JP7652073B2 - Polymer-containing material, its manufacturing method, and film - Google Patents

Description

The present invention relates to a polymer-containing material, a method for producing the polymer-containing material, and a film, and in particular to a polymer-containing material containing a hydrogenated cyclic olefin ring-opening polymer, a method for producing the same, and a film.

Conventionally, hydrogenated cyclic olefin ring-opening polymers have been used as optical materials due to their excellent transparency and optical properties. In particular, hydrogenated cyclic olefin ring-opening polymers having crystallinity have been attracting attention in recent years as materials that can exhibit excellent heat resistance, mechanical strength, and solvent resistance in addition to transparency and optical properties (see, for example, Patent Document 1).

As a technique for industrially producing crystalline cyclic olefin ring-opening polymer hydrogenation products in high yields, for example, a technique has been proposed in which a polar solvent is added to aggregate the cyclic olefin ring-opening polymer hydrogenation products to improve the deliquation efficiency during solid-liquid separation (see, for example, Patent Document 2). Specifically, Patent Document 2 proposes a technique in which a polar solvent is added to a slurry of crystalline cyclic olefin ring-opening polymer hydrogenation products obtained through ring-opening polymerization and hydrogenation reactions, the slurry is stirred, and the solids in the slurry are separated using a centrifugal dehydrator, and then a polar solvent is added again to the obtained solids and stirred to form a second slurry, and the solids in the second slurry are further separated using a centrifugal dehydrator, thereby obtaining a crystalline cyclic olefin ring-opening polymer hydrogenation product in high yields.

JP 2013-249432 A JP 2014-118475 A

However, the crystalline hydrogenated cyclic olefin ring-opening polymer produced using the above-mentioned conventional manufacturing method had the problem that surface defects such as die lines could occur when molded into films or other molded articles.

Therefore, an object of the present invention is to provide a polymer-containing material which contains a hydrogenated cyclic olefin ring-opening polymer having crystallinity and is less likely to cause surface defects when molded into a molded product such as a film.
Another object of the present invention is to provide a film formed using the polymer-containing material, in which the occurrence of surface defects is suppressed.

The present inventors have conducted intensive research to achieve the above object. The present inventors have found that a crystalline cyclic olefin ring-opening polymer hydrogenated product produced using a conventional production method contains a specific compound as an impurity, and that reducing the content of the specific compound can suppress the occurrence of surface defects when the product is molded. The present inventors have also found that washing the cyclic olefin ring-opening polymer hydrogenated product with a non-polar solvent having a specific carbon number can easily reduce the content of the specific compound. The present inventors have completed the present invention based on the above new findings.

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 object of the present invention is to advantageously solve the above problems, and the polymer-containing material of the present invention is represented by the following formula (1):

The present invention relates to a hydrogenated cyclic olefin ring-opening polymer having crystallinity, which has a polymer chain containing a repeating unit represented by the following formula (2):

[wherein R is an alkyl group, a hydroxyl group, a hydrogen atom, or a chlorine atom, and * is a bond.], the total content of compounds having a molecular weight of 200 or more and 800 or less is 30 mass ppm or less. In this way, if the total content of compounds having a molecular weight of 200 or more and 800 or less, including a structure represented by formula (2), is 0 mass ppm or more and 30 mass ppm or less, the occurrence of surface defects can be suppressed when the product is formed into a molded product such as a film.
In the present invention, the "racemo-dyad ratio" can be measured by nuclear magnetic resonance spectroscopy (NMR) according to the method described in the Examples.
In the present invention, the "total content of compounds containing a structure represented by formula (2) and having a molecular weight of 200 or more and 800 or less" can be measured using the method described in the Examples.

