JP2021138879A - Olefinic resin composition and molded article - Google Patents

Abstract

To provide an olefinic resin composition capable of achieving a molded article which suppresses bleed-out of a lubricant to the surface of the molded article and generation of a gelatinous material.SOLUTION: The olefinic resin composition contains a cyclic olefin copolymer (A) and a silylated polyolefin (B). The cyclic olefin copolymer (A) contains at least one olefin-derived repeating unit (a) and at least one cyclic olefin-derived repeating unit (b).SELECTED DRAWING: None

Description

The present invention relates to an olefin resin composition and a molded product.

As a transparent base film, various organic polymer film materials that replace glass are being studied.
Patent Document 1 describes a base film of a transparent conductive sheet containing an alicyclic structure-containing polymer.

Not only has sufficient transparency and optical properties, but also has excellent water absorption, low dielectric constant, low dielectric loss, etc., and is further uniaxially or biaxially stretched in the in-plane and thickness directions. Cyclic olefin copolymer resins have been widely studied because the retardation value of the above can be controlled. On the other hand, when the cyclic olefin copolymer resin is melt-molded, a gel-like substance is generated and the transparency is lowered, and the molded surface may be roughened and the appearance characteristics may be deteriorated. It is known that this phenomenon has a great influence when a cyclic olefin copolymer resin is used as a material as a transparent molded product.

In the gel-like product, a strong pressure and shearing force are applied to the cyclic olefin copolymer resin before melting in the step of heat-plasticizing the cyclic olefin copolymer resin during molding, and the cyclic olefin copolymer resin forms a crosslinked structure. It is known that it occurs by doing so.
As a method for suppressing the generation of gel-like substances as described above, a method of adding a phenol-based antioxidant, a fatty acid amide-based lubricant, a metal soap-based lubricant, or the like is known (see, for example, Patent Documents 2 and 3).

Patent Document 2 describes a sheet containing a cyclic olefin copolymer resin having improved transparency (haze) by coating with a powder and / or liquid coating agent and then melt-molding with a molding machine. There is.
Further, in Patent Document 3, a fatty acid metal salt or a fatty acid amide is added as a lubricant to a resin pellet containing a cyclic olefin-based copolymer, the added mixture is melt-kneaded and then molded into a premolded product, and then the preformed product is formed. A method for molding a cyclic olefin copolymer, which is characterized by stretch molding, is described.
Further, in Patent Document 4, it was obtained by adding an organic compound having a hydrophilic group at one end of a linear hydrocarbon and having 14 or more carbon atoms to a cyclic olefin resin polymerization solution, and then removing the polymerization solvent. A molded product made from pellets produced using a resin composition is described.

Japanese Unexamined Patent Publication No. 11-228625 Patent No. 3377833 Patent No. 3460457 Patent No. 5670688

As a result of the examination by the present inventor, it has been clarified that the above-mentioned method using the above-mentioned lubricant may not have an sufficient effect of suppressing the generation of gel-like substances during molding. Further, when a fatty acid metal salt or a fatty acid amide is used as the lubricant, the lubricant bleeds out from the molded film, the effect of suppressing the generation of gel-like substances becomes insufficient, and the film surface becomes sticky. It was clarified that film blocking may occur when the film is wound.

The present invention has been made in view of the above circumstances, and provides an olefin-based resin composition capable of realizing a molded product in which bleed-out of a lubricant on the surface of the molded product and generation of a gel-like substance are suppressed. ..

According to the present invention, the following olefin-based resin compositions and molded articles are provided.

〔前記一般式（Ｉ）において、Ｒ^３００は水素原子又は炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。〕

（上記一般式（ＩＩ）において、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^７５〜Ｒ^７８は、互いに結合して単環または多環を形成していてもよい。）

（上記一般式（ＩＩＩ）において、ｘおよびｄは０または１以上の整数であり、ｙおよびｚは０、１または２であり、Ｒ^８１〜Ｒ^９９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基若しくは炭素原子数３〜１５のシクロアルキル基である脂肪族炭化水素基、炭素原子数６〜２０の芳香族炭化水素基またはアルコキシ基であり、Ｒ^８９およびＲ^９０が結合している炭素原子と、Ｒ^９３が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ^９５とＲ^９２またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。）

（上記一般式（ＩＶ）において、Ｒ^１００、Ｒ^１０１は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基を示し、ｆは１≦ｆ≦１８である。）
［２］
上記［１］に記載のオレフィン系樹脂組成物において、
前記環状オレフィン重合体（Ａ）が、下記一般式（Ｉ）で表される少なくとも１種のオレフィン由来の繰り返し単位（ａ）と、下記一般式（ＩＩ）で表される繰り返し単位と、を含む共重合体であるオレフィン系樹脂組成物。

（上記一般式（Ｉ）において、Ｒ³⁰⁰は水素原子又は炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。）

（上記一般式（ＩＩ）において、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ^７５〜Ｒ^７８は、互いに結合して単環または多環を形成していてもよい。）
［３］
上記［１］または［２］に記載のオレフィン系樹脂組成物において、
前記シリル化ポリオレフィン（Ｂ）が下記式（１）で表されるシリル化ポリオレフィンを含むオレフィン系樹脂組成物。

（前記式（１）において、Ａ^１、Ａ^２およびＡ^３は各々独立に、ポリオレフィン鎖または炭素数１〜２０の炭化水素基である。Ｒは炭素数１〜２０の炭化水素基である。各Ｒは同一でも異なっていてもよい。ｍは１〜１０，０００の整数である。Ａ^３が複数存在する場合、各Ａ^３は同一でも異なっていてもよい。ただし、Ａ^１、Ａ^２、Ａ^３のうち、少なくとも１つはポリオレフィン鎖を表す。）
［４］
上記［１］乃至［３］のいずれか一つに記載のオレフィン系樹脂組成物において、
前記環状オレフィン重合体（Ａ）のガラス転移温度が１００℃以上１８０℃以下であるオレフィン系樹脂組成物。
［５］
上記［１］乃至［４］のいずれか一つに記載のオレフィン系樹脂組成物において、
前記環状オレフィン共重合体（Ａ）のガラス転移温度が１１０℃以上１６０℃以下であるオレフィン系樹脂組成物。
［６］
上記［１］乃至［５］のいずれか一つに記載のオレフィン系樹脂組成物において、
前記オレフィン系樹脂組成物中の前記環状オレフィン共重合体（Ａ）の含有量に対する前記シリル化ポリオレフィン（Ｂ）の含有量の質量比が１．０×１０^−５以上１．０×１０^−３以下であるオレフィン系樹脂組成物。
［７］
上記［１］乃至［６］のいずれか一つに記載のオレフィン系樹脂組成物を成形してなる成形体。
［８］
上記［７］に記載の成形体において、
フィルムまたはシートである成形体。 [1]
The cyclic olefin copolymer (A) and the silylated polyolefin (B) are contained.
The cyclic olefin copolymer (A)
The repeating unit (a) derived from at least one olefin represented by the following general formula (I) and
At least one ring selected from the group consisting of a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and a repeating unit represented by the following general formula (IV). An olefin resin composition which is a copolymer containing a repeating unit (b) derived from an olefin.

