JP2021138867A

JP2021138867A - Molded body

Info

Publication number: JP2021138867A
Application number: JP2020038759A
Authority: JP
Inventors: 彰太石原; Shota Ishihara; 豊明佐々木; Toyoaki Sasaki; 智昭松木; Tomoaki Matsuki
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 2020-03-06
Filing date: 2020-03-06
Publication date: 2021-09-16

Abstract

SOLUTION: A molded body including a hinge part is formed of 4-methyl-1-pentene copolymer composition (X) including (A) 10-50 pts.mass of a 4-methyl-1-pentene (co)polymer satisfying the following requirement (A-1), and (B) 50-90 pts.mass of a 4-methyl-1-pentene copolymer satisfying the following requirement (B-1), in which a total of the (co)polymer (A) and the copolymer (B) is 100 pts.mass. (A-1) A content of a constitutional unit derived from 4-methyl-1-pentene is more than 95.0 mol% and 100 mol% or less, a content of a constitutional unit derived from at least one kind of olefin selected from α-olefins having C2-C20 except for 4-methyl-1-pentene is 0 mol% or more and less than 5.0 mol%. (B-1) A content of the constitutional unit derived from 4-methyl-1-pentene is 40.0 to 95.0 mol%, and a content of the constitutional unit derived from at least one kind of olefin selected from α-olefins having C2-C20 except for 4-methyl-1-pentene is 5.0-60.0 mol%.EFFECT: According to the invention, a molded body excellent in transparency, weight saving property, chemical resistance, food product safety property, and folding resistance can be acquired, and the molded body has high folding resistance at a hinge part such as a movable part which is repeatedly bent and curved.SELECTED DRAWING: None

Description

本発明は、ヒンジ部を有する成形体に関し、詳しくは、４−メチル−１−ペンテン系重合体から形成された、耐折曲げ性に優れた成形体に関する。 The present invention relates to a molded product having a hinge portion, and more particularly to a molded product formed from a 4-methyl-1-pentene polymer and having excellent bending resistance.

４−メチル−１−ペンテン系重合体は、ポリプロピレン等の他のポリオレフィン樹脂と比較して耐熱性、透明性、離型性に優れた特性を示す。加えて、４−メチル−１−ペンテン系重合体は、ポリオレフィンであることから食品安全性を有し、ポリエチレンテレフタレートなど極性基を持つ樹脂と比較して耐薬品性に優れる。そのため、４−メチル−１−ペンテン系重合体は、フレキシブル基板用離型フィルム、合皮離型紙、各種成形体など様々な用途に応用されている。 The 4-methyl-1-pentene polymer exhibits excellent heat resistance, transparency, and releasability as compared with other polyolefin resins such as polypropylene. In addition, since the 4-methyl-1-pentene polymer is a polyolefin, it has food safety and is excellent in chemical resistance as compared with a resin having a polar group such as polyethylene terephthalate. Therefore, the 4-methyl-1-pentene polymer is applied to various applications such as a release film for a flexible substrate, a synthetic leather release paper, and various molded products.

４−メチル−１−ペンテン系重合体に関しては、特許文献１では、容器をはじめとする成形体用途において優れた耐熱性、透明性や耐薬品性、食品安全性を活かした耐熱容器が、特許文献２では食品用容器・薬品向け器具への応用が検討されている。 Regarding 4-methyl-1-pentene-based polymers, in Patent Document 1, a heat-resistant container that utilizes excellent heat resistance, transparency, chemical resistance, and food safety in molded body applications such as containers is patented. In Document 2, application to food containers and appliances for pharmaceuticals is being studied.

一方、４−メチル−１−ペンテン系重合体は耐折曲げ性に乏しく、蓋部が接合する部分や、繰返し屈曲、湾曲する可動部などのいわゆるヒンジ部に用いると、ヒンジ部が劣化あるいは白化するなどの問題が起こるので、ヒンジ部に用いることは困難であった。 On the other hand, 4-methyl-1-pentene-based polymers have poor bending resistance, and when used for so-called hinge parts such as parts where lids are joined and movable parts that are repeatedly bent or curved, the hinge parts deteriorate or whiten. It was difficult to use it for the hinge part because of problems such as

従来、ヒンジ部には主に別種のポリオレフィン系樹脂が用いられていた。例えば、特許文献３では、蓋部と栓体部との接合部分にエチレン系エラストマーを用いた食品用容器が、特許文献４では、屈曲部分にポリプロピレンを用いた密封容器が報告されている。 Conventionally, another type of polyolefin resin has been mainly used for the hinge portion. For example, Patent Document 3 reports a food container using an ethylene-based elastomer for a joint portion between a lid portion and a plug portion, and Patent Document 4 reports a sealed container using polypropylene for a bent portion.

特開２０１５−１８３１４１号公報Japanese Unexamined Patent Publication No. 2015-183141 ＷＯ２０１７／１５０２６５WO2017 / 150265 特開２００２−２５５２０５公報JP-A-2002-255205 特開平１０−１１９９９５号公報Japanese Unexamined Patent Publication No. 10-1995

上述の通り、従来繰返し屈曲、湾曲する可動部など、耐折曲げ性が必要とされるヒンジ部にはポリオレフィン系の別種の樹脂が用いられていた。しかし、これらの樹脂は、４−メチル−１−ペンテン系重合体と比較して不透明であり、また耐熱性をはじめとする特性に乏しいので、例えば食品用途や薬品用途など視認性と耐熱性を求められる用途への応用は難しい。実用上はすべての部位が４−メチル−１−ペンテンで構成される成形体が望まれる。 As described above, in the past, a different type of polyolefin-based resin was used for the hinge portion that requires bending resistance, such as a movable portion that repeatedly bends and bends. However, these resins are opaque as compared with 4-methyl-1-pentene polymers and lack heat resistance and other properties. Therefore, for example, visibility and heat resistance are improved for food applications and chemical applications. It is difficult to apply it to the required applications. Practically, a molded product in which all parts are composed of 4-methyl-1-pentene is desired.

本発明では、４−メチル−１−ペンテン系重合体から形成される成形体であって、４−メチル−１−ペンテン系重合体が有する優れた耐熱性、透明性、耐薬品性、食品安全性を維持しつつ、耐折曲げ性にも優れた成形体を提供することを目的とする。 In the present invention, it is a molded product formed from a 4-methyl-1-pentene polymer, and has excellent heat resistance, transparency, chemical resistance, and food safety that the 4-methyl-1-pentene polymer has. It is an object of the present invention to provide a molded product having excellent bending resistance while maintaining properties.

本発明では、α-オレフィンから導かれる構成単位を含む特定の４−メチル−１−ペンテン系重合体を用いることにより、耐熱性、透明性、耐薬品性、食品安全性等の物性を保ったまま、耐折曲げ性が改善され、繰返し屈曲、湾曲する可動部や蓋部を接合する部分などのヒンジ部を有する成形体にも好適に適用できる成形体が得られることを見出した。 In the present invention, physical properties such as heat resistance, transparency, chemical resistance, and food safety are maintained by using a specific 4-methyl-1-pentene polymer containing a structural unit derived from an α-olefin. As it is, it has been found that the bending resistance is improved, and a molded body that can be suitably applied to a molded body having a hinged portion such as a movable portion that bends and bends repeatedly and a portion that joins a lid portion can be obtained.

