Polymer-containing material, its manufacturing method, and film

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

[Technical field]

[0001] 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. [Background technology]

[0002] Conventionally, hydrogenated cyclic olefin ring-opening polymers have been suitably 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).

[0003] As a technique for industrially producing a crystalline hydrogenated cyclic olefin ring-opening polymer in high yield, for example, a technique for improving the liquid removal efficiency during solid-liquid separation by adding a polar solvent to aggregate the hydrogenated cyclic olefin ring-opening polymer has been proposed (for example, see Patent Document 2). Specifically, Patent Document 2 proposes a technique for obtaining a crystalline hydrogenated cyclic olefin ring-opening polymer in high yield by adding a polar solvent to a slurry of the hydrogenated cyclic olefin ring-opening polymer having crystallinity obtained through ring-opening polymerization and hydrogenation reaction, stirring the mixture, and then separating the solid content in the slurry using a centrifugal dehydrator, and then adding a polar solvent to the obtained solid content again and stirring the mixture to obtain a second slurry, and further separating the solid content in the second slurry using a centrifugal dehydrator. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2013-249432 A [Patent Document 2] JP 2014-118475 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the hydrogenated cyclic olefin ring-opening polymer having crystallinity produced by the above-mentioned conventional production methods has a problem that, when it is molded into a film or other molded article, surface defects such as die lines may occur.

[0006] 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. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to achieve the above object. The present inventors have found that a crystalline hydrogenated cyclic olefin ring-opening polymer produced by 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 into a molded product. The present inventors have also found that washing the hydrogenated cyclic olefin ring-opening polymer 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.

[0008] 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): [ka] 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) as a main structural unit, and in which the proportion of racemo-dyads of the repeating units represented by the formula (1) in the polymer chain is 30% or less or 60% or more. [ka] [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 composition is formed into a molded product such as a film. In the present invention, the "ratio of racemo-dyads" can be measured by the method described in the Examples using nuclear magnetic resonance spectroscopy (NMR). 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.

[0009] 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 reacting a polymer having a molecular weight of 1,000 to 1,000,000, the polymer being reacted with a polymer having a molecular weight of 1,000 to 1 ... [ka] The present invention is characterized by comprising the steps of: preparing a crude polymer-containing product containing a crystalline hydrogenated cyclic olefin ring-opening polymer, the hydrogenated product having a polymer chain containing a repeating unit represented by the formula (1) as a main structural unit, and the 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; 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 above formula (2) contained in the crude polymer-containing product can be easily reduced, and a polymer-containing product that is less likely to cause surface defects when molded into a molded product such as a film can be obtained.

[0010] Here, in the method for producing a polymer-containing material of the present invention, the solvent is preferably a non-polar organic solvent having a carbon number of 8 or less. By using a non-polar organic solvent having a carbon number of 8 or less, it is possible to suppress the solvent from remaining in the obtained polymer-containing material.

[0011] The present invention aims to advantageously solve the above problems, and the film of the present invention is characterized in that it is 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. Effect of the Invention

[0012] 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 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.

[0014] (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 residues of a solvent used during production and by-products.

[0015] <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.

[0016] [Polymer chain] Specifically, the hydrogenated cyclic olefin ring-opening polymer is represented by the following formula (1): [ka] The polymer chain contains a repeating unit represented by the formula (1) as a main constituent unit, and the proportion of racemo-dyads of the repeating unit represented by the formula (1) is 30% or less or 60% or more.

[0017] 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. Either isomer may be used alone, or an isomer 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.

[0018] The proportion of the repeating unit represented by 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 proportion of the repeating unit represented by formula (1) is equal to or more than the lower limit, the crystallinity of the hydrogenated cyclic olefin ring-opening polymer can be further increased.

[0019] 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 not having a ring structure condensed to the norbornene skeleton, monocyclic olefins and cyclic dienes, and derivatives thereof.

[0020] 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.

[0021] [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.

[0022] The weight average molecular weight of the hydrogenated cyclic olefin ring-opening polymer is not particularly limited, and is preferably at least 10,000, more preferably at least 15,000, and is preferably at most 100,000, and more preferably at most 80,000. The hydrogenated cyclic olefin ring-opening polymer having the above-mentioned weight average molecular weight is preferable in that it has excellent moldability and the obtained molded article has excellent heat resistance.

[0023] [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.

[0024] <Compound (A)> The compound (A) is represented by the following formula (2): [ka] and a molecular weight of the compound is 200 or more and 800 or less.

[0025] 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, etc.; a hydroxyl group; a hydrogen atom; or a chlorine atom. In the formula (2), * indicates the position of a bond. Among them, R is preferably an n-hexyl group.

[0026] 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. If the amount of the compound (A) is the above upper limit or less, it is possible to suppress the occurrence of surface defects when the polymer-containing material is molded into a molded product such as a film.

[0027] The compound (A) containing the structure represented by the above formula (2) is not particularly limited, and examples thereof include by-products generated during synthesis of hydrogenated cyclic olefin ring-opening polymers. 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.

[0028] <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 solvents 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)).

[0029] The amount of residual solvent contained in the polymer-containing composition of the present invention is preferably 500 ppm by mass or less, and more preferably 300 ppm by mass or less.

[0030] (Method of manufacturing 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.