[In the general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. ]

(In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring.)

(In the above general formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same or different from each other. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aliphatic hydrocarbon group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. Yes, the ^{carbon atom to which R 89} and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded directly or have an alkylene group having 1 to 3 carbon atoms. They may be bonded via each other, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. good.)

(In the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. .)
[2]
In the olefin resin composition according to the above [1],
The cyclic olefin polymer (A) contains a repeating unit (a) derived from at least one olefin represented by the following general formula (I) and a repeating unit represented by the following general formula (II). An olefin resin composition that is a copolymer.

(In the above general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.)

(In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring.)
[3]
In the olefin resin composition according to the above [1] or [2],
An olefin-based resin composition in which the silylated polyolefin (B) contains a silylated polyolefin represented by the following formula (1).

(In the above formula (1), A ¹ , A ² and A ³ are independently polyolefin chains or hydrocarbon groups having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. each R If good .m be the same or different where .A ³ is an integer of 1 to 10,000 is more present, each ^{a 3} may be the same or different. ^However, a 1, ^{a 2} of the ^{a 3,} represents at least one polyolefin chain.)
[4]
In the olefin resin composition according to any one of the above [1] to [3],
An olefin resin composition in which the glass transition temperature of the cyclic olefin polymer (A) is 100 ° C. or higher and 180 ° C. or lower.
[5]
In the olefin resin composition according to any one of the above [1] to [4],
An olefin resin composition in which the glass transition temperature of the cyclic olefin copolymer (A) is 110 ° C. or higher and 160 ° C. or lower.
[6]
In the olefin resin composition according to any one of the above [1] to [5],
The mass ratio of the content of the silylated polyolefin (B) to the content of the cyclic olefin copolymer (A) in the olefin resin composition is 1.0 × 10 ^-5 or more and 1.0 × 10 ^-3. The following olefin resin composition.
[7]
A molded product obtained by molding the olefin resin composition according to any one of the above [1] to [6].
[8]
In the molded product according to the above [7],
A molded product that is a film or sheet.

According to the present invention, it is possible to provide an olefin-based resin composition capable of realizing a molded product in which bleed-out of a lubricant on the surface of the molded product and generation of a gel-like substance are suppressed.

Hereinafter, the olefin-based resin composition according to the present embodiment will be described in detail, but the present invention is not limited to the following embodiments, and appropriate modifications are made within the scope of the object of the present invention. Can be carried out.
In the present embodiment, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value. In the numerical range described stepwise in the present embodiment, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present embodiment, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the embodiment.

<Olefin resin composition>
The olefin-based resin composition according to the present embodiment contains a cyclic olefin copolymer (A) and a silylated polyolefin (B).

Since the fatty acid metal salt generally used as a lubricant that suppresses the generation of gel-like substances has low compatibility with the cyclic olefin copolymer, the lubricant located on the surface of the resin composition falls off from the resin composition over time. However, the turbidity of the film may deteriorate. Further, fatty acid amides and organic compounds having a hydrophilic group at one end of the linear hydrocarbon and having 14 or more carbon atoms have good compatibility with the cyclic olefin copolymer, but on the other hand, these compounds are There is a possibility that the lubricant bleeds out from the film obtained by molding the olefin resin composition, and the adhesiveness is developed and the film is blocked when the film is wound up. Further, when incorporating the additive into a product as a part, there is a problem that the transfer of the additive to various processing equipment may affect the productivity. In addition, some of the higher fatty acids are known to be sensitizing, which can make specifications difficult for applications that come into contact with the skin.

On the other hand, the silylated polyolefin (B) has high compatibility with the cyclic olefin copolymer (A), and the molecular weight of the silylated polyolefin (B) is relatively high, so that it is difficult to bleed out and gel-like substances are generated. The inhibitory effect can be maintained.
The olefin-based resin composition containing the cyclic olefin copolymer (A) and the silylated polyolefin (B) has a high surface silicon concentration and suppresses surface free energy, so that the generation of gel-like substances is suppressed. The present inventors speculate.
Since the highly polar silyl group has low affinity with the cyclic olefin copolymer (A), it is arranged outward on the surface of the resin composition, and the olefin moiety of the silylated polyolefin (B) is a cyclic olefin copolymer (cyclic olefin copolymer (B). Since the affinity with A) is high, the olefin moiety interacts with the cyclic olefin copolymer (A). As a result, the silylated polyolefin (B) is less likely to fall off from the surface of the resin composition, and as a result, deterioration of turbidity and bleed-out of the film can be suppressed, and the generation of gel-like substances is suppressed. Are guessing.
Further, as compared with the conventional lubricant, the silylated polyolefin (B) tends to be uniformly present on the surface of the resin composition, so that the bleed-out of the cyclic olefin copolymer (A) is suppressed evenly on the entire surface of the composition. The present inventors speculate that this is the case.

In the olefin-based resin composition according to the present embodiment, the mass ratio of the content of the silylated polyolefin (B) to the content of the cyclic olefin copolymer (A) in the olefin-based resin composition (that is, the silylated polyolefin (that is, the silylated polyolefin) The content of B) / the content of the cyclic olefin copolymer (A)) is preferably 1.0 from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant. × ^10-5 or more, more preferably 5.0 × ^10-5 or more, further preferably 1.0 × 10 ^-4 or more, particularly preferably 2.0 × 10 ^-4 or more, moldability, and other weights. From the viewpoint of compatibility with the coalescence and maintaining the characteristics and physical properties of other polymers, it is preferably 1.0 × 10 ^-3 or less, more preferably 8.0 × 10 ^-4 or less, and further preferably 7.5. It is × 10 ^-4 or less.

