KR20220069920A - Polymer inclusions and methods for making the same, and films - Google Patents

Abstract

The present invention provides a polymer-containing material that contains a hydride of a cyclic olefin ring-opened polymer having crystallinity and is unlikely to cause surface defects when used as a molded article such as a film. The polymer-containing material of the present invention has a polymer chain including a repeating unit represented by the following formula (1) as a main structural unit, and further, in the polymer chain, racemo· of the repeating unit represented by the formula (1) The total content of compounds having a molecular weight of 200 to 800, including a hydride of a cyclic olefin ring-opened polymer having crystallinity in which the proportion of dyad is 30% or less or 60% or more, and including a structure represented by the following formula (2) This 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 a bond.

Description

Polymer inclusions and methods for making the same, and films

The present invention relates to a polymer-containing material and a method for producing the polymer-containing material, and to a film, and more particularly, to a polymer-containing material comprising a hydride of a cyclic olefin ring-opened polymer, a method for producing the same, and a film.

Conventionally, the hydride of a cyclic olefin ring-opened polymer is used suitably as an optical material from the transparency and favorable optical characteristic. Among them, in recent years, a hydride of a cyclic olefin ring-opened polymer having crystallinity has attracted attention as a material capable of exhibiting excellent heat resistance, mechanical strength, and solvent resistance in addition to transparency and optical properties (for example, Patent Documents) see 1).

And, as a technique for industrially producing a hydride of a cyclic olefin ring-opened polymer having crystallinity in a high yield, for example, by adding a polar solvent to agglomerate the hydride of a cyclic olefin ring-opened polymer, liquid removal at the time of solid-liquid separation The technique which improves efficiency is proposed (for example, refer patent document 2). Specifically, in Patent Document 2, a polar solvent is added to a slurry of a hydride of a cyclic olefin ring-opened polymer having crystallinity obtained through ring-opening polymerization and hydrogenation reaction, followed by stirring, and then using a centrifugal dehydrator in the slurry. After separating the solid content, a polar solvent is added to the obtained solid content and stirred to obtain a second slurry, and again by separating the solid content in the second slurry using a centrifugal dehydrator, a hydride of a cyclic olefin ring-opened polymer having crystallinity A technique for obtaining a high yield of

Japanese Laid-Open Patent Publication No. 2013-249432 Japanese Patent Laid-Open No. 2014-118475

However, there existed a problem that surface defects, such as a die line, may generate|occur|produce in the hydride of the cyclic olefin ring-opened polymer which has crystallinity manufactured using the said conventional manufacturing method when it is set as molded bodies, such as a film.

Then, an object of this invention is to provide the polymer-containing material which contains the hydride of the cyclic olefin ring-opened polymer which has crystallinity, and is hard to generate|occur|produce a surface defect when it is set as molded bodies, such as a film.

Moreover, an object of this invention is to provide the film by which generation|occurrence|production of the surface defect was suppressed, which was formed using the said polymer containing material.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined in order to achieve the said objective. Then, the present inventors have found that the hydride of a cyclic olefin ring-opened polymer having crystallinity produced using a conventional production method contains a predetermined compound as an impurity, and if the content of the predetermined compound is reduced, It discovered that generation|occurrence|production of the surface defect at the time of setting it as a molded object could be suppressed. Moreover, this inventor discovered that content of the said predetermined|prescribed compound could be reduced easily when the hydride of a cyclic olefin ring-opened polymer was wash|cleaned with the nonpolar solvent which has predetermined carbon number. And this inventor completed this invention based on the said new knowledge.

That is, this invention aims at solving the said subject advantageously, and the polymer-containing material of this invention is following formula (1):

[Formula 1]

has a polymer chain comprising a repeating unit represented by The above, including a cyclic olefin ring-opened polymer hydride having crystallinity, the following formula (2):

[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 and 30 mass ppm or less characterized in that In this way, when the total content of the compound having a molecular weight of 200 or more and 800 or less, including the structure represented by Formula (2), is 0 mass ppm or more and 30 mass ppm or less, surface defects occur when a molded article such as a film is formed. can be suppressed

In addition, in the present invention, the "ratio of racemo-dyad" can be measured by the method described in Examples using nuclear magnetic resonance spectroscopy (NMR).