すなわち本発明は、例えば以下の［１］〜［３］に関する。
［１］下記要件（Ａ−１）を満たす４−メチル−１−ペンテン（共）重合体（Ａ）１０〜５０質量部と、
下記要件（Ｂ−１）を満たす４−メチル−１−ペンテン共重合体（Ｂ）５０〜９０質量部（ただし、前記（共）重合体（Ａ）および共重合体（Ｂ）の合計を１００質量部とする）と
を含む４−メチル−１−ペンテン共重合体組成物（Ｘ）からなる、ヒンジ部を有する成形体。
（Ａ−１）４−メチル−１−ペンテンから導かれる構成単位の含有量が９５．０ｍｏｌ％を超え１００ｍｏｌ％以下であり、４−メチル−１−ペンテンを除く炭素原子数２〜２０のα−オレフィンから選ばれる少なくとも１種のオレフィンから導かれる構成単位の含有量が０モル％以上５．０モル％未満である。
（Ｂ−１）４−メチル−１−ペンテンから導かれる構成単位の含有量が４０．０〜９５．０ｍｏｌ％であり、４−メチル−１−ペンテンを除く炭素原子数２〜２０のα−オレフィンから選ばれる少なくとも１種のオレフィンから導かれる構成単位の含有量が５．０〜６０．０モル％である。
［２］前記要件（Ａ−１）および（Ｂ−１）α−オレフィンが、４−メチル−１−ペンテンを除く炭素数６〜２０のα−オレフィンである、前記［１］に記載の成形体。
［３］前記４−メチル−１−ペンテン共重合体組成物（Ｘ）の、ＤＳＣで測定した融点（Ｔｍ）が、２００〜２５０℃の範囲にある、前記［１］または［２］に記載の成形体。 That is, the present invention relates to, for example, the following [1] to [3].
[1] 10 to 50 parts by mass of 4-methyl-1-pentene (co) polymer (A) satisfying the following requirement (A-1).
50 to 90 parts by mass of the 4-methyl-1-pentene copolymer (B) satisfying the following requirement (B-1) (however, the total of the (co) polymer (A) and the copolymer (B) is 100. A molded product having a hinged portion, which comprises the 4-methyl-1-pentene copolymer composition (X) containing (part by mass).
(A-1) The content of the structural unit derived from 4-methyl-1-pentene is more than 95.0 mol% and 100 mol% or less, and α having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. -The content of the structural unit derived from at least one olefin selected from the olefin is 0 mol% or more and less than 5.0 mol%.
(B-1) The content of the structural unit derived from 4-methyl-1-pentene is 40.0 to 95.0 mol%, and α- with 2 to 20 carbon atoms excluding 4-methyl-1-pentene. The content of the structural unit derived from at least one olefin selected from the olefin is 5.0 to 60.0 mol%.
[2] The molding according to the above [1], wherein the requirements (A-1) and (B-1) α-olefin are α-olefins having 6 to 20 carbon atoms excluding 4-methyl-1-pentene. body.
[3] The above-mentioned [1] or [2], wherein the melting point (Tm) of the 4-methyl-1-pentene copolymer composition (X) measured by DSC is in the range of 200 to 250 ° C. Molded body.

本発明によれば、透明性、軽量性、耐薬品性、食品安全性に加え耐折曲げ性にも優れた成形体が得られる、繰返し屈曲、湾曲する可動部などのヒンジ部においても高い耐折曲げ性を備えた成形体を得ることができる。 According to the present invention, a molded product having excellent transparency, light weight, chemical resistance, food safety and bending resistance can be obtained, and high resistance to hinges such as repeatedly bent and curved movable parts can be obtained. A molded product having bendability can be obtained.

以下、本発明の具体的な実施形態について詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and the present invention is carried out with appropriate modifications within the scope of the object of the present invention. be able to.

本発明は、４−メチル−１−ペンテン（共）重合体（Ａ）と４−メチル−１−ペンテン共重合体（Ｂ）とを含む４−メチル−１−ペンテン共重合体組成物（Ｘ）からなる、ヒンジ部を有する成形体である。なお、「（共）重合体」とは、１種のモノマーから得られる単独重合体と、２種以上のモノマーから得られる共重合体とを含む概念である。 The present invention is a 4-methyl-1-pentene copolymer composition (X) containing a 4-methyl-1-pentene (co) polymer (A) and a 4-methyl-1-pentene copolymer (B). ), Which is a molded body having a hinged portion. The "(co) polymer" is a concept including a homopolymer obtained from one kind of monomer and a copolymer obtained from two or more kinds of monomers.

[４−メチル−１−ペンテン（共）重合体組成物（Ｘ）]
本発明の４−メチル−１−ペンテン（共）重合体組成物（Ｘ）は、下記要件(Ａ−１)を満たす４−メチル−１−ペンテン（共）重合体（Ａ）１０〜５０質量部と、下記要件（Ｂ−１）を満たす４−メチル−１−ペンテン共重合体（Ｂ）５０〜９０質量部とを含有する。ここで、前記（共）重合体（Ａ）および重合体（Ｂ）の合計量を１００質量部とする。 [4-Methyl-1-pentene (co) polymer composition (X)]
The 4-methyl-1-pentene (co) polymer composition (X) of the present invention has a mass of 4-methyl-1-pentene (co) polymer (A) of 10 to 50 mass, which satisfies the following requirement (A-1). A portion and 50 to 90 parts by mass of a 4-methyl-1-pentene copolymer (B) satisfying the following requirement (B-1) are contained. Here, the total amount of the (co) polymer (A) and the polymer (B) is 100 parts by mass.

４−メチル−１−ペンテン（共）重合体（Ａ）の含有量は、好ましくは１０〜４０質量部、より好ましくは１０〜３５質量部、さらに好ましくは１０〜３０質量部である。
４−メチル−１−ペンテン共重合体（Ｂ）の含有量は、好ましくは６０〜９０質量部、より好ましくは６５〜９０質量部、さらに好ましくは７０〜９０質量部である。
４−メチル−１−ペンテン共重合体組成物（Ｘ）のＤＳＣで測定した融点は、耐熱性を担保するために２００〜２５０℃の範囲にあることが好ましく、より好ましくは２１０〜２４０℃である。 The content of the 4-methyl-1-pentene (co) polymer (A) is preferably 10 to 40 parts by mass, more preferably 10 to 35 parts by mass, and further preferably 10 to 30 parts by mass.
The content of the 4-methyl-1-pentene copolymer (B) is preferably 60 to 90 parts by mass, more preferably 65 to 90 parts by mass, and further preferably 70 to 90 parts by mass.
The melting point of the 4-methyl-1-pentene copolymer composition (X) measured by DSC is preferably in the range of 200 to 250 ° C., more preferably 210 to 240 ° C. in order to ensure heat resistance. be.