In the olefin resin composition according to the present embodiment, the total content of the cyclic olefin copolymer (A) and the silylated polyolefin (B) is preferably 100% by mass based on the total content of the olefin resin composition. Is 20% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The shape of the olefin resin composition according to the present embodiment is not particularly limited, and examples thereof include pellets, veils, lumps, and sheets.

Hereinafter, each component constituting the olefin resin composition according to the present embodiment will be described.

<Cyclic olefin copolymer (A)>
The cyclic olefin copolymer (A) according to the present embodiment is a polymer having a repeating unit derived from the cyclic olefin as an essential constituent unit.
The cyclic olefin copolymer (A) according to the present embodiment has a repeating unit (a) derived from at least one olefin represented by the following general formula (I) and a repeating unit represented by the following general formula (II). The unit includes a repeating unit (b) derived from at least one cyclic olefin selected from the group consisting of a repeating unit represented by the following general formula (III) and a repeating unit represented by the following general formula (IV). It is a copolymer.
The cyclic olefin copolymer (A) according to the present embodiment is a repeating unit (a) derived from at least one type of olefin represented by the following general formula (I) from the viewpoint of improving the moldability of the olefin resin composition. ) And a repeating unit represented by the following general formula (II), preferably a copolymer containing.

上記一般式（Ｉ）において、Ｒ³⁰⁰は水素原子または炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。

In the above general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

上記一般式（ＩＩ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ⁷⁵〜Ｒ⁷⁸は互いに結合して単環または多環を形成していてもよい。

In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring.

上記一般式（ＩＩＩ）において、ｘおよびｄは０または１以上の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｙおよびｚは０、１または２であり、Ｒ^８１〜Ｒ^９９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基若しくは炭素原子数３〜１５のシクロアルキル基である脂肪族炭化水素基、炭素原子数６〜２０の芳香族炭化水素基またはアルコキシ基であり、Ｒ^８９およびＲ^９０が結合している炭素原子と、Ｒ^９３が結合している炭素原子またはＲ^９１が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ^９５とＲ^９２またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。

In the above general formula (III), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R. ^{81 to} R ⁹⁹ may be the same as or different from each other, and are an aliphatic hydrocarbon group or carbon which is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. It is an aromatic hydrocarbon group or alkoxy group having 6 to 20 ^{atoms, and a carbon atom to which R 89} and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or a carbon atom to which R ⁹¹ is bonded. May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other. It may form a monocyclic or polycyclic aromatic ring.

上記一般式（ＩＶ）において、Ｒ^１００、Ｒ^１０１は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基を示し、ｆは１≦ｆ≦１８である。

In the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18.

<Olefin monomer>
The olefin monomer, which is one of the copolymerization raw materials of the cyclic olefin copolymer (A) according to the present embodiment, is addition-copolymerized to form a structural unit represented by the above general formula (I). Specifically, an olefin monomer represented by the following general formula (Ia) corresponding to the above general formula (I) is used.

上記一般式（Ｉａ）において、Ｒ^３００は水素原子または炭素原子数１〜２９の直鎖状または分岐状の炭化水素基を示す。上記一般式（Ｉａ）で表されるオレフィンモノマーとしては、例えば、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン等が挙げられる。より優れた耐熱性、機械的特性および光学特性を有する成形体を得る観点から、これらのなかでも、上記一般式（Ｉａ）で表されるオレフィンモノマーとしては、エチレンおよびプロピレンから選択される少なくとも一種が好ましく、エチレンがさらに好ましい。上記一般式（Ｉａ）で表されるオレフィンモノマーは、１種単独でも２種類以上を用いてもよい。

In the above general formula (Ia), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin monomer represented by the general formula (Ia) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 3 -Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene , 4-Ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among these, at least one selected from ethylene and propylene as the olefin monomer represented by the above general formula (Ia) from the viewpoint of obtaining a molded product having better heat resistance, mechanical properties and optical properties. Is preferable, and ethylene is more preferable. The olefin monomer represented by the general formula (Ia) may be used alone or in combination of two or more.

When the total constituent units constituting the cyclic olefin copolymer (A) according to the present embodiment are 100 mol%, the proportion of the repeating unit (a) derived from the olefin is preferably 1 mol% or more and 95 mol% or less. , More preferably 20 mol% or more and 90 mol% or less, further preferably 40 mol% or more and 85 mol% or less, and particularly preferably 50 mol% or more and 80 mol% or less.
The proportion of the repeating unit (a) derived from olefin can be measured by ^{13 C-NMR.}

<Cyclic olefin monomer (b)>
The cyclic olefin monomer (b) constituting the cyclic olefin copolymer (A) according to the present embodiment is not particularly limited, and for example, the cyclic olefin monomer described in paragraphs 0037 to 0063 of International Publication No. 2006/0118261. Can be mentioned.
The cyclic olefin monomer (b), which is one of the copolymerization raw materials of the cyclic olefin copolymer (A) according to the present embodiment, is subjected to ring-opening polymerization or addition copolymerization to the above general formula (II) and the above general formula (III). ) Or the repeating unit (b) derived from the cyclic olefin represented by the above general formula (IV). Specifically, the cyclic olefins represented by the general formulas (IIa), (IIIa), and (IVa) corresponding to the general formula (II), the general formula (III), and the general formula (IV), respectively. Monomer (b) is used.

上記一般式（ＩＩａ）において、ｕは０または１であり、ｖは０または正の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｗは０または１であり、Ｒ^６１〜Ｒ^７８ならびにＲ^ａ１およびＲ^ｂ１は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、炭素原子数３〜１５のシクロアルキル基、または炭素原子数６〜２０の芳香族炭化水素基であり、Ｒ⁷⁵〜Ｒ⁷⁸は、互いに結合して単環または多環を形成していてもよい。

In the above general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and w is 0 or 1. R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, and are hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkyl halide group having 1 to 20 carbon atoms, and the like. It is a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocyclic or polycyclic ring. ..

