm, and even more preferably 5 to 50 μm. The D50 in the volume statistical value can be obtained by a laser diffraction / scattering method using, for example, MT3300EX II manufactured by Microtrac.

<Organic compound component (d)>
The metallocene catalyst can further contain the organic compound component (d), if necessary. The organic compound component (d) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of the organic compound component (d) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers and sulfonates.

<< Polymerization conditions >>
The polymerization of 4-methyl-1-pentene and α-olefin for obtaining the copolymer (A) and the copolymer (B) is a liquid phase polymerization method such as dissolution polymerization or suspension polymerization, or a gas phase polymerization method. It can be carried out in any of the above.

In the liquid phase polymerization method, an inert hydrocarbon solvent can be used, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; cyclopentane, Alicyclic hydrocarbons such as cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane; Two or more mixed solvents selected may be mentioned. Further, the olefin itself containing 4-methyl-1-pentene can be used as the polymerization solvent.

In the case of olefin polymerization, the usage and addition order of each component are arbitrarily selected, and the following methods are exemplified. Hereinafter, the metallocene compound (a), the cocatalyst (b), the carrier (c), and the organic compound component (d) are also referred to as “components (a) to (d)”, respectively.
(I) A method of adding components (a) to (c) to a polymerizer in an arbitrary order.
(Ii) A method of adding a catalyst component having components (a) to (b) supported on the component (c) to a polymerizer.

In each of the above methods (i) to (ii), the component (d) may be further added at an arbitrary stage. Moreover, at least two of each catalyst component may be contacted in advance.
Further, in the solid catalyst component in which the component (a) is supported on the component (c), olefins such as 4-methyl-1-pentene and 3-methyl-1-pentene may be prepolymerized, and the prepolymerization may be performed. A catalyst component may be further supported on the solid catalyst component.

Further, an antistatic agent, an anti-fouling agent, or the like can be used for the purpose of allowing the polymerization to proceed smoothly.
When polymerizing an olefin using a metallocene catalyst, the amount of each component that can constitute the metallocene catalyst is as follows. Hereinafter, the metallocene compounds (a) and (b-1) to (b-3) exemplified in the column of the co-catalyst (b) are also referred to as components (a) and components (b-1) to (b-3), respectively. ..

The component (a) can be used in an amount such that it is ^{usually 10 -10} to ^10-2 mol, preferably 10 ^-9 to 10 ^-3 mol, per liter of the reaction volume.
The component (b-1) has a molar ratio [(b-1) / M] of the component (b-1) and the transition metal atom (M; transition metal of Group 4 of the periodic table) in the component (a). , Usually 10 to 10000, preferably 30 to 2000, more preferably 50 to 1000.

The molar ratio [Al / M] of the aluminum atom (Al) in the component (b-2) and the transition metal atom (M) in the component (a) of the component (b-2) is usually 10 to 10. It can be used in an amount such that it is 10000, preferably 30 to 2000, and more preferably 50 to 1000.

The molar ratio [(b-3) / M] of the component (b-3) to the transition metal atom (M) in the component (a) is usually 1 to 10000, preferably 1 to 10000. Can be used in an amount such that 2 to 2000, more preferably 10 to 500.

The polymerization temperature is usually −50 to 200 ° C., preferably 0 to 100 ° C., and more preferably 20 to 100 ° C. The polymerization pressure is usually under normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Hydrogen can be added to the polymerization system for the purpose of controlling the molecular weight or polymerization activity of the produced polymer, and the amount of hydrogen added is appropriately about 0.001 to 100 NL per 1 kg of olefin.

As the polymerization condition, it is also possible to adopt multi-stage polymerization in which two or more stages of polymerization having different reaction conditions are carried out. For example, the molecular weight distribution or composition distribution can be determined by carrying out stepwise polymerization under two conditions different in the amount of hydrogen used or the ratio of 4-methyl-1-pentene to α-olefin having 2 to 20 carbon atoms. It is possible to make adjustments.

<Other polymers>
As the raw material of the film (α), other polymers can be further used as described above. Examples of other polymers include α-olefin polymer (C) and elastomers other than these.

