WO2021060061A1 - Polymer-containing material and method for producing same, and film - Google Patents
Polymer-containing material and method for producing same, and film Download PDFInfo
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- WO2021060061A1 WO2021060061A1 PCT/JP2020/034793 JP2020034793W WO2021060061A1 WO 2021060061 A1 WO2021060061 A1 WO 2021060061A1 JP 2020034793 W JP2020034793 W JP 2020034793W WO 2021060061 A1 WO2021060061 A1 WO 2021060061A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Definitions
- the method for producing a polymer-containing product of the present invention includes a step (A) of preparing a crude polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and 90% by mass or more of a non-polar organic solvent.
- the step (D) of granulating and pelletizing the product is further included.
- the solvent is not particularly limited as long as it contains a non-polar organic solvent in a proportion of 90% by mass or more and optionally contains a polar organic solvent or water in a proportion of 10% by mass or less.
- Any solvent can be used.
- the amount of the obtained washed wet cake (washed product) was 240 parts.
- ⁇ Drying of washed material (step (C))> The washed wet cake obtained by solid-liquid separation is supplied to a continuous groove type dryer (CD-80 manufactured by Kurimoto, Ltd.), and volatile components (mainly solvent) contained in the wet cake under the following drying conditions. Was removed to obtain a dry product powder.
- This film forming machine was operated under the following operating conditions to continuously produce a long unstretched film (thickness 150 ⁇ m, width 120 mm) by winding it on a roll at a speed of 2 m / min for 4 hours. A film sample was taken after 4 hours, and the presence or absence of a die line was confirmed.
- Table 1 The results are shown in Table 1. -Operating conditions- Barrel temperature setting: 280 ° C to 290 ° C Die temperature: 270 ° C Screw rotation speed: 30 rpm
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- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a polymer-containing material that includes a crystalline cyclic olefin ring-opening polymer hydride and is unlikely to develop surface defects when made into a molded article such as a film. The polymer-containing material of the present invention includes a crystalline cyclic olefin ring-opening polymer hydride having a polymer chain that includes a repeating unit represented by formula (1) as a main structural unit and a racemo diad ratio of the repeating unit represented by formula (1) of 30% or lower or 60% or higher in the polymer chain, and the total content of compounds having a molecular weight of 200-800, including structures represented by formula (2), is 30 mass ppm or lower. Furthermore, R is an alkyl group, a hydroxyl group, a hydrogen atom, or a chlorine atom, and * is a bonding partner.
Description
本発明は、重合体含有物および重合体含有物の製造方法、並びに、フィルムに関し、特に、環状オレフィン開環重合体水素化物を含む重合体含有物およびその製造方法、並びに、フィルムに関するものである。
The present invention relates to a polymer-containing material and a method for producing a polymer-containing product, and a film, and more particularly to a polymer-containing material containing a cyclic olefin ring-opening polymer hydride and a method for producing the same, and a film. ..
従来、環状オレフィン開環重合体水素化物は、その透明性や光学特性の良好さから光学材料として好適に用いられている。中でも、近年では、結晶性を有する環状オレフィン開環重合体水素化物が、透明性や光学特性に加え、優れた耐熱性、機械強度および耐溶剤性を発揮し得る材料として注目されている（例えば、特許文献１参照）。
Conventionally, a cyclic olefin ring-opening polymer hydride has been suitably used as an optical material because of its transparency and good optical properties. Among them, in recent years, crystalline cyclic olefin ring-opening polymer hydrides have been attracting attention as materials capable of exhibiting excellent heat resistance, mechanical strength and solvent resistance in addition to transparency and optical properties (for example). , Patent Document 1).
そして、結晶性を有する環状オレフィン開環重合体水素化物を高収率で工業的に製造する技術としては、例えば、極性溶媒を添加して環状オレフィン開環重合体水素化物を凝集させることにより固液分離時の脱液効率を向上させる技術が提案されている（例えば、特許文献２参照）。具体的には、特許文献２では、開環重合および水素化反応を経て得られる、結晶性を有する環状オレフィン開環重合体水素化物のスラリーに極性溶媒を添加し、撹拌し、次いで、遠心脱水機を用いてスラリー中の固形分を分離した後、得られた固形分に対して再び極性溶媒を添加して撹拌することにより第二のスラリーとし、更に遠心脱水機を用いて第二のスラリー中の固形分を分離することにより、結晶性を有する環状オレフィン開環重合体水素化物を高収率で得る技術が提案されている。
As a technique for industrially producing a crystalline cyclic olefin ring-opening polymer hydride in high yield, for example, a polar solvent is added to aggregate the cyclic olefin ring-opening polymer hydride to solidify it. A technique for improving the liquid removal efficiency at the time of liquid separation has been proposed (see, for example, Patent Document 2). Specifically, in Patent Document 2, a polar solvent is added to a slurry of a crystalline cyclic olefin ring-opening polymer hydride obtained through ring-opening polymerization and a hydrogenation reaction, and the mixture is stirred and then centrifugally dehydrated. After separating the solid content in the slurry using a machine, a polar solvent is added again to the obtained solid content and stirred to obtain a second slurry, and then a second slurry is obtained using a centrifugal dehydrator. A technique has been proposed for obtaining a crystalline cyclic olefin ring-opening polymer hydride in high yield by separating the solid content therein.
しかし、上記従来の製造方法を用いて製造した結晶性を有する環状オレフィン開環重合体水素化物には、フィルムなどの成形体にした際に、ダイライン等の表面欠陥が生じることがあるという問題があった。
However, the crystalline cyclic olefin ring-opening polymer hydride produced by using the above-mentioned conventional production method has a problem that surface defects such as die lines may occur when it is formed into a molded product such as a film. there were.
そこで、本発明は、結晶性を有する環状オレフィン開環重合体水素化物を含み、フィルムなどの成形体にした際に表面欠陥が生じにくい重合体含有物を提供することを目的とする。
また、本発明は、当該重合体含有物を用いて形成した、表面欠陥の発生が抑制されたフィルムを提供することを目的とする。 Therefore, an object of the present invention is to provide a polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and which is less likely to cause surface defects when formed into a molded product such as a film.
Another object of the present invention is to provide a film formed by using the polymer-containing material and in which the occurrence of surface defects is suppressed.
また、本発明は、当該重合体含有物を用いて形成した、表面欠陥の発生が抑制されたフィルムを提供することを目的とする。 Therefore, an object of the present invention is to provide a polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and which is less likely to cause surface defects when formed into a molded product such as a film.
Another object of the present invention is to provide a film formed by using the polymer-containing material and in which the occurrence of surface defects is suppressed.
本発明者は、上記目的を達成するために鋭意検討を行った。そして、本発明者は、従来の製造方法を用いて製造した結晶性を有する環状オレフィン開環重合体水素化物には、所定の化合物が不純物として含まれていること、および、当該所定の化合物の含有量を低減させれば、成形体にした際の表面欠陥の発生を抑制し得ることを見出した。また、本発明者は、所定の炭素数を有する非極性溶媒で環状オレフィン開環重合体水素化物を洗浄すれば、上記所定の化合物の含有量を容易に低減させ得ることを見出した。そして、本発明者は、上記新たな知見に基づいて本発明を完成させた。
The present inventor has conducted diligent studies to achieve the above object. Then, the present inventor states that the crystalline cyclic olefin ring-opening polymer hydride produced by using the conventional production method contains a predetermined compound as an impurity, and that the predetermined compound is contained. It has been found that if the content is reduced, the occurrence of surface defects in the molded product can be suppressed. Further, the present inventor has found that the content of the above-mentioned predetermined compound can be easily reduced by washing the cyclic olefin ring-opening polymer hydride with a non-polar solvent having a predetermined number of carbon atoms. Then, the present inventor has completed the present invention based on the above new findings.
即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の重合体含有物は、下記式（１）：
で表される繰り返し単位を主たる構成単位として含む重合体鎖を有し、且つ、前記重合体鎖において、前記式（１）で表される繰り返し単位のラセモ・ダイアッドの割合が３０％以下または６０％以上である、結晶性を有する環状オレフィン開環重合体水素化物を含み、下記式（２）：
［式中、Ｒは、アルキル基、ヒドロキシル基、水素原子または塩素原子であり、＊は、結合手である。］で表される構造を含む分子量が２００以上８００以下の化合物の合計含有量が３０質量ｐｐｍ以下であることを特徴とする。このように、式（２）で表される構造を含む、分子量が２００以上８００以下の化合物の合計含有量が０質量ｐｐｍ以上３０質量ｐｐｍ以下であれば、フィルムなどの成形体にした際に、表面欠陥が生じるのを抑制することができる。
なお、本発明において、「ラセモ・ダイアッドの割合」は、核磁気共鳴分光（ＮＭＲ）法を使用し、実施例に記載の方法により測定することができる。
また、本発明において、「式（２）で表される構造を含む、分子量が２００以上８００以下の化合物の合計含有量」は、実施例に記載の方法を用いて測定することができる。 That is, the present invention is intended to solve the above problems advantageously, and the polymer-containing product of the present invention has the following formula (1) :.
It has a polymer chain containing a repeating unit represented by the above as a main constituent unit, and the proportion of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60. A cyclic olefin ring-opening polymer hydride having a crystallinity of% or more is contained, and the following formula (2):
[In the formula, R is an alkyl group, a hydroxyl group, a hydrogen atom or a chlorine atom, and * is a bond. ], The total content of the compounds having a molecular weight of 200 or more and 800 or less including the structure represented by [] is 30 mass ppm or less. As described above, when the total content of the compounds having a molecular weight of 200 or more and 800 or less, including the structure represented by the formula (2), is 0 mass ppm or more and 30 mass ppm or less, when a molded product such as a film is formed. , It is possible to suppress the occurrence of surface defects.
In the present invention, the "ratio of racemo diads" can be measured by the method described in Examples using a nuclear magnetic resonance spectroscopy (NMR) method.
Further, in the present invention, "the total content of compounds having a molecular weight of 200 or more and 800 or less, including the structure represented by the formula (2)" can be measured by using the method described in Examples.
なお、本発明において、「ラセモ・ダイアッドの割合」は、核磁気共鳴分光（ＮＭＲ）法を使用し、実施例に記載の方法により測定することができる。
また、本発明において、「式（２）で表される構造を含む、分子量が２００以上８００以下の化合物の合計含有量」は、実施例に記載の方法を用いて測定することができる。 That is, the present invention is intended to solve the above problems advantageously, and the polymer-containing product of the present invention has the following formula (1) :.
In the present invention, the "ratio of racemo diads" can be measured by the method described in Examples using a nuclear magnetic resonance spectroscopy (NMR) method.
Further, in the present invention, "the total content of compounds having a molecular weight of 200 or more and 800 or less, including the structure represented by the formula (2)" can be measured by using the method described in Examples.
また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の重合体含有物の製造方法は、下記式（１）：
で表される繰り返し単位を主たる構成単位として含む重合体鎖を有し、且つ、前記重合体鎖において、前記式（１）で表される繰り返し単位のラセモ・ダイアッドの割合が３０％以下または６０％以上である、結晶性を有する環状オレフィン開環重合体水素化物を含有する粗重合体含有物を調製する工程と、非極性有機溶媒を９０質量％以上１００質量％以下の割合で含有する溶媒で前記粗重合体含有物を洗浄する工程とを含むことを特徴とする。このように、非極性有機溶媒を９０質量％以上１００質量％以下の割合で含有する溶媒で粗重合体含有物を洗浄すれば、粗重合体含有物に含まれている、上述した式（２）で表される構造を含む分子量が２００以上８００以下の化合物の含有量を容易に低減することができるので、フィルムなどの成形体にした際に表面欠陥が生じ難い重合体含有物を得ることができる。
Further, the present invention is intended to advantageously solve the above problems, and the method for producing a polymer-containing product of the present invention is described in the following formula (1):
It has a polymer chain containing a repeating unit represented by the above as a main constituent unit, and the proportion of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60. % Or more, a step of preparing a crude polymer-containing material containing a crystalline cyclic olefin ring-opening polymer hydride, and a solvent containing a non-polar organic solvent in a proportion of 90% by mass or more and 100% by mass or less. It is characterized by including a step of washing the crude polymer-containing material. As described above, if the crude polymer-containing material is washed with a solvent containing a non-polar organic solvent in a proportion of 90% by mass or more and 100% by mass or less, the crude polymer-containing material is contained in the above-mentioned formula (2). Since the content of the compound having a molecular weight of 200 or more and 800 or less including the represented structure can be easily reduced, a polymer-containing material in which surface defects are unlikely to occur when formed into a molded product such as a film can be obtained. ..