上記一般式（ＩＩＩａ）において、ｘおよびｄは０または１以上の整数、好ましくは０以上２以下の整数、より好ましくは０または１であり、ｙおよびｚは０、１または２であり、Ｒ^８１〜Ｒ^９９は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基若しくは炭素原子数３〜１５のシクロアルキル基である脂肪族炭化水素基、炭素原子数６〜２０の芳香族炭化水素基またはアルコキシ基であり、Ｒ^８９およびＲ^９０が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ^９１が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ^９５とＲ^９２またはＲ^９５とＲ^９９とは互いに結合して単環または多環の芳香族環を形成していてもよい。

In the above general formula (IIIa), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1 or 2, and R. ^{81 to} R ⁹⁹ may be the same as or different from each other, and are an aliphatic hydrocarbon group or carbon which is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. It is an aromatic hydrocarbon group or alkoxy group having 6 to 20 ^{atoms, and a carbon atom to which R 89} and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or a carbon atom to which R ⁹¹ is bonded. May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other. It may form a monocyclic or polycyclic aromatic ring.

上記一般式（ＩＶａ）において、Ｒ¹⁰⁰、Ｒ¹⁰¹は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基を示し、ｆは１≦ｆ≦１８である。
共重合成分として、上述した一般式（Ｉａ）で表されるオレフィンモノマー、一般式（ＩＩａ）、（ＩＩＩａ）または（ＩＶａ）で表される環状オレフィンモノマー（ｂ）を用いることにより、フィルムを成形する際の成形性がより良好となる。

In the above general formula (IVa), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18.
A film is formed by using the olefin monomer represented by the general formula (Ia) and the cyclic olefin monomer (b) represented by the general formula (IIa), (IIIa) or (IVa) as the copolymerization component. The moldability is improved.

Specifically, bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclo Pentadecadien derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5 -Heneikosen derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacosene derivative, cyclopentadiene-acenaftylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, Examples thereof include 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivatives and cycloalkylene derivatives having 3 to 20 carbon atoms.

From the viewpoint of further suppressing the generation of gel-like substances, among the cyclic olefin monomers (b) represented by the general formulas (IIa), (IIIa) or (IVa), the cyclic olefin represented by the general formula (IIa). , And more preferably a cyclic olefin represented by the general formula (I), representing a repeating unit of a four-ring cyclic olefin. Specific examples thereof include tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene (also simply referred to as tetracyclododecene), 8-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] Dodeca-3-ene, 8-vinyltetracyclo [4,4.0.1, ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene and other 4-ring cyclic olefins can be mentioned. As a cyclic olefin, tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] It is more preferable to include dodeca-3-ene (tetracyclododecene) as a repeating unit.

From the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant when the total number of the constituent units constituting the cyclic olefin polymer (A) according to the present embodiment is 100 mol%. Therefore, the ratio of the repeating unit (b) derived from the cyclic olefin monomer (b) is preferably 5 mol% or more and 100 mol% or less, more preferably 10 mol% or more and 80 mol% or less, and further preferably 20 mol% or more and 50. It is less than mol%. The ratio of the repeating units (a) and (b) is preferably (a) / (b) = 60/40 to 40/60 in terms of molar ratio.

In addition to the repeating units (a) and (b), the cyclic olefin polymer (A) according to the present embodiment contains a small amount of repeating units made of other copolymerizable vinyl monomers as long as the object of the present invention is not impaired. For example, it may be contained in an amount of preferably 10 mol% or less, more preferably about 5 mol% or less, based on the total of the repeating units (a) and (b). Specific examples of the vinyl monomer include cyclic olefins different from the cyclic olefin monomer (b). For example, bicyclo [2.2.1] hept-2-ene, 6-methylbicyclo [2.2.1] hept-2-ene, 5,6-dimethylbicyclo [2.2.1] hept-2-ene. , 6-Ethylbicyclo [2.2.1] hept-2-ene, 6-butylbicyclo [2.2.1] hept-2-ene and the like. Of these, bicyclo [2.2.1] hept-2-ene and 1-hexene are preferable.

The cyclic olefin copolymer (A) has a weight average molecular weight (Mw) and a number average molecular weight (Mn) from the viewpoint of uniformly stretching the film or sheet during production and further suppressing the generation of gel-like substances. ), The molecular weight distribution (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.2 to 2.5, and even more preferably 1.2 to 2.0. The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) can be adjusted by changing the molecular skeleton of the cyclic olefin copolymer (A) and the like.

The cyclic olefin copolymer (A) has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC), preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 110 ° C. or higher and 160 ° C. or lower, further preferably. Is in the range of 120 ° C. or higher and 150 ° C. or lower. By setting the glass transition temperature (Tg) in the above range, the generation of gel-like substances can be further suppressed. The glass transition temperature (Tg) changes the molecular skeleton of the cyclic olefin copolymer (A), the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) which is a ratio thereof. It can be adjusted by.

The content of the cyclic olefin copolymer (A) in the olefin resin composition according to the present embodiment is not particularly limited, but is preferably 30% by mass or more when the total content of the olefin resin composition is 100% by mass. , More preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 60% by mass or more, preferably 99.8% by mass or less, more preferably 99.5% by mass or less, still more preferably 99. It is 0.0% by mass or less, still more preferably 98.0% by mass or less, and particularly preferably 97.0% by mass or less. Within the above range, the generation of gel-like substances is further suppressed, and an olefin-based resin composition having more excellent moldability can be obtained.

<Cyrilized polyolefin (B)>
The silylated polyolefin (B) according to the present embodiment may have any structure as long as it has a silicone chain and a polyolefin chain. For example, a silicone graft polyolefin having a structure in which polyolefin is grafted to polyolefin, a block copolymer of polyolefin and silicone, a structure in which polyolefin is grafted to silicone, a structure in which polyolefin is grafted to the silicone portion of the block copolymer, and the like can be mentioned. Can be done. The silylated polyolefin (B) may be used alone or in combination of two or more.

Examples of the block copolymer include a block copolymer bonded in the order of (polyolefin chain)-(silicone chain), a block copolymer bonded in the order of (polyolefin chain)-(silicone chain)-(polyolefin chain), and the like. be able to.
As the polyolefin chain, for example, a polymer chain containing a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms can be exemplified. Among these, those having a structure represented by the following general formula (1) are preferable.