In addition, in this invention, "the total content of the compound whose molecular weight is 200 or more and 800 or less including the structure represented by Formula (2)" can be measured using the method as described in an Example.

Moreover, this invention aims at solving the said subject advantageously, The manufacturing method of the polymer containing material of this invention is following formula (1):

[Formula 3]

has a polymer chain comprising a repeating unit represented by The above steps of preparing a crude polymer-containing material containing a hydride of a cyclic olefin ring-opened polymer having crystallinity, and a solvent containing 90 mass% or more and 100 mass% or less of a non-polar organic solvent and a step of cleaning the polymer content. As described above, when the crude polymer-containing material is washed with a solvent containing a non-polar organic solvent in a ratio of 90 mass% or more and 100 mass% or less, the structure represented by the above formula (2) contained in the crude polymer-containing material is obtained. Since content of the compound which contains molecular weight 200 or more and 800 or less can be reduced easily, when it is set as molded objects, such as a film, the polymer containing material which a surface defect does not generate|occur|produce easily can be obtained.

Here, in the method for producing a polymer-containing material of the present invention, the solvent is preferably a non-polar organic solvent having 8 or less carbon atoms. When a C8 or less nonpolar organic solvent is used, it can suppress that a solvent remains in the polymer-containing material obtained.

And this invention aims at solving the said subject advantageously, and the film of this invention is formed using the above-mentioned polymer containing material, It is characterized by the above-mentioned. In this way, when the above-mentioned polymer-containing material is used, the occurrence of surface defects can be suppressed.

ADVANTAGE OF THE INVENTION According to this invention, when it is set as molded objects, such as a film, containing the cyclic olefin ring-opened polymer hydride which has crystallinity, the polymer containing material which a surface defect does not generate|occur|produce easily is obtained.

Moreover, according to this invention, the film by which generation|occurrence|production of a surface defect was suppressed is obtained.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

Here, the polymer-containing material of the present invention can be produced, for example, by using the method for producing the polymer-containing material of the present invention, and is not particularly limited, and can be suitably used as a material for various molded articles such as films.

(Polymer content)

The polymer-containing material of the present invention contains a hydride of a cyclic olefin ring-opened polymer, and the content of the compound (A) having a predetermined structure and molecular weight is 0 mass ppm or more and 30 mass ppm or less. In addition, the polymer-containing material of this invention may further contain other components, such as a residue of the solvent used at the time of manufacture, and a by-product.

<Hydrogenated Cyclic Olefin Ring-Opened Polymer>

Here, the hydrogenated cyclic olefin ring-opened polymer contained in the polymer-containing material of the present invention is a crystalline high molecular compound having a predetermined polymer chain.

[Polymer chain]

Specifically, the hydrogenated cyclic olefin ring-opened polymer is represented by the following formula (1):

[Formula 4]

It has a polymer chain which contains the repeating unit represented by as a main structural unit, and the ratio of racemo-dyad of the repeating unit represented by said formula (1) is 30% or less or 60% or more.

Here, the repeating unit represented by the formula (1) is subjected to ring-opening polymerization using, for example, a monomer composition containing dicyclopentadiene as a monomer, and then hydrogenates the obtained ring-opening polymer to obtain dicyclo in the ring-opening polymer. By hydrogenating the structural unit derived from pentadiene, it can be introduced into the polymer chain.

On the other hand, in dicyclopentadiene, stereoisomers of an endo- and exo-form exist, either of which can be used as a monomer, and either isomer may be used alone, and an endo- and exo-form in any ratio A mixture of isomers present as However, from the viewpoint of improving the crystallinity of the hydrogenated cyclic olefin ring-opened polymer, it is preferable to increase the ratio of one stereoisomer, for example, the ratio of the endo- or exo-form is preferably 80% or more, 90 % or more is more preferable, and 95% or more is particularly preferable. And, it is preferable that the stereoisomer which raises a ratio is an endo form from a viewpoint of synthetic|combination easiness.

Moreover, it is preferable that they are 98 mass % or more and 100 mass % or less, and, as for the ratio which the repeating unit represented by said Formula (1) occupies in a polymer chain, it is more preferable that it is 99 mass % or more. The crystallinity of the hydrogenated cyclic olefin ring-opened polymer can be further improved as the ratio of the repeating unit represented by said formula (1) is more than the said lower limit.