ここで、本発明の重合体含有物の製造方法において、前記溶媒は炭素数８以下の非極性有機溶媒からなることが好ましい。炭素数８以下の非極性有機溶媒を使用すれば、得られる重合体含有物中に溶剤が残存するのを抑制することができる。
Here, in the method for producing a polymer-containing product of the present invention, the solvent is preferably composed of a non-polar organic solvent having 8 or less carbon atoms. By using a non-polar organic solvent having 8 or less carbon atoms, it is possible to prevent the solvent from remaining in the obtained polymer-containing material.
そして、この発明は、上記課題を有利に解決することを目的とするものであり、本発明のフィルムは、上述した重合体含有物を用いて形成したことを特徴とする。このように、上述した重合体含有物を使用すれば、表面欠陥の発生を抑制することができる。
The present invention is intended to solve the above problems advantageously, and the film of the present invention is characterized in that it is formed by using the above-mentioned polymer-containing material. As described above, by using the above-mentioned polymer-containing material, the occurrence of surface defects can be suppressed.
本発明によれば、結晶性を有する環状オレフィン開環重合体水素化物を含み、フィルムなどの成形体にした際に表面欠陥が生じにくい重合体含有物が得られる。
また、本発明によれば、表面欠陥の発生が抑制されたフィルムが得られる。 According to the present invention, it is possible to obtain a polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and which is less likely to cause surface defects when formed into a molded product such as a film.
Further, according to the present invention, a film in which the occurrence of surface defects is suppressed can be obtained.
また、本発明によれば、表面欠陥の発生が抑制されたフィルムが得られる。 According to the present invention, it is possible to obtain a polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and which is less likely to cause surface defects when formed into a molded product such as a film.
Further, according to the present invention, a film in which the occurrence of surface defects is suppressed can be obtained.
以下、本発明の実施形態について詳細に説明する。
ここで、本発明の重合体含有物は、例えば本発明の重合体含有物の製造方法を用いて製造することができ、特に限定されることなく、フィルムなどの各種成形品の材料として好適に用いることができる。 Hereinafter, embodiments of the present invention will be described in detail.
Here, the polymer-containing product of the present invention can be produced, for example, by using the method for producing the polymer-containing product of the present invention, and is not particularly limited, and is suitable as a material for various molded products such as films. Can be used.
ここで、本発明の重合体含有物は、例えば本発明の重合体含有物の製造方法を用いて製造することができ、特に限定されることなく、フィルムなどの各種成形品の材料として好適に用いることができる。 Hereinafter, embodiments of the present invention will be described in detail.
Here, the polymer-containing product of the present invention can be produced, for example, by using the method for producing the polymer-containing product of the present invention, and is not particularly limited, and is suitable as a material for various molded products such as films. Can be used.
（重合体含有物）
本発明の重合体含有物は、環状オレフィン開環重合体水素化物を含み、所定の構造および分子量を有する化合物（Ａ）の含有量が０質量ｐｐｍ以上３０質量ｐｐｍ以下であるものである。なお、本発明の重合体含有物は、製造時に使用した溶媒の残留物や副生成物などのその他の成分を更に含有していてもよい。 (Polymer-containing material)
The polymer-containing material of the present invention contains a cyclic olefin ring-opening polymer hydride, and the content of the compound (A) having a predetermined structure and molecular weight is 0 mass ppm or more and 30 mass ppm or less. The polymer-containing product of the present invention may further contain other components such as solvent residues and by-products used in the production.
本発明の重合体含有物は、環状オレフィン開環重合体水素化物を含み、所定の構造および分子量を有する化合物（Ａ）の含有量が０質量ｐｐｍ以上３０質量ｐｐｍ以下であるものである。なお、本発明の重合体含有物は、製造時に使用した溶媒の残留物や副生成物などのその他の成分を更に含有していてもよい。 (Polymer-containing material)
The polymer-containing material of the present invention contains a cyclic olefin ring-opening polymer hydride, and the content of the compound (A) having a predetermined structure and molecular weight is 0 mass ppm or more and 30 mass ppm or less. The polymer-containing product of the present invention may further contain other components such as solvent residues and by-products used in the production.
＜環状オレフィン開環重合体水素化物＞
ここで、本発明の重合体含有物に含まれる環状オレフィン開環重合体水素化物は、所定の重合体鎖を有する結晶性の高分子化合物である。 <Hydride of cyclic olefin ring-opening polymer>
Here, the cyclic olefin ring-opening polymer hydride contained in the polymer-containing material of the present invention is a crystalline polymer compound having a predetermined polymer chain.
ここで、本発明の重合体含有物に含まれる環状オレフィン開環重合体水素化物は、所定の重合体鎖を有する結晶性の高分子化合物である。 <Hydride of cyclic olefin ring-opening polymer>
Here, the cyclic olefin ring-opening polymer hydride contained in the polymer-containing material of the present invention is a crystalline polymer compound having a predetermined polymer chain.
［重合体鎖］
具体的には、環状オレフィン開環重合体水素化物は、下記式（１）：
で表される繰り返し単位を主たる構成単位として含み、且つ、上記式（１）で表される繰り返し単位のラセモ・ダイアッドの割合が３０％以下または６０％以上である重合体鎖を有する。
[Polymer chain]
Specifically, the cyclic olefin ring-opening polymer hydride is described by the following formula (1):
It has a polymer chain containing a repeating unit represented by (1) as a main constituent unit and having a ratio of racemo-diad of the repeating unit represented by the above formula (1) of 30% or less or 60% or more.
具体的には、環状オレフィン開環重合体水素化物は、下記式（１）：
Specifically, the cyclic olefin ring-opening polymer hydride is described by the following formula (1):
ここで、上記式（１）で表される繰り返し単位は、例えば、単量体としてジシクロペンタジエンを含む単量体組成物を用いて開環重合を行った後、得られた開環重合体を水素化し、開環重合体中のジシクロペンタジエンに由来する構造単位を水素化することにより、重合体鎖に導入することができる。
なお、ジシクロペンタジエンには、エンド体およびエキソ体の立体異性体が存在するが、そのどちらも単量体として用いることが可能であり、一方の異性体を単独で用いてもよいし、エンド体およびエキソ体が任意の割合で存在する異性体混合物を用いてもよい。但し、環状オレフィン開環重合体水素化物の結晶性を高める観点からは、一方の立体異性体の割合を高くすることが好ましく、例えば、エンド体またはエキソ体の割合が、８０％以上であることが好ましく、９０％以上であることがより好ましく、９５％以上であることが特に好ましい。そして、割合を高くする立体異性体は、合成容易性の観点から、エンド体であることが好ましい。 Here, the repeating unit represented by the above formula (1) is a ring-opening polymer obtained after performing ring-opening polymerization using, for example, a monomer composition containing dicyclopentadiene as a monomer. Can be introduced into the polymer chain by hydrogenating the structural unit derived from dicyclopentadiene in the ring-opening polymer.
Dicyclopentadiene has endo- and exo-stereoisomers, both of which can be used as monomers, and one of the isomers may be used alone or endo. An isomer mixture in which the body and the exo form are present in any proportion may be used. However, from the viewpoint of increasing the crystallinity of the cyclic olefin ring-opening polymer hydride, it is preferable to increase the proportion of one of the stereoisomers, for example, the proportion of the endo isomer or the exo isomer is 80% or more. Is preferable, 90% or more is more preferable, and 95% or more is particularly preferable. The stereoisomer having a high proportion is preferably an end form from the viewpoint of easiness of synthesis.
なお、ジシクロペンタジエンには、エンド体およびエキソ体の立体異性体が存在するが、そのどちらも単量体として用いることが可能であり、一方の異性体を単独で用いてもよいし、エンド体およびエキソ体が任意の割合で存在する異性体混合物を用いてもよい。但し、環状オレフィン開環重合体水素化物の結晶性を高める観点からは、一方の立体異性体の割合を高くすることが好ましく、例えば、エンド体またはエキソ体の割合が、８０％以上であることが好ましく、９０％以上であることがより好ましく、９５％以上であることが特に好ましい。そして、割合を高くする立体異性体は、合成容易性の観点から、エンド体であることが好ましい。 Here, the repeating unit represented by the above formula (1) is a ring-opening polymer obtained after performing ring-opening polymerization using, for example, a monomer composition containing dicyclopentadiene as a monomer. Can be introduced into the polymer chain by hydrogenating the structural unit derived from dicyclopentadiene in the ring-opening polymer.
Dicyclopentadiene has endo- and exo-stereoisomers, both of which can be used as monomers, and one of the isomers may be used alone or endo. An isomer mixture in which the body and the exo form are present in any proportion may be used. However, from the viewpoint of increasing the crystallinity of the cyclic olefin ring-opening polymer hydride, it is preferable to increase the proportion of one of the stereoisomers, for example, the proportion of the endo isomer or the exo isomer is 80% or more. Is preferable, 90% or more is more preferable, and 95% or more is particularly preferable. The stereoisomer having a high proportion is preferably an end form from the viewpoint of easiness of synthesis.
また、重合体鎖中において上記式（１）で表される繰り返し単位が占める割合は、９８質量％以上１００質量％以下であることが好ましく、９９質量％以上であることがより好ましい。上記式（１）で表される繰り返し単位の割合が上記下限値以上であれば、環状オレフィン開環重合体水素化物の結晶性を更に高めることができる。
Further, the ratio of the repeating unit represented by the above formula (1) in the polymer chain is preferably 98% by mass or more and 100% by mass or less, and more preferably 99% by mass or more. When the ratio of the repeating unit represented by the above formula (1) is not more than the above lower limit value, the crystallinity of the cyclic olefin ring-opening polymer hydride can be further enhanced.
なお、重合体鎖は、上記式（１）で表される繰り返し単位以外の繰り返し単位を含んでいてもよい。具体的には、重合体鎖は、ジシクロペンタジエンと共重合可能な単量体に由来する繰り返し単位を含んでいてもよい。
ここで、ジシクロペンタジエンと共重合可能な単量体としては、特に限定されることなく、例えば、ジシクロペンタジエン以外の多環式ノルボルネン系化合物、ノルボルネン骨格に縮合した環構造を有しない２環のノルボルネン系化合物、モノ環状オレフィンおよび環状ジエン、並びに、これらの誘導体が挙げられる。 The polymer chain may contain a repeating unit other than the repeating unit represented by the above formula (1). Specifically, the polymer chain may contain repeating units derived from a monomer copolymerizable with dicyclopentadiene.
Here, the monomer copolymerizable with dicyclopentadiene is not particularly limited, for example, a polycyclic norbornene compound other than dicyclopentadiene, or a bicycle having no ring structure condensed on the norbornene skeleton. Norbornene compounds, monocyclic olefins and cyclic dienes, and derivatives thereof.
ここで、ジシクロペンタジエンと共重合可能な単量体としては、特に限定されることなく、例えば、ジシクロペンタジエン以外の多環式ノルボルネン系化合物、ノルボルネン骨格に縮合した環構造を有しない２環のノルボルネン系化合物、モノ環状オレフィンおよび環状ジエン、並びに、これらの誘導体が挙げられる。 The polymer chain may contain a repeating unit other than the repeating unit represented by the above formula (1). Specifically, the polymer chain may contain repeating units derived from a monomer copolymerizable with dicyclopentadiene.
Here, the monomer copolymerizable with dicyclopentadiene is not particularly limited, for example, a polycyclic norbornene compound other than dicyclopentadiene, or a bicycle having no ring structure condensed on the norbornene skeleton. Norbornene compounds, monocyclic olefins and cyclic dienes, and derivatives thereof.
そして、重合体鎖において、上記式（１）で表される繰り返し単位のラセモ・ダイアッドの割合は、３０％以下または６０％以上であれば特に制限されないが、ラセモ・ダイアッドの割合は、２５％以下であることが好ましく、２０％以下であることがより好ましい。或いは、ラセモ・ダイアッドの割合は、６５％以上であることが好ましく、７０％以上であることがより好ましい。
なお、ラセモ・ダイアッドの割合は、例えば開環重合に使用する触媒の種類や重合条件などを変更することにより調整することができる。 In the polymer chain, the proportion of the repeating unit racemo-diad represented by the above formula (1) is not particularly limited as long as it is 30% or less or 60% or more, but the proportion of racemo-diad is 25%. It is preferably less than or equal to, more preferably 20% or less. Alternatively, the proportion of racemo diad is preferably 65% or more, more preferably 70% or more.
The ratio of racemo-diad can be adjusted by changing, for example, the type of catalyst used for ring-opening polymerization and the polymerization conditions.
