TW202112882A - Polymer-containing material and method for producing same, and film - Google Patents

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

Polymer-containing material and its manufacturing method and film

The present invention relates to a polymer-containing object and a method for producing a polymer-containing object and a film, and particularly relates to a polymer-containing object including a hydrogenated cycloolefin ring-opening polymer, a method for producing the same, and a film.

In the past, the hydrogenated cycloolefin ring-opening polymer was suitably used as an optical material because of its good transparency and optical properties. Among them, in recent years, the crystalline hydrogenated cycloolefin ring-opening polymer has attracted attention as a material that exhibits excellent heat resistance, mechanical strength, and solvent resistance in addition to transparency and optical properties (see, for example, Patent Document 1) .

Moreover, as a technology for industrially producing crystalline cycloolefin ring-opening polymer hydrogenated products with high yields, for example, a polar solvent is added to agglomerate the cycloolefin ring-opening polymer hydrogenated products to improve solid-liquid separation. The technology of the efficiency of liquid removal at the time (see, for example, Patent Document 2). Specifically, in Patent Document 2, the following technology has been proposed in which a polar solvent is added to the slurry of a crystalline hydrogenated cycloolefin ring-opening polymer obtained through ring-opening polymerization and hydrogenation, followed by stirring, After separating the solids in the slurry with a centrifugal dehydrator, add a polar solvent to the obtained solids and stir to make a second slurry, and then use a centrifugal dehydrator to separate the solids in the second slurry Therefore, the hydrogenated cycloolefin ring-opening polymer with crystallinity can be obtained with high yield.

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

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

Therefore, an object of the present invention is to provide a polymer-containing product that contains a crystalline hydrogenated cycloolefin ring-opening polymer and is less likely to cause surface defects when formed into a molded body such as a film.

In addition, an object of the present invention is to provide a film in which "the occurrence of surface defects is suppressed" formed by using the polymer-containing material.

In order to achieve the above-mentioned object, the inventors have devoted themselves to research. Then, the present inventors discovered that the crystalline hydrogenated cycloolefin ring-opening polymer produced by the conventional production method contains a specified compound as an impurity, and if the content of the specified compound is reduced, it can be suppressed. The occurrence of surface defects when forming a molded body. In addition, the inventors discovered that if a non-polar solvent with a specified carbon number is used to clean the hydrogenated cycloolefin ring-opening polymer, the content of the specified compound can be easily reduced. Then, the inventors completed the present invention based on the above-mentioned new findings.

所示之重複單元作為主要構造單元的聚合物鏈且在前述聚合物鏈中由前述式（1）所示之重複單元的外消旋二單元組之比例為30%以下或60%以上，其中由下述式（2）： 『化2』

［式中，R係烷基、羥基、氫原子或氯原子，＊係原子鍵。］所示之結構之分子量為200以上且800以下之化合物的合計含量為30質量ppm以下。若如此包含由式（2）所示之結構之分子量為200以上且800以下之化合物的合計含量為0質量ppm以上且30質量ppm以下，則可抑制在做成薄膜等成形體時產生表面缺陷一事。That is, this invention aims to solve the above-mentioned problems smoothly. The polymer-containing material of the present invention is characterized in that it contains a crystalline cycloolefin ring-opening polymer hydrogenated product, and the crystalline cycloolefin open The hydrogenated cyclic polymer has the following formula (1): 『化1』

The repeating unit shown as the main structural unit of the polymer chain and the proportion of the racemic diunit group of the repeating unit represented by the aforementioned formula (1) in the aforementioned polymer chain is 30% or less or 60% or more, wherein From the following formula (2): 『化2』

[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 with a molecular weight of 200 or more and 800 or less of the structure shown is 30 mass ppm or less. If the total content of compounds 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, it is possible to suppress the occurrence of surface defects when forming a molded body such as a film One thing.