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。 The present invention also aims to advantageously solve the above problems, and the method for producing a polymer-containing material of the present invention comprises the steps of:

The process comprises the steps of preparing a crude polymer-containing product containing a crystalline cyclic olefin ring-opening polymer hydrogenated product, the crude polymer-containing product having a polymer chain containing a repeating unit represented by the formula (1) as a main structural unit, and the ratio of the racemo-dyad of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60% or more, and washing the crude polymer-containing product with a solvent containing a non-polar organic solvent at a ratio of 90% by mass to 100% by mass. In this way, by washing the crude polymer-containing product with a solvent containing a non-polar organic solvent at a ratio of 90% by mass to 100% by mass, the content of the compound having a molecular weight of 200 to 800 and containing the structure represented by the formula (2) contained in the crude polymer-containing product can be easily reduced, so that a polymer-containing product that is less likely to cause surface defects when molded into a film or other molded product can be obtained.

Here, in the method for producing a polymer-containing material of the present invention, it is preferable that the solvent is 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.

The present invention aims to advantageously solve the above problems, and the film of the present invention is characterized by being formed using the above-mentioned polymer-containing material. In this way, the use of the above-mentioned polymer-containing material can suppress the occurrence of surface defects.

According to the present invention, a polymer-containing material can be obtained which contains a hydrogenated cyclic olefin ring-opening polymer having crystallinity and which is less likely to cause surface defects when molded into a film or other molded article.
Furthermore, according to the present invention, a film in which the occurrence of surface defects is suppressed can be obtained.

Hereinafter, an embodiment of the present invention will be described in detail.
Here, the polymer-containing material of the present invention can be produced, for example, by using the method for producing a polymer-containing material of the present invention, and can be suitably used as a material for various molded products such as films, without any particular limitations.

(Polymer-containing material)
The polymer-containing material of the present invention contains a hydrogenated cyclic olefin ring-opening polymer, and has a content of a compound (A) having a predetermined structure and molecular weight of 0 ppm by mass or more and 30 ppm by mass or less. The polymer-containing material of the present invention may further contain other components such as a residue of a solvent used during production or a by-product.

<Hydrogenated Cyclic Olefin Ring-Opening Polymer>
Here, the hydrogenated cyclic olefin ring-opening polymer contained in the polymer-containing material of the present invention is a crystalline polymer compound having a predetermined polymer chain.

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 hydrogenated cyclic olefin ring-opening polymer has the following formula (1):

and has a polymer chain in which the ratio of racemo-dyads of the repeating unit represented by the above formula (1) is 30% or less or 60% or more.

Here, the repeating unit represented by the above formula (1) can be introduced into a polymer chain, for example, by carrying out ring-opening polymerization using a monomer composition containing dicyclopentadiene as a monomer, and then hydrogenating the resulting ring-opened polymer to hydrogenate a structural unit derived from dicyclopentadiene in the ring-opened polymer.
Dicyclopentadiene has endo and exo stereoisomers, both of which can be used as monomers. One isomer may be used alone, or an isomeric mixture in which the endo and exo isomers exist in any ratio may be used. However, from the viewpoint of increasing the crystallinity of the hydrogenated cyclic olefin ring-opening polymer, it is preferable to increase the ratio of one stereoisomer, and for example, the ratio of the endo isomer or the exo isomer is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. From the viewpoint of ease of synthesis, the stereoisomer whose ratio is increased is preferably the endo isomer.

In addition, the proportion of the repeating units 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. If the proportion of the repeating units represented by the above formula (1) is equal to or more than the above lower limit, the crystallinity of the hydrogenated cyclic olefin ring-opening polymer can be further increased.

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 a repeating unit derived from a monomer copolymerizable with dicyclopentadiene.
Here, the monomer copolymerizable with dicyclopentadiene is not particularly limited, and examples thereof include polycyclic norbornene compounds other than dicyclopentadiene, bicyclic norbornene compounds having no ring structure condensed to the norbornene skeleton, monocyclic olefins and cyclic dienes, and derivatives thereof.

In the polymer chain, the ratio of the racemo-dyads of the repeating units represented by the above formula (1) is not particularly limited as long as it is 30% or less or 60% or more, but the ratio of the racemo-dyads is preferably 25% or less, more preferably 20% or less, or preferably 65% or more, more preferably 70% or more.
The ratio of the racemo-dyad can be adjusted by, for example, changing the type of catalyst used in the ring-opening polymerization or the polymerization conditions.