なお、ラセモ・ダイアッドの割合は、例えば開環重合に使用する触媒の種類や重合条件などを変更することにより調整することができる。 In the polymer chain, the proportion of the repeating unit racemo-diad represented by the above formula (1) is not particularly limited as long as it is 30% or less or 60% or more, but the proportion of racemo-diad is 25%. It is preferably less than or equal to, more preferably 20% or less. Alternatively, the proportion of racemo diad is preferably 65% or more, more preferably 70% or more.
The ratio of racemo-diad can be adjusted by changing, for example, the type of catalyst used for ring-opening polymerization and the polymerization conditions.
［性状］
環状オレフィン開環重合体水素化物は、結晶性を有しており、通常、融点を有している。そして、重合体含有物を用いて形成した成形体の耐熱性を向上させる観点からは、環状オレフィン開環重合体水素化物の融点は、２００℃以上であることが好ましく、２３０℃以上であることがより好ましい。なお、環状オレフィン開環重合体水素化物の融点は、通常、２９０℃以下である。 [Characteristics]
The cyclic olefin ring-opening polymer hydride has crystallinity and usually has a melting point. From the viewpoint of improving the heat resistance of the molded product formed by using the polymer-containing material, the melting point of the cyclic olefin ring-opening polymer hydride is preferably 200 ° C. or higher, preferably 230 ° C. or higher. Is more preferable. The melting point of the cyclic olefin ring-opening polymer hydride is usually 290 ° C. or lower.
環状オレフィン開環重合体水素化物は、結晶性を有しており、通常、融点を有している。そして、重合体含有物を用いて形成した成形体の耐熱性を向上させる観点からは、環状オレフィン開環重合体水素化物の融点は、２００℃以上であることが好ましく、２３０℃以上であることがより好ましい。なお、環状オレフィン開環重合体水素化物の融点は、通常、２９０℃以下である。 [Characteristics]
The cyclic olefin ring-opening polymer hydride has crystallinity and usually has a melting point. From the viewpoint of improving the heat resistance of the molded product formed by using the polymer-containing material, the melting point of the cyclic olefin ring-opening polymer hydride is preferably 200 ° C. or higher, preferably 230 ° C. or higher. Is more preferable. The melting point of the cyclic olefin ring-opening polymer hydride is usually 290 ° C. or lower.
また、環状オレフィン開環重合体水素化物の重量平均分子量は、特に限定されることなく、１０，０００以上であることが好ましく、１５，０００以上であることがより好ましく、１００，０００以下であることが好ましく、８０，０００以下であることがより好ましい。上述した重量平均分子量を有する環状オレフィン開環重合体水素化物は、成形性に優れており、また、得られる成形体の耐熱性が優れる点で好ましい。
The weight average molecular weight of the cyclic olefin ring-opening polymer hydride is not particularly limited, and is preferably 10,000 or more, more preferably 15,000 or more, and 100,000 or less. It is preferably 80,000 or less, and more preferably 80,000 or less. The cyclic olefin ring-opening polymer hydride having the above-mentioned weight average molecular weight is preferable in that it is excellent in moldability and the heat resistance of the obtained molded product is excellent.
［含有量］
なお、本発明の重合体含有物中で上述した環状オレフィン開環重合体水素化物が占める割合は、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましい。 [Content]
The proportion of the above-mentioned cyclic olefin ring-opening polymer hydride in the polymer-containing material of the present invention is preferably 90% by mass or more, and more preferably 95% by mass or more.
なお、本発明の重合体含有物中で上述した環状オレフィン開環重合体水素化物が占める割合は、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましい。 [Content]
The proportion of the above-mentioned cyclic olefin ring-opening polymer hydride in the polymer-containing material of the present invention is preferably 90% by mass or more, and more preferably 95% by mass or more.
＜化合物（Ａ）＞
化合物（Ａ）は、下記式（２）：
で表される構造を含む化合物であって、分子量が２００以上８００以下の化合物である。
<Compound (A)>
Compound (A) has the following formula (2):
It is a compound having a structure represented by, and has a molecular weight of 200 or more and 800 or less.
化合物（Ａ）は、下記式（２）：
Compound (A) has the following formula (2):
ここで、式（２）中、Ｒは、メチル基、エチル基、プロピル基、ブチル基、ｎ－ヘキシル基、ｎ－オクチル基等のアルキル基；ヒドロキシル基；水素原子；または塩素原子である、また、式（２）中、＊は、結合手の位置を示す。中でも、Ｒは、ｎ－ヘキシル基であることが好ましい。
Here, in the formula (2), R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an n-hexyl group, an n-octyl group; a hydroxyl group; a hydrogen atom; or a chlorine atom. Further, in the formula (2), * indicates the position of the joint. Above all, R is preferably an n-hexyl group.
そして、本発明の重合体含有物に含まれる化合物（Ａ）の量は、合計で３０質量ｐｐｍ以下であれば特に制限されないが、１０質量ｐｐｍ以下であることが好ましい。化合物（Ａ）の量が上記上限値以下であれば、重合体含有物をフィルムなどの成形体にした際に、表面欠陥が生じるのを抑制することができる。
The amount of the compound (A) contained in the polymer-containing material of the present invention is not particularly limited as long as it is 30 mass ppm or less in total, but is preferably 10 mass ppm or less. When the amount of the compound (A) is not more than the above upper limit value, it is possible to suppress the occurrence of surface defects when the polymer-containing material is made into a molded product such as a film.
なお、上記式（２）で表される構造を含む化合物（Ａ）としては、特に限定されることなく、例えば、環状オレフィン開環重合体水素化物の合成時に生成した副生成物等を挙げることができる。具体的には、副生成物としては、例えば、単量体としてジシクロペンタジエンを含む単量体組成物を用いて開環重合を行った際に生成したジシクロペンタジエンの二量体または三量体の水素化物などが挙げられる。
The compound (A) containing the structure represented by the above formula (2) is not particularly limited, and examples thereof include by-products produced during the synthesis of the cyclic olefin ring-opening polymer hydride. Can be done. Specifically, the by-product is, for example, a dimer or trimer of dicyclopentadiene produced when ring-opening polymerization is carried out using a monomer composition containing dicyclopentadiene as a monomer. Examples include body hydrides.
＜その他の成分＞
本発明の重合体含有物に含まれ得るその他の成分としては、特に限定されることなく、重合体含有物を調製する際に用いた溶媒の残留物や、環状オレフィン開環重合体水素化物の合成時に生成した副生成物（但し、上記化合物（Ａ）に該当するものを除く）等が挙げられる。 <Other ingredients>
Other components that can be contained in the polymer-containing material of the present invention are not particularly limited, and are the residue of the solvent used in preparing the polymer-containing material and the cyclic olefin ring-opening polymer hydride. Examples thereof include by-products produced during synthesis (excluding those corresponding to the above compound (A)).
本発明の重合体含有物に含まれ得るその他の成分としては、特に限定されることなく、重合体含有物を調製する際に用いた溶媒の残留物や、環状オレフィン開環重合体水素化物の合成時に生成した副生成物（但し、上記化合物（Ａ）に該当するものを除く）等が挙げられる。 <Other ingredients>
Other components that can be contained in the polymer-containing material of the present invention are not particularly limited, and are the residue of the solvent used in preparing the polymer-containing material and the cyclic olefin ring-opening polymer hydride. Examples thereof include by-products produced during synthesis (excluding those corresponding to the above compound (A)).
そして、本発明の重合体含有物に含まれる残留溶媒の量は、５００質量ｐｐｍ以下であることが好ましく、３００質量ｐｐｍ以下であることがより好ましい。
The amount of the residual solvent contained in the polymer-containing material of the present invention is preferably 500 mass ppm or less, and more preferably 300 mass ppm or less.
（重合体含有物の製造方法）
本発明の重合体含有物の製造方法は、結晶性を有する環状オレフィン開環重合体水素化物を含有する粗重合体含有物を調製する工程（Ａ）と、非極性有機溶媒を９０質量％以上１００質量％以下の割合で含有する溶媒で粗重合体含有物を洗浄する工程（Ｂ）とを含み、任意に、粗重合体含有物を洗浄して得られた洗浄物を乾燥する工程（Ｃ）および乾燥物を造粒してペレット化する工程（Ｄ）を更に含む。 (Method for producing polymer-containing material)
The method for producing a polymer-containing product of the present invention includes a step (A) of preparing a crude polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and 90% by mass or more of a non-polar organic solvent. A step (C) of washing the crude polymer-containing material with a solvent contained in a proportion of mass% or less, and optionally a step (C) of washing the crude polymer-containing material and drying the obtained washed product, and drying. The step (D) of granulating and pelletizing the product is further included.
本発明の重合体含有物の製造方法は、結晶性を有する環状オレフィン開環重合体水素化物を含有する粗重合体含有物を調製する工程（Ａ）と、非極性有機溶媒を９０質量％以上１００質量％以下の割合で含有する溶媒で粗重合体含有物を洗浄する工程（Ｂ）とを含み、任意に、粗重合体含有物を洗浄して得られた洗浄物を乾燥する工程（Ｃ）および乾燥物を造粒してペレット化する工程（Ｄ）を更に含む。 (Method for producing polymer-containing material)
The method for producing a polymer-containing product of the present invention includes a step (A) of preparing a crude polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and 90% by mass or more of a non-polar organic solvent. A step (C) of washing the crude polymer-containing material with a solvent contained in a proportion of mass% or less, and optionally a step (C) of washing the crude polymer-containing material and drying the obtained washed product, and drying. The step (D) of granulating and pelletizing the product is further included.
＜工程（Ａ）＞
工程（Ａ）では、下記式（１）：
で表される繰り返し単位を主たる構成単位として含む重合体鎖を有し、且つ、重合体鎖において、式（１）で表される繰り返し単位のラセモ・ダイアッドの割合が３０％以下または６０％以上である、結晶性を有する環状オレフィン開環重合体水素化物を含有する粗重合体含有物を調製する。
<Process (A)>
In the step (A), the following formula (1):
It has a polymer chain containing a repeating unit represented by the above as a main constituent unit, and the proportion of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60% or more. A crude polymer-containing material containing a crystalline cyclic olefin ring-opening polymer hydride is prepared.
工程（Ａ）では、下記式（１）：
In the step (A), the following formula (1):
具体的には、工程（Ａ）では、単量体としてジシクロペンタジエンを含み、任意にジシクロペンタジエンと共重合可能な単量体を更に含有する単量体組成物を用いて開環重合を行った後、得られた開環重合体を水素化することにより、結晶性を有する環状オレフィン開環重合体水素化物を含有する粗重合体含有物を調製する。
Specifically, in the step (A), ring-opening polymerization is carried out using a monomer composition containing dicyclopentadiene as a monomer and further containing a monomer optionally copolymerizable with dicyclopentadiene. After that, the obtained ring-opening polymer is hydrogenated to prepare a crude polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride.
ここで、開環重合および水素化を用いた粗重合体含有物の調製は、特に限定されることなく、例えば、特開２０１４－１１８４７５号公報、特開２０１６－１８３２２１号公報、特開２０１５－８３７０５号公報、特開２０１５－１７８５６１号公報に記載の方法および条件を用いて行うことができる。
なお、工程（Ａ）において粗重合体含有物が液中に分散したスラリー状態で得られた場合には、粗重合体含有物は、遠心脱水機などの既知の固液分離装置を用いて固液分離してから工程（Ｂ）へと供することができる。 Here, the preparation of the crude polymer-containing material using ring-opening polymerization and hydrogenation is not particularly limited, and for example, JP-A-2014-118475, JP-A-2016-183221, JP-A-2015-83705 It can be carried out by using the methods and conditions described in Japanese Patent Application Laid-Open No. 2015-178651.
When the crude polymer-containing material is obtained in a slurry state in which the crude polymer-containing material is dispersed in the liquid in the step (A), the crude polymer-containing material is solid-liquid separated using a known solid-liquid separation device such as a centrifugal dehydrator. Then, it can be subjected to the step (B).
なお、工程（Ａ）において粗重合体含有物が液中に分散したスラリー状態で得られた場合には、粗重合体含有物は、遠心脱水機などの既知の固液分離装置を用いて固液分離してから工程（Ｂ）へと供することができる。 Here, the preparation of the crude polymer-containing material using ring-opening polymerization and hydrogenation is not particularly limited, and for example, JP-A-2014-118475, JP-A-2016-183221, JP-A-2015-83705 It can be carried out by using the methods and conditions described in Japanese Patent Application Laid-Open No. 2015-178651.
When the crude polymer-containing material is obtained in a slurry state in which the crude polymer-containing material is dispersed in the liquid in the step (A), the crude polymer-containing material is solid-liquid separated using a known solid-liquid separation device such as a centrifugal dehydrator. Then, it can be subjected to the step (B).