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

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

所示之重複單元作為主要構造單元的聚合物鏈且在前述聚合物鏈中由前述式（1）所述之重複單元的外消旋二單元組之比例為30%以下或60%以上；以及利用以90質量%以上且100質量%以下之比例含有非極性有機溶媒的溶媒清洗前述含聚合物之粗產物的工序。若如此利用以90質量%以上且100質量%以下之比例含有非極性有機溶媒的溶媒清洗含聚合物之粗產物，由於可輕易減低含聚合物之粗產物所包含之包含由於上已述之式（2）所示之結構之分子量為200以上且800以下之化合物的含量，故可獲得在做成薄膜等成形體時不易產生表面缺陷的含聚合物之物。In addition, this invention aims at solving the above-mentioned problems smoothly. The method for producing a polymer-containing material of the present invention is characterized in that it comprises: preparing a polymer-containing product containing "hydrogenated cycloolefin ring-opening polymer with crystallinity". In the process of the crude product of the product, the crystalline hydrogenated cycloolefin ring-opening polymer has the following formula (1): "Chemical 3"

The repeating unit shown is a polymer chain as the main structural unit, and the proportion of the racemic diad of the repeating unit described in the aforementioned formula (1) in the aforementioned polymer chain is 30% or less or 60% or more; and A step of washing the aforementioned crude polymer-containing product with a solvent containing a non-polar organic solvent in a ratio of 90% by mass or more and 100% by mass or less. If a solvent containing a non-polar organic solvent in a ratio of 90% by mass to 100% by mass is used to clean the crude polymer-containing product, the polymer-containing crude product can be easily reduced due to the above-mentioned formula (2) The structure shown has a content of a compound with a molecular weight of 200 or more and 800 or less, so that a polymer-containing product that is unlikely to cause surface defects when formed into a film or other molded body can be obtained.

Here, in the method for producing a polymer-containing product of the present invention, the aforementioned solvent is preferably a non-polar organic solvent having a carbon number of 8 or less. If a non-polar organic solvent with a carbon number of 8 or less is used, it is possible to prevent the solvent from remaining in the obtained polymer-containing material.

Moreover, this invention aims at solving the above-mentioned problems smoothly, and the film of the invention is characterized in that it is formed by using the polymer-containing material described above. If used in the above-mentioned polymer-containing material in this way, the occurrence of surface defects can be suppressed.

According to the present invention, it is possible to obtain a polymer-containing product that contains a crystalline hydrogenated cycloolefin ring-opening polymer and is less likely to cause surface defects when formed into a molded body such as a film.

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

The following describes the implementation of the present invention in detail.

Here, the polymer-containing material of the present invention can be manufactured using, for example, the method for manufacturing the polymer-containing material of the present invention, and it can be suitably used as a material for various molded products such as films, and is not particularly limited.

(Things containing polymers)

The polymer-containing material of the present invention includes a hydrogenated cycloolefin ring-opening polymer, 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 residues or by-products of the solvent used in the production.

<Hydrogenated cycloolefin ring-opening polymer>

Here, the hydrogenated cycloolefin ring-opening polymer contained in the polymer-containing material of the present invention is a high molecular compound having the crystallinity of a specified polymer chain.

[Polymer Chain]

所示之重複單元作為主要構造單元且由上述式（1）所示之重複單元的外消旋二單元組之比例為30%以下或60%以上。Specifically, the hydrogenated cycloolefin ring-opening polymer has a polymer chain, and the polymer chain is composed of the following formula (1): "Chemical 4"

The repeating unit shown is the main structural unit and the ratio of the racemic diad 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 hydrogenated after ring-opening polymerization using a monomer composition containing dicyclopentadiene as a monomer The structural unit derived from dicyclopentadiene in the ring-opening polymer is hydrogenated, thereby introducing the polymer chain.

In addition, dicyclopentadiene has stereoisomers of endo isomers and exo isomers, but either can be used as a monomer. One of the isomers can be used alone or in any ratio. There are isomer mixtures of endo isomers and exo isomers. However, from the viewpoint of improving the crystallinity of the hydrogenated cycloolefin ring-opening polymer, it is better to increase the ratio of one of the stereoisomers. For example, the ratio of the endo-isomer or the exo-isomer is More than 80% is preferable, more than 90% is more preferable, and more than 95% is particularly preferable. Furthermore, from the viewpoint of ease of synthesis, the stereoisomer with an increased ratio is preferably the endoisomer.

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

In addition, the polymer chain may include repeating units other than the repeating unit represented by the above formula (1). Specifically, the polymer chain may also include repeating units derived from monomers that can be copolymerized with dicyclopentadiene.

Here, the monomer that can be copolymerized with dicyclopentadiene is not particularly limited, and examples include: polycyclic norene-based compounds other than dicyclopentadiene, and a ring that does not condense to norringene skeleton The structure of bicyclic norene compounds, monocyclic olefins and cyclodienes, and their derivatives.