上記式（１）において、Ａ^１、Ａ^２およびＡ^３は各々独立に、ポリオレフィン鎖または炭素数１〜２０の炭化水素基である。Ｒは炭素数１〜２０の炭化水素基である。各Ｒは同一でも異なっていてもよい。ｍは１〜１０，０００の整数である。Ａ^３が複数存在する場合、各Ａ^３は同一でも異なっていてもよい。ただし、Ａ^１、Ａ^２、Ａ^３のうち、少なくとも１つはポリオレフィン鎖を表す。

In the above formula (1), A ¹ , A ² and A ³ are independently polyolefin chains or hydrocarbon groups having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer of 1 to 10,000. If A ³ there are multiple, each A ³ may be the same or different. However, ^{at least one of A 1} , A ² , and A ³ represents a polyolefin chain.

The ^{polyolefin chain in A 1} , A ² and A ³ is a polymer chain containing a structural unit derived from, for example, an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms.
Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and α-olefin having 3 to 50 carbon atoms (propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4). -Methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1 -Pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-hexene, 3,4-dimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-octadecene, 1-eicosene, vinylcyclohexane, etc.) and the like.
Of these, at least one selected from ethylene and α-olefins having 3 to 12 carbon atoms is preferable from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant, and ethylene is preferable. And at least one selected from α-olefins having 3 to 8 carbon atoms is more preferable, and ethylene is even more preferable.

The polyolefin chain may be a homopolymer chain or a copolymer chain.
Among them, a polymer chain composed of only ethylene and an olefin having 2 to 50 carbon atoms selected from an α-olefin having 3 to 50 carbon atoms is preferable, and further, an ethylene homopolymer chain and a propylene homopolymer chain, Alternatively, an ethylene / α-olefin copolymer chain having 3 to 20 carbon atoms is preferable. In the ethylene / α-olefin copolymer chain having 3 to 20 carbon atoms, when the total structural unit is 100 mol%, the structural unit derived from the α-olefin having 3 to 20 carbon atoms exceeds, for example, 0 mol%. It can be 20 mol% or less, and can be more than 0 mol% and 10 mol% or less.

Further, the polyolefin chain may contain structural units derived from other olefins, if desired. Other olefins include olefins containing an internal double bond such as cis-2-butene; vinylidene compounds such as isobutene; arylvinyl compounds such as styrene; arylvinylidene compounds such as α-methylstyrene; functionals such as methyl methacrylate. Group-substituted vinylidene compounds; aliphatic cyclic olefins containing internal double bonds such as 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, dicyclopentadiene; cyclic olefins containing aromatic rings such as inden; butadiene, Examples thereof include chain or cyclic polyenes such as isoprene, etiliden norbornene, and vinyl norbornene.

The content of structural units derived from other olefins is 100 mol% of all the structural units constituting the polyolefin chain from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant. When this is done, 0 to 10 mol% is preferable, and 0 to 5 mol% is more preferable.

The polyolefin chain has a number average molecular weight of 100 or more and 500,000 or less determined by the following GPC method from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant. Is more preferable, 200 or more and 100,000 or less is more preferable, 500 or more and 50,000 or less is further preferable, and 700 or more and 10,000 or less is further preferable.
Further, the polyolefin chain has a molecular weight distribution (Mw / Mn) of 1.1 obtained by the following GPC method from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant. It is preferably in the range of ~ 3.0.

GPC measurement method:
GPC measurement is performed using orthodichlorobenzene as a solvent at a temperature of 140 ° C., and analytical values (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn) can be obtained as polyethylene equivalent values. ..
The measurement can be performed under the following conditions. In addition, the molecular weight can be determined based on the following conversion method by preparing a calibration curve using commercially available monodisperse standard polystyrene.
Equipment: Gel permeation chromatograph Alliance GPC2000 type (manufactured by Waters)
Solvent: o-dichlorobenzene Column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mLo-dichlorobenzene solution Temperature: 140 ° C
Molecular weight conversion: PS conversion / general-purpose calibration method The coefficient of the Mark-Houwink viscosity formula shown below can be used for the calculation of general-purpose calibration.
Polystyrene (PS) coefficient: KPS = 1.38 × 10-4, aPS = 0.70
Coefficient of polyethylene (PE): KPE = 5.06 × 10-4, aPE = 0.70

In the above A ¹ , A ² , A ³ and R, examples of the hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms include an alkyl group, an arylalkyl group, an alkenyl group and an aryl group. ..
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group and an octadecyl group. Such as linear or branched alkyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, norbornyl group and the like.
Examples of the arylalkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group and the like.
Examples of the alkenyl group include a vinyl group, a propenyl group, a cyclohexenyl group and the like.
Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a naphthyl group and the like.

In the above formula (1), m is an integer of 1 to 10,000. From the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant, m is preferably 5 or more, and more preferably 10 or more. Further, m is preferably 1,000 or less, more preferably 300 or less, and more preferably 50 or less.

The above A ¹ , A ² , singular or plural A ³ may be all polyolefin chains, or some groups may be polyolefin chains and others may be hydrocarbon groups having 1 to 20 carbon atoms. ..
In the above formula (1), m is equal to or greater than 2, when at least one of A ³ that is different from the other A ^3, but plural kinds of the following units are present, not particularly limited in its aligned sequence, block It may be targeted or random.

As the above formula (1), a structure represented by the following (1A), (1B) or (1C) is preferable, and among them, (1A) is more preferable.
(1A) In the above formula (1), A ¹ and A ² are polyolefin chains, and A ³ is a hydrocarbon group having 1 to 20 carbon atoms.
(1B) In the above formula (1), one of A ¹ and A ² is a polyolefin chain, the other is a hydrocarbon group having 1 to 20 carbon atoms, and A ³ is a hydrocarbon group having 1 to 20 carbon atoms. There is a structure.
(1C) In the above formula (1), A ¹ and A ² are hydrocarbon groups having 1 to 20 carbon atoms, and ^{at least one of A 3} is a polyolefin chain.

In the silylated polyolefin (B) according to the present embodiment, the silicone chain / polyolefin chain (mass ratio) is not particularly limited, but is preferably, for example, 5/95 to 99/1, more preferably 10. It is / 90 to 95/5.