[Properties]
The hydrogenated cyclic olefin ring-opening polymer has crystallinity and usually has a melting point. From the viewpoint of improving the heat resistance of a molded article formed using the polymer-containing material, the melting point of the hydrogenated cyclic olefin ring-opening polymer is preferably 200° C. or higher, more preferably 230° C. or higher. The melting point of the hydrogenated cyclic olefin ring-opening polymer is usually 290° C. or lower.

The weight average molecular weight of the hydrogenated cyclic olefin ring-opening polymer is not particularly limited, but is preferably 10,000 or more, more preferably 15,000 or more, and is preferably 100,000 or less, and more preferably 80,000 or less. Hydrogenated cyclic olefin ring-opening polymers having the above-mentioned weight average molecular weight are preferred in that they have excellent moldability and the heat resistance of the resulting molded products is excellent.

[Content]
The proportion of the hydrogenated cyclic olefin ring-opening polymer in the polymer-containing composition of the present invention is preferably 90% by mass or more, and more preferably 95% by mass or more.

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)>
The compound (A) is represented by the following formula (2):

and a molecular weight of the compound is 200 or more and 800 or less.

Here, in 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, or an n-octyl group; a hydroxyl group; a hydrogen atom; or a chlorine atom. In formula (2), * indicates the position of the bond. Of these, it is preferable that R is an n-hexyl group.

The amount of compound (A) contained in the polymer-containing material of the present invention is not particularly limited as long as it is 30 ppm by mass or less in total, but is preferably 10 ppm by mass or less. If the amount of compound (A) is equal to or less than the above upper limit, the occurrence of surface defects can be suppressed when the polymer-containing material is molded into a molded product such as a film.

The compound (A) containing the structure represented by the above formula (2) is not particularly limited, and examples thereof include by-products generated during the synthesis of a cyclic olefin ring-opening polymer hydrogenation product. Specifically, examples of the by-products include hydrogenated dicyclopentadiene dimers or trimers generated during ring-opening polymerization using a monomer composition containing dicyclopentadiene as a monomer.

<Other ingredients>
Other components that may be contained in the polymer-containing composition of the present invention are not particularly limited, and examples thereof include residues of the solvent used in preparing the polymer-containing composition and by-products generated during the synthesis of the hydrogenated cyclic olefin ring-opening polymer (excluding those corresponding to the above compound (A)).

The amount of residual solvent contained in the polymer-containing material of the present invention is preferably 500 ppm by mass or less, and more preferably 300 ppm by mass or less.

(Method for producing polymer-containing material)
The method for producing a polymer-containing material of the present invention includes a step (A) of preparing a crude polymer-containing material containing a hydrogenated cyclic olefin ring-opening polymer having crystallinity, and a step (B) of washing the crude polymer-containing material with a solvent containing a non-polar organic solvent in a ratio of 90% by mass or more and 100% by mass or less, and optionally further includes a step (C) of drying the washed material obtained by washing the crude polymer-containing material, and a step (D) of granulating the dried material into pellets.

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。 <Step (A)>
In step (A), a compound represented by the following formula (1):

The present invention provides a crude polymer-containing material containing a crystalline hydrogenated cyclic olefin ring-opening polymer, the hydrogenated cyclic olefin ring-opening polymer having a polymer chain containing a repeating unit represented by formula (1) as a main structural unit, and a ratio of racemo-dyads of the repeating unit represented by formula (1) in the polymer chain being 30% or less or 60% or more.

Specifically, in step (A), a monomer composition containing dicyclopentadiene as a monomer and optionally further containing a monomer copolymerizable with dicyclopentadiene is used to carry out ring-opening polymerization, and the resulting ring-opened polymer is then hydrogenated to prepare a crude polymer-containing material containing a hydrogenated cyclic olefin ring-opening polymer having crystallinity.

Here, the preparation of the crude polymer-containing material using ring-opening polymerization and hydrogenation is not particularly limited, and can be carried out using the methods and conditions described in, for example, JP-A-2014-118475, JP-A-2016-183221, JP-A-2015-83705, and JP-A-2015-178561.
In addition, when the crude polymer-containing material is obtained in a slurry state in which the crude polymer-containing material is dispersed in a liquid in step (A), the crude polymer-containing material can be subjected to solid-liquid separation using a known solid-liquid separation device such as a centrifugal dehydrator before being subjected to step (B).