The α-olefin polymer (C) is, for example, a polymer of an α-olefin having 2 to 20 carbon atoms (excluding the above-mentioned copolymer (A) and copolymer (B)), and is carbon. Examples thereof include homopolymers or copolymers of α-olefins having a number of 2 to 20.

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene and 1-tetradecene. Linear α-olefins such as 1-hexadecene, 1-octadecene, 1-eicosene; isobutene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- Branches of 1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc. The state α-olefin can be mentioned. Among these, α-olefins having 15 or less carbon atoms are preferable, and α-olefins having 10 or less carbon atoms are more preferable.

The α-olefin polymer (C) can further have a structural unit derived from the other polymerizable compounds described above in the copolymer (A) as long as the object of the present invention is not impaired.
In the α-olefin polymer (C), the content ratio of the structural unit derived from the other polymerizable compound is usually 10 mol% or less, preferably 5 in 100 mol% of all the structural units constituting the (C). It is less than or equal to mol%, more preferably less than or equal to 3 mol%.

Specific examples of the α-olefin polymer (C) include low-density polyethylene, high-density polyethylene, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, and ethylene / propylene / 1-butene random. Copolymers, ethylene / 1-hexene random copolymers, ethylene / 1-octene random copolymers, ethylene / propylene / ethylidenenorbornene random copolymers, ethylene / propylene / 1-butene / ethylidenenorbornene random copolymers, Ethylene copolymers such as ethylene / 1-butene / 1-octene random copolymers, propylene homopolymers, propylene / 1-butene random copolymers, propylene / 1-hexene random copolymers, propylene / 1-octene A propylene copolymer such as a random copolymer, a 1-butene homopolymer, a 1-butene / 1-hexene random copolymer, a butene copolymer such as a 1-butene / 1-octene random copolymer, 4- 4-Methyl-1-pentene copolymers such as methyl-1-pentene homopolymers and 4-methyl-1-pentene / 1-hexene copolymers (provided that the above-mentioned copolymer (A) and copolymer weight are used. (Excluding coalescence (B)).

_{The ultimate viscosity [η] C} of the α-olefin polymer (C) measured in decalin at 135 ° C. is usually 0.1 to 10 dL / g, preferably 0.5 to 5 dL / g.
As the raw material of the film (α), one kind or two or more kinds of α-olefin polymers (C) may be used.

When the α-olefin polymer (C) is used as the raw material (α), the α-olefin polymer (C) is taken as a total of 100 parts by mass of the copolymer (A) and the copolymer (B). ) Is usually 40 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 1 part by mass or less.

<Additives>
As the raw material (α), various additives can be used as the components other than the copolymer (A) and the copolymer (B). As various additives, various additives can be used without particular limitation, including conventionally known additives.

Additives include, for example, secondary antioxidants, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. Examples include fillers and hydrochloric acid absorbers. The content of the additive is not particularly limited,
The amount of the additive is usually 0 to 50 parts by mass, preferably 0 to 10 parts by mass with respect to 100 parts by mass of the total of the copolymer (A) and the copolymer (B). As the raw material (α), one kind or two or more kinds of additives can be used.

<Manufacturing method of raw material (α)>
The raw material (α) is, for example, the above-mentioned copolymer (A) and copolymer (B), and if necessary, components other than the copolymer (A) and the copolymer (B) (for example, other components). It can be obtained by mixing with the above-mentioned polymer and various additives).

As for the mixing method of each component, various known methods, for example, a method of mixing each component using an apparatus such as a plast mill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler, a blender, a kneader ruder, etc .; A method can be adopted in which the obtained mixture is further melt-kneaded with an apparatus such as a uniaxial extruder, a twin-screw extruder, a kneader, and a Banbury mixer, and then the obtained melt-kneaded product is granulated or pulverized.

Further, a mixture of the copolymer (A) and the copolymer (B) can also be obtained by the following multi-stage polymerization method. Specifically, in the presence of the step (1) for producing the 4-methyl-1-pentene copolymer (B) preferably by slurry polymerization and the copolymer (B) obtained in the step (1). , 4-Methyl-1-pentene copolymer (A), when the total amount of the copolymer (A) and the copolymer (B) is 100 parts by mass, the amount of the copolymer (A) is usually The mixture can be produced in the range of 5 to 90 parts by mass, preferably by a multi-stage polymerization method including the step (2) of producing by slurry polymerization.