Moreover, in the polymer chain, the proportion of the racemic diad 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 racemic diad The ratio is preferably 25% or less, and more preferably 20% or less. Alternatively, the proportion of the racemic diad is preferably 65% or more, more preferably 70% or more.

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

[Properties]

The hydrogenated cycloolefin ring-opening polymer has crystallinity and usually has a melting point. Furthermore, from the viewpoint of improving the heat resistance of a molded body formed by using a polymer-containing material, the melting point of the hydrogenated cycloolefin ring-opening polymer is preferably 200°C or higher, and more preferably 230°C or higher. In addition, the melting point of the hydrogenated cycloolefin ring-opening polymer is usually 290°C or less.

In addition, the weight average molecular weight of the hydrogenated cycloolefin ring-opening polymer is not particularly limited, and is preferably 10,000 or more, more preferably 15,000 or more, more preferably 100,000 or less, and more preferably 80,000 or less. The hydrogenated cycloolefin ring-opening polymer having the above-mentioned weight average molecular weight is excellent in moldability and the obtained molded body is excellent in heat resistance.

[content]

In addition, the proportion of the hydrogenated cycloolefin ring-opening polymer described above in the polymer-containing product of the present invention is preferably 90% by mass or more, and more preferably 95% by mass or more.

〈Compound (A)〉

所示之結構的化合物且係分子量為200以上且800以下的化合物。Compound (A) is composed of the following formula (2): "Chemical 5"

The compound of the structure shown is a compound with 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, and n-octyl; hydroxyl group; hydrogen atom; or chlorine atom. In addition, in formula (2), * represents the position of an 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 is 30 ppm by mass or less, but it is preferably 10 ppm by mass or less. When the amount of the compound (A) is not more than the above upper limit, it is possible to suppress the occurrence of surface defects when the polymer-containing material is formed into a molded body such as a film.

In addition, the compound (A) containing the structure represented by the above formula (2) is not particularly limited, and for example, by-products generated during the synthesis of the hydrogenated cycloolefin ring-opening polymer can be cited. Specifically, as a by-product, for example, a hydrogenated product of a dimer or trimer of dicyclopentadiene produced when a monomer composition containing dicyclopentadiene as a monomer is used for ring-opening polymerization, etc. .

〈Other ingredients〉

There are no particular restrictions on the other ingredients that can be included in the polymer-containing material of the present invention. Examples include: residues of the solvent used in the preparation of the polymer-containing material, or in the hydrogenated cycloolefin ring-opening polymer By-products generated during synthesis (except those that meet the above-mentioned compound (A)), etc.

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

(Method of manufacturing polymer-containing objects)

The method for producing a polymer-containing product of the present invention includes the step (A) of preparing a crude polymer-containing product containing a "hydrogenated cycloolefin ring-opening polymer with crystallinity", and using a polymer containing at least 90% by mass and The step (B) of washing the crude polymer-containing product with a solvent containing a non-polar organic solvent at a ratio of 100% by mass or less, further optionally includes the step of drying the washed product obtained by washing the polymer-containing crude product (C ), and the step (D) of granulating the dried material to be granulated.

〈Process (A)〉

所示之重複單元作為主要構造單元的聚合物鏈且在聚合物鏈中由式（1）所示之重複單元的外消旋二單元組之比例為30%以下或60%以上。In step (A), a crude polymer-containing product containing "hydrogenated cycloolefin ring-opening polymer with crystallinity" is prepared, and the hydrogenated cycloolefin ring-opening polymer with crystallinity has the following components: Formula (1): "Hua 6"

The repeating unit shown is the main structural unit of the polymer chain, and the proportion of the 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 the step (A), after ring-opening polymerization is performed using a monomer composition containing dicyclopentadiene as a monomer and more optionally a monomer copolymerizable with dicyclopentadiene, the obtained The ring-opening polymer is hydrogenated to prepare a crude polymer-containing product containing "crystalline cyclic olefin ring-opening polymer hydrogenated product".

Here, the preparation of a crude polymer-containing product using ring-opening polymerization and hydrogenation is not particularly limited. For example, Japanese Patent Publication No. 2014-118475, Japanese Patent Publication No. 2016-183221, and Japanese Patent The method and conditions described in No. 2015-83705 and Japanese Patent Publication No. 2015-178561 are published.