In addition, the polymer chain may contain repeating units other than the repeating unit represented by said 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 for example, polycyclic norbornene-based compounds other than dicyclopentadiene, bicyclic compounds having no ring structure condensed on the norbornene skeleton norbornene-based compounds, monocyclic olefins and cyclic dienes, and derivatives thereof.

In addition, in the polymer chain, the ratio of racemo-dyad of the repeating unit represented by the formula (1) is not particularly limited as long as it is 30% or less or 60% or more, but the ratio of racemo-dyad is 25 % or less, and more preferably 20% or less. Alternatively, the ratio of racemo dyad is preferably 65% or more, and more preferably 70% or more.

In addition, the ratio of racemo-dyad can be adjusted by changing the kind of catalyst used for ring-opening polymerization, polymerization conditions, etc., for example.

[Appearance]

The hydride of a cyclic olefin ring-opened polymer has crystallinity, and has melting|fusing point normally. And, from the viewpoint of improving the heat resistance of the molded article formed using the polymer-containing material, the melting point of the hydride of the cyclic olefin ring-opened polymer is preferably 200°C or higher, and more preferably 230°C or higher. On the other hand, melting|fusing point of the hydrogenated cyclic olefin ring-opened polymer is 290 degrees C or less normally.

Moreover, the weight average molecular weight of the hydride of a cyclic olefin ring-opened polymer is not specifically limited, It is preferable that it is 10,000 or more, It is more preferable that it is 15,000 or more, It is preferable that it is 100,000 or less, It is more preferable that it is 80,000 or less. The hydride of the cyclic olefin ring-opened polymer having the above-mentioned weight average molecular weight is preferable from the viewpoint of excellent moldability and excellent heat resistance of the molded article obtained.

[content]

On the other hand, it is preferable that it is 90 mass % or more, and, as for the ratio which the above-mentioned cyclic olefin ring-opened polymer hydride occupies in the polymer-containing material of this invention, it is more preferable that it is 95 mass % or more.

<Compound (A)>

Compound (A), the following formula (2):

[Formula 5]

It is a compound containing the structure represented by, and is a compound whose molecular weight 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, n-hexyl group, and n-octyl group; hydroxyl group; hydrogen atom; or a chlorine atom. In addition, in Formula (2), * shows the position of a bond. Especially, it is preferable that R is an n-hexyl group.

The amount of the compound (A) contained in the polymer-containing material of the present invention is not particularly limited as long as it is 30 mass ppm or less in total, but is preferably 10 mass ppm or less. When the quantity of a compound (A) is below the said upper limit and a polymer-containing material is made into molded objects, such as a film, it can suppress that a surface defect arises.

In addition, it does not specifically limit as compound (A) containing the structure represented by said Formula (2), For example, the by-product etc. which were produced|generated at the time of the synthesis|combination of the cyclic olefin ring-opened polymer hydride are mentioned. Specifically, as the by-product, for example, a dimer or a hydride of a trimer of dicyclopentadiene produced when ring-opening polymerization is performed using a monomer composition containing dicyclopentadiene as a monomer. can be heard

<Other ingredients>

Other components that can be included in the polymer-containing material of the present invention are not particularly limited, and residues of the solvent used when preparing the polymer-containing material and by-products generated during the synthesis of the hydride of the cyclic olefin ring-opened polymer (However, the thing applicable to the said compound (A) is excluded) etc. are mentioned.

And, it is preferable that it is 500 mass ppm or less, and, as for the quantity of the residual solvent contained in the polymer-containing material of this invention, it is more preferable that it is 300 mass ppm or less.

(Method for producing polymer inclusions)

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

<Process (A)>

In the process (A), the following formula (1):

[Formula 6]

has a polymer chain comprising a repeating unit represented by A crude polymer-containing material containing a hydride of a cyclic olefin ring-opened polymer having crystallinity is prepared.

Specifically, in the step (A), ring-opening polymerization is carried out using a monomer composition containing dicyclopentadiene as a monomer and optionally further containing a monomer copolymerizable with dicyclopentadiene, followed by hydrogenating the obtained ring-opening polymer. , a crude polymer-containing material containing a hydride of a cyclic olefin ring-opened polymer having crystallinity is prepared.