The multi-stage polymerization method has a step (1) and a step (2) having different polymerization conditions, but the two-step polymerization of the steps (1) and (2) may be performed, and in addition to the steps (1) and (2). It may be a three-stage or higher polymerization including further steps.

<< Process (1) >>
In step (1), the 4-methyl-1-pentene copolymer (B) is preferably produced by slurry polymerization. In the step (1), the supply amount ratio of 4-methyl-1-pentene and α-olefin having 2 to 20 carbon atoms is set so that the amount of the structural unit derived from each is in the above range.

In step (1), a slurry containing the copolymer (B) is obtained. The slurry concentration, that is, the copolymer (B) particle concentration is usually 0.015 to 45% by mass, preferably 0.03 to 35% by mass.

<< Process (2) >>
In the step (2), the 4-methyl-1-pentene copolymer (A) is preferably produced by slurry polymerization in the presence of the copolymer (B) obtained in the step (1). In the step (2), the supply amount ratio of 4-methyl-1-pentene and α-olefin having 5 to 20 carbon atoms is set so that the amount of the structural unit derived from each is in the above range.

In the step (2), when the total amount of the copolymer (B) obtained in the step (1) and the copolymer (A) obtained in the step (2) is 100 parts by mass, the copolymer (2) The copolymer (A) is produced in a range in which the amount of A) is usually 5 to 90 parts by mass.

In one embodiment of step (2), 4-methyl-1-pentene and α-olefin having 5 to 20 carbon atoms are added to the slurry containing the copolymer (B), and the slurry polymerization of these monomers is performed. Can be done.

In step (2), a slurry containing particles containing the copolymer (A) and the copolymer (B) is obtained. The slurry concentration, that is, the particle concentration is usually 3 to 50% by mass, preferably 5 to 40% by mass.

In the above-mentioned multi-stage polymerization method, slurry polymerization is usually adopted, but in "slurry polymerization", the polymer produced by the polymerization is dispersed in the above-mentioned medium as, for example, fine particles without being substantially dissolved in the above-mentioned medium used at the time of polymerization. It refers to polymerization characterized by being present in a slurried form.

<< Solid-liquid separation process >>
The slurry containing the copolymer (A) and the copolymer (B) -containing 4-methyl-1-pentene polymer particles obtained in the step (2) is solid-liquid separated, for example, filtered. Therefore, the particles can be separated and recovered.

<< Post-processing process >>
For 4-methyl-1-pentene polymer particles obtained by the above-mentioned multi-stage polymerization method, for example, particles obtained by the above-mentioned solid-liquid separation step, after being produced by the above-mentioned method, a known catalyst is required. Post-treatment steps such as a deactivation treatment step, a catalyst residue removal step, and a drying step may be performed.
As described above, a mixture of the copolymer (A) and the copolymer (B) can be obtained.

[Characteristics of film (β)]
The film (β) of the present invention has high heat resistance that can maintain the quality even when used in a high temperature environment, and the film is less likely to tear. Therefore, the film (β) is preferably used in applications where it is expected to be used at a high temperature or in applications where the film is used after undergoing a processing step.

As the application of the film (β) of the present invention, it is preferable that it is a film for a capacitor such as a film for a dielectric as described above.
The thickness of the film (β) is preferably 1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 1 to 20 μm.

When the film (β) is a film for a capacitor, its thickness is preferably 1 to 50 μm, more preferably 1 to 30 μm, and further preferably 1.5 to 10 μm.
From the viewpoint of dimensional stability, the film for capacitors of the present invention preferably has a heat shrinkage rate of MD (machine direction) of 3% or less when heated at 150 ° C. for 30 minutes.

Here, MD (also referred to as a longitudinal direction) refers to a flow direction when forming a film, and TD (transverse direction) (also referred to as a width direction) refers to a direction orthogonal to it.

The film (β) of the present invention has a ratio of the tensile breaking strength of MD (machine direction) to the tensile breaking strength of TD (transverse direction) (the tensile breaking strength of MD / the tensile breaking strength of TD) of 0.5 to 3. It is in the range of .0, and the ratio is preferably in the range of 0.5 to 2.5, and more preferably in the range of 0.5 to 2.0.
Details of the measurement conditions for the above characteristics are described in the Examples column.