[0031] <Process (A)> In step (A), a compound represented by the following formula (1): [ka] A crude polymer-containing material is prepared which contains a crystalline hydrogenated cyclic olefin ring-opening polymer having a polymer chain containing a repeating unit represented by formula (1) as a main structural unit, and in which the proportion of racemo-dyads of the repeating unit represented by formula (1) in the polymer chain is 30% or less or 60% or more.

[0032] 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.

[0033] 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, for example, in 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).

[0034] The crude polymer-containing material prepared as described above usually contains by-products, etc., 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.

[0035] <Process (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), compound (A) is usually removed from the crude polymer-containing material by dissolving or diffusing in the solvent.

[0036] [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.

[0037] 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; and 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.

[0038] [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.

[0039] 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 (T1) and lower than the boiling point (T2), but is preferably, for example, T1+5°C or higher and T2-5°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.

[0040] 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 mass ppm or less.

[0041] <Process (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 mass ppm or less, and more preferably 300 mass ppm or less.

[0042] <Process (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.

[0043] (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. EXAMPLES

[0044] The present invention will be described in more detail below with reference to examples and comparative examples. However, 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.

[0045] 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 (Tosoh Corporation, HLC-8320) 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.) at 210°C using 1-chloronaphthalene as the solvent. (3) Hydrogenation rate 1 It was determined based on H-NMR measurement. (4) Melting point of hydrogenated ring-opened polymer Using a differential scanning calorimeter (DSC), the sample was heated to 300°C in a nitrogen atmosphere, then quenched with liquid nitrogen, and heated again at a rate of 10°C / min for measurement. (5) Ratio of racemo-dyads in the polymer chain of ring-opened polymer hydrides Using orthodichlorobenzene-d4 as a solvent, the inverse-gated decoupling method was applied at 150 °C. 13 C-NMR measurements were performed, and the proportion of racemo-dyads was calculated based on the intensity ratio of the signal at 43.35 ppm from the meso-dyad to the signal at 43.43 ppm from the racemo-dyad, with the peak at 127.5 ppm of ortho-dichlorobenzene-d4 as the reference shift. (6) Content of compound (A) First, when pelletizing using a twin-screw extruder (TEX-30), the material that had accumulated in the gas-liquid separator installed in the vent was removed. 1 Compound (A) was characterized by analyzing with 1 H-NMR and GC-MS and identifying its molecular weight. Next, compound (A) collected during the qualitative analysis was diluted with cyclohexane to prepare a cyclohexane solution of 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 during the measurement was obtained, the peaks were assigned, and a calibration curve was created from the relationship between the compound (A) concentration and the RI peak area. The columns used were three Tosoh Corporation TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL connected in series, and the measurements were performed under the conditions of a flow rate of 1.0 ml / min, sample injection volume of 100 μml, and 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 the compound (A) in the pellets into cyclohexane. The resulting extract was filtered to remove insoluble matter, and then measured by GPC. The concentration of the compound (A) in the pellets was calculated from the RI peak area of ​​the compound (A) in the extract using the above calibration curve as follows. <Calculate the concentration of compound (A)> Calibration curve: [Concentration of compound (A) in cyclohexane] (%) = f × [RI area] [Concentration of compound (A) in pellet] (ppm) = [Concentration of compound (A) in cyclohexane] (%) ÷ 100 × [Weight of cyclohexane] (g) ÷ [Weight of pellets] (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 amount of the residual solvent was determined by a gas chromatograph (manufactured by HEWLETT PACKARD, HP6850A Series). The measurements were performed using an Agilent HP-1 (30 m × 0.32 mm × 0.25 μm) column with a vaporizer temperature of 240°C, column temperature of 35°C at the start and increased to 280°C at 10°C / min, detector temperature of 310°C, and injection volume of 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 shadows projected on the screen were observed. The presence or absence of defects was evaluated according to the following criteria. ○: Nothing is visible and uniform. ×: Die lines are visible.

[0046] 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 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 (manufactured by Sumitomo Heavy Industries, Ltd.) equipped with a stirrer and a temperature-controlled jacket, and then 600 parts of cyclohexane and 0.1 parts of chlorohydridocarbonyltris(triphenylphosphine)ruthenium were added so that the concentration of 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 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, high-speed decanter) having a rotating bowl inside the device and a screw conveyor for conveying cake inside the bowl, and solid-liquid separation was carried out under the conditions of a bowl 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 material) was 240 parts. <Drying the washed items (step (C))> The washed wet cake obtained by solid-liquid separation was fed into 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 drying conditions described below to obtain a dried powder. - Drying conditions - Dryer temperature: 170℃ Nitrogen flow rate: 50NL / min Disk rotation speed: 30 rpm <Granulation of dried material (process (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: 60kN [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 obtained were used to measure the melting point of the hydrogenated ring-opening polymer, the racemo-dyad ratio in 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. This 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℃~290℃ Die temperature: 270℃ Screw rotation speed: 30 rpm

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] [Table 1]

[0055] From Table 1, it is 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. [Industrial Applicability]

[0056] 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

1. The following formula (1): 【Chemistry 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): 【Chemistry 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:

2. The following formula (1): 【Chemistry 3】 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:

3. The method for producing a polymer-containing material according to claim 2 , wherein the solvent comprises a non-polar organic solvent having 8 or less carbon atoms.

4. A film formed using the polymer-containing material according to claim 1.

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