Here, preparation of the crude polymer-containing material using ring-opening polymerization and hydrogenation is not specifically limited, For example, Unexamined-Japanese-Patent No. 2014-118475, Unexamined-Japanese-Patent No. 2016-183221, Unexamined-Japanese-Patent No. 2015-83705. , can be carried out using the method and conditions described in Japanese Patent Application Laid-Open No. 2015-178561.

On the other hand, 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 is subjected to solid-liquid separation using a known solid-liquid separation device such as a centrifugal dehydrator, followed by step (B) can be provided to

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

<Process (B)>

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

[menstruum]

Here, the solvent is not particularly limited as long as it contains a non-polar organic solvent in a proportion of 90% by mass or more and optionally contains a polar organic solvent or water in a proportion of 10% by mass or less, and any solvent can be used. Especially, it is preferable to use the solvent which consists of a nonpolar organic solvent as a solvent from a viewpoint of removing compound (A) favorably.

Moreover, it does not specifically limit as a non-polar organic solvent, For example, Saturated aliphatic hydrocarbons, such as n-hexane, cyclohexane, cyclooctane, methylcyclohexane, and tert-1-methyl-2-propylcyclohexane; aromatic hydrocarbons such as toluene and xylene; or a mixture of two or more thereof; etc. can be used. Among them, from the viewpoint of suppressing the solvent from remaining in the obtained polymer-containing material, as the non-polar organic solvent, it is preferable to use a non-polar organic solvent having 8 or less carbon atoms, and xylene, toluene, cyclohexane or methyl cyclohexane is used. It is more preferable to

Moreover, from a viewpoint of suppressing that a solvent remains in the polymer-containing material obtained, it is preferable that it is 180 degrees C or less, and, as for the boiling point under atmospheric pressure of a nonpolar organic solvent, it is more preferable that it is 150 degrees C or less.

[washing]

The washing of the crude polymer-containing material is not particularly limited, and for example, the crude polymer-containing material is dispersed in a solvent under stirring, and then the solvent is removed 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 may be, for example, 10 minutes or more and 5 hours or less.

In addition, the temperature of the solvent used for 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 more and T ₂ - 5 ° C. or less. .

In addition, it is preferable that the quantity of the solvent used for washing|cleaning is 4 times or more and 20 times or less of the quantity of a crude polymer-containing material in mass ratio.

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

<Process (C)>

In the step (C), the washed product obtained by washing the crude polymer-containing material in the step (B) is dried. Here, drying of a washing|cleaning object is not specifically limited, It can perform using arbitrary drying methods, such as hot air drying, vacuum drying, and spin drying. Especially, from a viewpoint of suppressing that a solvent remains in the polymer-containing material obtained, it is preferable to dry a washing|cleaning material using vacuum drying.

On the other hand, 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 is performed until it becomes 300 mass ppm or less. more preferably.

<Process (D)>

In the step (D), the dried product obtained in the step (C) is granulated to obtain a pellet-form polymer-containing material. Here, granulation of a dried object is not specifically limited, It can perform using known granulation apparatuses, such as a twin screw extruder.

(film)

The film of the present invention can be obtained by molding the above-described polymer-containing material of the present invention into a film shape. And since the polymer-containing material mentioned above is used for the film of this invention, there are few surface defects.

In addition, the method and conditions for shape|molding a polymer-containing material into a film form are not specifically limited, It can be set as arbitrary methods and conditions.

[Example]

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. In addition, this invention is not limited at all to these examples. In the following, "part", "%" and "ppm" are based on mass, and pressure is a gauge pressure, unless otherwise specified.

In addition, the measurement and evaluation in each example were performed with the following method.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of ring-opened polymer

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

(2) Weight average molecular weight (Mw) and number average molecular weight (Mn) of ring-opened polymer hydride

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opened polymer hydride were measured as polystyrene conversion values using a gel permeation chromatography (GPC) system (manufactured by Senshu Scientific, SSC-7100). On the other hand, a GPC3506 column (manufactured by Senshu Scientific) was used for the column, and 1-chloronaphthalene was used as a solvent for measurement at 210°C.