The method for producing the silylated polyolefin (B) according to the present embodiment is not particularly limited, and is described in, for example, paragraphs 0008 to 0145 and paragraphs 0196 to 0207 of International Publication No. 2012/098865. Can be manufactured by

The content of the silylated polymer (B) in the olefin-based resin composition according to the present embodiment is olefin-based from the viewpoint of further suppressing the generation of gel-like substances and further suppressing the bleed-out of the lubricant. When the total amount of the resin composition is 100% by mass, it is preferably 1.0 × 10 ^-4 % by mass or more, more preferably 1.0 × 10 ^-3 % by mass or more, and further preferably 5.0 × 10 ^{-2. It is preferably 8.0 × 10-2} % by mass or less, more preferably 7 from the viewpoint of maintaining moldability, compatibility with other polymers, and characteristics / physical properties of other polymers. It is 5.5 × ^10-2 % by mass or less, more preferably 7.0 × ^10-2 % by mass or less, and even more preferably 6.5 × ^10-2 % by mass or less.

<Other polymers>
The olefin-based resin composition according to the present embodiment may contain a polymer other than the cyclic olefin copolymer (A) and the silylated polyolefin (B).
Examples of other polymers include polyolefins other than the cyclic olefin copolymer (A) and the silylated polyolefin (B), polystyrene, polyvinyl chloride, polyvinylidene chloride, ethylene / vinyl acetate copolymer, and ethylene (meth). ) Acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, polyester such as polyethylene terephthalate, polycarbonate, polyamide, ABS resin, polyacetal resin, polyimide, polyurethane, polylactic acid, phenol resin, epoxy resin, silicone resin , (Meta) acrylic resin, fluororesin and the like.

<Additives>
If desired, the olefin-based resin composition according to the present embodiment may contain various known additives used in the production of polyolefin products, as long as the object of the present invention is not impaired. Examples of such additives include phenol-based antioxidants, phosphorus-based stabilizers, sulfur-based stabilizers, ultraviolet absorbers, fatty acids, fatty acid salts, polyhydric alcohol fatty acid esters, amide compounds, waxes, and oils. Be done. For example, phenol-based antioxidants, phosphorus-based stabilizers, sulfur-based stabilizers, and ultraviolet absorbers are known to have an antioxidative effect on the heat-melted cyclic olefin copolymer (A). Further, fatty acids, fatty acid salts, polyhydric alcohol fatty acid esters, amide compounds, waxes, and oils are known to have an action of coating the cyclic olefin copolymer (A).

<Antioxidant>
When producing the molded product, an antioxidant or the like may be added for the purpose of assisting the effect of reducing the amount of the gelled product of the silylated polyolefin (B) and foreign substances such as charring. Examples of antioxidants include tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionic acid alkyl ester and 2,2'-oxamidbis [ethyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl)] Phenolic antioxidants such as propionate, tris (2,4-di-) tert-butylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4-biphenylenediphosphonite, etc. Phenyl stabilizers, as well as sulfur stabilizers such as dilaurylthiodipropionate, laurylstearylthiodipropionate, distearylthiodipropionate and penta (erythrityl-tetra-β-mercaptolauryl) propionate. .. The antioxidant is preferably added to the cyclic olefin copolymer (A) in the range of 100 to 3,000 ppm, more preferably 200 to 5,000 ppm.

Since the above additive needs to be added before the olefin resin composition is completely melted at the time of molding, it is preferable that the additive can be maintained in a powder state at room temperature, and the melting point of the additive is 120. More preferably, it is at ° C. or higher.

When the cyclic olefin copolymer (A) and the additive constituting the olefin resin composition have either a melting point or a glass transition temperature, the olefin resin composition and the additive are used. As a method of kneading, the mixture is mixed with a mixer tumbler or the like at a temperature below the melting point or the glass transition point, and then supplied to the hopper of the molding machine, or extruded while mixing the additives with a mixing feeder or the like. A known method such as a method of supplying to a machine, a method of side-feeding to an extruder hopper or the like can be used.

<Molded body>
The molded product according to the present embodiment is molded from the olefin resin composition according to the present embodiment. The molded product according to the present embodiment may have any shape, but is preferably a film, a sheet, a non-woven fabric or a foam, and more preferably a film shape.

The molded product according to the present embodiment is prepared by adding an external additive to the pellets of the olefin resin composition and forming a film by a known melt extrusion method to produce an unaligned film, and then, if necessary, satisfying the required mechanical properties. Post-processing such as annealing and stretching is performed for the purpose.

In the melt extrusion method, a method of extruding a resin using a T-die and sending it to a cooling roll is generally used. The temperature at the time of extrusion is determined in consideration of the melt viscosity and thermal stability of the cyclic olefin copolymer, but since the film is required to have heat resistance due to its usage environment, the glass is above the operating environment temperature of the film. It is necessary to use a cyclic olefin copolymer resin having a transition temperature (Tg) (generally 100 ° C to 180 ° C is suitable), and the molding conditions for melt extrusion show that the cylinder temperature is Usually, the glass transition temperature (Tg) of the cyclic olefin copolymer (Tg) + 50 ° C. to (Tg) + 200 ° C., preferably (Tg) + 70 ° C. to (Tg) + 170 ° C., and more preferably (Tg) + 100 ° C. to (Tg) +150. Set the temperature in the range of ° C.

The cyclic olefin copolymer (A) according to this embodiment is preferably carried out in the range of 210 ° C. to 280 ° C. Below 210 ° C, the melt viscosity of the copolymer becomes too high, and above 300 ° C, foaming due to decomposition of the copolymer, coloring due to high-temperature oxidative deterioration, generation of black spots, cross-linking gelation, transparency and homogeneity of the film. Sexuality may be impaired.
The resin extruded from the T-die solidifies on the cooling roll and the shape as a film is determined. However, if the cooling roll temperature is too low, poor adhesion to the roll causes poor appearance and poor stretchability, resulting in a cooling roll temperature. Is preferably equal to or higher than the glass transition temperature of the cyclic olefin copolymer (A).
However, in the case of an amorphous film such as the cyclic olefin copolymer (A), the strain applied in the process is alleviated when the temperature rises above the glass transition temperature (Tg). Therefore, if the cooling temperature is too high, dimensional stability cannot be obtained and there is a concern that it may cause poor uniformity. Therefore, it is desirable to set the temperature to about (Tg) to (Tg) + 20 ° C.

The thickness of the unstretched film is determined by the part where the film is used and the thickness required for the shape, but if it is too thick, uneven distortion will be applied to the film due to uneven cooling, which will cause deformation during use. Since problems such as deterioration of productivity and inability to perform uniform stretching are likely to occur, the film is usually formed in a size of 50 μm to 400 μm, preferably 80 μm to 250 μm.