そして、上述したようにして調製した粗重合体含有物は、通常、上述した結晶性を有する環状オレフィン開環重合体水素化物以外に、副生成物等を含有する。具体的には、粗重合体含有物は、通常、副生成物として、前述した化合物（Ａ）を、３００質量ｐｐｍ超の割合で含有する。
Then, the crude polymer-containing product prepared as described above usually contains a by-product or the like in addition to the above-mentioned crystalline cyclic olefin ring-opening polymer hydride having crystallinity. Specifically, the crude polymer-containing product usually contains the above-mentioned compound (A) as a by-product in a proportion of more than 300 mass ppm.
＜工程（Ｂ）＞
工程（Ｂ）では、工程（Ａ）で得られた粗重合体含有物を、非極性有機溶媒を９０質量％以上１００質量％以下の割合で含有する溶媒で洗浄する。そして、工程（Ｂ）では、通常、化合物（Ａ）が溶媒中に溶解または拡散することにより粗重合体含有物から除去される。 <Process (B)>
In the step (B), the crude polymer-containing material obtained in the step (A) is washed with a solvent containing 90% by mass or more and 100% by mass or less of a non-polar organic solvent. Then, in the step (B), the compound (A) is usually removed from the crude polymer-containing substance by dissolving or diffusing in the solvent.
工程（Ｂ）では、工程（Ａ）で得られた粗重合体含有物を、非極性有機溶媒を９０質量％以上１００質量％以下の割合で含有する溶媒で洗浄する。そして、工程（Ｂ）では、通常、化合物（Ａ）が溶媒中に溶解または拡散することにより粗重合体含有物から除去される。 <Process (B)>
In the step (B), the crude polymer-containing material obtained in the step (A) is washed with a solvent containing 90% by mass or more and 100% by mass or less of a non-polar organic solvent. Then, in the step (B), the compound (A) is usually removed from the crude polymer-containing substance by dissolving or diffusing in the solvent.
［溶媒］
ここで、溶媒としては、非極性有機溶媒を９０質量％以上の割合で含有し、任意に極性有機溶媒や水を１０質量％以下の割合で含有するものであれば、特に限定されることなく、任意の溶媒を用いることができる。中でも、化合物（Ａ）を良好に除去する観点からは、溶媒としては、非極性有機溶媒からなる溶媒を用いることが好ましい。 [solvent]
Here, the solvent is not particularly limited as long as it contains a non-polar organic solvent in a proportion of 90% by mass or more and optionally contains a polar organic solvent or water in a proportion of 10% by mass or less. , Any solvent can be used. Above all, from the viewpoint of satisfactorily removing the compound (A), it is preferable to use a solvent composed of a non-polar organic solvent as the solvent.
ここで、溶媒としては、非極性有機溶媒を９０質量％以上の割合で含有し、任意に極性有機溶媒や水を１０質量％以下の割合で含有するものであれば、特に限定されることなく、任意の溶媒を用いることができる。中でも、化合物（Ａ）を良好に除去する観点からは、溶媒としては、非極性有機溶媒からなる溶媒を用いることが好ましい。 [solvent]
Here, the solvent is not particularly limited as long as it contains a non-polar organic solvent in a proportion of 90% by mass or more and optionally contains a polar organic solvent or water in a proportion of 10% by mass or less. , Any solvent can be used. Above all, from the viewpoint of satisfactorily removing the compound (A), it is preferable to use a solvent composed of a non-polar organic solvent as the solvent.
また、非極性有機溶媒としては、特に限定されることなく、例えば、ｎ－ヘキサン、シクロヘキサン、シクロオクタン、メチルシクロヘキサン、ｔｅｒｔ－１－メチル－２－プロピルシクロヘキサン等の飽和脂肪族炭化水素；トルエン、キシレン等の芳香族炭化水素；或いは、これらの２種以上の混合物；などを用いることができる。中でも、得られる重合体含有物中に溶剤が残存するのを抑制する観点からは、非極性有機溶媒としては、炭素数８以下の非極性有機溶媒を用いることが好ましく、キシレン、トルエン、シクロヘキサンまたはメチルシクロヘキサンを用いることがより好ましい。
更に、得られる重合体含有物中に溶剤が残存するのを抑制する観点からは、非極性有機溶媒の大気圧下における沸点は、１８０℃以下であることが好ましく、１５０℃以下であることがより好ましい。 The non-polar organic solvent is not particularly limited, and for example, saturated aliphatic hydrocarbons such as n-hexane, cyclohexane, cyclooctane, methylcyclohexane, and tert-1-methyl-2-propylcyclohexane; toluene, Aromatic hydrocarbons such as xylene; or mixtures of two or more of these; and the like can be used. Above all, from the viewpoint of suppressing the residual solvent in the obtained polymer-containing material, it is preferable to use a non-polar organic solvent having 8 or less carbon atoms as the non-polar organic solvent, and xylene, toluene, cyclohexane or the like. It is more preferable to use methylcyclohexane.
Further, from the viewpoint of suppressing the solvent from remaining in the obtained polymer-containing material, the boiling point of the non-polar organic solvent under atmospheric pressure is preferably 180 ° C. or lower, preferably 150 ° C. or lower. More preferred.
更に、得られる重合体含有物中に溶剤が残存するのを抑制する観点からは、非極性有機溶媒の大気圧下における沸点は、１８０℃以下であることが好ましく、１５０℃以下であることがより好ましい。 The non-polar organic solvent is not particularly limited, and for example, saturated aliphatic hydrocarbons such as n-hexane, cyclohexane, cyclooctane, methylcyclohexane, and tert-1-methyl-2-propylcyclohexane; toluene, Aromatic hydrocarbons such as xylene; or mixtures of two or more of these; and the like can be used. Above all, from the viewpoint of suppressing the residual solvent in the obtained polymer-containing material, it is preferable to use a non-polar organic solvent having 8 or less carbon atoms as the non-polar organic solvent, and xylene, toluene, cyclohexane or the like. It is more preferable to use methylcyclohexane.
Further, from the viewpoint of suppressing the solvent from remaining in the obtained polymer-containing material, the boiling point of the non-polar organic solvent under atmospheric pressure is preferably 180 ° C. or lower, preferably 150 ° C. or lower. More preferred.
［洗浄］
そして、粗重合体含有物の洗浄は、特に限定されることなく、例えば撹拌下で溶媒中に粗重合体含有物を分散させた後、遠心脱水機などの既知の固液分離装置を用いて溶媒を除去することにより、行うことができる。 [Washing]
The washing of the crude polymer-containing material is not particularly limited, and for example, after the crude polymer-containing material is dispersed in the solvent under stirring, the solvent is used using a known solid-liquid separator such as a centrifugal dehydrator. It can be done by removing it.
そして、粗重合体含有物の洗浄は、特に限定されることなく、例えば撹拌下で溶媒中に粗重合体含有物を分散させた後、遠心脱水機などの既知の固液分離装置を用いて溶媒を除去することにより、行うことができる。 [Washing]
The washing of the crude polymer-containing material is not particularly limited, and for example, after the crude polymer-containing material is dispersed in the solvent under stirring, the solvent is used using a known solid-liquid separator such as a centrifugal dehydrator. It can be done by removing it.
ここで、粗重合体含有物を洗浄する時間は、特に限定されることなく、例えば１０分以上５時間以下とすることができる。
また、洗浄に用いる溶媒の温度は、凝固点（Ｔ1）よりも高く、沸点（Ｔ2）よりも低ければ特に限定されないが、例えばＴ1＋５℃以上Ｔ2－５℃以下であることが好ましい。
更に、洗浄に用いる溶媒の量は、質量比で、粗重合体含有物の量の４倍以上２０倍以下であることが好ましい。 Here, the time for washing the crude polymer-containing material is not particularly limited, and may be, for example, 10 minutes or more and 5 hours or less.
The temperature of the solvent used for washing, freezing point (T 1) higher than, but not particularly limited as lower than the boiling point (T 2), it is preferable that for example, T 1 + 5 ° C. or more T 2 -5 ° C. or less ..
Further, the amount of the solvent used for washing is preferably 4 times or more and 20 times or less the amount of the crude polymer-containing substance in terms of mass ratio.
また、洗浄に用いる溶媒の温度は、凝固点（Ｔ1）よりも高く、沸点（Ｔ2）よりも低ければ特に限定されないが、例えばＴ1＋５℃以上Ｔ2－５℃以下であることが好ましい。
更に、洗浄に用いる溶媒の量は、質量比で、粗重合体含有物の量の４倍以上２０倍以下であることが好ましい。 Here, the time for washing the crude polymer-containing material is not particularly limited, and may be, for example, 10 minutes or more and 5 hours or less.
The temperature of the solvent used for washing, freezing point (T 1) higher than, but not particularly limited as lower than the boiling point (T 2), it is preferable that for example, T 1 + 5 ° C. or more T 2 -5 ° C. or less ..
Further, the amount of the solvent used for washing is preferably 4 times or more and 20 times or less the amount of the crude polymer-containing substance in terms of mass ratio.
そして、工程（Ｂ）では、本発明の重合体含有物の製造方法により得られる重合体含有物中に含まれる化合物（Ａ）の量が３０質量ｐｐｍ以下となるまで粗重合体含有物を洗浄することが好ましい。
Then, in the step (B), the crude polymer-containing material is washed until the amount of the compound (A) contained in the polymer-containing material obtained by the method for producing the polymer-containing product of the present invention is 30 mass ppm or less. Is preferable.
＜工程（Ｃ）＞
工程（Ｃ）では、工程（Ｂ）において粗重合体含有物を洗浄して得られた洗浄物を乾燥する。ここで、洗浄物の乾燥は、特に限定されることなく、熱風乾燥、真空乾燥、スピン乾燥などの任意の乾燥方法を用いて行うことができる。中でも、得られる重合体含有物中に溶剤が残存するのを抑制する観点からは、真空乾燥を用いて洗浄物を乾燥することが好ましい。
なお、乾燥は、本発明の重合体含有物の製造方法により得られる重合体含有物中に含まれる残留溶媒の量が、５００質量ｐｐｍ以下となるまで行うことが好ましく、３００質量ｐｐｍ以下となるまで行うことがより好ましい。 <Process (C)>
In the step (C), the crude polymer-containing material is washed in the step (B), and the obtained washed product is dried. Here, the drying of the washed product is not particularly limited, and can be performed by using any drying method such as hot air drying, vacuum drying, and spin drying. Above all, from the viewpoint of suppressing the solvent from remaining in the obtained polymer-containing material, it is preferable to dry the washed product by using vacuum drying.
The drying is preferably carried out until the amount of the residual solvent contained in the polymer-containing material obtained by the method for producing the polymer-containing product of the present invention is 500 mass ppm or less, preferably 300 mass ppm or less. It is more preferable to do so.
工程（Ｃ）では、工程（Ｂ）において粗重合体含有物を洗浄して得られた洗浄物を乾燥する。ここで、洗浄物の乾燥は、特に限定されることなく、熱風乾燥、真空乾燥、スピン乾燥などの任意の乾燥方法を用いて行うことができる。中でも、得られる重合体含有物中に溶剤が残存するのを抑制する観点からは、真空乾燥を用いて洗浄物を乾燥することが好ましい。
なお、乾燥は、本発明の重合体含有物の製造方法により得られる重合体含有物中に含まれる残留溶媒の量が、５００質量ｐｐｍ以下となるまで行うことが好ましく、３００質量ｐｐｍ以下となるまで行うことがより好ましい。 <Process (C)>
In the step (C), the crude polymer-containing material is washed in the step (B), and the obtained washed product is dried. Here, the drying of the washed product is not particularly limited, and can be performed by using any drying method such as hot air drying, vacuum drying, and spin drying. Above all, from the viewpoint of suppressing the solvent from remaining in the obtained polymer-containing material, it is preferable to dry the washed product by using vacuum drying.
The drying is preferably carried out until the amount of the residual solvent contained in the polymer-containing material obtained by the method for producing the polymer-containing product of the present invention is 500 mass ppm or less, preferably 300 mass ppm or less. It is more preferable to do so.
＜工程（Ｄ）＞
工程（Ｄ）では、工程（Ｃ）で得られる乾燥物を造粒し、ペレット状の重合体含有物を得る。ここで、乾燥物の造粒は、特に限定されることなく、二軸押出機などの既知の造粒装置を用いて行うことができる。 <Process (D)>
In the step (D), the dried product obtained in the step (C) is granulated to obtain a pellet-shaped polymer-containing product. Here, the granulation of the dried product is not particularly limited, and can be performed using a known granulation device such as a twin-screw extruder.