[４−メチル−１−ペンテン（共）重合体（Ａ）]
４−メチル−１−ペンテン（共）重合体（Ａ）（以下、（共）重合体（Ａ）ともいう）は、下記要件（Ａ−１）を満たす。
（Ａ−１）４−メチル−１−ペンテン由来の構成単位の含有量が９５．０ｍｏｌ％を超え１００ｍｏｌ％以下であり、４−メチル−１−ペンテンを除く炭素原子数２〜２０のα-オレフィンから選ばれる少なくとも１種のオレフィン（以下、コモノマーともいう）から導かれる構成単位の含有量が０ｍｏｌ％以上５．０ｍｏｌ％未満である。 [4-Methyl-1-pentene (co) polymer (A)]
The 4-methyl-1-pentene (co) polymer (A) (hereinafter, also referred to as (co) polymer (A)) satisfies the following requirement (A-1).
(A-1) The content of the structural unit derived from 4-methyl-1-pentene is more than 95.0 mol% and 100 mol% or less, and α having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. -The content of the structural unit derived from at least one olefin (hereinafter, also referred to as comonomer) selected from the olefin is 0 mol% or more and less than 5.0 mol%.

４−メチル−１−ペンテンから導かれる構成単位の含有量は、好ましくは９６．０〜１００ｍｏｌ％、より好ましくは９７．０〜１００ｍｏｌ％である。また、コモノマーから導かれる構成単位の含有量は、好ましくは０〜４．０ｍｏｌ％、より好ましくは０〜３．０ｍｏｌ％である。 The content of the structural unit derived from 4-methyl-1-pentene is preferably 96.0 to 100 mol%, more preferably 97.0 to 100 mol%. The content of the structural unit derived from the comonomer is preferably 0 to 4.0 mol%, more preferably 0 to 3.0 mol%.

前記炭素原子数２〜２０のα-オレフィンとしては、例えば、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−テトラデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−エイコセンが挙げられる。これらの中でも、炭素原子数６〜２０のα-オレフィンが好ましく、１−ヘキセン、１−オクテン、１−デセン、１−テトラデセン、１−ヘキサデセン、１−ヘプタデセンおよび１−オクタデセンがより好ましい。 Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-. Examples thereof include heptene, 1-octadecene and 1-eikosen. Among these, α-olefins having 6 to 20 carbon atoms are preferable, and 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene are more preferable.

[４−メチル−１−ペンテン共重合体（Ｂ）]
４−メチル−１−ペンテン共重合体（Ｂ）（以下、共重合体（Ｂ）ともいう）は、下記要件（Ｂ−１）を満たす。
（Ｂ−１）４−メチル−１−ペンテンから導かれる構成単位の含有量が４０．０〜９５．０ｍｏｌ％であり、４−メチル−１−ペンテンを除く炭素原子数２〜２０のα-オレフィンから選ばれる少なくとも1種のオレフィン（以下、コモノマーともいう）から導かれる構成単位の含有量が５．０〜６０．０ｍｏｌ％である。 [4-Methyl-1-pentene copolymer (B)]
The 4-methyl-1-pentene copolymer (B) (hereinafter, also referred to as the copolymer (B)) satisfies the following requirement (B-1).
(B-1) The content of the structural unit derived from 4-methyl-1-pentene is 40.0 to 95.0 mol%, and α having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. -The content of the structural unit derived from at least one olefin selected from olefins (hereinafter, also referred to as commonomer) is 5.0 to 60.0 mol%.

４−メチル−１−ペンテン共重合体（Ｂ）におけるコモノマーの含有量は、４−メチル−１−ペンテン（共）重合体（Ａ）におけるコモノマーの含有量よりも多い。成形体の耐折曲げ性を高めるためには、４−メチル−１−ペンテン共重合体（Ｂ）におけるコモノマー量が多いことが望ましい。 The content of the comonomer in the 4-methyl-1-pentene copolymer (B) is higher than the content of the comonomer in the 4-methyl-1-pentene (co) copolymer (A). In order to improve the bending resistance of the molded product, it is desirable that the amount of comonomer in the 4-methyl-1-pentene copolymer (B) is large.

４−メチル−１−ペンテンから導かれる構成単位の含有量は、好ましくは４０．０〜９４．０ｍｏｌ％、より好ましくは４０．０〜９２．０ｍｏｌ％である。また、４−メチル−１−ペンテンを除く炭素原子数２〜２０のα-オレフィンから選ばれる少なくとも1種のオレフィンから導かれる構成単位の含有量は、好ましくは６．０〜６０．０ｍｏｌ％、より好ましくは８．０〜６０．０ｍｏｌ％である。 The content of the structural unit derived from 4-methyl-1-pentene is preferably 40.0 to 94.0 mol%, more preferably 40.0 to 92.0 mol%. The content of the structural unit derived from at least one olefin selected from α-olefins having 2 to 20 carbon atoms excluding 4-methyl-1-pentene is preferably 6.0 to 60.0 mol%. , More preferably 8.0 to 60.0 mol%.

前記炭素原子数２〜２０のα-オレフィンとしては、例えば、エチレン、プロピレン、1-ブテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−テトラデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−エイコセンが挙げられる。前記オレフィンは、成形体の用途や必要とする物性に応じて適宜選択することができる。例えば、優れた耐折曲げ性を付与するためには、炭素原子数６〜２０のα-オレフィンが好ましく、１−ヘキセン、１−オクテン、１−デセン、１−テトラデセン、１−ヘキサデセン、１−ヘプタデセンおよび１−オクタデセンがより好ましい。 Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-. Examples thereof include heptene, 1-octadecene and 1-eikosen. The olefin can be appropriately selected depending on the intended use of the molded product and the required physical properties. For example, in order to impart excellent bending resistance, α-olefins having 6 to 20 carbon atoms are preferable, and 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1- Heptadecenes and 1-octadecenes are more preferred.

４−メチル−１−ペンテン（共）重合体（Ａ）および４−メチル−１−ペンテン共重合体（Ｂ）は、本発明の効果を損なわない範囲で、４−メチル−１−ペンテンから導かれる構成単位および前記コモノマーから導かれる構成単位以外の構成単位（以下「その他の構成単位」ともいう）を有してもよい。その他の構成単位の含有量は、例えば０〜４．０ｍｏｌ％である。 The 4-methyl-1-pentene (co) polymer (A) and the 4-methyl-1-pentene copolymer (B) are derived from 4-methyl-1-pentene as long as the effects of the present invention are not impaired. It may have a structural unit other than the structural unit to be obtained and the structural unit derived from the copolymer (hereinafter, also referred to as “other structural unit”). The content of the other structural units is, for example, 0 to 4.0 mol%.

その他の構成単位を導くモノマーとしては、例えば、環状オレフィン、芳香族ビニル化合物、共役ジエン、非共役ポリエン、官能ビニル化合物、水酸基含有オレフィン、ハロゲン化オレフィンが挙げられる。環状オレフィン、芳香族ビニル化合物、共役ジエン、非共役ポリエン、官能ビニル化合物、水酸基含有オレフィンおよびハロゲン化オレフィンとしては、例えば、特開２０１３−１６９６８５号公報の段落［００３５］〜［００４１］に記載の化合物を挙げることができる。 Examples of the monomer leading to other constituent units include cyclic olefins, aromatic vinyl compounds, conjugated diene, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins. Examples of the cyclic olefin, aromatic vinyl compound, conjugated diene, non-conjugated polyene, functional vinyl compound, hydroxyl group-containing olefin and halogenated olefin are described in paragraphs [0035] to [0041] of JP2013-169685A. Compounds can be mentioned.