In addition, in the case of obtaining the polymer-containing crude product as a slurry in the liquid in the step (A), the polymer-containing crude product can be solid-liquid using a known solid-liquid separation device such as a centrifugal dehydrator. Separate and supply to process (B).

Moreover, the crude polymer-containing product prepared as described above usually contains by-products and the like in addition to the above-mentioned hydrogenated cycloolefin ring-opening polymer having crystallinity. Specifically, the crude polymer-containing product usually contains the aforementioned compound (A) as a by-product at a ratio of more than 300 ppm by mass.

<Process (B)>

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

[Solvent]

Here, as the solvent, as long as it contains a non-polar organic solvent in a ratio of 90% by mass or more and optionally a polar organic solvent or water in a ratio of 10% by mass or less, there is no particular limitation, and any solvent can be used. Among them, from the viewpoint of good removal of the compound (A), it is preferable to use a solvent made of a non-polar organic solvent as the solvent.

Moreover, as a non-polar organic solvent, there is no particular limitation. For example, n-hexane, cyclohexane, cyclooctane, methylcyclohexane, tertiary butyl-1-methyl-2-propyl ring can be used. Saturated aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and xylene; or a mixture of two or more of these; etc. Among them, from the viewpoint of suppressing the solvent remaining in the obtained polymer-containing material, as the non-polar organic solvent, it is preferable to use a non-polar organic solvent with a carbon number of 8 or less, and to use xylene, toluene, and cyclohexane. Alkanes or methylcyclohexane are preferred.

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

[Cleaning]

Moreover, the cleaning of the polymer-containing crude product is not particularly limited. For example, after the polymer-containing crude product is dispersed into the solvent under stirring, the solvent can be removed using a known solid-liquid separation device such as a centrifugal dehydrator. To proceed.

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

In addition, the temperature of the solvent used in cleaning is not particularly limited as long as it is higher than the freezing point (T1) and lower than the boiling point (T2), but for example, T1+5°C or more and T2-5°C or less is preferable.

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

Furthermore, in the step (B), the amount of the compound (A) contained in the polymer-containing material obtained by the polymer-containing material production method of the present invention is 30 Mass ppm or less is better.

〈Process (C)〉

In the step (C), the washed product obtained by washing the crude polymer-containing product in the 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, and spin drying can be used. Among them, from the viewpoint of suppressing the solvent remaining in the obtained polymer-containing material, vacuum drying is preferably used to dry the cleaned product.

In addition, drying is performed until the amount of the residual solvent contained in the polymer-containing material obtained by the method for producing the polymer-containing material of the present invention becomes 500 mass ppm or less, and it is preferably performed until it becomes 300 mass ppm or less. Better.

〈Process (D)〉

In the step (D), the dried product obtained in the step (C) is granulated to obtain a pelletized polymer-containing product. Here, the granulation of the dried material is not particularly limited, and it can be carried out using a known granulation device such as a biaxial 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, since the film of the present invention is used for the above-mentioned polymer-containing material, there are few surface defects.

In addition, the method and conditions for forming the polymer-containing material into a film are not particularly limited, and any method and conditions can be set.

"Example"

Examples and comparative examples are listed below to further illustrate the present invention in detail. In addition, the present invention is not limited in any way by these examples. The following "parts", "%" and "ppm", unless otherwise noted, are quality standards, and pressures are gauge pressures.

In addition, the measurement or evaluation in each case was performed by the following method.

(1) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ring-opening polymer are measured in the form of polystyrene conversion values using a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320) . In addition, an H-type column (manufactured by Tosoh Corporation) was used as 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 hydrogenated ring-opening polymer

The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the hydrogenated ring-opening polymer are based on polystyrene using a gel permeation chromatography (GPC) system (manufactured by Senshu Scientific co., ltd., SSC-7100) Measurement in the form of converted value. In addition, a GPC3506 column (manufactured by Senshu Scientific co., ltd.) was used as the column, and 1-chloronaphthalene was used as a solvent, and the measurement was performed at 210°C.

(3) Hydrogenation rate

It is calculated based on ¹ H-NMR measurement.

(4) Melting point of hydrogenated ring-opening polymer

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

(5) The proportion of racemic diunits in the polymer chain of the hydrogenated ring-opening polymer

Using o-dichlorobenzene-d ₄ ^{as the solvent, the 13} C-NMR measurement was carried out by the inverse-gated decoupling method at 150℃, and the 127.5 ppm peak of o-dichlorobenzene-d ₄ As a reference displacement, the ratio of the racem diad was calculated based on the intensity ratio of the 43.35 ppm signal derived from the meso diad and the 43.43 ppm signal originated from the racem diad.