[Manufacturing method of film (β)]
The film (β) of the present invention is a film obtained by biaxially stretching the film (α).

The film (α) is a film containing the copolymer (A) and the copolymer (B). The film (α) can be obtained by processing the raw material (α) into a film, for example, the raw material (α) is formed into a film in the range of 180 to 300 ° C. by a T-die extrusion molding method or the like. A film (α) can be obtained by molding into. The film (β) can be obtained by biaxially stretching the film (α).

The thickness of the film (α) varies depending on the use and thickness of the film (β), but is preferably 10 to 2000 μm, more preferably 10 to 1000 μm, and even more preferably 20 to 500 μm.

The draw ratio when performing the biaxial stretching is preferably 1.1 to 100 times, more preferably 2 to 90 times, and further preferably 4 to 80 times in terms of area. When the draw ratio is within the above range, the withstand voltage characteristics required for a film capacitor are likely to be exhibited, which is particularly suitable when the film (β) is a film for a capacitor.

The stretching method may be either a sequential biaxial stretching method or a simultaneous biaxial stretching method, but the sequential biaxial stretching method is preferable from the viewpoint of film formation stability and thickness uniformity. Further, by sequentially biaxially stretching, the degree of orientation of the molecular chains in the plane direction due to stretching becomes stronger, and a film (β) having excellent insulation characteristics at high temperatures can be obtained.

In the case of the sequential biaxial stretching method, for example, an unstretched film (film (α)) is obtained by extruding the raw material (α) onto a cooling roll by a T-die extrusion molding method or the like, and then this unstretched film is preliminarily applied. The film is stretched in the film flow direction (MD) through a preheating roll set to the stretching temperature (longitudinal stretching), and then stretched in the film width direction (TD) while passing through a heating oven set to a predetermined stretching temperature. (Transverse stretching).

The stretching temperature for both longitudinal stretching and transverse stretching is preferably between the glass transition temperature (Tg) and the melting point (Tm) of a polymer such as 4-methyl-1-pentene copolymer (A) used for stretching. .. The stretching temperature is usually 60 to 200 ° C., preferably 60 to 150 ° C., more preferably 70 to 140 ° C. By setting this range, the degree of orientation of the molecular chains in the plane direction due to stretching becomes stronger, and a film (β) exhibiting withstand voltage characteristics can be obtained.

The draw ratio is usually 1.01 to 11.0 times, preferably 1.4 to 9.5 times, and more preferably 2.0 to 9.0 times independently in the film longitudinal direction and the film width direction, respectively. ..
Further, after biaxial stretching, the film MD or film TD may be re-stretched. Further, after biaxial stretching, annealing treatment may be performed. The annealing temperature is usually 100 to 230 ° C, preferably 130 to 220 ° C.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following description, "parts" means "parts by mass" unless otherwise specified.

[Measurement method of various physical properties]
<Constituent unit content in 4-methyl-1-pentene copolymer>
Amount of structural units derived from 4-methyl-1-pentene (4-methyl-1-pentene content) and amount of structural units derived from α-olefins other than 4-methyl-1-pentene (α-olefin content) ^{Was calculated from the 13} C-NMR spectrum under the following equipment and conditions.

Using ECP500 type nuclear magnetic resonance device manufactured by JEOL Ltd., orthodichlorobenzene / heavy benzene (80/20% by volume) mixed solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μsec (45 ° pulse), repetition time is 5.5 seconds, integration frequency is 10,000 times or more, 27.50 ppm is the standard for chemical shift. Measured as a value. The compositions of 4-methyl-1-pentene and α-olefin were quantified from the obtained ^{13 C-NMR spectrum.}

<Extreme viscosity [η]>
The ultimate viscosity [η] was measured at 135 ° C. using a decalin solvent. That is, about 20 mg of the polymerized powder, pellets or resin mass was dissolved in 15 mL of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting with 5 mL of decalin solvent added to this decalin solution, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice more, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the ultimate viscosity (see the formula below).
[Η] = lim (ηsp / C) (C → 0)

<Cross fractional chromatograph (CFC) analysis and molecular weight measurement>
CFC analysis and molecular weight measurement were performed under the following conditions.

