TWI840612B - Polymer-containing article, method for producing the same, and film - Google Patents

Abstract

The present invention provides: a polymer-containing object which contains a crystalline cycloolefin ring-opening polymer hydrogenate and is not prone to surface defects when formed into a shaped body such as a film. The polymer-containing object of the present invention contains a crystalline cycloolefin ring-opening polymer hydrogenate, wherein the crystalline cycloolefin ring-opening polymer hydrogenate has a polymer chain containing a repeating unit represented by the following formula (1) as a main structural unit, and the proportion of the racemic diunit group of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60% or more, and the total content of compounds having a molecular weight of 200 to 800 and a structure represented by the following formula (2) is 30 mass ppm or less. In addition, R is an alkyl group, a hydroxyl group, a hydrogen atom or a chlorine atom, and * is an atomic bond.

Description

Polymer-containing article, method for producing the same, and film

The present invention relates to a polymer-containing substance, a method for producing the polymer-containing substance, and a film, and more particularly to a polymer-containing substance comprising a cycloolefin ring-opening polymer hydrogenate, a method for producing the polymer-containing substance, and a film.

In the past, cycloolefin ring-opening polymer hydrogenates have been suitably used as optical materials due to their excellent transparency and optical properties. In particular, in recent years, crystalline cycloolefin ring-opening polymer hydrogenates have attracted attention as materials that exhibit excellent heat resistance, mechanical strength, and solvent resistance in addition to transparency and optical properties (see, for example, Patent Document 1).

Furthermore, as a technique for industrially producing crystalline cycloolefin ring-opening polymer hydrogenates with high yield, for example, a technique has been proposed in which a polar solvent is added to agglomerate the cycloolefin ring-opening polymer hydrogenates to enhance the dehydration efficiency during solid-liquid separation (see, for example, Patent Document 2). Specifically, in Patent Document 2, the following technology has been proposed: a polar solvent is added to a slurry of a crystalline cycloolefin ring-opening polymer hydrogenate obtained through ring-opening polymerization and hydrogenation reaction and the mixture is stirred, and then a second slurry is prepared by separating the solid components in the slurry using a centrifugal dehydrator and then adding a polar solvent to the obtained solid components and stirring the mixture to obtain the second slurry, and then a centrifugal dehydrator is used to separate the solid components in the second slurry, thereby obtaining a crystalline cycloolefin ring-opening polymer hydrogenate with a high yield.

『Patent Document』 《Patent Document 1》: Japanese Patent Publication No. 2013-249432 《Patent Document 2》: Japanese Patent Publication No. 2014-118475

However, the crystalline cycloolefin ring-opening polymer hydrogenate produced by the above-mentioned conventional production method has the problem that "surface defects such as mold marks may occur when forming a molded product such as a film".

Therefore, an object of the present invention is to provide a polymer-containing article which comprises a crystalline cycloolefin ring-opening polymer hydrogenate and which is less likely to have surface defects when formed into a shaped article such as a film.

Furthermore, an object of the present invention is to provide a film in which the generation of surface defects is suppressed and which is formed by using the polymer-containing material.

The inventors of the present invention have conducted intensive research to achieve the above-mentioned purpose. Then, the inventors of the present invention have found that the crystalline cycloolefin ring-opening polymer hydrogenate produced by the conventional production method contains a specified compound as an impurity, and if the content of the specified compound is reduced, the generation of surface defects when the molded body is formed can be suppressed. In addition, the inventors of the present invention have found that if the cycloolefin ring-opening polymer hydrogenate is washed with a non-polar solvent having a specified number of carbon atoms, the content of the above-mentioned specified compound can be easily reduced. Then, the inventors of the present invention have been completed based on the above-mentioned new insights.