(6) The content of compound (A)

First, when using a twin-shaft extruder (TEX-30) for granulation, ¹ H-NMR and GC-MS are used to analyze the substance deposited in the gas-liquid separator installed in the pressure guiding part, and the molecular weight is fixed, and the molecular weight is fixed by 1 H-NMR and GC-MS. This qualitative analysis of compound (A).

Next, the compound (A) collected in the qualitative analysis of the compound (A) is diluted with cyclohexane to prepare a cyclohexane solution of the compound (A) with a predetermined concentration. Then, each solution was measured with a gel permeation chromatography (GPC) system (manufactured by Tosoh Corporation, HLC-8320) at a perfusion volume of 100 μL to obtain the RI peak area at the time of measurement, and then to distinguish the peak, and A standard curve was drawn from the relationship between the concentration of compound (A) and the peak area of RI. In addition, three TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL manufactured by Tosoh Corporation were connected in series with the column, and the measurement was performed under the conditions of a flow rate of 1.0 mL/min, a sample injection volume of 100 μmL, and a column temperature of 40°C.

Then, 0.2 parts of particles and 3.3 parts of cyclohexane are placed in a pressure-resistant glass container, and heated at 150° C. for 6 hours to extract compound (A) in the particles in cyclohexane. After the obtained extract is filtered to remove insoluble components, the RI peak area of the compound (A) in the extract is measured by GPC, and the above-mentioned standard curve is used as described below to calculate the compound (A) in the particle )concentration.

<Calculate the concentration of compound (A)> Standard curve: [Concentration of compound (A) in cyclohexane] (%) = f × [RI area] [Concentration of compound (A) in particles] (ppm) = [Compound (A) concentration in cyclohexane] (%) ÷ 100 × [cyclohexane weight] (g) ÷ [particle weight] (g) × 1000000 ＝f×[RI area]÷100×[cyclohexane weight](g)÷[particle weight](g)×1000000

(7) The amount of residual solvent

Heat 2 parts of polymer-containing material, 0.1 part of o-dichlorobenzene and 32.9 parts of chlorobenzene in a pressure-resistant glass container at 120°C for 1 hour 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 by a gas chromatograph (manufactured by HEWLETTPACKARD, HP6850A Series).

In addition, the measurement system uses HP-1 (30 m×0.32 mm×0.25 μm) manufactured by Agilent as the column. The temperature of the gasification chamber: 240℃, and the column temperature: 35℃ at the beginning and 10℃/min. The temperature was raised to 280°C, the detector temperature: 310°C, and the injection volume: 1 μm.

(8) Existence of defects (mold streaks)

Place the film between the white screen and the projector in the dark room, and observe the shadows on the screen. Then, the following criteria were used to evaluate the presence or absence of defects. ○: Uniform without seeing any defects. ╳: Mold streaks can be confirmed.

(Example 1)

<Preparation of polymer-containing crude product (process (A))>

[Ring-opening polymerization]

Add 143 parts of 70% cyclohexane solution of dicyclopentadiene (endoisomer content of 99% or more) in a glass pressure-resistant reaction vessel replaced with nitrogen after sufficient drying (the amount of dicyclopentadiene is 100 Parts), 5.7 parts of 1-hexene, 166 parts of cyclohexane, and then add 0.62 parts of n-hexane solution of diethyl aluminum ethoxide with a concentration of 19% and stir. Subsequently, a solution in which 0.15 parts of phenylimine tetrachloride (tetrahydrofuran) tungsten complex was dissolved to 5 parts of toluene was added, and the solution was heated to 50° C. to initiate the ring-opening polymerization reaction. After 2 hours, 1.5 parts of methanol was added to terminate the ring-opening polymerization reaction. The weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer (cycloolefin 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 part of diatomaceous earth (manufactured by Showa Chemical Industry Co., Ltd., RADIOLITE#300) was added as a filter aid. This suspension was filtered with a leaf filter (manufactured by IHI, CFR2) to obtain a dicyclopentadiene ring-opening polymer solution.