４−メチル−１−ペンテン（共）重合体（Ａ）および４−メチル−１−ペンテン共重合体（Ｂ）がその他の構成単位を有する場合、その他の構成単位は１種のみであってもよく、２種以上であってもよい。 When the 4-methyl-1-pentene (co) polymer (A) and the 4-methyl-1-pentene copolymer (B) have other structural units, even if there is only one other structural unit. Often, there may be two or more types.

＜成形体＞
本発明の成形体は、前記４−メチル−１−ペンテン（共）重合体組成物（Ｘ）からなり、ヒンジ部を有する。ヒンジ部とは、成形体の構成部位であり、繰返し屈曲・湾曲させることが可能な可動部である。より具体的には、ヒンジ部は、成形体を構成する２つまたはそれ以上の部位を相互に接合し、繰返し屈曲・湾曲することにより、成形体の前記構成部位の相対的な位置を繰返し変化させることができる部位である。ヒンジ部の形状には特に制限はなく、例えば短冊状、蝶番状などを挙げることができる。 <Molded body>
The molded product of the present invention comprises the 4-methyl-1-pentene (co) polymer composition (X) and has a hinge portion. The hinge portion is a constituent part of the molded body, and is a movable portion that can be repeatedly bent and curved. More specifically, the hinge portion repeatedly changes the relative position of the constituent parts of the molded body by joining two or more parts constituting the molded body to each other and repeatedly bending and bending the hinge portion. It is a part that can be made to. The shape of the hinge portion is not particularly limited, and examples thereof include a strip shape and a hinge shape.

本発明の成形体としては、例えばヒンジ部により開閉可能な蓋部を持つ成形体が挙げられる。
前記成形体の一態様として、開口部を備えた本体部と、蓋部と、前記本体部と蓋部とを接続する短冊状のヒンジ部とを有する成形体を挙げることができる。前記開口部の形状は例えば円筒形、テーパ形であり、前記蓋部は前記開口部の先端に嵌合し得る形状を有する。荷重を加えヒンジ部を湾曲させ、蓋部に開口部を押し込むことにより成形体を密閉する。蓋部が開口部からはずされた状態で、ヒンジ部を、開口部に接続されたヒンジ部の一端と平行な平面から９０〜１８０°湾曲させることで、蓋部を開口部に装着し、成形体を密閉する。ヒンジ部をこれとは逆に作用させることで、蓋部を開口部から取り外し、成形体を開放する。ヒンジ部の厚みは、開閉の容易さと耐折曲げ性の観点から０．２〜３．０ｍｍが好ましく、より好ましくは０．２〜２．０ｍｍである。 Examples of the molded product of the present invention include a molded product having a lid portion that can be opened and closed by a hinge portion.
As one aspect of the molded body, a molded body having a main body portion having an opening, a lid portion, and a strip-shaped hinge portion connecting the main body portion and the lid portion can be mentioned. The shape of the opening is, for example, a cylindrical shape or a tapered shape, and the lid portion has a shape that can be fitted to the tip of the opening. A load is applied to bend the hinge portion, and the opening is pushed into the lid portion to seal the molded body. With the lid removed from the opening, the hinge is curved 90-180 ° from a plane parallel to one end of the hinge connected to the opening to attach the lid to the opening and mold it. Seal your body. By allowing the hinge portion to act in the opposite direction, the lid portion is removed from the opening and the molded body is opened. The thickness of the hinge portion is preferably 0.2 to 3.0 mm, more preferably 0.2 to 2.0 mm, from the viewpoint of ease of opening and closing and bending resistance.

前記成形体の他の態様として、開口部を備えた本体部と、蓋部と、前記本体部と蓋部とを接続する蝶番様のヒンジ部とを有し、前記本体部、蓋部およびヒンジ部が一体成形された成形体を挙げることができる。この態様では、ヒンジ部は目視で確認できる折り目を有し、ヒンジ部が蝶番様に動作することで蓋を開閉する。荷重を加えない状態では、蓋部は開口部から外れており、成形体は開口している。ヒンジ部を１８０°折り曲げることで、蓋部を開口部に装着することで成形体は密封される。ヒンジ部の厚みは、開閉の容易さと折曲げに対する強度の観点から０．２〜３．０ｍｍが好ましく、より好ましくは０．４〜３．０ｍｍである。 As another aspect of the molded body, the main body portion having an opening, a lid portion, and a hinge-like hinge portion connecting the main body portion and the lid portion are provided, and the main body portion, the lid portion, and the hinge portion are provided. Examples thereof include a molded body in which the portions are integrally molded. In this embodiment, the hinge portion has a crease that can be visually confirmed, and the hinge portion operates like a hinge to open and close the lid. When no load is applied, the lid is detached from the opening and the molded body is open. By bending the hinge portion by 180 °, the molded body is sealed by attaching the lid portion to the opening. The thickness of the hinge portion is preferably 0.2 to 3.0 mm, more preferably 0.4 to 3.0 mm, from the viewpoint of ease of opening and closing and strength against bending.

[成形体の用途]
本発明の成形体は、４−メチル−１−ペンテンの有する耐熱性、透明性、軽量性、耐水性、耐汚れ性、耐薬品性に加え、耐折曲げ性に優れることから、繰返し屈曲、湾曲可能な可動部であるヒンジ部を備えた成形体として好適に使用することができ、食品容器、薬品用途、生活雑貨など幅広い分野で用途に制約なく用いることが可能である。食品容器では、例えば耐熱真空成形容器、惣菜容器、調昧料容器、台所用品、食品保存用容器、冷凍保存容器、電子レンジ耐熱容器、冷凍食品容器、冷菓カップ、カップ、飲料ボトルなどが挙げられる。薬品用途、生活雑貨では、洗剤容器、漂白剤用容器、薬品用容器、理化学実験用容器、医療用容器などが挙げられる。
特に、耐折曲げ性が求められる用途として、調味料容器、台所用品、惣菜容器、飲料ボトル、洗剤容器、漂白剤容器、薬品容器、理化学実験用容器用途への使用が好ましい。 [Use of molded product]
The molded product of the present invention is excellent in bending resistance in addition to the heat resistance, transparency, light weight, water resistance, stain resistance, and chemical resistance of 4-methyl-1-pentene. It can be suitably used as a molded body having a hinge portion which is a bendable movable portion, and can be used in a wide range of fields such as food containers, chemical applications, and household goods without restrictions. Examples of food containers include heat-resistant vacuum-formed containers, prepared food containers, tampering containers, kitchen utensils, food storage containers, frozen storage containers, microwave heat-resistant containers, frozen food containers, chilled confectionery cups, cups, beverage bottles, and the like. .. Examples of chemical applications and household goods include detergent containers, bleach containers, chemical containers, physics and chemistry experiment containers, medical containers, and the like.
In particular, as applications that require bending resistance, it is preferably used for seasoning containers, kitchen utensils, prepared food containers, beverage bottles, detergent containers, bleach containers, chemical containers, and containers for physics and chemistry experiments.