工程（Ｄ）では、工程（Ｃ）で得られる乾燥物を造粒し、ペレット状の重合体含有物を得る。ここで、乾燥物の造粒は、特に限定されることなく、二軸押出機などの既知の造粒装置を用いて行うことができる。 <Process (D)>
In the step (D), the dried product obtained in the step (C) is granulated to obtain a pellet-shaped polymer-containing product. Here, the granulation of the dried product is not particularly limited, and can be performed using a known granulation device such as a twin-screw extruder.
（フィルム）
本発明のフィルムは、上述した本発明の重合体含有物をフィルム状に成形して得ることができる。そして、本発明のフィルムは、上述した重合体含有物を用いているので、表面欠陥が少ない。
なお、重合体含有物をフィルム状に成形する方法および条件は、特に限定されることなく、任意の方法および条件とすることができる。 (the film)
The film of the present invention can be obtained by molding the above-mentioned polymer-containing material of the present invention into a film. Since the film of the present invention uses the above-mentioned polymer-containing material, there are few surface defects.
The method and conditions for forming the polymer-containing material into a film are not particularly limited, and any method and conditions can be used.
本発明のフィルムは、上述した本発明の重合体含有物をフィルム状に成形して得ることができる。そして、本発明のフィルムは、上述した重合体含有物を用いているので、表面欠陥が少ない。
なお、重合体含有物をフィルム状に成形する方法および条件は、特に限定されることなく、任意の方法および条件とすることができる。 (the film)
The film of the present invention can be obtained by molding the above-mentioned polymer-containing material of the present invention into a film. Since the film of the present invention uses the above-mentioned polymer-containing material, there are few surface defects.
The method and conditions for forming the polymer-containing material into a film are not particularly limited, and any method and conditions can be used.
以下、実施例および比較例を挙げて、本発明をさらに詳細に説明する。なお、本発明はこれらの例に何ら限定されるものではない。以下において、「部」、「％」および「ｐｐｍ」は特に断りのない限り、質量基準であり、圧力はゲージ圧力である。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples. In the following, "parts", "%" and "ppm" are based on mass and pressure is gauge pressure unless otherwise specified.
また、各例における測定や評価は、以下の方法により行った。
（１）開環重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）
開環重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）システム（東ソー社製、ＨＬＣ－８３２０）を用いてポリスチレン換算値として測定した。なお、カラムにはＨタイプカラム（東ソー社製）を用い、テトラヒドロフランを溶媒として、４０℃で測定した。
（２）開環重合体水素化物の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）
開環重合体水素化物の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）システム（センシュー科学社製、ＳＳＣ－７１００）を用いてポリスチレン換算値として測定した。なお、カラムにはＧＰＣ３５０６カラム（センシュー科学社製）を用い、１－クロロナフタレンを溶媒として、２１０℃で測定した。
（３）水素化率
1Ｈ－ＮＭＲ測定に基づいて求めた。
（４）開環重合体水素化物の融点
示差走査熱量計（ＤＳＣ）を使用し、試料を窒素雰囲気下で３００℃に加熱した後、液体窒素で急冷し、再度１０℃／分で昇温して、測定した。
（５）開環重合体水素化物の重合体鎖のラセモ・ダイアッドの割合
オルトジクロロベンゼン－ｄ4を溶媒として、１５０℃でｉｎｖｅｒｓｅ－ｇａｔｅｄ ｄｅｃｏｕｐｌｉｎｇ法を適用して13Ｃ－ＮＭＲ測定を行い、オルトジクロロベンゼン－ｄ4の１２７．５ｐｐｍのピークを基準シフトとして、メソ・ダイアッド由来の４３．３５ｐｐｍのシグナルと、ラセモ・ダイアッド由来の４３．４３ｐｐｍのシグナルの強度比に基づいて、ラセモ・ダイアッドの割合を求めた。
（６）化合物（Ａ）の含有量
まず、二軸押出機（ＴＥＸ－３０）を用いてペレット化を行う際に、ベント部に設けた気液セパレーターに溜まった物質を1Ｈ－ＮＭＲおよびＧＣ－ＭＳで分析し、分子量を特定することにより、化合物（Ａ）を定性した。
次に、化合物（Ａ）の定性の際に採取した化合物（Ａ）を、シクロヘキサンで希釈して規定濃度の化合物（Ａ）のシクロヘキサン溶液を調製した。そして、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）システム（東ソー社製、ＨＬＣ－８３２０）で、各溶液を打ち込み量１００μＬで測定し、測定時のＲＩピーク面積を求め、ピークの帰属を行うと共に、化合物（Ａ）濃度とＲＩピーク面積との関係から検量線を作成した。なお、カラムには東ソー社製ＴＳＫｇｅｌＧ５０００ＨＸＬ、ＴＳＫｇｅｌＧ４０００ＨＸＬおよびＴＳＫｇｅｌＧ２０００ＨＸＬを３本直列に繋いで用い、流速１．０ｍｌ／分、サンプル注入量１００μｍｌ、カラム温度４０℃の条件で測定した。
そして、耐圧ガラス容器にペレット０．２部とシクロヘキサン３．３部とを入れて、１５０℃で６時間加熱し、ペレット中の化合物（Ａ）をシクロヘキサンに抽出した。得られた抽出液を、フィルターで不溶分を除去した後、ＧＰＣで測定し、抽出液中の化合物（Ａ）のＲＩピーク面積から上記検量線を用いて下記のようにしてペレット中の化合物（Ａ）の濃度を算出した。
＜化合物（Ａ）の濃度を算出＞
検量線：［シクロヘキサン中の化合物（Ａ）濃度］（％）＝ｆ×[ＲＩ面積]
［ペレット中の化合物（Ａ）濃度］（ｐｐｍ）
＝［シクロヘキサン中の化合物（Ａ）濃度］（％）÷１００×［シクロヘキサン重量］（ｇ）÷［ペレット重量］（ｇ）×１００００００
＝ｆ×［ＲＩ面積］÷１００×［シクロヘキサン重量］（ｇ）÷［ペレット重量］（ｇ）×１００００００
（７）残留溶媒量
重合体含有物２部と、ｏ－ジクロロベンゼン０．１部と、クロロベンゼン３２．９部とを、耐圧ガラス容器中において１２０℃で１時間加熱し、残留溶媒を抽出した。得られた溶液を、シリンジフィルター（ＡＤＶＡＮＴＥＣ社製、孔径：０．４５μｍ）でろ過し、ガスクロマトグラフ（ＨＥＷＬＥＴＴＰＡＣＫＡＲＤ社製、ＨＰ６８５０ＡＳｅｒｉｅｓ）により、残留溶媒量を求めた。
なお、測定は、カラムとしてAgilent社製のＨＰ－１（３０ｍ×０．３２ｍｍ×０．２５μｍ）を用い、気化室温度：２４０℃、カラム温度：スタート時３５℃、１０℃／分で２８０℃まで昇温、検出器温度：３１０℃、注入量：１μｍ、で行った。
（８）欠陥（ダイライン）の有無
暗室下で白色スクリーンと投影機との間にフィルムを配置して、スクリーンに写る陰影を観察した。そして、以下の基準で欠陥の有無を評価した。
○：何も見えず均一である。
×：ダイラインが確認できる。 In addition, the measurement and evaluation in each example were carried out by the following methods.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer were measured as polystyrene-equivalent values using a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320). An H-type column (manufactured by Tosoh Corporation) was used as the column, and the measurement was carried out at 40 ° C. using tetrahydrofuran as a solvent.
(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) of ring-opening polymer hydride
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer hydride are converted into polystyrene using a gel permeation chromatography (GPC) system (SSC-7100, manufactured by Senshu Kagaku Co., Ltd.). It was measured. A GPC3506 column (manufactured by Senshu Kagaku Co., Ltd.) was used as the column, and the measurement was carried out at 210 ° C. using 1-chloronaphthalene as a solvent.
(3) Hydrogenation rate 1 Obtained based on 1 H-NMR measurement.
(4) Melting Point of Ring-Opening Polymer Hydride Using a differential scanning calorimeter (DSC), the sample is heated to 300 ° C. in a nitrogen atmosphere, rapidly cooled with liquid nitrogen, and heated again at 10 ° C./min. And measured.
(5) Ratio of racemo-diad in the polymer chain of the ring-opened polymer hydride. Using ortodichlorobenzene-d 4 as a solvent, apply the inverse-gated decoupling method at 150 ° C. to perform 13 C-NMR measurement, and perform ortho. The proportion of racemo diad based on the intensity ratio of the signal from mesodiad at 43.35 ppm to the signal from racemo diad at 43.43 ppm, with the peak of 127.5 ppm of dichlorobenzene-d 4 as the reference shift. Asked.
(6) Content of compound (A) First, when pelletizing using a twin-screw extruder (TEX-30), the substances accumulated in the gas-liquid separator provided in the vent portion were collected by 1 H-NMR and GC. -Compound (A) was qualitative by analyzing with MS and specifying the molecular weight.
Next, the compound (A) collected during the qualitative analysis of the compound (A) was diluted with cyclohexane to prepare a cyclohexane solution of the compound (A) having a specified concentration. Then, with a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320), each solution is measured with a driving amount of 100 μL, the RI peak area at the time of measurement is obtained, and the peaks are assigned and assigned. A calibration curve was prepared from the relationship between the concentration of compound (A) and the RI peak area. For the column, three TSKgelG5000HXL, TSKgelG4000HXL, and TSKgelG2000HXL manufactured by Tosoh Corporation were connected in series, and the measurement was performed under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.
Then, 0.2 part of the pellet and 3.3 part of cyclohexane were placed in a pressure-resistant glass container and heated at 150 ° C. for 6 hours to extract the compound (A) in the pellet into cyclohexane. After removing the insoluble matter with a filter, the obtained extract was measured by GPC, and the compound in the pellet was measured from the RI peak area of the compound (A) in the extract using the above calibration curve as follows. The concentration of A) was calculated.
<Calculate the concentration of compound (A)>
Calibration curve: [Concentration of compound (A) in cyclohexane] (%) = f × [RI area]
[Concentration of compound (A) in pellets] (ppm)
= [Concentration of compound (A) in cyclohexane] (%) ÷ 100 × [Weight of cyclohexane] (g) ÷ [Weight of pellets] (g) × 1000000
= F x [RI area] ÷ 100 x [cyclohexane weight] (g) ÷ [pellet weight] (g) x 1000000
(7) Amount of Residual Solvent 2 parts of the polymer-containing material, 0.1 part of o-dichlorobenzene, and 32.9 parts of chlorobenzene were heated at 120 ° C. for 1 hour in a pressure-resistant glass container to extract the residual solvent. .. The obtained solution was filtered through a syringe filter (manufactured by ADVANTEC, pore size: 0.45 μm), and the amount of residual solvent was determined by a gas chromatograph (manufactured by HEWLETT PACKARD, HP6850 ASeries).
For the measurement, HP-1 (30 m × 0.32 mm × 0.25 μm) manufactured by Agilent was used as the column, the vaporization chamber temperature: 240 ° C., the column temperature: 35 ° C. at the start, and 280 ° C. at 10 ° C./min. The temperature was raised to 310 ° C., the injection amount was 1 μm, and the temperature was increased.
(8) Presence or absence of defects (die lines) A film was placed between the white screen and the projector in a dark room, and the shadows reflected on the screen were observed. Then, the presence or absence of defects was evaluated according to the following criteria.
◯: Nothing can be seen and it is uniform.
X: The die line can be confirmed.