Equipment: CFC type 2 cross fractionation chromatograph (Polymer Char)
Detector (built-in): IR4 type infrared spectrophotometer (Polymer Char)
Detection wavelength: 3.42 μm (2,920 cm ^-1 ); Fixed sample concentration: 30 mg / 30 mL (diluted with o-dichlorobenzene (ODCB))
Injection volume: 0.5 mL
Temperature conditions: The temperature was raised to 145 ° C. at 40 ° C./min and held for 30 minutes, cooled to 0 ° C. at 1 ° C./min and held for 60 minutes, and then the elution amount for each of the following elution categories was evaluated. The temperature change between the divisions was 40 ° C./min.
Elution classification: 0, 5, 10, 15, 20, 25, 30, 35, 50, 70, 90, 95, 100, 102, 104, 106 ° C, and from 108 ° C to 135 ° C in 1 ° C increments. Evaluate the amount of elution at 140,145 ° C.
GPC column: Shodex HT-806M x 3 (manufactured by Showa Denko)
GPC column temperature: 145 ° C
GPC column calibration: monodisperse polystyrene (Tosoh)
Molecular weight calibration method: Standard calibration method (polystyrene conversion)
Mobile phase: o-dichlorobenzene (ODCB), BHT added Flow rate: 1.0 mL / min

[Synthesis of metallocene compounds]
According to Synthesis Example 4 of WO2014 / 050817, (8-octamethylfluorene-12'-yl- (2- (adamantan-1-yl) -8-methyl-3,3b, 4,5,6, 7,7a, 8-octahydrocyclopenta [a] indene)) Zirconium dichloride (metallocene compound (a1)) was synthesized.

[Manufacturing Example 1]
In Production Example 1 (paragraphs [0182] to [0185]) of JP-A-2018-162408, the amount of linearene 168 (manufactured by Idemitsu Kosan) (1-hexadecene, 1-octadecene mixture) is changed to obtain a copolymer weight. The proportions of 4-methyl-1-pentene and linearene 168 used were changed so that the 4-methyl-1-pentene content and α-olefin (1-hexadecene, 1-octadecene) content in the coalescence were the values shown in Table 1. A 4-methyl-1-pentene copolymer (A-1) was obtained in accordance with the production example except that the value of [η] was set to the value shown in Table 1.

[Manufacturing Example 2]
In Production Example 1 ([0182] to [0185]) of JP-A-2018-162408, linearene 168 was changed to 1-decene, and the 4-methyl-1-pentene content and α- in the obtained copolymer were changed. The ratio of 4-methyl-1-pentene and 1-decene used was changed so that the olefin (1-decene) content was the value shown in Table 1, and the value of [η] was changed to the value shown in Table 1. A 4-methyl-1-pentene copolymer (A-2) was obtained in accordance with the production example except for the above.

[Preparation of solid catalyst components]
32 mL of purified decan and solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) were charged at 14.65 mmol in terms of aluminum atoms in a three-necked flask equipped with a 100 mL stirrer fully substituted with nitrogen at 30 ° C. under a nitrogen stream. It was added and made into a suspension.

50 mg (0.059 mmol in terms of zirconium atom) of the previously synthesized metallocene compound (a1) was used as a 4.6 mmol / L toluene solution.
12.75 mL of the toluene solution was added to the suspension with stirring. After 1.5 hours, stirring was stopped, and the obtained catalyst component was washed 3 times with 50 mL of decane by a decantation method and suspended in decane to obtain 50 mL of slurry liquid (B). The Zr loading ratio was 100% in this catalyst component.

[Preparation of prepolymerization catalyst components]
In the above slurry liquid (B), 0.4 mL of a decane solution of triethylaluminum (0.2 mmol / mL in terms of aluminum atom) and 7.5 mL (5.0 g) of 3-methyl-1-pentene were added under a nitrogen stream. I charged it. After 1.5 hours, stirring was stopped, and the obtained prepolymerization catalyst component was washed 3 times with 50 mL of decan by the decantation method. This prepolymerization catalyst component was suspended in decan to obtain 50 mL of decan slurry (C). The concentration of the prepolymerization catalyst component in the decan slurry (C) was 20 g / L, 1.05 mmol-Zr / L, and the Zr recovery rate was 90%.