That is, the present invention aims to solve the above-mentioned problems. The polymer-containing substance of the present invention is characterized in that it contains a crystalline cycloolefin ring-opening polymer hydrogenate, and the crystalline cycloolefin ring-opening polymer hydrogenate has the following formula (1): A polymer chain having the repeating unit represented by the formula (1) as a main structural unit and wherein the ratio of the racemic diunit group of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60% or more, wherein the following formula (2) is given: [In the formula, R is an alkyl group, a hydroxyl group, a hydrogen atom or a chlorine atom, and * is an atomic bond.] The total content of compounds having a molecular weight of 200 or more and 800 or less and including the structure represented by formula (2) is 30 mass ppm or less. If the total content of compounds having a molecular weight of 200 or more and 800 or less and including the structure represented by formula (2) is 0 mass ppm or more and 30 mass ppm or less, the occurrence of surface defects when forming a formed body such as a film can be suppressed.

In addition, in the present invention, the "ratio of the racemic dimeric monomers" can be measured using nuclear magnetic resonance spectroscopy (NMR) by the method described in the examples.

Furthermore, in the present invention, "the total content of compounds having a molecular weight of 200 or more and 800 or less and including a structure represented by formula (2)" can be measured using the method described in the Examples.

Furthermore, the present invention is aimed at successfully solving the above-mentioned problems. The method for producing a polymer-containing substance of the present invention is characterized in that it comprises: a step of preparing a crude polymer-containing product containing "a crystalline cycloolefin ring-opening polymer hydrogenate", wherein the crystalline cycloolefin ring-opening polymer hydrogenate has a structure represented by the following formula (1): A step of washing the crude polymer-containing product with a solvent containing a non-polar organic solvent in a ratio of 90 mass % to 100 mass %. When the crude polymer-containing product is washed with a solvent containing a non-polar organic solvent in a ratio of 90 mass % to 100 mass %, the content of the compound having a structure represented by the above formula (2) and a molecular weight of 200 to 800 contained in the crude polymer-containing product can be easily reduced, so that a polymer-containing product that is less likely to have surface defects when formed into a film or other shaped body can be obtained.

Here, in the method for producing a polymer-containing substance of the present invention, the solvent is preferably a non-polar organic solvent having a carbon number of 8 or less. If a non-polar organic solvent having a carbon number of 8 or less is used, the solvent can be prevented from remaining in the obtained polymer-containing substance.

Furthermore, this invention aims to solve the above-mentioned problems. The film of the present invention is characterized in that it is formed by using the above-mentioned polymer-containing material. If it is used in the above-mentioned polymer-containing material, the generation of surface defects can be suppressed.

According to the present invention, a polymer-containing material can be obtained which contains a crystalline cycloolefin ring-opening polymer hydrogenate and is less likely to have surface defects when formed into a shaped article such as a film.

Furthermore, according to the present invention, a thin film in which the generation of surface defects is suppressed can be obtained.

The following is a detailed description of the implementation of the present invention.

Here, the polymer-containing article of the present invention can be produced using, for example, the method for producing a polymer-containing article of the present invention, and can be suitably used as a material for various molded products such as films, without particular limitation.

(Containing polymers)

The polymer-containing material of the present invention comprises a cycloolefin ring-opening polymer hydrogenate, and the content of the compound (A) having a specified structure and molecular weight is 0 mass ppm or more and 30 mass ppm or less. In addition, the polymer-containing material of the present invention may further contain other components such as the residues or by-products of the solvent used in the production.

〈Cycloolefin ring-opening polymer hydrogenate〉

Here, the cycloolefin ring-opening polymer hydrogenate included in the polymer-containing material of the present invention is a crystalline high molecular compound having a predetermined polymer chain.

[Polymer chain]

Specifically, the cycloolefin ring-opening polymer hydrogenate has a polymer chain, and the polymer chain comprises the following formula (1): The repeating unit represented by the above formula (1) is used as the main structural unit and the ratio of the racemic diunit group 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), for example, can be introduced into the polymer chain by subjecting the obtained ring-opening polymer to ring-opening polymerization using a monomer composition containing dicyclopentadiene as a monomer and then hydrogenating the obtained ring-opening polymer to hydrogenate the structural unit derived from dicyclopentadiene in the ring-opening polymer.