（１）開環重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）
開環重合体の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）システム（東ソー社製、ＨＬＣ－８３２０）を用いてポリスチレン換算値として測定した。なお、カラムにはＨタイプカラム（東ソー社製）を用い、テトラヒドロフランを溶媒として、４０℃で測定した。
（２）開環重合体水素化物の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）
開環重合体水素化物の重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）システム（センシュー科学社製、ＳＳＣ－７１００）を用いてポリスチレン換算値として測定した。なお、カラムにはＧＰＣ３５０６カラム（センシュー科学社製）を用い、１－クロロナフタレンを溶媒として、２１０℃で測定した。
（３）水素化率
1Ｈ－ＮＭＲ測定に基づいて求めた。
（４）開環重合体水素化物の融点
示差走査熱量計（ＤＳＣ）を使用し、試料を窒素雰囲気下で３００℃に加熱した後、液体窒素で急冷し、再度１０℃／分で昇温して、測定した。
（５）開環重合体水素化物の重合体鎖のラセモ・ダイアッドの割合
オルトジクロロベンゼン－ｄ4を溶媒として、１５０℃でｉｎｖｅｒｓｅ－ｇａｔｅｄ ｄｅｃｏｕｐｌｉｎｇ法を適用して13Ｃ－ＮＭＲ測定を行い、オルトジクロロベンゼン－ｄ4の１２７．５ｐｐｍのピークを基準シフトとして、メソ・ダイアッド由来の４３．３５ｐｐｍのシグナルと、ラセモ・ダイアッド由来の４３．４３ｐｐｍのシグナルの強度比に基づいて、ラセモ・ダイアッドの割合を求めた。
（６）化合物（Ａ）の含有量
まず、二軸押出機（ＴＥＸ－３０）を用いてペレット化を行う際に、ベント部に設けた気液セパレーターに溜まった物質を1Ｈ－ＮＭＲおよびＧＣ－ＭＳで分析し、分子量を特定することにより、化合物（Ａ）を定性した。
次に、化合物（Ａ）の定性の際に採取した化合物（Ａ）を、シクロヘキサンで希釈して規定濃度の化合物（Ａ）のシクロヘキサン溶液を調製した。そして、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）システム（東ソー社製、ＨＬＣ－８３２０）で、各溶液を打ち込み量１００μＬで測定し、測定時のＲＩピーク面積を求め、ピークの帰属を行うと共に、化合物（Ａ）濃度とＲＩピーク面積との関係から検量線を作成した。なお、カラムには東ソー社製ＴＳＫｇｅｌＧ５０００ＨＸＬ、ＴＳＫｇｅｌＧ４０００ＨＸＬおよびＴＳＫｇｅｌＧ２０００ＨＸＬを３本直列に繋いで用い、流速１．０ｍｌ／分、サンプル注入量１００μｍｌ、カラム温度４０℃の条件で測定した。
そして、耐圧ガラス容器にペレット０．２部とシクロヘキサン３．３部とを入れて、１５０℃で６時間加熱し、ペレット中の化合物（Ａ）をシクロヘキサンに抽出した。得られた抽出液を、フィルターで不溶分を除去した後、ＧＰＣで測定し、抽出液中の化合物（Ａ）のＲＩピーク面積から上記検量線を用いて下記のようにしてペレット中の化合物（Ａ）の濃度を算出した。
＜化合物（Ａ）の濃度を算出＞
検量線：［シクロヘキサン中の化合物（Ａ）濃度］（％）＝ｆ×[ＲＩ面積]
［ペレット中の化合物（Ａ）濃度］（ｐｐｍ）
＝［シクロヘキサン中の化合物（Ａ）濃度］（％）÷１００×［シクロヘキサン重量］（ｇ）÷［ペレット重量］（ｇ）×１００００００
＝ｆ×［ＲＩ面積］÷１００×［シクロヘキサン重量］（ｇ）÷［ペレット重量］（ｇ）×１００００００
（７）残留溶媒量
重合体含有物２部と、ｏ－ジクロロベンゼン０．１部と、クロロベンゼン３２．９部とを、耐圧ガラス容器中において１２０℃で１時間加熱し、残留溶媒を抽出した。得られた溶液を、シリンジフィルター（ＡＤＶＡＮＴＥＣ社製、孔径：０．４５μｍ）でろ過し、ガスクロマトグラフ（ＨＥＷＬＥＴＴＰＡＣＫＡＲＤ社製、ＨＰ６８５０ＡＳｅｒｉｅｓ）により、残留溶媒量を求めた。
なお、測定は、カラムとしてAgilent社製のＨＰ－１（３０ｍ×０．３２ｍｍ×０．２５μｍ）を用い、気化室温度：２４０℃、カラム温度：スタート時３５℃、１０℃／分で２８０℃まで昇温、検出器温度：３１０℃、注入量：１μｍ、で行った。
（８）欠陥（ダイライン）の有無
暗室下で白色スクリーンと投影機との間にフィルムを配置して、スクリーンに写る陰影を観察した。そして、以下の基準で欠陥の有無を評価した。
○：何も見えず均一である。
×：ダイラインが確認できる。 In addition, the measurement and evaluation in each example were carried out by the following methods.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer were measured as polystyrene-equivalent values using a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320). An H-type column (manufactured by Tosoh Corporation) was used as the column, and the measurement was carried out at 40 ° C. using tetrahydrofuran as a solvent.
(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) of ring-opening polymer hydride
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer hydride are converted into polystyrene using a gel permeation chromatography (GPC) system (SSC-7100, manufactured by Senshu Kagaku Co., Ltd.). It was measured. A GPC3506 column (manufactured by Senshu Kagaku Co., Ltd.) was used as the column, and the measurement was carried out at 210 ° C. using 1-chloronaphthalene as a solvent.
(3) Hydrogenation rate 1 Obtained based on 1 H-NMR measurement.
(4) Melting Point of Ring-Opening Polymer Hydride Using a differential scanning calorimeter (DSC), the sample is heated to 300 ° C. in a nitrogen atmosphere, rapidly cooled with liquid nitrogen, and heated again at 10 ° C./min. And measured.
(5) Ratio of racemo-diad in the polymer chain of the ring-opened polymer hydride. Using ortodichlorobenzene-d 4 as a solvent, apply the inverse-gated decoupling method at 150 ° C. to perform 13 C-NMR measurement, and perform ortho. The proportion of racemo diad based on the intensity ratio of the signal from mesodiad at 43.35 ppm to the signal from racemo diad at 43.43 ppm, with the peak of 127.5 ppm of dichlorobenzene-d 4 as the reference shift. Asked.
(6) Content of compound (A) First, when pelletizing using a twin-screw extruder (TEX-30), the substances accumulated in the gas-liquid separator provided in the vent portion were collected by 1 H-NMR and GC. -Compound (A) was qualitative by analyzing with MS and specifying the molecular weight.
Next, the compound (A) collected during the qualitative analysis of the compound (A) was diluted with cyclohexane to prepare a cyclohexane solution of the compound (A) having a specified concentration. Then, with a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320), each solution is measured with a driving amount of 100 μL, the RI peak area at the time of measurement is obtained, and the peaks are assigned and assigned. A calibration curve was prepared from the relationship between the concentration of compound (A) and the RI peak area. For the column, three TSKgelG5000HXL, TSKgelG4000HXL, and TSKgelG2000HXL manufactured by Tosoh Corporation were connected in series, and the measurement was performed under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.
Then, 0.2 part of the pellet and 3.3 part of cyclohexane were placed in a pressure-resistant glass container and heated at 150 ° C. for 6 hours to extract the compound (A) in the pellet into cyclohexane. After removing the insoluble matter with a filter, the obtained extract was measured by GPC, and the compound in the pellet was measured from the RI peak area of the compound (A) in the extract using the above calibration curve as follows. The concentration of A) was calculated.
<Calculate the concentration of compound (A)>
Calibration curve: [Concentration of compound (A) in cyclohexane] (%) = f × [RI area]
[Concentration of compound (A) in pellets] (ppm)
= [Concentration of compound (A) in cyclohexane] (%) ÷ 100 × [Weight of cyclohexane] (g) ÷ [Weight of pellets] (g) × 1000000
= F x [RI area] ÷ 100 x [cyclohexane weight] (g) ÷ [pellet weight] (g) x 1000000
(7) Amount of Residual Solvent 2 parts of the polymer-containing material, 0.1 part of o-dichlorobenzene, and 32.9 parts of chlorobenzene were heated at 120 ° C. for 1 hour in a pressure-resistant glass container to extract the residual solvent. .. The obtained solution was filtered through a syringe filter (manufactured by ADVANTEC, pore size: 0.45 μm), and the amount of residual solvent was determined by a gas chromatograph (manufactured by HEWLETT PACKARD, HP6850 ASeries).
For the measurement, HP-1 (30 m × 0.32 mm × 0.25 μm) manufactured by Agilent was used as the column, the vaporization chamber temperature: 240 ° C., the column temperature: 35 ° C. at the start, and 280 ° C. at 10 ° C./min. The temperature was raised to 310 ° C., the injection amount was 1 μm, and the temperature was increased.
(8) Presence or absence of defects (die lines) A film was placed between the white screen and the projector in a dark room, and the shadows reflected on the screen were observed. Then, the presence or absence of defects was evaluated according to the following criteria.
◯: Nothing can be seen and it is uniform.
X: The die line can be confirmed.
（実施例１）
＜粗重合体含有物の調製（工程（Ａ））＞
［開環重合］
充分に乾燥した後に窒素置換したガラス製耐圧反応容器に、ジシクロペンタジエン（エンド体含有率９９％以上）の７０％シクロヘキサン溶液１４３部（ジシクロペンタジエンの量として１００部）、１－へキセン５．７部、シクロヘキサン１６６部を加え、続けて濃度１９％のジエチルアルミニウムエトキシドのｎ－ヘキサン溶液０．６２部を加えて撹拌した。次いで、テトラクロロタングステンフェニルイミド（テトラヒドロフラン）錯体０．１５部をトルエン５部に溶解した溶液を加えて、５０℃に加温して開環重合反応を開始した。２時間後、メタノール１．５部を加え、開環重合反応を停止させた。得られた重合反応溶液に含まれるジシクロペンタジエン開環重合体（環状オレフィン開環重合体）の重量平均分子量（Ｍｗ）は２８，７００であり、数平均分子量（Ｍｎ）は９，５７０であった。
得られた重合反応溶液に、ろ過助剤として珪藻土（昭和化学工業社製、ラヂオライト＃３００）０．５部を加えた。この懸濁液に対して、リーフフィルター（ＩＨＩ社製、ＣＦＲ２）にて濾過処理を行い、ジシクロペンタジエン開環重合体の溶液を得た。
［水素化］
次に、得られたジシクロペンタジエン開環重合体の溶液を、撹拌機および温調ジャケット付きの反応器（住友重機械工業社製）に移送した後、ジシクロペンタジエン開環重合体の濃度が９％になるようにシクロヘキサン６００部、クロロヒドリドカルボニルトリス（トリフェニルホスフィン）ルテニウム０．１部を加えた。次いで、全容を回転数６４ｒｐｍで撹拌しながら、水素圧４ＭＰａ、温度１８０℃にて６時間水素添加反応を行い、ジシクロペンタジエン開環重合体水素化物の粒子を含有するスラリーを得た。
なお、ジシクロペンタジエン開環重合体水素化物の水素化率は９９．５％であり、重量平均分子量（Ｍｗ）は６１，２００であり、数平均分子量（Ｍｎ）は１８，３０３であった。
難溶性環状オレフィン重合体（１）と可溶性不純物（１）の合計量（以下、この量を「重合体量」ということがある。）に対する可溶性不純物（１）の量は５％であった。
［固液分離］
機器内部に回転するボール部を有し、さらにボール部の内部にケーキ搬送用のスクリューコンベアを有する遠心脱水機（タナベウィルテック社製、高速デカンタ）に、前記スラリー１１００部を供給し、ボール部回転数４８００ｒｐｍ、差動回転数１５ｒｐｍの条件で固液分離を行った。得られたウエットケーキ（粗重合体含有物）の量は２４０部であった。
＜粗重合体含有物の洗浄（工程（Ｂ））＞
得られたウエットケーキ２４０部と、溶媒としてのキシレン２１６０部とを、傾斜パドル翼を備えた撹拌槽中に入れ、２００ｒｐｍの回転数で１時間撹拌し、キシレンスラリーを得た。
次に、機器内部に回転するボール部を有し、さらにボール部の内部にケーキ搬送用のスクリューコンベアを有する遠心脱水機（タナベウィルテック社製、高速デカンタ）に、前記キシレンスラリー２４００部を供給し、ボール部回転数４８００ｒｐｍ、差動回転数１５ｒｐｍの条件で固液分離を行った。得られた洗浄ウエットケーキ（洗浄物）の量は２４０部であった。
＜洗浄物の乾燥（工程（Ｃ））＞
固液分離により得られた洗浄ウエットケーキを、連続溝型乾燥機（栗本鐵工所社製、ＣＤ－８０）に供給し、下記の乾燥条件でウエットケーキに含まれる揮発分（主に溶媒）を除去することで、乾燥物の粉末を得た。
－乾燥条件－
乾燥機温度：１７０℃
窒素流量：５０ＮＬ／分
ディスク回転数：３０ｒｐｍ
＜乾燥物の造粒（工程（Ｄ））＞
［解砕］
乾燥により得られた乾燥物の粉末１００部に、酸化防止剤として、テトラキス［メチレン－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン（ＢＡＳＦジャパン社製、イルガノックス（登録商標）１０１０）０．５部を添加した。
得られた混合物を、加圧圧縮成形機（新東工業社製、ＢＧＳ－ＩＶ）を使用して圧縮することで短冊状の成形品を得た。次いで、この短冊状の成形品を、ロール式解砕機（フレーククラッシャー）を使用して下記の条件にて解砕し、フレーク状の粉塊を得た。
－解砕条件－
ロール回転数：１０ｒｐｍ
ロール加圧：６０ｋＮ
［ペレット化］
得られたフレーク状の粉塊を、内径３ｍｍのダイ穴を備えた二軸押し出し機（日本製鋼所社製、ＴＥＸ－３０）に投入し、下記条件にて熱溶融押し出し成形を行い、ストランドを得た。そして、ストランドをストランドカッターにて細断し、直径３ｍｍ×長さ３ｍｍの円筒状のペレット（重合体含有物）を得た。
－成形条件－
バレル設定温度：２８０℃
スクリュー回転数：３００ｒｐｍ
［分析］
そして、得られたペレットを用いて、開環重合体水素化物の融点、開環重合体水素化物の重合体鎖のラセモ・ダイアッドの割合、化合物（Ａ）の含有量および残留溶媒量の測定を行った。結果を表１に示す。
＜成膜＞
得られたペレットを、加熱し溶融させた状態で単層押出成形Ｔダイを備える熱溶融押出しフィルム成形機（Ｏｐｔｉｃａｌ Ｃｏｎｔｒｏｌ Ｓｙｓｔｅｍ（ＯＣＳ）社製）に供給した。このフィルム成形機を以下の運転条件で運転させて、長尺の未延伸フィルム（厚み１５０μｍ、幅１２０ｍｍ）を、２ｍ／分の速度でロールに巻き取る方法にて連続４時間製造した。４時間後のフィルムサンプルを採取し、ダイラインの有無を確認した。結果を表１に示す。
－運転条件－
バレル温度設定：２８０℃～２９０℃
ダイ温度：２７０℃
スクリュー回転数：３０ｒｐｍ (Example 1)
<Preparation of crude polymer-containing material (step (A))>
[Ring-opening polymerization]
In a glass pressure-resistant reaction vessel that has been sufficiently dried and then replaced with nitrogen, 143 parts of a 70% cyclohexane solution of dicyclopentadiene (endic substance content of 99% or more) (100 parts as the amount of dicyclopentadiene), 1-hexene 5 .7 parts and 166 parts of cyclohexane were added, and then 0.62 parts of an n-hexane solution of diethylaluminum ethoxide having a concentration of 19% was added and stirred. Next, a solution prepared by dissolving 0.15 parts of a tetrachlorotungsten phenylimide (tetrahydrofuran) complex in 5 parts of toluene was added, and the mixture was heated to 50 ° C. to initiate a ring-opening polymerization reaction. After 2 hours, 1.5 parts of methanol was added to stop the ring-opening polymerization reaction. The weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer (cyclic olefin ring-opening polymer) contained in the obtained polymerization reaction solution was 28,700, and the number average molecular weight (Mn) was 9,570. It was.