The crude polymer-containing material prepared as described above usually contains by-products and the like in addition to the hydrogenated cyclic olefin ring-opening polymer having the above-mentioned crystallinity. Specifically, the crude polymer-containing material usually contains the above-mentioned compound (A) as a by-product in a proportion of more than 300 ppm by mass.

<Step (B)>
In step (B), the crude polymer-containing material obtained in step (A) is washed with a solvent containing a non-polar organic solvent in a ratio of 90% by mass to 100% by mass. In step (B), the compound (A) is usually removed from the crude polymer-containing material by dissolving or diffusing in the solvent.

[solvent]
Here, the solvent is not particularly limited and any solvent can be used as long as it contains a non-polar organic solvent at a ratio of 90% by mass or more and optionally contains a polar organic solvent or water at a ratio of 10% by mass or less. Among them, from the viewpoint of removing the compound (A) well, it is preferable to use a solvent consisting of a non-polar organic solvent as the solvent.

The non-polar organic solvent is not particularly limited, and examples thereof include saturated aliphatic hydrocarbons such as n-hexane, cyclohexane, cyclooctane, methylcyclohexane, and tert-1-methyl-2-propylcyclohexane; aromatic hydrocarbons such as toluene and xylene; or mixtures of two or more of these. Among these, from the viewpoint of suppressing the solvent from remaining in the obtained polymer-containing material, it is preferable to use a non-polar organic solvent having 8 or less carbon atoms, and it is more preferable to use xylene, toluene, cyclohexane, or methylcyclohexane.
Furthermore, 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, and more preferably 150° C. or lower.

[Cleaning]
The method for washing the crude polymer-containing material is not particularly limited, and can be carried out, for example, by dispersing the crude polymer-containing material in a solvent under stirring, and then removing the solvent using a known solid-liquid separation device such as a centrifugal dehydrator.

Here, the time for washing the crude polymer-containing material is not particularly limited, and can be, for example, from 10 minutes to 5 hours.
The temperature of the solvent used in washing is not particularly limited as long as it is higher than the freezing point (T ₁ ) and lower than the boiling point (T ₂ ). For example, it is preferably T ₁ +5° C. or higher and T ₂ -5° C. or lower.
Furthermore, the amount of the solvent used for washing is preferably 4 to 20 times the amount of the crude polymer-containing material in terms of mass ratio.

In step (B), it is preferable to wash the crude polymer-containing material until the amount of compound (A) contained in the polymer-containing material obtained by the method for producing a polymer-containing material of the present invention is 30 ppm by mass or less.

<Step (C)>
In step (C), the washed product obtained by washing the crude polymer-containing material in step (B) is dried. Here, the method for drying the washed product is not particularly limited, and any drying method such as hot air drying, vacuum drying, spin drying, etc. Among them, from the viewpoint of suppressing the solvent from remaining in the obtained polymer-containing material, it is preferable to dry the washed product using vacuum drying.
The drying is preferably carried out until the amount of residual solvent contained in the polymer-containing material obtained by the method for producing a polymer-containing material of the present invention is 500 ppm by mass or less, and more preferably 300 ppm by mass or less.

<Step (D)>
In step (D), the dried product obtained in step (C) is granulated to obtain a pellet-shaped polymer-containing material. The granulation of the dried product is not particularly limited, and can be carried out using a known granulation device such as a twin-screw extruder.

(film)
The film of the present invention can be obtained by forming the above-mentioned polymer-containing material of the present invention into a film shape. Since the film of the present invention uses the above-mentioned polymer-containing material, it has 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.

The present invention will be described in more detail below with reference to examples and comparative examples. Note that the present invention is not limited to these examples. In the following, "parts", "%" and "ppm" are by mass unless otherwise specified, and pressure is gauge pressure.