[４−メチル−１−ペンテン共重合体組成物（Ｘ）の製造方法]
４−メチル−１−ペンテン共重合体組成物（Ｘ）は、４−メチル−１−ペンテン（共）重合体(Ａ)と４−メチル−１−ペンテン共重合体(Ｂ)とを溶融混練したブレンドであってもよく、または、４−メチル−１−ペンテン（共）重合体（Ａ）を製造する工程（１）と、前記工程（１）で得られた重合体（Ａ）の存在下で、４−メチル−１−ペンテン共重合体（Ｂ）を、前記（共）重合体（Ａ）および前記共重合体（Ｂ）の合計量を１００質量部とした場合に前記共重合体（Ｂ）の量が５．０〜９０．０質量部となる範囲で製造する工程（２）を有する２段式重合の製造方法で製造されてもよく、工程（１）および（２）に加えて他の工程をさらに含む３段式以上の重合の製造方法で製造されてもよい。 [Method for Producing 4-Methyl-1-pentene Copolymer Composition (X)]
In the 4-methyl-1-pentene copolymer composition (X), the 4-methyl-1-pentene (co) polymer (A) and the 4-methyl-1-pentene copolymer (B) are melt-kneaded. Or the presence of the polymer (A) obtained in the step (1) for producing the 4-methyl-1-pentene (co) polymer (A) and the step (1). Below, the 4-methyl-1-pentene copolymer (B) is the copolymer when the total amount of the (co) polymer (A) and the copolymer (B) is 100 parts by mass. It may be produced by a two-stage polymerization production method having a step (2) in which the amount of (B) is in the range of 5.0 to 90.0 parts by mass, and the steps (1) and (2) may be used. In addition, it may be produced by a three-stage or higher polymerization production method further including other steps.

４−メチル−１−ペンテン（共）重合体(Ａ)および４−メチル−１−ペンテン共重合体(Ｂ)は、それぞれメタロセン触媒を用いて製造することができる。メタロセン触媒は、メタロセン化合物を含み、担体をさらに含むことができる。 The 4-methyl-1-pentene (co) polymer (A) and the 4-methyl-1-pentene copolymer (B) can be produced using a metallocene catalyst, respectively. The metallocene catalyst contains a metallocene compound and can further include a carrier.

[成形手法]
本発明の成形体は、本発明の４−メチル−１−ペンテン系共重合体組成物（Ｘ）を成形することにより得られる。成形方法としては、公知の各種の成形方法が適用でき、例えば、射出成形、射出延伸ブロー成形、ブロー成形、プレス成形、スタンピング成形等の各種成形方法が挙げられる。 [Molding method]
The molded product of the present invention can be obtained by molding the 4-methyl-1-pentene copolymer composition (X) of the present invention. As the molding method, various known molding methods can be applied, and examples thereof include various molding methods such as injection molding, injection stretch blow molding, blow molding, press molding, and stamping molding.

[重合体の評価方法]
＜工程（１）、工程（２）で生成した重合体の質量割合＞
下記実施例で行った工程（１）および（２）を有する２段式重合による製造方法において、工程（１）の重合終了時に、得られた（共）重合体（ａ）スラリーを抜き出してスラリー濃度を測定し、工程（１）で生成した（共）重合体（ａ）の量を算出した。（共）重合体（ａ）の量とともに、工程（２）終了後に得られた全重合体の量を用いて、工程（１）で生成した（共）重合体（ａ）および工程（２）で生成した共重合体（ｂ）の質量割合を算出した。濾過時の温度を室温（２５℃）とし、濾過方法として、桐山ろ紙（目開き１μｍ）を用いてヘキサンで洗浄しながらの濾過を行い、前記スラリー濃度を算出した。以下の例において濾過はこの条件で行った。 [Polymer evaluation method]
<Mass ratio of polymer produced in step (1) and step (2)>
In the production method by two-stage polymerization having steps (1) and (2) carried out in the following examples, the obtained (co) polymer (a) slurry was extracted and slurry at the end of the polymerization of step (1). The concentration was measured, and the amount of the (co) polymer (a) produced in the step (1) was calculated. The (co) polymer (a) and the step (2) produced in the step (1) were used together with the amount of the (co) polymer (a) and the amount of the total polymer obtained after the completion of the step (2). The mass ratio of the copolymer (b) produced in the above was calculated. The temperature at the time of filtration was set to room temperature (25 ° C.), and as a filtration method, filtration was performed while washing with hexane using Kiriyama filter paper (opening 1 μm), and the slurry concentration was calculated. In the following example, filtration was performed under these conditions.

＜共重合体組成物および（共）重合体に含まれるコモノマーから導かれる構成単位の含有量＞
コモノマーから導かれる構成単位の含有量（コモノマー含量）は、以下の装置および条件により、¹³Ｃ−ＮＭＲスペクトルより算出した。
ブルカー・バイオスピン製ＡＶＡＮＣＥIIIｃｒｙｏ−５００型核磁気共鳴装置を用いて、溶媒はｏ−ジクロロベンゼン／ベンゼン−ｄ₆（４／１ｖ／ｖ）混合溶媒、試料濃度は５５ｍｇ／０．６ｍＬ、測定温度は１２０℃、観測核は¹³Ｃ（１２５ＭＨｚ）、シーケンスはシングルパルスフロトンブロードバンドデカップリング、パルス幅は５．０μ秒（４５°パルス）、繰返し時聞は５．５秒、積算回数は６４回とし、ベンゼン−ｄ₆の１２８ｐｐｍをケミカルシフトの基準値として測定した。主鎖メチンシグナルの積分値を用い、下記式によってコモノマー含量を算出した。
コモノマー含量（％）＝［Ｐ／（Ｐ＋Ｍ）］×１００
ここで、Ｐはコモノマー主鎖メチンシグナルの全ピーク面積を示し、Ｍは４−メチル−１−ペンテン主鎖メチンシグナルの全ピーク面積を示す。 <Contents of constituent units derived from the copolymer composition and the comonomer contained in the (co) polymer>
The content of the structural unit derived from the comonomer (comonomer content) was ^{calculated from the 13} C-NMR spectrum by the following equipment and conditions.
Using AVANCE III cryo-500 nuclear magnetic resonance system manufactured by Bruker Biospin, the solvent is o-dichlorobenzene / benzene-d ₆ (4/1 v / v) mixed solvent, the sample concentration is 55 mg / 0.6 mL, and the measurement temperature. Is 120 ° C, the observation nucleus is ¹³ C (125 MHz), the sequence is single-pulse Freton broadband decoupling, the pulse width is 5.0 μsec (45 ° pulse), the repetition time is 5.5 seconds, and the number of integrations is 64 times. Then, 128 ppm of benzene-d ₆ was measured as a reference value for chemical shift. The comonomer content was calculated by the following formula using the integrated value of the main chain methine signal.
Comonomer content (%) = [P / (P + M)] x 100
Here, P indicates the total peak area of the comonomer main chain methine signal, and M indicates the total peak area of the 4-methyl-1-pentene main chain methine signal.