To the obtained polymerization reaction solution, 0.5 part of diatomaceous earth (Radiolite # 300 manufactured by Showa Chemical Industry Co., Ltd.) was added as a filtration aid. This suspension was filtered with a leaf filter (CFR2 manufactured by IHI Corporation) to obtain a solution of dicyclopentadiene ring-opening polymer.
[Hydrogenation]
Next, the obtained solution of the dicyclopentadiene ring-opening polymer was transferred to a reactor with a stirrer and a temperature control jacket (manufactured by Sumitomo Heavy Industries, Ltd.), and then the concentration of the dicyclopentadiene ring-opening polymer was adjusted. 600 parts of cyclohexane and 0.1 part of chlorohydride carbonyltris (triphenylphosphine) ruthenium were added so as to be 9%. Next, a hydrogenation reaction was carried out at a hydrogen pressure of 4 MPa and a temperature of 180 ° C. for 6 hours while stirring the whole volume at a rotation speed of 64 rpm to obtain a slurry containing particles of a dicyclopentadiene ring-opening polymer hydride.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.5%, the weight average molecular weight (Mw) was 61,200, and the number average molecular weight (Mn) was 18,303.
The amount of the soluble impurity (1) with respect to the total amount of the poorly soluble cyclic olefin polymer (1) and the soluble impurity (1) (hereinafter, this amount may be referred to as “polymer amount”) was 5%.
[Solid-liquid separation]
1100 parts of the slurry is supplied to a centrifugal dehydrator (manufactured by Tanabe Wiltec, a high-speed decanter) having a rotating ball part inside the device and a screw conveyor for cake transfer inside the ball part. Solid-liquid separation was performed under the conditions of a rotation speed of 4800 rpm and a differential rotation speed of 15 rpm. The amount of the obtained wet cake (crude polymer content) was 240 parts.
<Washing of crude polymer-containing material (step (B))>
240 parts of the obtained wet cake and 2160 parts of xylene as a solvent were placed in a stirring tank equipped with an inclined paddle blade and stirred at a rotation speed of 200 rpm for 1 hour to obtain a xylene slurry.
Next, 2400 parts of the xylene slurry are supplied to a centrifugal dehydrator (manufactured by Tanabe Wiltec, a high-speed decanter) having a rotating ball portion inside the device and a screw conveyor for transporting cake inside the ball portion. Then, solid-liquid separation was performed under the conditions of a ball portion rotation speed of 4800 rpm and a differential rotation speed of 15 rpm. The amount of the obtained washed wet cake (washed product) was 240 parts.
<Drying of washed material (step (C))>
The washed wet cake obtained by solid-liquid separation is supplied to a continuous groove type dryer (CD-80 manufactured by Kurimoto, Ltd.), and volatile components (mainly solvent) contained in the wet cake under the following drying conditions. Was removed to obtain a dry product powder.
-Drying conditions-
Dryer temperature: 170 ° C
Nitrogen flow rate: 50 NL / min Disc rotation speed: 30 rpm
<Granulation of dried product (process (D))>
[Crushing]
Tetrakis [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane (BASF Japan, Inc.) was added to 100 parts of the dried product powder obtained by drying as an antioxidant. , Irganox (registered trademark) 1010) 0.5 part was added.
The obtained mixture was compressed using a pressure compression molding machine (BGS-IV manufactured by Shinto Kogyo Co., Ltd.) to obtain a strip-shaped molded product. Next, this strip-shaped molded product was crushed using a roll-type crusher (flake crusher) under the following conditions to obtain a flake-shaped powder mass.
-Crushing conditions-
Roll rotation speed: 10 rpm
Roll pressurization: 60kN
[Pelletization]
The obtained flake-shaped powder mass is put into a twin-screw extruder (manufactured by Japan Steel Works, TEX-30) equipped with a die hole having an inner diameter of 3 mm, and is subjected to hot melt extrusion under the following conditions to form a strand. Obtained. Then, the strands were shredded with a strand cutter to obtain cylindrical pellets (polymer-containing material) having a diameter of 3 mm and a length of 3 mm.
-Molding condition-
Barrel set temperature: 280 ° C
Screw rotation speed: 300 rpm
[analysis]
Then, using the obtained pellets, the melting point of the ring-opening polymer hydride, the ratio of the racemo-diad of the polymer chain of the ring-opening polymer hydride, the content of the compound (A) and the residual solvent amount were measured. went. The results are shown in Table 1.
<Film formation>
The obtained pellets were supplied to a hot melt extrusion film forming machine (manufactured by Optical Control System (OCS)) equipped with a single-layer extrusion molding T-die in a state of being heated and melted. This film forming machine was operated under the following operating conditions to continuously produce a long unstretched film (thickness 150 μm, width 120 mm) by winding it on a roll at a speed of 2 m / min for 4 hours. A film sample was taken after 4 hours, and the presence or absence of a die line was confirmed. The results are shown in Table 1.
-Operating conditions-
Barrel temperature setting: 280 ° C to 290 ° C
Die temperature: 270 ° C
Screw rotation speed: 30 rpm
＜粗重合体含有物の調製（工程（Ａ））＞
［開環重合］
充分に乾燥した後に窒素置換したガラス製耐圧反応容器に、ジシクロペンタジエン（エンド体含有率９９％以上）の７０％シクロヘキサン溶液１４３部（ジシクロペンタジエンの量として１００部）、１－へキセン５．７部、シクロヘキサン１６６部を加え、続けて濃度１９％のジエチルアルミニウムエトキシドのｎ－ヘキサン溶液０．６２部を加えて撹拌した。次いで、テトラクロロタングステンフェニルイミド（テトラヒドロフラン）錯体０．１５部をトルエン５部に溶解した溶液を加えて、５０℃に加温して開環重合反応を開始した。２時間後、メタノール１．５部を加え、開環重合反応を停止させた。得られた重合反応溶液に含まれるジシクロペンタジエン開環重合体（環状オレフィン開環重合体）の重量平均分子量（Ｍｗ）は２８，７００であり、数平均分子量（Ｍｎ）は９，５７０であった。
得られた重合反応溶液に、ろ過助剤として珪藻土（昭和化学工業社製、ラヂオライト＃３００）０．５部を加えた。この懸濁液に対して、リーフフィルター（ＩＨＩ社製、ＣＦＲ２）にて濾過処理を行い、ジシクロペンタジエン開環重合体の溶液を得た。
［水素化］
次に、得られたジシクロペンタジエン開環重合体の溶液を、撹拌機および温調ジャケット付きの反応器（住友重機械工業社製）に移送した後、ジシクロペンタジエン開環重合体の濃度が９％になるようにシクロヘキサン６００部、クロロヒドリドカルボニルトリス（トリフェニルホスフィン）ルテニウム０．１部を加えた。次いで、全容を回転数６４ｒｐｍで撹拌しながら、水素圧４ＭＰａ、温度１８０℃にて６時間水素添加反応を行い、ジシクロペンタジエン開環重合体水素化物の粒子を含有するスラリーを得た。
なお、ジシクロペンタジエン開環重合体水素化物の水素化率は９９．５％であり、重量平均分子量（Ｍｗ）は６１，２００であり、数平均分子量（Ｍｎ）は１８，３０３であった。
難溶性環状オレフィン重合体（１）と可溶性不純物（１）の合計量（以下、この量を「重合体量」ということがある。）に対する可溶性不純物（１）の量は５％であった。
［固液分離］
機器内部に回転するボール部を有し、さらにボール部の内部にケーキ搬送用のスクリューコンベアを有する遠心脱水機（タナベウィルテック社製、高速デカンタ）に、前記スラリー１１００部を供給し、ボール部回転数４８００ｒｐｍ、差動回転数１５ｒｐｍの条件で固液分離を行った。得られたウエットケーキ（粗重合体含有物）の量は２４０部であった。
＜粗重合体含有物の洗浄（工程（Ｂ））＞
得られたウエットケーキ２４０部と、溶媒としてのキシレン２１６０部とを、傾斜パドル翼を備えた撹拌槽中に入れ、２００ｒｐｍの回転数で１時間撹拌し、キシレンスラリーを得た。
次に、機器内部に回転するボール部を有し、さらにボール部の内部にケーキ搬送用のスクリューコンベアを有する遠心脱水機（タナベウィルテック社製、高速デカンタ）に、前記キシレンスラリー２４００部を供給し、ボール部回転数４８００ｒｐｍ、差動回転数１５ｒｐｍの条件で固液分離を行った。得られた洗浄ウエットケーキ（洗浄物）の量は２４０部であった。
＜洗浄物の乾燥（工程（Ｃ））＞
固液分離により得られた洗浄ウエットケーキを、連続溝型乾燥機（栗本鐵工所社製、ＣＤ－８０）に供給し、下記の乾燥条件でウエットケーキに含まれる揮発分（主に溶媒）を除去することで、乾燥物の粉末を得た。
－乾燥条件－
乾燥機温度：１７０℃
窒素流量：５０ＮＬ／分
ディスク回転数：３０ｒｐｍ
＜乾燥物の造粒（工程（Ｄ））＞
［解砕］
乾燥により得られた乾燥物の粉末１００部に、酸化防止剤として、テトラキス［メチレン－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン（ＢＡＳＦジャパン社製、イルガノックス（登録商標）１０１０）０．５部を添加した。
得られた混合物を、加圧圧縮成形機（新東工業社製、ＢＧＳ－ＩＶ）を使用して圧縮することで短冊状の成形品を得た。次いで、この短冊状の成形品を、ロール式解砕機（フレーククラッシャー）を使用して下記の条件にて解砕し、フレーク状の粉塊を得た。
－解砕条件－
ロール回転数：１０ｒｐｍ
ロール加圧：６０ｋＮ
［ペレット化］
得られたフレーク状の粉塊を、内径３ｍｍのダイ穴を備えた二軸押し出し機（日本製鋼所社製、ＴＥＸ－３０）に投入し、下記条件にて熱溶融押し出し成形を行い、ストランドを得た。そして、ストランドをストランドカッターにて細断し、直径３ｍｍ×長さ３ｍｍの円筒状のペレット（重合体含有物）を得た。
－成形条件－
バレル設定温度：２８０℃
スクリュー回転数：３００ｒｐｍ
［分析］
そして、得られたペレットを用いて、開環重合体水素化物の融点、開環重合体水素化物の重合体鎖のラセモ・ダイアッドの割合、化合物（Ａ）の含有量および残留溶媒量の測定を行った。結果を表１に示す。
＜成膜＞
得られたペレットを、加熱し溶融させた状態で単層押出成形Ｔダイを備える熱溶融押出しフィルム成形機（Ｏｐｔｉｃａｌ Ｃｏｎｔｒｏｌ Ｓｙｓｔｅｍ（ＯＣＳ）社製）に供給した。このフィルム成形機を以下の運転条件で運転させて、長尺の未延伸フィルム（厚み１５０μｍ、幅１２０ｍｍ）を、２ｍ／分の速度でロールに巻き取る方法にて連続４時間製造した。４時間後のフィルムサンプルを採取し、ダイラインの有無を確認した。結果を表１に示す。
－運転条件－
バレル温度設定：２８０℃～２９０℃
ダイ温度：２７０℃
スクリュー回転数：３０ｒｐｍ (Example 1)
<Preparation of crude polymer-containing material (step (A))>
[Ring-opening polymerization]
In a glass pressure-resistant reaction vessel that has been sufficiently dried and then replaced with nitrogen, 143 parts of a 70% cyclohexane solution of dicyclopentadiene (endic substance content of 99% or more) (100 parts as the amount of dicyclopentadiene), 1-hexene 5 .7 parts and 166 parts of cyclohexane were added, and then 0.62 parts of an n-hexane solution of diethylaluminum ethoxide having a concentration of 19% was added and stirred. Next, a solution prepared by dissolving 0.15 parts of a tetrachlorotungsten phenylimide (tetrahydrofuran) complex in 5 parts of toluene was added, and the mixture was heated to 50 ° C. to initiate a ring-opening polymerization reaction. After 2 hours, 1.5 parts of methanol was added to stop the ring-opening polymerization reaction. The weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer (cyclic olefin ring-opening polymer) contained in the obtained polymerization reaction solution was 28,700, and the number average molecular weight (Mn) was 9,570. It was.