[hydrogenation]

Next, the solution of the obtained dicyclopentadiene ring-opening polymer is transferred to a reactor (manufactured by Sumitomo Heavy Industries Co., Ltd.) equipped with a stirrer and a temperature adjustment jacket, and the concentration of the dicyclopentadiene ring-opening polymer becomes Add 600 parts of cyclohexane and 0.1 part of chlorohydrocarbonyl ginseng (triphenylphosphine) ruthenium in a 9% way. 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 speed of 64 rpm to obtain a slurry containing particles of the hydrogenated dicyclopentadiene ring-opening polymer.

In addition, 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) is 5% relative to the total amount of the poorly soluble cycloolefin polymer (1) and the soluble impurities (1) (hereinafter, this amount may be referred to as the "polymer amount").

[Solid-liquid separation]

A centrifugal dewatering machine (manufactured by TANABE WILLTEC INC., high-speed decanter) with a rotating bowl inside the machine and a screw conveyor inside the bowl for conveying filter cakes (manufactured by TANABE WILLTEC INC., high-speed decanter) was supplied with 1,100 parts of the aforementioned slurry. Solid-liquid separation is performed under the conditions of bowl rotation 4800 rpm and differential rotation 15 rpm. The amount of the obtained wet cake (crude polymer-containing product) was 240 parts.

<Cleaning of crude polymer-containing products (process (B))>

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

Secondly, supply the aforementioned xylene slurry to a centrifugal dehydrator (manufactured by TANABE WILLTEC INC., high-speed decanter) that has a rotating bowl inside the machine and a screw conveyor inside the bowl to transport the filter cake. 2400 parts, solid-liquid separation is performed under the conditions of bowl rotation 4800 rpm and differential rotation 15 rpm. The amount of the obtained washed wet cake (washed material) was 240 parts.

〈Drying the cleaned product (process (C))〉

The washed wet cake obtained by solid-liquid separation is supplied to a continuous groove dryer (manufactured by Kurimoto Iron Works Co., Ltd., CD-80), and the volatile components contained in the wet cake (mainly System solvent) to obtain dry powder. －Drying conditions－ Dryer temperature: 170℃ Nitrogen flow rate: 50 NL/min Disk revolution: 30 rpm

<Granulation of dried material (process (D))>

[Unbroken]

Add 100 parts of the dry powder obtained by drying as an antioxidant {3-[3′,5′-bis(tertiarybutyl)-4′-hydroxyphenyl]propionic acid methylene}methane (Manufactured by BASF Japan, IRGANOX (registered trademark) 1010) 0.5 copies.

By compressing the obtained mixture with a pressure compression molding machine (manufactured by Shinto Kogyo Co., Ltd., BGS-IV), a strip-shaped molded product is obtained. Then, use a roller crusher (sheet crusher) to break the strip-shaped molded product under the following conditions to obtain a sheet-shaped powder block. －Disintegration conditions－ Roll number: 10 rpm Roll pressure: 60 kN

[Granularization]

Put the obtained flake-like powder block into a biaxial extruder (manufactured by Nippon Steel Co., Ltd., TEX-30) with a die hole with an inner diameter of 3 mm, and perform hot melt extrusion molding under the following conditions to obtain a strand Matter. Then, the strand is finely cut with a strand cutter to obtain cylindrical particles (polymer-containing material) with a diameter of 3 mm and a length of 3 mm. －Forming conditions－ Set temperature of material barrel: 280℃ Screw revolution: 300 rpm

[analysis]

Then, using the obtained particles, the melting point of the hydrogenated ring-opening polymer, the ratio of the racemic diad of the polymer chain of the hydrogenated ring-opening polymer, the content of the compound (A), and the amount of residual solvent Measurement. The results are shown in Table 1.

〈Film formation〉

The obtained pellets are supplied to a hot-melt extruded film forming machine (manufactured by Optical Control System (OCS)) equipped with a T-die for single-layer extrusion in a state of being heated and melted. The film forming machine is operated under the following operating conditions, and a long unstretched film (thickness 150 μm, width 120 mm) is continuously manufactured by the method of winding into a roll at a speed of 2 m/min for 4 hours. Take a sample of the film after 4 hours to confirm the presence or absence of mold streaks. The results are shown in Table 1. －Operating conditions－ Tank temperature setting: 280℃～290℃ Mold temperature: 270℃ Screw revolution: 30 rpm

(Example 2)

Except for using toluene instead of xylene as a solvent in the cleaning of the polymer-containing crude product (step (B)), the operation of Example 1 was followed to produce particles (polymer-containing materials) and films. Then, follow the operation of Example 1 for analysis and evaluation. The results are shown in Table 1.