なお、工程（１）で生成した（共）重合体（ａ）中のコモノマー含量は、工程（１）の重合終了時に抜き出した重合体スラリーから得た重合体を用いて求め、工程（２）で生成した共重合体（ｂ）中のコモノマー含量は、工程（１）で得られた（共）重合体（ａ）中のコモノマー含量、工程（２）終了後の全重合体中のコモノマー含量、およびそれぞれの工程で生成した重合体の割合を用いて求めた。具体的には、工程（１）および（２）で生成した重合体の質量をそれぞれｍ₁およびｍ₂、全重合体中のコモノマーの質量をｍ_fとし、工程（１）および（２）で生成した重合体の質量割合をそれぞれｗ₁およびｗ₂とすると、ｍ₂＝（ｍ_f−ｗ₁・ｍ₁）／ｗ₂である。 The content of the comonomer in the (co) polymer (a) produced in the step (1) was determined by using a polymer obtained from the polymer slurry extracted at the end of the polymerization in the step (1), and the step (2). The content of the comonomer in the copolymer (b) produced in (1) is the content of the comonomer in the (co) polymer (a) obtained in the step (1) and the content of the comonomer in the total polymer after the completion of the step (2). , And the proportion of the polymer produced in each step. Specifically, the masses of the polymers produced in steps (1) and (2) are m ₁ and m ₂ , respectively, and the mass of comonomer in the total polymer is m _f, and in steps (1) and (2). Assuming that the mass ratios of the produced polymers are w ₁ and w ₂ , respectively, m ₂ = (m _f − w ₁ · m ₁ ) / w ₂ .

＜融点（Ｔｍ）＞
エスアイアイナノテクノロジ一社製ＥＸＳＴＡＲＤＳＣ６２２０を用い、窒素雰囲気下（３０ｍｌ／ｍｉｎ）、約４ｍｇの試料を３０℃から２８０℃まで昇温した。２８０℃で５分間保持した後、１０℃／ｍｉｎで−５０℃まで冷却した。−５０℃で５分間保持した後、１０℃／ｍｉｎで２８０℃まで昇温させた。２回目の昇温時に観測された結晶溶融ピークの頂点を融点（Ｔｍ）とした。各段階で生成した重合体についてピークが複数検出された場合は、温度が最大のものを融点（Ｔｍ）とした。工程（２）で生成した共重合体（ｂ）の融点（Ｔｍ）は、工程（１）で生成した（共）重合体（ａ）と、製造された全重合体とを分析することにより求めた。 <Melting point (Tm)>
Using EXSTAR DSC6220 manufactured by SII Nanotechnology Co., Ltd., the temperature of a sample of about 4 mg was raised from 30 ° C. to 280 ° C. under a nitrogen atmosphere (30 ml / min). After holding at 280 ° C. for 5 minutes, the mixture was cooled to −50 ° C. at 10 ° C./min. After holding at −50 ° C. for 5 minutes, the temperature was raised to 280 ° C. at 10 ° C./min. The apex of the crystal melting peak observed at the time of the second temperature rise was defined as the melting point (Tm). When a plurality of peaks were detected in the polymer produced at each stage, the one having the highest temperature was defined as the melting point (Tm). The melting point (Tm) of the copolymer (b) produced in the step (2) was determined by analyzing the (co) polymer (a) produced in the step (1) and the produced total polymer. rice field.

［合成例１］
〔遷移金属錯体（メタロセン化合物）の合成〕
国際公開第２０１４／０５０８１７号の合成例４に従い、（８−オクタメチルフルオレン−１２'−イル−（２−（アダマンタン−１−イル）−８−メチル−３,３ｂ,４,５,６,７,７ａ,８−オクタヒドロシクロペンタ［ａ］インデン））ジルコニウムジクロライド（メタロセン化合物）を合成した。 [Synthesis Example 1]
[Synthesis of transition metal complex (metallocene compound)]
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) was synthesized.

〔固体触媒成分（メタロセン触媒）の調製〕
担体として、粒子状でありＤ５０が８μｍ、アルミニウム原子含有量が４２質量％である固体状ポリメチルアルミノキサン（東ソーファインケム社製）を用いた。３０℃下、充分に窒素置換した、攪拌機を付けた１００ｍＬ三つ口フラスコ中に、窒素気流下で精製デカン２９．９ｍＬと、前記固体状ポリメチルアルミノキサンのヘキサン／デカン溶液７．２６ｍＬ（アルミニウム原子換算で１４．３ｍｍｏｌ）とを装入し、懸濁液とした。その懸濁液に、先に合成したメタロセン化合物５０ｍｇ（ジルコニウム原子換算で０．０５８６ｍｍｏｌ）を４．５９ｍｍｏｌ／Ｌのトルエン溶液として１２．８ｍＬを撹拌しながら加えた。１．５時間後攪拌を止め、デカンによるデカンテーション洗浄を行い（洗浄効率９８％）、スラリー液５０ｍＬとした（Ｚｒ担持率９６％）。得られた固体触媒成分（メタロセン触媒）は粒子状であり、そのＤ５０は８μｍであった。 [Preparation of solid catalyst component (metallocene catalyst)]
As the carrier, solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.), which is in the form of particles, has a D50 of 8 μm, and has an aluminum atom content of 42% by mass, was used. In a 100 mL three-necked flask equipped with a stirrer, which was sufficiently nitrogen-substituted at 30 ° C., 29.9 mL of purified decane and 7.26 mL of a hexane / decane solution of the solid polymethylaluminoxane (aluminum atom) were placed under a nitrogen stream. (14.3 mmol in terms of conversion) was charged to prepare a suspension. To the suspension, 50 mg (0.0586 mmol in terms of zirconium atom) of the previously synthesized metallocene compound was added as a 4.59 mmol / L toluene solution with stirring 12.8 mL. After 1.5 hours, the stirring was stopped and decantation washing with a decane was performed (cleaning efficiency 98%) to prepare 50 mL of the slurry liquid (Zr carrying rate 96%). The obtained solid catalyst component (metallocene catalyst) was in the form of particles, and its D50 was 8 μm.

〔予備重合触媒成分の調製〕
上記のとおり調製したスラリー液に、窒素気流下、ジイソブチルアルミニウムハイドライドのデカン溶液（アルミニウム原子換算で１ｍｏｌ／Ｌ）を４．０ｍＬ、さらに３−メチル−１−ペンテン１５ｍＬ（１０．０ｇ）を装入した。１．５時間後攪拌を止め、デカンによるデカンテーション洗浄を行い（洗浄効率９５％）、予備重合触媒成分のデカンスラリー１００ｍＬとした（Ｚｒ回収率９３％、ジルコニウム原子換算で０．５４８ｍｍｏｌ／Ｌ）。 [Preparation of prepolymerization catalyst components]
To the slurry liquid prepared as described above, 4.0 mL of a decane solution of diisobutylaluminum hydride (1 mol / L in terms of aluminum atoms) and 15 mL (10.0 g) of 3-methyl-1-pentene were charged under a nitrogen stream. bottom. After 1.5 hours, stirring was stopped and decantation cleaning was performed with decan (cleaning efficiency 95%) to obtain 100 mL of decan slurry as a prepolymerization catalyst component (Zr recovery rate 93%, 0.548 mmol / L in terms of zirconium atom). ..