[Manufacturing Example 3]
425 mL of purified decane and 0.4 mL (0.4 mmol) of triethylaluminum decane solution (1.0 mmol / mL in terms of aluminum atom) were placed in a SUS polymerizer equipped with a stirrer with an internal volume of 1 L under a nitrogen stream at room temperature. , 0.0005 mmol of the prepolymerized catalyst component decane slurry (C) prepared above was added in terms of zirconium atom, and 40 NmL of hydrogen was charged (first hydrogen charge). Then, a mixed solution of 106 mL of 4-methyl-1-pentene and 5.9 mL of linearene 168 was continuously charged into the polymerizer at a constant rate over 2 hours. The start of polymerization was defined as the start of polymerization, the temperature was raised to 45 ° C. over 30 minutes from the start of polymerization, then kept at 45 ° C. for 4 hours, and 90 NmL of hydrogen was charged 3 hours after the start of polymerization (second hydrogen charge). Charge). After 4.5 hours from the start of the polymerization, the temperature was lowered to room temperature, the pressure was depressurized, and then the polymerization solution containing the white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80 ° C. for 8 hours to obtain a 4-methyl-1-pentene copolymer (B-1).

[Manufacturing Example 4]
A SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently substituted with nitrogen was charged with 300 ml of normal hexane (dried on a dry nitrogen atmosphere and activated alumina) and 450 ml of 4-methyl-1-pentene at 23 ° C. bottom. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into this autoclave, and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with ethylene so that the total pressure became 0.10 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance in terms of Al, diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium 0.34 ml of a toluene solution containing 0.01 mmol of dichloride was press-fitted into an autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the temperature inside the autoclave was 60 ° C. 60 minutes after the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.
The obtained powdery polymer containing the solvent was dried at 100 ° C. under reduced pressure for 12 hours to obtain a 4-methyl-1-pentene copolymer (B-2).

[Manufacturing Example 5]
Using 1-decene instead of linearene 168, the values of 4-methyl-1-pentene and α-olefin (1-decene) and [η] in the obtained copolymer are as shown in Table 1. A 4-methyl-1-pentene copolymer (B-3) was obtained in accordance with Production Example 3 except that each usage ratio was changed as described above.

[Manufacturing Example 6]
In Example 1, linearene 168 was changed to propylene so that the 4-methyl-1-pentene content and the α-olefin (propylene) content in the obtained copolymer had the values shown in Table 1. 4-Methyl-1-pentene copolymer (C -1) was obtained.

[product]
As the α-olefin polymer, homopolypropylene (C-2) (manufactured by Prime Polymer Co., Ltd., product number: F123P) was used.

[Manufacturing Example 7]
According to the polymerization method described in Comparative Example 9 of International Publication No. 2006/054613, except that 4-methyl-1-pentene, a mixture of 1-hexadeceene and 1-octadecene having an equal mass, and the ratio of hydrogen were changed. , 4-Methyl-1-pentene copolymer (C-3) was obtained. That is, the copolymer (C-3) is a solid titanium catalyst obtained by reacting anhydrous magnesium chloride, 2-ethylhexyl alcohol, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and titanium tetrachloride. Was obtained as a catalyst for polymerization.

Table 1 shows the physical characteristics of each polymer.

[Example 1]
For a mixture of 31.5 parts of 4-methyl-1-pentene copolymer (A-1) and 68.5 parts of (B-1), n-octadecyl-3- (4'-) as a heat-resistant stabilizer. 0.5 part of hydroxy-3', 5'-di-t-butylphenyl) propinate was blended. Next, the obtained compound was used in a twin-screw extruder BT-30 (screw system 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd. at a set temperature of 270 ° C. and a resin extrusion amount of 60 g / min. Granulation was performed under the conditions of 200 rpm and pellets were obtained.