In some cases, the unstretched film thus obtained removes the strain imparted during the manufacturing process, imparts photoisotropy, imparts the elastic modulus required for the form at the time of use, and provides crack resistance and tear resistance. For the purpose of improvement, the unaligned film is annealed or stretched at the same magnification in the biaxial direction.
In the case of a stretched film, the stretched film may satisfy the requirements of the present invention. The stretching method is not particularly limited, and a known method such as sequential biaxial stretching in which vertical uniaxial stretching is performed between two or a plurality of rolls and then horizontal uniaxial stretching using a tenter or the like, and simultaneous biaxial stretching in which they are combined is used. This makes it possible to obtain a film that is not oriented in a specific direction in the plane. When biaxial stretching is performed, it is possible to prevent an increase in the in-plane phase difference by setting the stretching ratios in the MD direction and the TD direction to the same magnification. Further, it is preferable to carry out the stretching continuously from the viewpoint of productivity, but it may be carried out by a batch method.

The stretching temperature is in the range of Tg to (Tg + 30 ° C.), preferably (Tg + 10 ° C.) to (Tg + 20 ° C.), with respect to the glass transition temperature (Tg) of the cyclic olefin copolymer (A). It is within the range.
The draw ratio is determined by the phase difference after film stretching, the mechanical property value required for the usage pattern, the thickness, etc., but since the maximum draw ratio that is possible differs depending on the cyclic olefin copolymer (A) as a raw material, MD , The TD direction may be set in the range of 1.05 to 6.0 times each.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto.

1. 1. Measurement and Evaluation Method (1) Composition of Cyclic Olefin Copolymer (A) The content of each structural unit of the cyclic olefin copolymer (A) was determined by the measured value by ^{13 C-NMR.} Measurements using ECA500 type nuclear magnetic resonance apparatus (manufactured by JEOL), measurement temperature: 120 ° C., measurement solvent: heavy tetrachloroethane, number of integrations: at 6,000 to 16,000 times, of the ¹³ C-NMR of the copolymer Obtained by measuring the spectrum.

(2) Glass transition temperature (Tg)
The glass transition temperatures of the cyclic olefin copolymer (A) and the polymer (C) are supplemented at a heating rate of 10 ° C./min using differential scanning calorimetry (DSC) in accordance with JIS K7121. It was determined as the glass transition start temperature.

(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
GPC measurement is performed using a polystyrene calibration curve at a temperature of 140 ° C. using orthodichlorobenzene as a solvent, and analytical values (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn) as polyethylene equivalent values. ) Can be obtained. The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the olefin polymer (A) and the silylated polyolefin (B) were measured under the following conditions, respectively.

Measurement conditions for silylated polyolefin (B):
A calibration curve was prepared using commercially available monodisperse standard polystyrene, and the calibration curve was determined based on the following conversion method.
-Device: Gel permeation chromatograph Alliance GPC2000 type (manufactured by Waters)
-Solvent: o-dichlorobenzene-Column: A configuration in which four TSKgel columns manufactured by Tosoh Corporation are connected in series-Flow velocity: 1.0 ml / min-Temperature: 140 ° C.
-Sample: 0.15 mg / mLo-dichlorobenzene solution-Molecular weight conversion: PS conversion / general-purpose calibration method The coefficients of the Mark-Houwink viscosity formula shown below were used for the calculation of general-purpose calibration.
Polystyrene (PS) coefficient: KPS = 1.38 × 10-4, aPS = 0.70
Coefficient of polyethylene (PE): KPE = 5.06 × 10-4, aPE = 0.70

(4) Evaluation method of gel-like substance It was visually confirmed whether or not gelled product was generated in the single-layer film obtained by the method described later, and this was evaluated as the degree of generation of gel-like substance as follows. ..
⊚: Number of gelled substances per 5 cm × 5 cm is 0 to 5 〇: Number of gelled substances per 5 cm × 5 cm is 6 to 20 pieces Δ: Number of gelled substances per 5 cm × 5 cm is 21 to 50 pieces ×: 5 cm × 5 cm 51 to 100 gelled products per XX: 101 or more gelled products per 5 cm x 5 cm

(5) Method for evaluating bleed-out property The sheet prepared by the following method was treated at 80 ° C. for 10 hours and evaluated by observing a change in appearance. The results are shown in Table X. In the table, "Yes" means that there is bleed-out of additives or the like from the test piece, and "No" means that there is no bleed-out.

2. Raw Materials The raw materials used in Examples and Comparative Examples are shown below.
(1) Cyclic olefin copolymer (A)
The cyclic olefin polymer (A-1) used in Examples and Comparative Examples was synthesized by a method according to the synthesis example described in Examples of International Publication No. 2008/068897.
A-1: ethylene and a cyclic olefin (tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodeca-3-ene), a copolymer (ethylene content: 69 mol%, tetracyclo [4.4 .0.1 ^2,5 .1 ^7,10] dodeca-3-ene content: 31 mol%, the glass transition temperature (Tg): 125 ℃)

(2) Cyrilized polyolefin (B)
[Synthesis Example 1]
(Synthesis of polyethylene having a vinyl group at one end)
A one-terminal vinyl group-containing ethylene-based polymer (P-1) was synthesized according to the method described in Synthesis Example 2 of International Publication No. 2012/098865.
^{1 By 1} H-NMR measurement, it was clarified that the obtained polymer was homopolyethylene and contained a double bond only at one end. The physical characteristics of this single-ended double bond-containing ethylene-based polymer (P-1) (elemental substance) were as follows.
Melting point (Tm) 127 ° C
Mw = 4770, Mw / Mn = 2.25 (GPC)
End unsaturated rate = 97%

[Synthesis Example 2]
(Preparation of Platinum Catalyst Composition (C-1))
In a 50 ml sample tube containing a magnetic stirrer chip, 0.50 g of platinum (II) chloride was suspended in hydrosilane A (HS (A), manufactured by Gelest, Inc., DMS-H11) (10 ml) having the following structure. The mixture was stirred at room temperature under a nitrogen stream. After stirring for 190 hours, about 0.4 ml of the reaction solution was collected with a syringe, filtered using a 0.45 μm PTFE filter, and the filtrate was collected in a 10 ml sample tube. A platinum catalyst having a platinum concentration of 3.8% by mass. The composition (C-1) was obtained.
Hydrosilane _{A (HS (A)):} HSi (CH 3) 2 O - (- Si (CH 3) 2 -O-) n-Si (CH 3) 2 H
(N = 12-13)