(Example 3)

Except that methylcyclohexane was used as a solvent instead of xylene in the cleaning of the crude polymer-containing product (step (B)), the operation of Example 1 was followed to produce particles (polymer-containing materials) and films. Then, follow the operation of Example 1 for analysis and evaluation. The results are shown in Table 1.

(Example 4)

Except that cyclohexane was used as a solvent instead of xylene in the cleaning of the crude polymer-containing product (step (B)), the operation of Example 1 was followed to produce particles (polymer-containing materials) and films. Then, follow the operation of Example 1 for analysis and evaluation. The results are shown in Table 1.

(Example 5)

Except that tertiary butyl-1-methyl-2-propylcyclohexane was used as a solvent instead of xylene in the cleaning of the crude polymer-containing product (step (B)), the operation of Example 1 was followed to produce particles ( Containing polymer) and film. Then, follow the operation of Example 1 for analysis and evaluation. The results are shown in Table 1.

(Comparative example 1)

Except that the polymer-containing crude product is not cleaned (process (B)), and the wet cake (polymer-containing crude product) is used in the process (C) instead of washing the wet cake, the manufacturing method is as in Example 1 Particles (materials containing polymers) and films. Then, follow the operation of Example 1 for analysis and evaluation. The results are shown in Table 1.

(Comparative example 2)

Except that isopropanol, which is a polar organic solvent, is used as a solvent instead of xylene in the cleaning of crude polymer-containing products (step (B)), the operation of Example 1 is followed to produce particles (polymer-containing materials) and films . Then, follow the operation of Example 1 for analysis and evaluation. The results are shown in Table 1.

(Comparative example 3)

Except that acetone, which is a polar organic solvent, was used as a solvent instead of xylene in the cleaning of the crude polymer-containing product (step (B)), the operation of Example 1 was followed to produce particles (polymer-containing materials) and films. Then, follow the operation of Example 1 for analysis and evaluation. The results are shown in Table 1.

"Table 1" Proportion of racem two unit group [%] Melting point (℃) Solvent The amount of compound (A) [mass ppm] Residual solvent amount [mass ppm] Existence of mold streaks Example 1 81 266 Xylene 12 215 ○ Example 2 81 266 Toluene 29 138 ○ Example 3 81 267 Methylcyclohexane 19 81 ○ Example 4 81 266 Cyclohexane 7 42 ○ Example 5 81 266 Tertiary butyl-1-methyl-2-propyl cyclohexane 18 7122 ○ Comparative example 1 81 265 - 335 88 ╳ Comparative example 2 81 265 Isopropanol 119 0 ╳ Comparative example 3 81 264 acetone 123 0 ╳

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

According to the present invention, it is possible to obtain a polymer-containing product that contains a crystalline hydrogenated cycloolefin ring-opening polymer and is less likely to cause surface defects when formed into a molded body such as a film.

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

no.

no.

no.

Claims (4)

A polymer-containing material comprising a hydrogenated cycloolefin ring-opening polymer having crystallinity, and the hydrogenated cycloolefin ring-opening polymer having crystallinity has the following formula (1): [化1]

The repeating unit shown as the main structural unit of the polymer chain and the proportion of the racemic diunit group of the repeating unit represented by the aforementioned formula (1) in the aforementioned polymer chain is 30% or less or 60% or more, wherein Contains the following formula (2): "Hua 2"

[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 is 30 mass ppm or less. A method for producing a polymer-containing material, comprising: a step of preparing a crude polymer-containing product containing a "hydrogenated cyclic olefin ring-opening polymer with crystallinity", the ring-opening polymerization of the crystalline cyclic olefin The compound hydride has the following formula (1): "Chemical 3"

The repeating unit shown is the main structural unit of the polymer chain and the proportion of the racemic diad of the repeating unit represented by the aforementioned formula (1) in the aforementioned polymer chain is 30% or less or 60% or more; and A step of washing the aforementioned crude polymer-containing product with a solvent containing a non-polar organic solvent in a ratio of 90% by mass or more and 100% by mass or less. The method for producing a polymer-containing material according to claim 2, wherein the solvent is made of a non-polar organic solvent having a carbon number of 8 or less. A film formed by using the polymer-containing material as described in claim 1.