The obtained pellets were supplied to a single-screw extruder, melt-kneaded at 270 ° C., and melt-extruded into a film from a T-shaped slit die. Next, the obtained film was cooled and solidified on a metal cooling roll controlled at 80 ° C. while being brought into close contact with air pressure to obtain an unstretched film having a thickness of 200 μm. The unstretched film obtained here was preheated with a heated metal roll to raise the film temperature to 130 ° C., and the unstretched film was vertically stretched three times between a pair of rolls having different peripheral speeds to obtain a uniaxially stretched film. bottom. Next, both ends of the uniaxially stretched film in the width direction were gripped with clips and guided to a heating oven, preheated to 120 ° C., and then laterally stretched 5.5 times in the width direction to obtain a biaxially stretched film. After that, the biaxially stretched film was heated to 200 ° C. for annealing treatment. Both ends of the biaxially stretched film thus obtained were cut by a leather cut using a leather blade, subjected to a corona discharge treatment, and then wound into a roll. The characteristics of the obtained biaxially stretched film were determined by the following evaluation method.

[thickness]
Using a micrometer, the thickness of the biaxially stretched film or unstretched film was measured at 10 points in the width direction and 10 points in the length direction, and the average value was taken as the thickness of the biaxially stretched film or unstretched film.

[Tensile breaking strength]
The stretched film was cut into strips having a length of 150 mm and a width of 15 mm to prepare a test piece for evaluating the tensile breaking strength of the MD.

The stretched film was cut into strips having a length of 150 mm and a width of 15 mm to prepare a test piece for evaluating the tensile breaking strength of the LD.
Tensile stress was measured using a universal tensile tester 3380 manufactured by Instron with a tensile speed of 200 mm / min and a gripping interval of 100 mm in accordance with JIS K678. For the tensile strength at break, which is a tensile property, the stress at the time when the film was broken was evaluated.

[Tearability]
In the leather cutting process using a leather blade, the case where the leather cutting was possible continuously without breaking for 30 minutes or more was defined as AA. When the film was torn in less than 30 minutes during continuous leather cutting, it was defined as BB.

[Dielectric breakdown strength (120 ° C)]
The dielectric breakdown strength (V / μm) was measured according to ASTM-D149 using a dielectric breakdown tester manufactured by Yamayo Tester Co., Ltd. With respect to the biaxially stretched film or the unstretched film, a voltage was applied at a step-up speed of 500 V / sec at 120 ° C., and the breakdown withstand voltage was measured. The case where the dielectric breakdown strength at 120 ° C. was 300 V / μm or more was defined as AA, the case where the dielectric breakdown strength was 250 V / μm or more and less than 300 V / μm was defined as BB, and the case where the dielectric breakdown strength was less than 250 V / μ m was defined as CC.

[Heat shrinkage rate (130 ° C)]
The film was sampled in the MD (longitudinal direction) to a length of 260 mm and a width of 10 mm, and marks were placed 30 mm from both ends, and the length between the marks was set to L0 (200 mm). A load of 3 g was applied to the lower end of each sample, and the sample was hung in an oven at 130 ° C. and heat-treated for 30 minutes. After that, the sample was taken out, the length L1 between the marks was measured, and the heat shrinkage rate (%) = [(L0-L1) / L0] × 100 was calculated. The case where the heat shrinkage rate was less than 3% was defined as AA, and the case where the heat shrinkage rate was 3% or more was defined as BB.

[Stretchability]
The same procedure was carried out except that the stretching ratio was changed from the above method, and the stretching ratio of the unstretched film was gradually increased to verify at what ratio the unstretched film was broken. The level at which stretching was possible without breaking to a higher magnification was defined as the level with excellent stretchability. As for the stretching ratio, MD and TD were set to the same magnification, and the stretching was sequentially performed so as to be 2.5, 3.0, 3.5, 4.0, and classified as follows according to the breaking ratio.

AA: Can be stretched up to 4.0 times x 4.0 times BB: Can be stretched up to 3.5 times x 3.5 times CC: Can be stretched up to 3.0 times x 3.0 times DD: 2.5 times x 2 .Can or cannot be stretched up to 5 times

[Examples 2 to 5, Comparative Examples 1 to 8]
The above-mentioned 4-methyl-1-pentene copolymers (A) [(A-1) and (A-2)], 4-methyl-1-pentene copolymers (B) [(B-1), ( B-2) and (B-3)] and the polymers (C-1), (C-2) and (C-3) were blended in the types and amounts shown in Table 2 to make 100 parts. A biaxially stretched film was obtained in the same manner as in Example 1 except that it was carried out under the film forming conditions shown in Table 2.