In addition, dicyclopentadiene has stereoisomers of endo-isomers and exo-isomers, but either of them can be used as a monomer. One of the isomers can be used alone, or a mixture of endo-isomers and exo-isomers in any ratio can be used. However, from the viewpoint of improving the crystallinity of the cycloolefin ring-opening polymer hydrogenate, it is preferred to increase the ratio of one of the stereoisomers. 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. Moreover, from the viewpoint of ease of synthesis, the stereoisomer with an increased ratio is preferably the endo-isomer.

Furthermore, the ratio of the repeating units represented by the above formula (1) in the polymer chain is preferably 98 mass % or more and 100 mass % or less, and more preferably 99 mass % or more. If the ratio of the repeating units represented by the above formula (1) is greater than the above lower limit, the crystallinity of the cycloolefin ring-opening polymer hydrogenate can be further improved.

Furthermore, the polymer chain may also contain repeating units other than the repeating units represented by the above formula (1). Specifically, the polymer chain may also contain repeating units derived from monomers copolymerizable with dicyclopentadiene.

Here, the monomers copolymerizable with dicyclopentadiene are not particularly limited, and examples thereof include: polycyclic norbutylene compounds other than dicyclopentadiene, bicyclic norbutylene compounds not having a ring structure condensed to a norbutylene skeleton, monocyclic alkenes and cyclodienes, and derivatives thereof.

Furthermore, in the polymer chain, the proportion of the racemic diunit of the repeating unit 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 the racemic diunit is preferably 25% or less, more preferably 20% or less. Alternatively, the proportion of the racemic diunit is preferably 65% or more, more preferably 70% or more.

Furthermore, the ratio of the racemic diunits can be adjusted, for example, by changing the type of catalyst used in the ring-opening polymerization or the polymerization conditions.

[Properties]

Cycloolefin ring-opening polymer hydrogenates are crystalline and usually have a melting point. In addition, from the viewpoint of improving the heat resistance of a molded body formed using a polymer-containing substance, the melting point of the cycloolefin ring-opening polymer hydrogenate is preferably 200°C or higher, more preferably 230°C or higher. In addition, the melting point of the cycloolefin ring-opening polymer hydrogenate is usually 290°C or lower.

The weight average molecular weight of the cycloolefin olefin ring-opening polymer hydrogenate is not particularly limited, but is preferably 10,000 or more, more preferably 15,000 or more, and preferably 100,000 or less, more preferably 80,000 or less. The cycloolefin olefin ring-opening polymer hydrogenate having the weight average molecular weight described above is excellent in moldability, and the obtained molded article is preferably excellent in heat resistance.

[content]

In addition, the proportion of the above-mentioned cycloolefin ring-opening polymer hydrogenate in the polymer-containing material of the present invention is preferably 90 mass % or more, more preferably 95 mass % or more.

<Compound (A)>

The compound (A) comprises the following formula (2): The compound having the structure shown has a molecular weight of 200 or more and 800 or less.

Here, in formula (2), R is an alkyl group such as methyl, ethyl, propyl, butyl, n-hexyl, n-octyl, etc.; a hydroxyl group; a hydrogen atom; or a chlorine atom. In formula (2), * represents the position of the atomic bond. Among them, R is preferably n-hexyl.

Furthermore, the amount of the compound (A) contained in the polymer-containing material of the present invention is not particularly limited as long as the total amount is 30 mass ppm or less, but is preferably 10 mass ppm or less. If the amount of the compound (A) is below the above upper limit, the occurrence of surface defects when the polymer-containing material is formed into a film or other shaped body can be suppressed.

In addition, the compound (A) having the structure represented by the above formula (2) is not particularly limited, and examples thereof include byproducts generated during the synthesis of cycloolefin ring-opening polymer hydrogenates. Specifically, examples of byproducts include hydrogenates of dicyclopentadiene dimers or trimers generated during ring-opening polymerization using a monomer composition containing dicyclopentadiene as a monomer.