The measurements and evaluations in each example were carried out by the following methods.
(1) Weight-average molecular weight (Mw) and number-average molecular weight (Mn) of ring-opening polymer
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer were measured in terms of polystyrene using a gel permeation chromatography (GPC) system (HLC-8320, manufactured by Tosoh Corporation). The measurements were performed using an H-type column (manufactured by Tosoh Corporation) at 40° C. using tetrahydrofuran as a solvent.
(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) of hydrogenated ring-opened polymer
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated ring-opening polymer were measured in terms of polystyrene using a gel permeation chromatography (GPC) system (SSC-7100, manufactured by Senshu Scientific Co., Ltd.) using a GPC3506 column (manufactured by Senshu Scientific Co., Ltd.) at 210°C with 1-chloronaphthalene as a solvent.
(3) Hydrogenation rate
It was determined based on ¹ H-NMR measurement.
(4) Melting Point of Hydrogenated Ring-Opened Polymer The melting point of a sample was measured using a differential scanning calorimeter (DSC) by heating the sample to 300° C. in a nitrogen atmosphere, then quenching with liquid nitrogen and heating it again at a rate of 10° C./min.
(5) Ratio of racemo dyads in the polymer chain of the ring-opened polymer hydrogenation product ¹³ C-NMR measurement was performed by applying the inverse-gated decoupling method at 150 ° C. using orthodichlorobenzene- _d4 as a solvent, and the ratio of racemo dyads was calculated based on the intensity ratio of the signal at 43.35 ppm derived from the meso dyad and the signal at 43.43 ppm derived from the racemo dyad, with the peak at 127.5 ppm of orthodichlorobenzene- _d4 as the reference shift.
(6) Content of Compound (A) First, when pelletizing using a twin-screw extruder (TEX-30), the substance accumulated in the gas-liquid separator installed in the vent section was analyzed by ^1H -NMR and GC-MS to identify the molecular weight, thereby qualitatively identifying compound (A).
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) at a specified concentration. Then, each solution was measured with a gel permeation chromatography (GPC) system (Tosoh Corporation, HLC-8320) with an injection volume of 100 μL, and the RI peak area at the time of measurement was obtained, and the peak was assigned, and a calibration curve was created from the relationship between the compound (A) concentration and the RI peak area. In addition, three columns, TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL, manufactured by Tosoh Corporation, were used in series, and the measurement was performed under the conditions of a flow rate of 1.0 ml/min, a sample injection volume of 100 μml, and a column temperature of 40° C.
Then, 0.2 parts of the pellets and 3.3 parts of cyclohexane were placed in a pressure-resistant glass container and heated at 150° C. for 6 hours to extract compound (A) in the pellets into cyclohexane. The resulting extract was filtered to remove insoluble matter, and then measured by GPC. The concentration of compound (A) in the pellets was calculated from the RI peak area of compound (A) in the extract using the above calibration curve as follows.
<Calculation of 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 pellet] (g) × 1,000,000
= f × [RI area] ÷ 100 × [cyclohexane weight] (g) ÷ [pellet weight] (g) × 1,000,000
(7) Residual Solvent Amount 2 parts of the polymer-containing material, 0.1 parts of o-dichlorobenzene, and 32.9 parts of chlorobenzene were heated in a pressure-resistant glass vessel at 120° C. for 1 hour to extract the residual solvent. The resulting solution was filtered through a syringe filter (manufactured by ADVANTEC, pore size: 0.45 μm), and the residual solvent amount was determined by a gas chromatograph (manufactured by HEWLETTPACKARD, HP6850A Series).
The measurements were performed using an Agilent HP-1 (30 m × 0.32 mm × 0.25 μm) column under the following conditions: vaporizer temperature: 240°C; column temperature: 35°C at the start, heated to 280°C at 10°C/min; detector temperature: 310°C; injection volume: 1 μm.
(8) Presence or absence of defects (die lines): The film was placed between a white screen and a projector in a dark room, and the shadow projected on the screen was observed. The presence or absence of defects was evaluated according to the following criteria.
◯: Nothing is visible and uniform.
×: Die lines are visible.