In Comparative Example 7, the heat shrinkage at 130 ° C. was large and the heat resistance was poor.
Further, in Comparative Example 8, when the biaxial stretching was attempted, if the longitudinal stretching ratio was 2 times or more, the film may be broken or the thickness unevenness of the film may be increased, so that uniform stretching could not be performed. ..

Table 2 shows the physical characteristics of the polymers used in each of the examples and comparative examples, the stretching conditions, the physical properties of the stretched film, and the like.

Claims (8)

90 to 5 parts by mass of 4-methyl-1-pentene copolymer (A) satisfying the following requirements (Aa) to (Ad), and the following requirements (Ba) to (Bd) and ( 10 to 95 parts by mass of the 4-methyl-1-pentene copolymer (B) satisfying B-a1) (however, the total of the copolymer (A) and the copolymer (B) is 100 parts by mass). The ratio of the tensile breaking strength of MD (polymer direction) to the tensile breaking strength of TD (transverse direction) (tensile breaking strength of MD / tensile breaking strength of TD) obtained by biaxially stretching the containing film (α) is A film (β) in the range of 0.5 to 3.0.
(A-a) The amount (U3) of the structural unit derived from 4-methyl-1-pentene is 20.0 to 98.0 mol%, and the number of carbon atoms other than 4-methyl-1-pentene is 5 to 20. The amount (U4) of the building blocks derived from the α-olefin is 80.0 to 2.0 mol%. (However, the total of the U3 and the U4 is 100 mol%).
(A-b) The ultimate viscosity [η] _A measured in decalin at 135 ° C. is 1.7 to 8.0 dL / g.
(Ac) When the copolymer (A) is measured by a cross-separation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the amount of eluted components is in the range of 0 ° C. or higher and lower than 100 ° C. There is at least one peak of.
(Ad) When the copolymer (A) is measured with a cross fractionation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the elution components in the range of 0 ° C. or higher and lower than 100 ° C. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 1.0 to 7.0.
(BA) The amount (U5) of the structural unit derived from 4-methyl-1-pentene is 80.0 to 99.9 mol%, and has 2 to 20 carbon atoms other than 4-methyl-1-pentene. The amount (U6) of the structural unit derived from the α-olefin is 20.0 to 0.1 mol%. (However, the total of the U5 and the U6 is 100 mol%).
(B-b) The ultimate viscosity [η] _B measured in decalin at 135 ° C. is 0.5 to 5.0 dL / g.
(B-c) When the copolymer (B) is measured by a cross-separation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the amount of eluted components is in the range of 100 ° C. or higher and lower than 140 ° C. There is at least one peak of.
(B-d) When the copolymer (B) is measured with a cross fractionation chromatograph (CFC) apparatus using an infrared spectrophotometer in the detection unit, the elution components in the range of 100 ° C. or higher and lower than 140 ° C. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 1.0 to 3.5.
(B-a1) The ratio (U4 / U6) of U4 (mol%) described in the requirement (A-a) to U6 (mol%) described in the requirement (B-a) is 1.0. Exceeded and less than 50.0. The film (β) according to claim 1, wherein the film (β) is a film obtained by sequentially biaxially stretching the film (α). The film (β) according to claim 1 or 2, wherein the α-olefin in the copolymer (B) is an α-olefin having 5 to 20 carbon atoms other than 4-methyl-1-pentene. The film according to any one of claims 1 to 3, wherein the α-olefins in the copolymer (A) and the copolymer (B) are independently α-olefins having 10 to 20 carbon atoms. β). The film (β) according to any one of claims 1 to 4, wherein the stretch ratio in the biaxial stretching is 1.1 to 100 times in terms of area. The film (β) according to any one of claims 1 to 5, which has a thickness of 1 to 100 μm. The film (β) according to any one of claims 1 to 6, which is a film for a capacitor. The film (β) according to any one of claims 1 to 7, which is a film for a dielectric of a film capacitor.