〈Other ingredients〉

The other components that may be contained in the polymer-containing material of the present invention are not particularly limited, and examples thereof include: residues of a solvent used in the preparation of the polymer-containing material, or by-products generated during the synthesis of a cycloolefin ring-opening polymer hydrogenate (but excluding those that meet the above-mentioned compound (A)).

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

(Method for producing polymer-containing article)

The method for producing a polymer-containing substance of the present invention comprises: a step (A) of preparing a crude polymer-containing product containing "crystalline cycloolefin ring-opening polymer hydrogenate", and a step (B) of washing the crude polymer-containing product with a solvent containing a non-polar organic solvent in a ratio of 90 mass % or more and 100 mass % or less, and further optionally comprises: a step (C) of drying the washed product obtained by washing the crude polymer-containing product, and a step (D) of granulating the dried product.

〈Process (A)〉

In step (A), a crude polymer-containing product containing a "crystalline cycloolefin ring-opening polymer hydrogenate" is prepared, wherein the crystalline cycloolefin ring-opening polymer hydrogenate has a structure represented by the following formula (1): A polymer chain having the repeating unit represented by formula (1) as a main structural unit and a ratio of a racemic diunit group of the repeating unit represented by formula (1) in the polymer chain is 30% or less or 60% or more.

Specifically, in step (A), after ring-opening polymerization is carried out using a monomer composition comprising dicyclopentadiene as a monomer and optionally containing a monomer copolymerizable with dicyclopentadiene, the obtained ring-opening polymer is hydrogenated to prepare a crude polymer-containing product containing a "crystalline cycloolefin ring-opening polymer hydrogenate".

Here, the preparation of the crude product containing the polymer using ring-opening polymerization and hydrogenation is not particularly limited, and can be carried out using, for example, the methods and conditions described in Japanese Patent Publication No. 2014-118475, Japanese Patent Publication No. 2016-183221, Japanese Patent Publication No. 2015-83705, and Japanese Patent Publication No. 2015-178561.

In addition, when the polymer-containing crude product is obtained in the form of a slurry in which the polymer-containing crude product is dispersed in a liquid in step (A), the polymer-containing crude product can be separated into solid and liquid using a known solid-liquid separation device such as a centrifugal dehydrator and then supplied to step (B).

Furthermore, the crude polymer-containing product prepared as described above usually contains by-products in addition to the crystalline cycloolefin ring-opening polymer hydrogenate described above. Specifically, the crude polymer-containing product usually contains the compound (A) described above as a by-product at a ratio of more than 300 mass ppm.

〈Process (B)〉

In step (B), the crude product containing the polymer obtained in step (A) is washed with a solvent containing a non-polar organic solvent in an amount of 90 mass % or more and 100 mass % or less. In step (B), the compound (A) is usually removed from the crude product containing the polymer by dissolving or diffusing in the solvent.

[Solvent]

Here, as a solvent, any solvent can be used without particular limitation as long as it contains a non-polar organic solvent at a ratio of 90 mass % or more and a polar organic solvent or water at a ratio of 10 mass % or less. Among them, from the viewpoint of good removal of compound (A), it is preferable to use a solvent composed of a non-polar organic solvent.

Furthermore, the non-polar organic solvent is not particularly limited, and for example, saturated aliphatic hydrocarbons such as n-hexane, cyclohexane, cyclooctane, methylcyclohexane, and tertiary butyl-1-methyl-2-propylcyclohexane; aromatic hydrocarbons such as toluene and xylene; or a mixture of two or more thereof; etc. Among them, from the viewpoint of suppressing the residual solvent in the obtained polymer-containing material, it is preferred to use a non-polar organic solvent with a carbon number of 8 or less, and it is more preferred to use xylene, toluene, cyclohexane, or methylcyclohexane.

Furthermore, from the viewpoint of further suppressing the residual solvent in the obtained polymer-containing material, the boiling point of the non-polar organic solvent under atmospheric pressure is preferably 180°C or lower, more preferably 150°C or lower.