［実施例１］
室温（２５℃）、窒素気流下で、内容積１Ｌの攪拌機を付けたＳＵＳ製重合器に、精製デカンを４２５ｍＬ、トリエチルアルミニウム溶液（アルミニウム原子換算で１．０ｍｍｏｌ／ｍＬ）を０．４ｍＬ（アルミニウム原子換算で０．４ｍｍｏｌ）装入した。次いで、先に調製した予備重合触媒成分のデカンスラリーをジルコニウム原子換算で０．００１４ｍｍｏｌ加え、４０℃まで昇温した。４０℃到達後、水素を３０ＮｍＬ装入し、次いで、４−メチル−１−ペンテン（４ＭＰ−１）１０６ｍＬを３０分かけて重合器内へ連続的に一定の速度で装入した。この装入開始時点を重合開始とし、４５℃で３時間保持した（工程（１））。３時間経過後、４５℃にて系内を脱圧、残存水素を系外に排出するため、窒素（０．６ＭＰａ）による加圧・脱圧を３回行った。その後、４５℃、窒素気流下で、水素を３０ＮｍＬ装入し、次いで、４−メチル−１−ペンテン７９．４ｍＬと１−デセン２１．８ｍＬとの混合溶液を３０分かけて重合器内へ連続的に一定の速度で装入した。この装入開始時点を重合開始とし、４５℃で３時間保持した（工程（２））。重合開始から３時間経過後、室温まで降温し、脱圧した後、ただちに白色固体を含む重合液（スラリー）を濾過して固体状物質を得た。この固体状物質を減圧下、８０℃で８時間乾燥し、表１に記載の４−メチル−１−ペンテン共重合体組成物を得た。 [Example 1]
In a SUS polymerizer equipped with a stirrer with an internal volume of 1 L at room temperature (25 ° C) and under a nitrogen stream, 425 mL of purified decan and 0.4 mL (aluminum) of triethylaluminum solution (1.0 mmol / mL in terms of aluminum atoms) were added. (0.4 mmol in terms of atoms) was charged. Next, 0.0014 mmol of the previously prepared decan slurry of the prepolymerization catalyst component was added in terms of zirconium atoms, and the temperature was raised to 40 ° C. After reaching 40 ° C., 30 NmL of hydrogen was charged, and then 106 mL of 4-methyl-1-pentene (4MP-1) was continuously charged into the polymer over 30 minutes at a constant rate. The start of this charging was defined as the start of polymerization, and the mixture was held at 45 ° C. for 3 hours (step (1)). After 3 hours had passed, pressurization and depressurization with nitrogen (0.6 MPa) were performed three times in order to depressurize the inside of the system at 45 ° C. and discharge residual hydrogen to the outside of the system. Then, 30 NmL of hydrogen was charged under a nitrogen stream at 45 ° C., and then a mixed solution of 79.4 mL of 4-methyl-1-pentene and 21.8 mL of 1-decene was continuously introduced into the polymer over 30 minutes. It was charged at a constant speed. The start of this charging was defined as the start of polymerization, and the mixture was held at 45 ° C. for 3 hours (step (2)). After 3 hours from the start of the polymerization, the temperature was lowered to room temperature, the pressure was depressurized, and then the polymerization solution (slurry) containing a 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 the 4-methyl-1-pentene copolymer composition shown in Table 1.

［実施例２］
工程（２）において１−デセンの装入量を１５ｍＬ、工程（１）および（２）において水素の装入量をそれぞれ３０ＮｍＬおよび３５ＮｍＬに変更した以外は実施例１と同様の手順により表１に記載の４−メチル−１−ペンテン共重合体組成物を得た。 [Example 2]
Table 1 shows the same procedure as in Example 1 except that the charge amount of 1-decene was changed to 15 mL in step (2) and the charge amount of hydrogen was changed to 30 NmL and 35 NmL in steps (1) and (2), respectively. The described 4-methyl-1-pentene copolymer composition was obtained.

［実施例３］
工程（１）において４ＭＰ−１１０６ｍＬに代えて、４ＭＰ−１１０６ｍＬおよび１−ヘキセン２．８ｍＬを装入し、工程（２）において４ＭＰ−１７９．４ｍＬおよび１−デセン２１．８ｍＬに代えて、４ＭＰ−１８６．１ｍＬおよび１−ヘキセン２６．０ｍＬを装入し、（２）において水素の装入量を２５ＮｍＬに変更した以外は実施例１と同様の手順により表１に記載の４−メチル−１−ペンテン共重合体組成物を得た。 [Example 3]
In step (1), instead of 4MP-1 106 mL, 4MP-1 106 mL and 1-hexene 2.8 mL were charged, and in step (2), 4MP-1 79.4 mL and 1-decene 21.8 mL were replaced. , 4MP-1 86.1 mL and 1-hexene 26.0 mL were charged, and 4- shown in Table 1 was carried out in the same procedure as in Example 1 except that the hydrogen charge amount was changed to 25 NmL in (2). A methyl-1-pentene copolymer composition was obtained.

［比較例１］
工程（２）において１−デセンの装入量を１．２ｍＬ、工程（１）および（２）において水素の装入量をそれぞれ３０ＮｍＬおよび３０ＮｍＬに変更した以外は実施例１と同様の手順により表１に記載の４−メチル−１−ペンテン共重合体組成物を得た。 [Comparative Example 1]
Table was obtained by the same procedure as in Example 1 except that the charge amount of 1-decene was changed to 1.2 mL in step (2) and the charge amount of hydrogen was changed to 30 NmL and 30 NmL in steps (1) and (2), respectively. The 4-methyl-1-pentene copolymer composition described in 1 was obtained.

［比較例２］
国際公開第２００６／０５４６１３号の比較例９に記載の重合方法に準じて、コモノマー種を１−デセンとして、表１に記載の４−メチル−１−ペンテン系共重合体を得た。すなわちこれは、無水塩化マグネシウム、２−エチルヘキシルアルコ-ル、２−イソブチル−２−イソプロピル−１，３−ジメトキシプロパンおよび四塩化チタンを反応させて得られる固体状チタン触媒を重合用触媒として用いて単段重合で得られたことになる。 [Comparative Example 2]
The 4-methyl-1-pentene copolymer shown in Table 1 was obtained by using the comonomer species as 1-decene according to the polymerization method described in Comparative Example 9 of International Publication No. 2006/054613. That is, this uses a solid titanium catalyst obtained by reacting anhydrous magnesium chloride, 2-ethylhexyl alcohol, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and titanium tetrachloride as a polymerization catalyst. This means that it was obtained by single-stage polymerization.

［比較例３］
比較例２で、コモノマー種類を１−ヘキサデセンと１−オクタデセンの混合物（混合モル比（１−ヘキサデセン／１−オクタデセン）４３／５７）とし、水素の割合を０．７倍に変更することによって、表１に記載の重合体を得た。 [Comparative Example 3]
In Comparative Example 2, the comonomer type was a mixture of 1-hexadecene and 1-octadecene (mixed molar ratio (1-hexadecene / 1-octadecene) 43/57), and the ratio of hydrogen was changed to 0.7 times. The polymers shown in Table 1 were obtained.

［比較例４］
工程（２）において１−デセンの装入量を１５ｍＬ、工程（１）および（２）において水素の装入量をそれぞれ３０ＮｍＬおよび２５ＮｍＬに変更した以外は実施例１と同様の手順により表１に記載の４−メチル−１−ペンテン共重合体組成物を得た。 [Comparative Example 4]
Table 1 shows the same procedure as in Example 1 except that the charge amount of 1-decene was changed to 15 mL in step (2) and the charge amount of hydrogen was changed to 30 NmL and 25 NmL in steps (1) and (2), respectively. The described 4-methyl-1-pentene copolymer composition was obtained.