[Synthesis Example 3]
(Introduction of polyethylene having a terminal vinyl group into hydrosilane)
25.1 g (11.8 mmol) of the one-terminal vinyl group-containing ethylene-based polymer (P-1) obtained in [Synthesis Example 1] was charged into a 300 ml two-necked flask, and hydrosilane A was charged under a nitrogen atmosphere. (HS (A)) 6.7 g (5.9 mmol; equivalent to 11.8 mmol as Si—H group) and the platinum catalyst composition (C-1) prepared in [Synthesis Example 2] were combined with hydrosilane A (HS (A)). )) 200-fold diluted (C-1a) 150 μl (1.4 × ^10-6 mmol in terms of Pt) was further charged. The two-necked flask was set in an oil bath whose internal temperature had been raised to 130 ° C. in advance, and the mixture was stirred. After about 3 minutes the polymer melted. Then, after 6 hours, the mixture was cooled, about 200 ml of methanol was added, the contents were taken out into a 300 ml beaker, and the mixture was stirred for 2 hours. Then, the solid was collected by filtration, washed with methanol, and dried at 60 ° C. under a reduced pressure of 2 hPa or less to obtain 33.1 g of a silylated polyolefin (B-1) as a white solid. As a result of NMR analysis, the yield was 98%, the olefin conversion rate was 100%, and the isomerization rate was 2%. The MFR was equal to or higher than the upper limit of measurement (MFR> 100 g / 10 min), and the polyorganosiloxane content in (B-1) calculated from the molecular formula was 23% by mass.

(3) Additive Ethylene bisstearic acid amide (Kaohwax EB-FF (trade name), manufactured by Kao)

[Example 1]
The cyclic olefin copolymer (A-1) contains the silylated polyolefin (B-1), and the mass ratio of the content of the silylated polyolefin (B-1) to the content of the cyclic olefin copolymer (A-1). There were mixed by a tumbler type blender such as a 3.0 × ^{10 -4,} using a single-screw melt extruder (thermo plastic Kogyo full flight screw L / D = 27 compression ratio = 2.9), the width of 300mm It was melt-extruded from the T-die, molded with a cast roller, cooled, and continuously wound to form a film. The film forming conditions were a cylinder temperature of 220 ° C., a T-die temperature of 220 ° C., a cooling roller temperature of 90 ° C., and a film forming speed of 0.8 m / min. The thickness of the monolayer film was 50 μm. The obtained film was used to evaluate gels and bleed-outs. The results obtained are shown in Table 1.

[Examples 2 to 4]
The same operation as in Example 1 was carried out except that the mass ratio of the content of the silylated polyolefin (B-1) to the content of the cyclic olefin copolymer (A-1) was changed to the value shown in Table 1. Each single layer film was molded. The thickness of each single-layer film was 50 μm. The obtained film was used to evaluate gels and bleed-outs. The results obtained are shown in Table 1.

[Comparative Example 1]
A single-layer film was formed by performing the same operation as in Example 1 except that the silylated polyolefin (B-1) was not used. The thickness of the monolayer film was 50 μm. The bleed-out was evaluated using the obtained film. The results obtained are shown in Table 1.

[Comparative Examples 2 and 3]
The same operation as in Examples 1 and 2 was performed except that the silylated polyolefin (B-1) was changed to ethylene bisstearic acid amide (Kaowax EB-FF (trade name), manufactured by Kao Corporation), and the single-layer film was formed. Was molded respectively. The thickness of each single-layer film was 50 μm. The obtained films were used to evaluate bleed-out. The results obtained are shown in Table 1.

Claims (8)

The cyclic olefin copolymer (A) and the silylated polyolefin (B) are contained.
The cyclic olefin copolymer (A)
The repeating unit (a) derived from at least one olefin represented by the following general formula (I) and
At least one ring selected from the group consisting of a repeating unit represented by the following general formula (II), a repeating unit represented by the following general formula (III), and a repeating unit represented by the following general formula (IV). An olefin resin composition which is a copolymer containing a repeating unit (b) derived from an olefin.

[In the general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. ]

(In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring.)

(In the above general formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ may be the same or different from each other. A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aliphatic hydrocarbon group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group. Yes, the ^{carbon atom to which R 89} and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded directly or have an alkylene group having 1 to 3 carbon atoms. They may be bonded via each other, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. good.)

(In the above general formula (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. .) In the olefin resin composition according to claim 1,
The cyclic olefin polymer (A) contains a repeating unit (a) derived from at least one olefin represented by the following general formula (I) and a repeating unit represented by the following general formula (II). An olefin resin composition that is a copolymer.

(In the above general formula (I), R ³⁰⁰ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.)

(In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are identical to each other. However, they may be different, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or 6 carbon atoms. It is an aromatic hydrocarbon group of ~ 20, and R ⁷⁵ ~ R ⁷⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring.) In the olefin resin composition according to claim 1 or 2.
An olefin-based resin composition in which the silylated polyolefin (B) contains a silylated polyolefin represented by the following formula (1).

(In the above formula (1), A ¹ , A ² and A ³ are independently polyolefin chains or hydrocarbon groups having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. each R If good .m be the same or different where .A ³ is an integer of 1 to 10,000 is more present, each ^{a 3} may be the same or different. ^However, a 1, ^{a 2} of the ^{a 3,} represents at least one polyolefin chain.) The olefin-based resin composition according to any one of claims 1 to 3.
An olefin resin composition in which the glass transition temperature of the cyclic olefin polymer (A) is 100 ° C. or higher and 180 ° C. or lower. In the olefin-based resin composition according to any one of claims 1 to 4.
An olefin resin composition in which the glass transition temperature of the cyclic olefin copolymer (A) is 110 ° C. or higher and 160 ° C. or lower. The olefin-based resin composition according to any one of claims 1 to 5.
The mass ratio of the content of the silylated polyolefin (B) to the content of the cyclic olefin copolymer (A) in the olefin resin composition is 1.0 × 10 ^-5 or more and 1.0 × 10 ^-3. The following olefin resin composition. A molded product obtained by molding the olefin resin composition according to any one of claims 1 to 6. In the molded product according to claim 7,
A molded product that is a film or sheet.