[Cleaning]

Furthermore, the washing of the crude polymer-containing product is not particularly limited and can be carried out by, for example, dispersing the crude polymer-containing product in a solvent under stirring and then removing the solvent using a known solid-liquid separation device such as a centrifuge dehydrator.

Here, the time for washing the crude product containing the polymer is not particularly limited, and can be set, for example, to be 10 minutes or more and 5 hours or less.

The temperature of the solvent used in the cleaning 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, higher than T1+5°C and lower than T2-5°C.

Furthermore, the amount of the solvent used in the washing is preferably 4 times or more and 20 times or less the amount of the crude product containing the polymer in terms of mass ratio.

Furthermore, in step (B), the crude polymer-containing product is preferably washed 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.

〈Process (C)〉

In step (C), the washed product obtained by washing the polymer-containing crude product in step (B) is dried. Here, the drying of the washed product is not particularly limited, and any drying method such as hot air drying, vacuum drying, spin drying, etc. can be used. Among them, from the viewpoint of suppressing the residual solvent in the obtained polymer-containing product, it is preferable to dry the washed product by vacuum drying.

Furthermore, the drying is preferably performed 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 becomes 500 mass ppm or less, and more preferably, it is performed until it becomes 300 mass ppm or less.

〈Process (D)〉

In step (D), the dried product obtained in step (C) is granulated to obtain a granular polymer-containing product. Here, the granulation of the dried product is not particularly limited, and it can be carried out using a known granulation device such as a double-screw extruder.

(film)

The film of the present invention can be obtained by forming the polymer-containing material of the present invention described above into a film shape. Furthermore, the film of the present invention has few surface defects because it is used in the polymer-containing material described above.

Furthermore, the method and conditions for forming the polymer-containing material into a film are not particularly limited, and any method and conditions may be used.

『Implementation example』

The present invention is further described in detail with the following examples and comparative examples. In addition, the present invention is not limited by these examples. Unless otherwise specified, the following "parts", "%" and "ppm" are based on mass, and the pressure is the gauge pressure.

Furthermore, the measurement or evaluation in each case is performed by the following method.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of ring-opening polymers

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer were measured in the form of polystyrene conversion using a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320). In addition, the column used was an H-type column (manufactured by Tosoh Corporation), and the measurement was performed at 40°C using tetrahydrofuran as the solvent.

(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) of ring-opening polymer hydrogenates

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer hydrogenate were measured in the form of polystyrene conversion using a gel permeation chromatography (GPC) system (Senshu Scientific Co., Ltd., SSC-7100). In addition, the column used was a GPC3506 column (Senshu Scientific Co., Ltd.), with 1-chloronaphthalene as the solvent, and the measurement was performed at 210°C.

(3) Hydrogenation rate

Calculated by ¹ H-NMR measurement.

(4) Melting point of ring-opening polymer hydride

Using a differential scanning calorimeter (DSC), the sample was heated to 300°C in a nitrogen environment, rapidly cooled with liquid nitrogen, and then measured again at a temperature increase of 10°C/min.

(5) The ratio of racemic dimeric units in the polymer chain of the ring-opening polymer hydrogenate

¹³ C-NMR measurements were performed using the inverse-gated decoupling method at 150°C using o-dichlorobenzene-d ₄ as the solvent. The peak of 127.5 ppm of o-dichlorobenzene-d ₄ was used as the reference shift. The ratio of the racemic bisunit was determined based on the intensity ratio of the signal at 43.35 ppm derived from the meso bisunit to the signal at 43.43 ppm derived from the racemic bisunit.

(6) Content of compound (A)

First, during granulation using a twin-screw extruder (TEX-30), the substance accumulated in the gas-liquid separator installed in the pressure-conducting external introduction section was analyzed by ¹ H-NMR and GC-MS, and the molecular weight was fixed to thereby qualitatively analyze the compound (A).