Example 1
<Preparation of crude polymer-containing material (step (A))>
[Ring-opening polymerization]
In a glass pressure-resistant reaction vessel that had been thoroughly dried and then substituted with nitrogen, 143 parts of a 70% cyclohexane solution of dicyclopentadiene (endo isomer content of 99% or more) (100 parts as the amount of dicyclopentadiene), 5.7 parts of 1-hexene, and 166 parts of cyclohexane were added, followed by adding 0.62 parts of a 19% concentration n-hexane solution of diethylaluminum ethoxide and stirring. Next, a solution in which 0.15 parts of tetrachlorotungsten phenylimide (tetrahydrofuran) complex was dissolved 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 were added to terminate 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.
To the obtained polymerization reaction solution, 0.5 parts of diatomaceous earth (Radiolite #300, manufactured by Showa Chemical Industry Co., Ltd.) was added as a filter aid. This suspension was filtered using a leaf filter (CFR2, manufactured by IHI Corporation) to obtain a solution of a dicyclopentadiene ring-opening polymer.
[Hydrogenation]
Next, the obtained solution of dicyclopentadiene ring-opening polymer was transferred to a reactor equipped with a stirrer and a temperature-controlled jacket (manufactured by Sumitomo Heavy Industries, Ltd.), and then 600 parts of cyclohexane and 0.1 parts of chlorohydridocarbonyltris(triphenylphosphine)ruthenium were added so that the concentration of the dicyclopentadiene ring-opening polymer became 9%. Next, while stirring the entire volume at a rotation speed of 64 rpm, a hydrogenation reaction was carried out at a hydrogen pressure of 4 MPa and a temperature of 180° C. for 6 hours to obtain a slurry containing particles of a hydrogenated dicyclopentadiene ring-opening polymer.
The hydrogenation rate of the hydrogenated dicyclopentadiene ring-opening polymer 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 impurities (1) was 5% based on the total amount of the poorly soluble cyclic olefin polymer (1) and the soluble impurities (1) (hereinafter, this amount may be referred to as the "polymer amount").
[Solid-liquid separation]
1100 parts of the slurry was fed to a centrifugal dehydrator (Tanabe Wiltec Co., Ltd., high-speed decanter) having a rotating bowl section inside the device and a screw conveyor for conveying cake inside the bowl section, and solid-liquid separation was carried out under the conditions of a bowl section rotation speed of 4800 rpm and a differential rotation speed of 15 rpm. The amount of the obtained wet cake (crude polymer-containing material) was 240 parts.
<Cleaning of crude polymer-containing material (step (B))>
240 parts of the obtained wet cake and 2,160 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 was fed into a centrifugal dehydrator (Tanabe Wiltec, high-speed decanter) having a rotating bowl section inside the device and a screw conveyor for conveying cake inside the bowl section, and solid-liquid separation was carried out under the conditions of a bowl section 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 items (step (C))>
The washed wet cake obtained by solid-liquid separation was supplied to a continuous groove type dryer (CD-80, manufactured by Kurimoto Iron Works, Ltd.), and the volatile matter (mainly the solvent) contained in the wet cake was removed under the following drying conditions to obtain a dried powder.
- Drying conditions -
Dryer temperature: 170℃
Nitrogen flow rate: 50 NL/min Disk rotation speed: 30 rpm
<Granulation of dried product (step (D))>
[Crushing]
To 100 parts of the dried powder obtained by drying, 0.5 parts of tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane (manufactured by BASF Japan, Irganox (registered trademark) 1010) was added as an antioxidant.
The mixture was compressed using a pressure compression molding machine (Shinto Kogyo Co., Ltd., BGS-IV) to obtain a rectangular molded product. The rectangular molded product was then crushed using a roll crusher (flake crusher) under the following conditions to obtain a flake-like powder mass.
- Crushing conditions -
Roll rotation speed: 10 rpm
Roll pressure: 60 kN
[Pelletization]
The obtained flake-like powder mass was fed into a twin-screw extruder (TEX-30, manufactured by Japan Steel Works, Ltd.) equipped with a die hole with an inner diameter of 3 mm, and subjected to hot melt extrusion molding under the following conditions to obtain strands. The strands were then chopped with a strand cutter to obtain cylindrical pellets (polymer-containing material) with a diameter of 3 mm and a length of 3 mm.
- Molding conditions -
Barrel temperature setting: 280℃
Screw rotation speed: 300 rpm
[analysis]
The pellets thus obtained were used to measure the melting point of the hydrogenated ring-opening polymer, the racemo-dyad ratio of the polymer chain of the hydrogenated ring-opening polymer, the content of compound (A), and the amount of residual solvent. The results are shown in Table 1.
<Film formation>
The obtained pellets were heated and melted and fed to a hot melt extrusion film molding machine (Optical Control System (OCS)) equipped with a single layer extrusion molding T-die. The film molding machine was operated under the following operating conditions, and a long unstretched film (thickness 150 μm, width 120 mm) was continuously produced for 4 hours by winding it up on a roll at a speed of 2 m/min. After 4 hours, a film sample was taken and the presence or absence of a die line was confirmed. The results are shown in Table 1.
- Operating conditions -
Barrel temperature setting: 280℃ to 290℃
Die temperature: 270°C
Screw rotation speed: 30 rpm