(3) hydrogenation rate

It was calculated|required based on ¹ H-NMR measurement.

(4) Melting point of ring-opened polymer hydride

Using a differential scanning calorimeter (DSC), the sample was heated to 300° C. under a nitrogen atmosphere, then quenched with liquid nitrogen, and then heated again at 10° C./min for measurement.

(5) Ratio of racemo-dyad of the polymer chain of the ring-opened polymer hydride

Using orthodichlorobenzene-d ₄ as a solvent, ¹³ C-NMR measurement was performed by applying the inverse-gated decoupling method at 150° C., and the peak of 127.5 ppm of orthodichlorobenzene-d ₄ was taken as the reference shift, and meso-di Based on the intensity ratio of the 43.35 ppm signal derived from AD and the 43.43 ppm signal derived from racemo dyad, the ratio of racemo dyad was calculated.

(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 part is analyzed by ¹ H-NMR and GC-MS, and the molecular weight is specified by analyzing the compound (A ) was determined.

Next, the compound (A) collected at the time of the qualification of the compound (A) was diluted with cyclohexane to prepare a cyclohexane solution of the compound (A) having a prescribed concentration. Then, with a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320), each solution is measured at an injection amount of 100 μL, the RI peak area at the time of measurement is obtained, and the attribution of the peak is performed, A calibration curve was prepared from the relationship between the compound (A) concentration and the RI peak area. On the other hand, for the column, TSKgelG5000HXL, TSKgelG4000HXL, and TSKgelG2000HXL manufactured by Tosoh Corporation were connected and used in series, and the measurement was performed under the conditions of a flow rate of 1.0 ml/min, a sample injection amount of 100 μl, and a column temperature of 40°C.

Then, 0.2 parts of pellets and 3.3 parts of cyclohexane were put in a pressure-resistant glass container, heated at 150° C. for 6 hours, and the compound (A) in the pellets was extracted with cyclohexane. The obtained extract was measured by GPC after removing insoluble content with a filter, and from the RI peak area of the compound (A) in the extract, the concentration of compound (A) in the pellet was calculated as follows using the above calibration curve.

<Calculating the concentration of compound (A)>

Calibration curve: [Concentration of compound (A) in cyclohexane] (%) = f × [area of RI]

[Concentration of compound (A) in the pellet] (ppm)

= [Concentration of compound (A) in cyclohexane] (%) ÷ 100 × [Weight of cyclohexane] (g) ÷ [Weight of pellets] (g) × 1000000

= f × [RI area] ÷ 100 × [Cyclohexane weight](g) ÷ [Pellets weight](g) × 1000000

(7) Residual solvent amount

2 parts of polymer-containing material, 0.1 part of o-dichlorobenzene, and 32.9 parts of chlorobenzene were heated at 120 degreeC in a pressure-resistant glass container for 1 hour, and the residual solvent was extracted. 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 by a gas chromatograph (manufactured by HEWLETTPACKARD, HP6850ASeries).

On the other hand, for the measurement, HP-1 (30 m × 0.32 mm × 0.25 μm) manufactured by Agilent was used as a column, vaporization chamber temperature: 240° C., column temperature: 35° C. at start time, 280° C. at 10° C./min. The temperature was raised to 310°C, the detector temperature was 310°C, and the injection amount was 1 µm.

(8) presence or absence of defects (die lines)

The film was placed between the white screen and the projector in the dark to observe the shadows reflected on the screen. And the following criteria evaluated the presence or absence of a defect.

(circle): It is uniform without seeing anything.

x: A die line can be confirmed.

(Example 1)

<Preparation of crude polymer-containing material (step (A))>

[Ring-opening polymerization]

In a glass pressure-resistant reaction vessel purged with nitrogen after drying sufficiently, 143 parts of a 70% cyclohexane solution of dicyclopentadiene (99% or more of endoisomer content) (100 parts as the amount of dicyclopentadiene), 5.7 parts of 1-hexene, 166 parts of cyclohexane was added, and then 0.62 parts of an n-hexane solution of diethylaluminum ethoxide having a concentration of 19% was added and stirred. Then, a solution in which 0.15 parts of a tetrachlorotungstenphenylimide (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 was added to stop the ring-opening polymerization reaction. The weight average molecular weight (Mw) of the dicyclopentadiene ring-opened polymer (cyclic olefin ring-opened 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 part of diatomaceous earth (The Showa Chemical Industry make, Radiolite #300) was added as a filter aid. This suspension was filtered with a leaf filter (manufactured by IHI, CFR2) to obtain a solution of a dicyclopentadiene ring-opened polymer.