Next, compound (A) collected during the qualitative analysis of compound (A) was diluted with cyclohexane to prepare a cyclohexane solution of compound (A) of a specified concentration. Then, each solution was measured with a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320) at an injection volume of 100 μL, and the RI peak area during the measurement was calculated to identify the peak, and a standard curve was drawn from the relationship between the concentration of compound (A) and the RI peak area. In addition, three columns, TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL manufactured by Tosoh Corporation, were connected in series and measured at 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 particles 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 particles with cyclohexane. After the obtained extract was filtered to remove insoluble components, the RI peak area of the compound (A) in the extract was measured by GPC, and the concentration of the compound (A) in the particles was calculated using the above-mentioned standard curve as described below.

〈Calculate the concentration of compound (A)〉 Standard curve: [Concentration of compound (A) in cyclohexane] (%) = f × [RI area] [Concentration of compound (A) in particles] (ppm) = [Concentration of compound (A) in cyclohexane] (%) ÷ 100 × [Weight of cyclohexane] (g) ÷ [Weight of particles] (g) × 1,000,000 = f × [RI area] ÷ 100 × [Weight of cyclohexane] (g) ÷ [Weight of particles] (g) × 1,000,000

(7) Residual solvent amount

2 parts of the polymer-containing substance, 0.1 parts 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 with a syringe filter (manufactured by ADVANTEC, pore size: 0.45 μm), and the amount of residual solvent was determined using a gas chromatograph (manufactured by HEWLETT PACKARD, HP6850ASeries).

In addition, the measurement was performed using HP-1 (30 m×0.32 mm×0.25 μm) manufactured by Agilent as the column, under the conditions of vaporizer temperature: 240°C, column temperature: 35°C at the beginning and increased to 280°C at 10°C/min, detector temperature: 310°C, injection volume: 1 μm.

(8) Presence of defects (mold streaks)

Place the film between a white screen and a projector in a dark room and observe the shadow projected on the screen. Then, evaluate the presence or absence of defects using the following criteria. ○: Uniform and no defects are observed. ╳: Mold streaks can be confirmed.

(Example 1)

<Preparation of a crude product containing a polymer (step (A))>

[Ring-opening polymerization]

In a fully dried and nitrogen-purged glass pressure-resistant reaction vessel, 143 parts (based on 100 parts of dicyclopentadiene) of a 70% cyclohexane solution of dicyclopentadiene (endo-isomer content 99% or more), 5.7 parts of 1-hexene, and 166 parts of cyclohexane were added, followed by 0.62 parts of a 19% solution of diethylaluminum ethoxide in n-hexane and stirred. Subsequently, a solution of 0.15 parts of tetrachlorophenylimide (tetrahydrofuran) tungsten complex 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 was added to terminate the ring-opening polymerization reaction. The obtained polymerization solution contained a dicyclopentadiene ring-opening polymer (cycloolefin ring-opening polymer) having a weight average molecular weight (Mw) of 28,700 and a number average molecular weight (Mn) of 9,570.

0.5 parts of diatomaceous earth (RADIOLITE #300 manufactured by Showa Chemical Industry Co., Ltd.) was added to the obtained polymerization reaction solution as a filtering aid. The suspension was filtered using a leaf filter (CFR2 manufactured by IHI Corporation) to obtain a solution of dicyclopentadiene ring-opening polymer.

[Hydrogenation]

Next, the obtained dicyclopentadiene ring-opening polymer solution was transferred to a reactor (manufactured by Sumitomo Heavy Industries, Ltd.) equipped with a stirrer and a temperature regulating jacket, and then 600 parts of cyclohexane and 0.1 parts of carbonyltris(triphenylphosphine)ruthenium chloride hydrochloride were added so that the concentration of the dicyclopentadiene ring-opening polymer became 9%. Subsequently, the hydrogenation reaction was carried out at a hydrogen pressure of 4 MPa and a temperature of 180°C for 6 hours while stirring at a rotation speed of 64 rpm to obtain a slurry containing particles of the dicyclopentadiene ring-opening polymer hydrogenate.