Example 2
Pellets (polymer-containing material) and a film were produced in the same manner as in Example 1, except that toluene was used instead of xylene as a solvent during washing of the crude polymer-containing material (step (B)). Analysis and evaluation were then carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 3
Pellets (polymer-containing material) and a film were produced in the same manner as in Example 1, except that methylcyclohexane was used instead of xylene as a solvent during washing of the crude polymer-containing material (step (B)). Analysis and evaluation were then carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Pellets (polymer-containing material) and a film were produced in the same manner as in Example 1, except that cyclohexane was used instead of xylene as a solvent during washing of the crude polymer-containing material (step (B)). Analysis and evaluation were then carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 5
Pellets (polymer-containing material) and a film were produced in the same manner 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)). Analysis and evaluation were then carried out in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
Pellets (polymer-containing material) and a film were produced in the same manner as in Example 1, except that the crude polymer-containing material was not washed (step (B)) and a wet cake (crude polymer-containing material) was used instead of the washed wet cake in step (C). Analysis and evaluation were then performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
Pellets (polymer-containing material) and a film were produced in the same manner as in Example 1, except that isopropanol, a polar organic solvent, was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Analysis and evaluation were then carried out in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
Pellets (polymer-containing material) and a film were produced in the same manner as in Example 1, except that acetone, a polar organic solvent, was used instead of xylene as the solvent during washing of the crude polymer-containing material (step (B)). Analysis and evaluation were then carried out in the same manner as in Example 1. The results are shown in Table 1.

From Table 1, it can be seen that in Examples 1 to 5, in which washing was performed with a non-polar organic solvent to reduce the content of compound (A), the occurrence of surface defects in the film can be suppressed.

According to the present invention, a polymer-containing material can be obtained which contains a hydrogenated cyclic olefin ring-opening polymer having crystallinity and which is less likely to cause surface defects when molded into a film or other molded article.
Furthermore, according to the present invention, a film in which the occurrence of surface defects is suppressed can be obtained.

Claims (4)

The following formula (1):

The present invention relates to a hydrogenated cyclic olefin ring-opening polymer having crystallinity, which has a polymer chain containing a repeating unit represented by the formula (1) as a main structural unit, and in which the ratio of racemo-dyads of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60% or more,
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 polymer-containing material has a total content of compounds having a molecular weight of 200 or more and 800 or less and containing a structure represented by the following formula: The following formula (1):
and preparing a crude polymer-containing material containing a crystalline hydrogenated cyclic olefin ring-opening polymer, the hydrogenated cyclic olefin ring-opening polymer having a polymer chain containing a repeating unit represented by the formula (1) as a main structural unit, and a ratio of racemo-dyads of the repeating unit represented by the formula (1) in the polymer chain being 30% or less or 60% or more;
A step of washing the crude polymer-containing material with a solvent containing a non-polar organic solvent in a ratio of 90% by mass to 100% by mass;
The method for producing the polymer-containing material according to claim 1 , comprising: The method for producing a polymer-containing material according to claim 2, wherein the solvent is a non-polar organic solvent having 8 or less carbon atoms. A film formed using the polymer-containing material according to claim 1.