[Hydrogenation]

Next, after transferring the obtained solution of the dicyclopentadiene ring-opened polymer to a reactor (manufactured by Sumitomo Heavy Industries, Ltd.) equipped with a stirrer and a temperature control jacket, cyclohexane 600 so that the concentration of the dicyclopentadiene ring-opened polymer is 9% parts, 0.1 parts of chlorohydridecarbonyltris(triphenylphosphine)ruthenium were added. Subsequently, a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and a temperature of 180°C for 6 hours while stirring the whole at a rotational speed of 64 rpm to obtain a slurry containing particles of a hydride of a dicyclopentadiene ring-opened polymer.

On the other hand, the hydrogenation rate of the dicyclopentadiene ring-opened polymer hydride was 99.5%, the weight average molecular weight (Mw) was 61,200, and the number average molecular weight (Mn) was 18,303.

The amount of the soluble impurity (1) with respect to the total amount of the sparingly soluble cyclic olefin polymer (1) and the soluble impurity (1) (hereinafter, this amount may be referred to as "amount of polymer") was 5%.

[Solid-liquid separation]

1100 parts of the slurry is supplied to a centrifugal dehydrator (manufactured by Tanabe Wiltech, high-speed decanter) having a rotating ball part inside the device and a screw conveyor for conveying cake inside the bowl part, and the ball part rotation speed is 4800 rpm, differential rotation Solid-liquid separation was performed under conditions of several 15 rpm. The amount of the obtained wet cake (copolymer-containing material) was 240 parts.

<Washing of crude polymer-containing material (step (B))>

240 parts of the obtained wet cake and 2160 parts of xylene as a solvent were put in the stirring tank provided with the inclined paddle blade|wing, it stirred at the rotation speed of 200 rpm for 1 hour, and the xylene slurry was obtained.

Next, 2400 parts of the xylene slurry is supplied to a centrifugal dehydrator (manufactured by Tanabe Wiltec, a high-speed decanter) having a rotating bowl part inside the device and a screw conveyor for conveying cake inside the bowl part, and the ball part rotation speed is 4800 Solid-liquid separation was performed under the conditions of rpm and a differential rotation speed of 15 rpm. The quantity of the obtained washing|cleaning wet cake (washing material) was 240 parts.

<Drying of the washing material (step (C))>

The washed wet cake obtained by solid-liquid separation is supplied to a continuous groove dryer (manufactured by Kurimoto Ironworks Co., Ltd., CD-80), and volatile matter (mainly solvent) contained in the wet cake is removed under the following drying conditions. got

-dry conditions-

Dryer Temperature: 170℃

Nitrogen flow rate: 50 NL/min

Disc speed: 30 rpm

<Assembly of building material (step (D))>

[Dissolve]

To 100 parts of powder of the dried product obtained by drying, as an antioxidant, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane (BASF Japan) 0.5 part of IRGANOX (trademark) 1010) manufactured by the company was added.

The obtained mixture was compressed using a pressure compression molding machine (manufactured by Shinto Kogyo Co., Ltd., BGS-IV) to obtain a rectangular molded article. Next, this rectangular molded article was crushed using a roll crusher (flake crusher) under the following conditions, and flake-shaped crushing was obtained.

-Disintegration conditions-

Roll speed: 10 rpm

Roll pressurization: 60 kN

[Pelletization]

The obtained flake-like powder was put into a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX-30) equipped with a die hole having an inner diameter of 3 mm, and subjected to hot melt extrusion molding under the following conditions to obtain a strand. Then, the strand was cut with a strand cutter to obtain cylindrical pellets (polymer-containing material) having a diameter of 3 mm and a length of 3 mm.

-Molding conditions-

Barrel set temperature: 280℃

Screw speed: 300 rpm

[analysis]

And using the obtained pellet, the melting|fusing point of the hydride of a ring-opened polymer, the ratio of racemo-dyad of the polymer chain of a hydride of a ring-opened polymer, content of compound (A), and the amount of residual solvent were measured. A result is shown in Table 1.