In addition, the hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenate 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 cycloolefin polymer (1) and the soluble impurities (1) (hereinafter, this amount may be referred to as "polymer amount").

[Solid-liquid separation]

1100 parts of the slurry were supplied to a centrifugal dehydrator (TANABE WILLTEC INC., high-speed decanter) having a rotating bowl inside the machine and a screw conveyor inside the bowl for conveying filter cakes, and solid-liquid separation was performed under the conditions of bowl speed of 4800 rpm and differential speed of 15 rpm. The amount of wet filter cakes (crude product containing polymer) obtained was 240 parts.

<Washing of the crude product containing polymer (step (B))>

240 parts of the obtained wet filter cake and 2160 parts of xylene as a solvent were placed in a stirring tank equipped with inclined blades and stirred at 200 rpm for 1 hour to obtain a xylene slurry.

Next, 2400 parts of the xylene slurry were supplied to a centrifugal dehydrator (TANABE WILLTEC INC., high-speed decanter) with a rotating bowl inside the machine and a screw conveyor inside the bowl for conveying filter cakes, and solid-liquid separation was performed under the conditions of bowl speed of 4800 rpm and differential speed of 15 rpm. The amount of clean wet filter cakes (cleaned products) obtained was 240 parts.

〈Drying of washed materials (process (C))〉

The cleaned wet filter cake obtained by solid-liquid separation was supplied to a continuous trough dryer (CD-80, manufactured by Kurimoto Iron Works Co., Ltd.), and the volatile components (mainly solvent) contained in the wet filter cake were removed under the following drying conditions to obtain a dry powder. - Drying conditions - Dryer temperature: 170°C Nitrogen flow rate: 50 NL/min Disc speed: 30 rpm

〈Granulation of dried product (step (D))〉

[Disintegration]

To 100 parts of the powder of the dried product obtained by drying, 0.5 parts of tetra-{3-[3′,5′-di(tert-butyl)-4′-hydroxyphenyl]propionic acid methylene}methane (manufactured by BASF Japan, IRGANOX (registered trademark) 1010) was added as an antioxidant.

The obtained mixture was compressed using a pressure compression molding machine (BGS-IV, manufactured by Shinto Industry Co., Ltd.) to obtain a strip-shaped molded product. Subsequently, the strip-shaped molded product was crushed using a roller crusher (thin sheet crusher) under the following conditions to obtain a flake-shaped powder block. - Crushing conditions- Roller speed: 10 rpm Roller pressure: 60 kN

[Granulation]

The obtained flake-shaped powder block is placed in a double-spindle extruder (TEX-30, manufactured by Nippon Steel Works) with a die hole of 3 mm inner diameter, and hot melt extrusion molding is performed under the following conditions to obtain a strand. Then, the strand is finely cut with a strand cutter to obtain cylindrical pellets (containing polymer) with a diameter of 3 mm and a length of 3 mm. - Molding conditions - Barrel set temperature: 280℃ Screw speed: 300 rpm

[analyze]

Then, the obtained particles were used to measure the melting point of the ring-opening polymer hydrogenate, the ratio of the racemic dimeric units in the polymer chain of the ring-opening polymer hydrogenate, the content of the compound (A), and the amount of the residual solvent. 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 forming T-die in a heated and molten state. The film forming 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 into a roll at a speed of 2 m/min. Film samples were taken after 4 hours to confirm the presence or absence of die streaks. The results are shown in Table 1. -Operation conditions- Barrel temperature setting: 280℃～290℃ Mold temperature: 270℃ Screw speed: 30 rpm

(Example 2)

Except that toluene was used as a solvent instead of xylene during the washing of the polymer-containing crude product (step (B)), the particles (polymer-containing product) and the film were produced in accordance with the operation of Example 1. Then, the analysis and evaluation were performed in accordance with the operation of Example 1. The results are shown in Table 1.