To the obtained polymerization reaction solution, 0.5 part of diatomaceous earth (Radiolite # 300 manufactured by Showa Chemical Industry Co., Ltd.) was added as a filtration aid. This suspension was filtered with a leaf filter (CFR2 manufactured by IHI Corporation) to obtain a solution of dicyclopentadiene ring-opening polymer.
[Hydrogenation]
Next, the obtained solution of the dicyclopentadiene ring-opening polymer was transferred to a reactor with a stirrer and a temperature control jacket (manufactured by Sumitomo Heavy Industries, Ltd.), and then the concentration of the dicyclopentadiene ring-opening polymer was adjusted. 600 parts of cyclohexane and 0.1 part of chlorohydride carbonyltris (triphenylphosphine) ruthenium were added so as to be 9%. Next, a hydrogenation reaction was carried out at a hydrogen pressure of 4 MPa and a temperature of 180 ° C. for 6 hours while stirring the whole volume at a rotation speed of 64 rpm to obtain a slurry containing particles of a dicyclopentadiene ring-opening polymer hydride.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.5%, the weight average molecular weight (Mw) was 61,200, and the number average molecular weight (Mn) was 18,303.
The amount of the soluble impurity (1) with respect to the total amount of the poorly soluble cyclic olefin polymer (1) and the soluble impurity (1) (hereinafter, this amount may be referred to as “polymer amount”) was 5%.
[Solid-liquid separation]
1100 parts of the slurry is supplied to a centrifugal dehydrator (manufactured by Tanabe Wiltec, a high-speed decanter) having a rotating ball part inside the device and a screw conveyor for cake transfer inside the ball part. Solid-liquid separation was performed under the conditions of a rotation speed of 4800 rpm and a differential rotation speed of 15 rpm. The amount of the obtained wet cake (crude polymer content) was 240 parts.
<Washing of crude polymer-containing material (step (B))>
240 parts of the obtained wet cake and 2160 parts of xylene as a solvent were placed in a stirring tank equipped with an inclined paddle blade and stirred at a rotation speed of 200 rpm for 1 hour to obtain a xylene slurry.
Next, 2400 parts of the xylene slurry are supplied to a centrifugal dehydrator (manufactured by Tanabe Wiltec, a high-speed decanter) having a rotating ball portion inside the device and a screw conveyor for transporting cake inside the ball portion. Then, solid-liquid separation was performed under the conditions of a ball portion rotation speed of 4800 rpm and a differential rotation speed of 15 rpm. The amount of the obtained washed wet cake (washed product) was 240 parts.
<Drying of washed material (step (C))>
The washed wet cake obtained by solid-liquid separation is supplied to a continuous groove type dryer (CD-80 manufactured by Kurimoto, Ltd.), and volatile components (mainly solvent) contained in the wet cake under the following drying conditions. Was removed to obtain a dry product powder.
-Drying conditions-
Dryer temperature: 170 ° C
Nitrogen flow rate: 50 NL / min Disc rotation speed: 30 rpm
<Granulation of dried product (process (D))>
[Crushing]
Tetrakis [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane (BASF Japan, Inc.) was added to 100 parts of the dried product powder obtained by drying as an antioxidant. , Irganox (registered trademark) 1010) 0.5 part was added.
The obtained mixture was compressed using a pressure compression molding machine (BGS-IV manufactured by Shinto Kogyo Co., Ltd.) to obtain a strip-shaped molded product. Next, this strip-shaped molded product was crushed using a roll-type crusher (flake crusher) under the following conditions to obtain a flake-shaped powder mass.
-Crushing conditions-
Roll rotation speed: 10 rpm
Roll pressurization: 60kN
[Pelletization]
The obtained flake-shaped powder mass is put into a twin-screw extruder (manufactured by Japan Steel Works, TEX-30) equipped with a die hole having an inner diameter of 3 mm, and is subjected to hot melt extrusion under the following conditions to form a strand. Obtained. Then, the strands were shredded with a strand cutter to obtain cylindrical pellets (polymer-containing material) having a diameter of 3 mm and a length of 3 mm.
-Molding condition-
Barrel set temperature: 280 ° C
Screw rotation speed: 300 rpm
[analysis]
Then, using the obtained pellets, the melting point of the ring-opening polymer hydride, the ratio of the racemo-diad of the polymer chain of the ring-opening polymer hydride, the content of the compound (A) and the residual solvent amount were measured. went. The results are shown in Table 1.
<Film formation>
The obtained pellets were supplied to a hot melt extrusion film forming machine (manufactured by Optical Control System (OCS)) equipped with a single-layer extrusion molding T-die in a state of being heated and melted. This film forming machine was operated under the following operating conditions to continuously produce a long unstretched film (thickness 150 μm, width 120 mm) by winding it on a roll at a speed of 2 m / min for 4 hours. A film sample was taken after 4 hours, and the presence or absence of a die line was confirmed. The results are shown in Table 1.
-Operating conditions-
Barrel temperature setting: 280 ° C to 290 ° C
Die temperature: 270 ° C
Screw rotation speed: 30 rpm
（実施例２）
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてトルエンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 2)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that toluene was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてトルエンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 2)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that toluene was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例３）
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてメチルシクロヘキサンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 3)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that methylcyclohexane was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてメチルシクロヘキサンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 3)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that methylcyclohexane was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例４）
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてシクロヘキサンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 4)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that cyclohexane was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてシクロヘキサンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 4)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that cyclohexane was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
（実施例５）
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてｔｅｒｔ－１－メチル－２－プロピルシクロヘキサンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 5)
The pellets (polymer-containing material) and pellets (polymer-containing material) and the same as in Example 1 except that tert-1-methyl-2-propylcyclohexane was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Manufactured the film. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えてｔｅｒｔ－１－メチル－２－プロピルシクロヘキサンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Example 5)
The pellets (polymer-containing material) and pellets (polymer-containing material) and the same as in Example 1 except that tert-1-methyl-2-propylcyclohexane was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Manufactured the film. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
（比較例１）
粗重合体含有物の洗浄（工程（Ｂ））を行うことなく、工程（Ｃ）において洗浄ウエットケーキに替えてウエットケーキ（粗重合体含有物）を用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Comparative Example 1)
Pellets in the same manner as in Example 1 except that the wet cake (crude polymer-containing material) was used instead of the washed wet cake in the step (C) without washing the crude polymer-containing material (step (B)). (Polymer-containing material) and a film were produced. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
粗重合体含有物の洗浄（工程（Ｂ））を行うことなく、工程（Ｃ）において洗浄ウエットケーキに替えてウエットケーキ（粗重合体含有物）を用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Comparative Example 1)
Pellets in the same manner as in Example 1 except that the wet cake (crude polymer-containing material) was used instead of the washed wet cake in the step (C) without washing the crude polymer-containing material (step (B)). (Polymer-containing material) and a film were produced. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
（比較例２）
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えて極性有機溶媒であるイソプロパノールを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Comparative Example 2)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that isopropanol, which is a polar organic solvent, was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). .. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えて極性有機溶媒であるイソプロパノールを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Comparative Example 2)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that isopropanol, which is a polar organic solvent, was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). .. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
（比較例３）
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えて極性有機溶媒であるアセトンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Comparative Example 3)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that acetone, which is a polar organic solvent, was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). .. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
粗重合体含有物の洗浄（工程（Ｂ））時に溶媒としてキシレンに替えて極性有機溶媒であるアセトンを用いた以外は、実施例１と同様にしてペレット（重合体含有物）およびフィルムを製造した。そして、実施例１と同様にして分析および評価を行った。結果を表１に示す。 (Comparative Example 3)
Pellets (polymer-containing material) and film were produced in the same manner as in Example 1 except that acetone, which is a polar organic solvent, was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). .. Then, analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.
表１より、非極性有機溶媒で洗浄を行い、化合物（Ａ）の含有量を低減させた実施例１～５では、フィルムに表面欠陥が発生するのを抑制し得ることが分かる。
From Table 1, it can be seen that in Examples 1 to 5 in which the content of the compound (A) was reduced by washing with a non-polar organic solvent, the occurrence of surface defects on the film could be suppressed.
本発明によれば、結晶性を有する環状オレフィン開環重合体水素化物を含み、フィルムなどの成形体にした際に表面欠陥が生じにくい重合体含有物が得られる。
また、本発明によれば、表面欠陥の発生が抑制されたフィルムが得られる。 According to the present invention, it is possible to obtain a polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and which is less likely to cause surface defects when formed into a molded product such as a film.
Further, according to the present invention, a film in which the occurrence of surface defects is suppressed can be obtained.
また、本発明によれば、表面欠陥の発生が抑制されたフィルムが得られる。 According to the present invention, it is possible to obtain a polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydride and which is less likely to cause surface defects when formed into a molded product such as a film.
Further, according to the present invention, a film in which the occurrence of surface defects is suppressed can be obtained.
Claims (4)
- 下記式（１）：
下記式（２）：
で表される構造を含む分子量が２００以上８００以下の化合物の合計含有量が３０質量ｐｐｍ以下である、重合体含有物。 The following formula (1):
The following formula (2):
A polymer-containing compound having a total content of compounds having a molecular weight of 200 or more and 800 or less and having a molecular weight of 200 or more and 800 or less by mass ppm or less. - 下記式（１）：
非極性有機溶媒を９０質量％以上１００質量％以下の割合で含有する溶媒で前記粗重合体含有物を洗浄する工程と、
を含む、重合体含有物の製造方法。 The following formula (1):
A step of washing the crude polymer-containing material with a solvent containing a non-polar organic solvent in a proportion of 90% by mass or more and 100% by mass or less.
A method for producing a polymer-containing product, which comprises. - 前記溶媒が炭素数８以下の非極性有機溶媒からなる、請求項２に記載の重合体含有物の製造方法。 The method for producing a polymer-containing product according to claim 2, wherein the solvent is a non-polar organic solvent having 8 or less carbon atoms.
- 請求項１に記載の重合体含有物を用いて形成したフィルム。 A film formed by using the polymer-containing material according to claim 1.
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