<The Tabernacle>

The obtained pellets were supplied to a hot melt extrusion film molding machine (manufactured by Optical Control System (OCS)) equipped with a single-layer extrusion molding T-die in a state in which it was melted by heating. This film forming machine was operated under the following operating conditions, and a long, unstretched film (thickness 150 µm, width 120 mm) was wound up on a roll at a speed of 2 m/min to manufacture continuously for 4 hours. The film sample after 4 hours was taken and the presence or absence of a die line was confirmed. A result is shown in Table 1.

-Driving conditions-

Barrel temperature setting: 280℃~290℃

Die temperature: 270℃

Screw speed: 30 rpm

(Example 2)

Pellets (polymer-containing material) and films were prepared 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)). And it carried out similarly to Example 1, and performed the analysis and evaluation. A result is shown in Table 1.

(Example 3)

Pellets (polymer-containing material) and films were prepared 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)). And it carried out similarly to Example 1, and performed the analysis and evaluation. A result is shown in Table 1.

(Example 4)

Pellets (polymer-containing material) and films were prepared 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)). And it carried out similarly to Example 1, and performed the analysis and evaluation. A result is shown in Table 1.

(Example 5)

Pellets (polymer-containing material) and film were prepared 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)). prepared. And it carried out similarly to Example 1, and performed the analysis and evaluation. A result is shown in Table 1.

(Comparative Example 1)

In the same manner as in Example 1, pellets (containing polymer) were performed in the same manner as in Example 1, except that the crude polymer-containing material was not washed (step (B)) and a wet cake (copolymer-containing material) was used instead of the washed wet cake in the step (C). water) and a film. And it carried out similarly to Example 1, and performed the analysis and evaluation. A result is shown in Table 1.

(Comparative Example 2)

Pellets (polymer-containing material) and films were prepared in the same manner as in Example 1, except that isopropanol, a polar organic solvent, was used instead of xylene as a solvent during washing of the crude polymer-containing material (step (B)). And it carried out similarly to Example 1, and performed the analysis and evaluation. A result is shown in Table 1.

(Comparative Example 3)

Pellets (polymer-containing material) and films were prepared in the same manner as in Example 1, except that acetone, a polar organic solvent, was used instead of xylene as a solvent during washing of the crude polymer-containing material (step (B)). And it carried out similarly to Example 1, and performed the analysis and evaluation. A result is shown in Table 1.

From Table 1, it washes with a nonpolar organic solvent, and in Examples 1-5 in which content of the compound (A) was reduced, it turns out that it can suppress that a surface defect generate|occur|produces in a film.

[Industrial Applicability]

ADVANTAGE OF THE INVENTION According to this invention, when it is set as molded bodies, such as a film, containing the cyclic olefin ring-opened polymer hydride which has crystallinity, the polymer containing material which a surface defect does not generate|occur|produce easily is obtained.

Moreover, according to this invention, the film by which generation|occurrence|production of a surface defect was suppressed is obtained.

Claims (4)

Equation (1):
[Formula 1]

has a polymer chain comprising a repeating unit represented by or more, including a cyclic olefin ring-opened polymer hydride having crystallinity,
Equation (2):
[Formula 2]

[Wherein, R is an alkyl group, a hydroxyl group, a hydrogen atom or a chlorine atom, and * is a bond.]
The polymer-containing material, wherein the total content of the compound having a molecular weight of 200 or more and 800 or less including the structure represented by is 30 mass ppm or less. Equation (1):
[Formula 3]

has a polymer chain comprising a repeating unit represented by The above-mentioned process of preparing the crude polymer-containing material containing the hydride of the cyclic olefin ring-opened polymer which has crystallinity;
A step of washing the crude polymer-containing material with a solvent containing a non-polar organic solvent in a proportion of 90% by mass or more and 100% by mass or less
A method for producing a polymer-containing material comprising: 3. The method of claim 2,
The method for producing a polymer-containing material, wherein the solvent consists of a non-polar organic solvent having 8 or less carbon atoms. A film formed using the polymer-containing material according to claim 1.