[成形体の作成・評価方法]
＜耐折曲げ性評価＞
１００質量部の重合体組成物または重合体に、二次抗酸化剤としてトリ（２，４−ジ−ｔ−ブチルフェニル）フォスフェートを０．１質量部、耐熱安定剤としてｎ−オクタデシル−３−（４’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）プロピネートを０．１質量部配合し、混合物を得た。(株）プラスチック工学研究所社製２軸押出機ＢＴ−３０（スクリュー系３０ｍｍφ、Ｌ／Ｄ４６）を用い、設定温度２６０℃、樹脂押出量６０ｇ／ｍｉｎおよび回転数２００ｒｐｍの条件で上記混合物を造粒して得られた樹脂組成物を原料にして、射出成形機((株)名機製作所製Ｍ−７０Ｂ)を用い、シリンダー温度２９０℃、金型温度６０℃の条件で、長さ１２０ｍｍ、幅１５ｍｍ、厚み０．４ｍｍの短冊状に射出成形し、評価用試験片を得た。 [How to create and evaluate molded products]
<Bending resistance evaluation>
To 100 parts by mass of the polymer composition or polymer, 0.1 parts by mass of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3 as a heat-resistant stabilizer. -(4'-Hydroxy-3', 5'-di-t-butylphenyl) propinate was blended in an amount of 0.1 parts by mass to obtain a mixture. Using a twin-screw extruder BT-30 (screw system 30 mmφ, L / D 46) manufactured by Plastic Engineering Laboratory Co., Ltd., the above mixture was prepared under the conditions of a set temperature of 260 ° C., a resin extrusion rate of 60 g / min, and a rotation speed of 200 rpm. Using the resin composition obtained by granulation as a raw material, using an injection molding machine (M-70B manufactured by Meiki Seisakusho Co., Ltd.), the length is 120 under the conditions of a cylinder temperature of 290 ° C and a mold temperature of 60 ° C. An evaluation test piece was obtained by injection molding into a strip having a mm, a width of 15 mm, and a thickness of 0.4 mm.

試験機にはＭＩＴ型耐折試験機を用い、折り曲げ速度を１７５回／ｍｉｎ, 荷重を９．８Ｎ、折り曲げ角度を２７０°として、耐折曲げ試験を行った。破断までの折り曲げ回数が１５００回未満であった成形体を×、１５００回以上３０００回未満であった成形体を〇、３０００回以上であった成形体を◎と評価した。 A MIT type folding resistance tester was used as the testing machine, and the bending resistance test was performed with a bending speed of 175 times / min, a load of 9.8 N, and a bending angle of 270 °. A molded product having been bent less than 1500 times before breaking was evaluated as ×, a molded product having 1500 times or more and less than 3000 times was evaluated as 〇, and a molded product having 3000 times or more was evaluated as ⊚.

＜Ｈａｚｅ＞
測定には、上記耐折り曲げ性試験と同様の条件で、長さ２００ｍｍ、幅２００ｍｍ、厚み２ｍｍのシート状に射出成形した試料片を用いた。ＪＩＳＫ７１３６に則り、Ｄ６５光源、室温（２３℃）で、ヘイズメーター(村上色彩技術研究所製、ＨＭ―１５０)を用いて測定を行った。 <Haze>
For the measurement, a sample piece injection-molded into a sheet having a length of 200 mm, a width of 200 mm, and a thickness of 2 mm was used under the same conditions as the bending resistance test. Measurements were performed in accordance with JIS K7136 at a D65 light source and room temperature (23 ° C.) using a haze meter (HM-150, manufactured by Murakami Color Technology Laboratory).

＜折り曲げ耐白化性評価＞
上記耐折曲げ試験と同様の条件で造粒した樹脂組成物を原料にして、射出成形機((株)名機製作所製Ｍ−７０Ｂ)を用い、長さ２００ｍｍ、幅４１ｍｍ、厚み２ｍｍの短冊状試験片を成形した。試験片を常温（２３℃）で９０°折り曲げた際に、目視で白化が確認された成形体を×、白化が確認できなかった成形体を〇と評価した。
上記の評価結果を表１に示す。 <Bending whitening resistance evaluation>
Using a resin composition granulated under the same conditions as the bending resistance test as a raw material, an injection molding machine (M-70B manufactured by Meiki Seisakusho Co., Ltd.) was used, and the length was 200 mm, the width was 41 mm, and the thickness was 2. A strip-shaped test piece of mm was formed. When the test piece was bent 90 ° at room temperature (23 ° C.), the molded product in which whitening was visually confirmed was evaluated as x, and the molded product in which whitening could not be confirmed was evaluated as 〇.
The above evaluation results are shown in Table 1.

＜実施例と比較例の対比＞
実施例１〜３は、破断までの折り曲げ回数が１５００回以上と良好であった。特に実施例２は４０００回以上と非常に良好であった。また、折り曲げ白化性評価も、白化は起こらず良好であった。
比較例１〜４の重合体組成物または重合体は、本発明の要件（重合体（Ｂ）のコモノマー含量、または、重合体（Ｂ）の配合質量％）を満たさず、耐折り曲げ性および耐白化性は実施例に比べて十分でないことがわかる。 <Comparison between Examples and Comparative Examples>
In Examples 1 to 3, the number of times of bending until breaking was as good as 1500 times or more. In particular, Example 2 was very good at 4000 times or more. In addition, the bending whitening property evaluation was also good without whitening.
The polymer compositions or polymers of Comparative Examples 1 to 4 do not satisfy the requirements of the present invention (comonomer content of polymer (B) or compounding mass% of polymer (B)), and have bending resistance and bending resistance. It can be seen that the whitening property is not sufficient as compared with the examples.

Claims

10 to 50 parts by mass of 4-methyl-1-pentene (co) polymer (A) satisfying the following requirement (A-1) and 4-methyl-1-pentene copolymer satisfying the following requirement (B-1) (B) 4-Methyl-1-pentene copolymer composition containing 50 to 90 parts by mass (however, the total of the (co) polymer (A) and the copolymer (B) is 100 parts by mass). A molded body having a hinge portion, which is made of an object (X).
(A-1) The content of the structural unit derived from 4-methyl-1-pentene is more than 95.0 mol% and 100 mol% or less, and α having 2 to 20 carbon atoms excluding 4-methyl-1-pentene. -The content of the structural unit derived from at least one olefin selected from the olefin is 0 mol% or more and less than 5.0 mol%.
(B-1) The content of the structural unit derived from 4-methyl-1-pentene is 40.0 to 95.0 mol%, and α- with 2 to 20 carbon atoms excluding 4-methyl-1-pentene. The content of the structural unit derived from at least one olefin selected from the olefin is 5.0 to 60.0 mol%.

The molded product according to claim 1, wherein the α-olefin in the requirements (A-1) and (B-1) is an α-olefin having 6 to 20 carbon atoms excluding 4-methyl-1-pentene.

The molded product according to claim 1 or 2, wherein the melting point (Tm) of the 4-methyl-1-pentene copolymer composition (X) measured by DSC is in the range of 200 to 250 ° C.