(Example 3)

The particles (polymer-containing product) and the film were prepared in the same manner as in Example 1, except that methylcyclohexane was used instead of xylene as the solvent during the washing of the polymer-containing crude product (step (B)). Then, the analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 4)

Except that cyclohexane was used as a solvent instead of xylene during the washing of the polymer-containing crude product (step (B)), the particles (polymer-containing product) and the film were prepared in the same manner as in Example 1. Then, the analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)

The particles (polymer-containing product) and film were prepared in the same manner as in Example 1, except that tertiary butyl-1-methyl-2-propylcyclohexane was used instead of xylene as the solvent during the washing of the polymer-containing crude product (step (B)). Then, the analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparison Example 1)

The particles (polymer-containing product) and the film were prepared in the same manner as in Example 1, except that the polymer-containing crude product was not washed (step (B)) and the wet filter cake (polymer-containing crude product) was used instead of the washed wet filter cake in step (C). Then, the analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparison Example 2)

The particles (polymer-containing product) and the film were prepared in the same manner as in Example 1, except that isopropyl alcohol, which is a polar organic solvent, was used instead of xylene as the solvent during the washing of the polymer-containing crude product (step (B)). Then, the analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparison Example 3)

The particles (polymer-containing product) and the film were prepared in the same manner as in Example 1, except that acetone, a polar organic solvent, was used instead of xylene as the solvent during the washing of the polymer-containing crude product (step (B)). Then, the analysis and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

"Table 1" Ratio of racemic diunits [%] Melting point(℃) Solvent Amount of compound (A) [mass ppm] Residual solvent content [ppm] Presence of mold streaks Embodiment 1 81 266 Xylene 12 215 ○ Embodiment 2 81 266 Toluene 29 138 ○ Embodiment 3 81 267 Methylcyclohexane 19 81 ○ Embodiment 4 81 266 Cyclohexane 7 42 ○ Embodiment 5 81 266 Tert-butyl-1-methyl-2-propylcyclohexane 18 7122 ○ Comparison Example 1 81 265 - 335 88 ╳ Comparison Example 2 81 265 Isopropyl alcohol 119 0 ╳ Comparison Example 3 81 264 acetone 123 0 ╳

As can be seen from Table 1, in Examples 1 to 5 in which the content of the compound (A) was reduced by washing with a non-polar organic solvent, the generation of surface defects in the thin film was suppressed.

According to the present invention, a polymer-containing material can be obtained which contains a crystalline cycloolefin ring-opening polymer hydrogenate and is less likely to have surface defects when formed into a shaped article such as a film.

Furthermore, according to the present invention, a thin film in which the generation of surface defects is suppressed can be obtained.

without.

without.

without.

Claims (4)

A polymer-containing substance comprises a crystalline cycloolefin ring-opening polymer hydrogenate, wherein the crystalline cycloolefin ring-opening polymer hydrogenate has the following formula (1):

A polymer chain having a repeating unit represented by the formula (1) as a main structural unit and wherein the ratio of the racemic diunit group of the repeating unit represented by the formula (1) in the polymer chain is 30% or less or 60% or more, including a polymer chain having the formula (2) as follows:

The total content of compounds having a structure represented by [wherein R is an alkyl group, a hydroxyl group, a hydrogen atom or a chlorine atom, and * is an atomic bond] and a molecular weight of 200 or more and 800 or less is 30 mass ppm or less. A method for producing a polymer-containing substance as described in claim 1, comprising: a step of preparing a crude polymer-containing product containing "a crystalline cycloolefin ring-opening polymer hydrogenate", wherein the crystalline cycloolefin ring-opening polymer hydrogenate has a structure represented by the following formula (1):

A process for washing the crude polymer-containing product with a solvent containing a non-polar organic solvent in a ratio of 90 mass % to 100 mass % is used. The method for producing a polymer-containing substance as described in claim 2, wherein the aforementioned solvent is composed of a non-polar organic solvent having a carbon number of less than 8. A film formed using the polymer-containing substance as described in claim 1.