JP5842569B2 - Cyclic olefin ring-opening polymer for molding material and process for producing the same - Google Patents

Description

  The present invention relates to a cyclic olefin-based ring-opening polymer for molding materials that can be stretched at a relatively low temperature without causing problems such as cloudiness, a method for producing the same, and a film. In particular, the present invention relates to a cyclic olefin-based ring-opening polymer for molding materials that can be used as a film, a sheet, a retardation plate, a touch panel substrate, and a light guide plate, and a method for producing the same.

Cyclic olefin ring-opening polymers (hereinafter also referred to as polymers including copolymers) have a high glass transition temperature due to the rigidity of the main chain structure, and there are bulky groups in the main chain structure. Therefore, it has features such as amorphous, high light transmittance, low birefringence due to low refraction anisotropy, and excellent heat resistance, transparency and optical properties. It is attracting attention as a plastic resin. Examples of such cyclic olefin-based ring-opening polymers include those described in Patent Documents 1-6.
In recent years, application of cyclic olefin-based ring-opening polymers has been studied in the fields of optical materials such as optical discs, optical lenses and optical fibers, and sealing materials such as optical semiconductor sealing, using the above characteristics. ing. In addition, attempts have been made to improve the problems of conventional optical films by applying to films or sheets (hereinafter referred to as films including sheets).
In other words, films such as polycarbonate, polyester, and triacetyl acetate that have been used as optical films in the past have a large photoelastic coefficient. In order to solve these problems, films made of cyclic olefin-based ring-opening polymers have been proposed as various optical films. For example, Patent Documents 7 to 10 describe a retardation plate (an optical film having a function of imparting a retardation to transmitted light, also referred to as a retardation film) made of a film of a cyclic olefin ring-opening polymer. . Patent Documents 11 to 13 describe that a film of a cyclic olefin-based ring-opening polymer is used as a protective film for a polarizing plate. Furthermore, Patent Document 14 describes a substrate for a liquid crystal display element comprising a film of a cyclic olefin-based ring-opening polymer.

As a film for optical use, a method of forming a film by a casting method and a method of forming a film by an extrusion method are known. In terms of cost, a method of forming a film by an extrusion method is advantageous, and development of a polymer having good extrusion film forming property has been demanded. However, when extrusion film formation is performed, the polymer is exposed to a high temperature exceeding the glass transition temperature, so that there is a problem that yellowing and gel-like defects occur in the produced film. On the other hand, if the temperature during extrusion film formation is set low, there is a problem that quality troubles derived from the high viscosity of the polymer such as die line occur.
In recent years, with the increase in size and functionality of liquid crystal display elements (LCDs), the required characteristics for retardation plates used in LCDs have become more sophisticated. For example, the phase difference is uniform for larger LCDs and lighter weights. There is a demand for a higher level of stability and no optical axis blurring, and control of the phase difference in the thickness direction has been required for improving the viewing angle of LCDs. Therefore, in order to meet these requirements, ring-opening homopolymers (homopolymers) and ring-opening copolymers of various cyclic olefin monomers have been proposed as materials for retardation plates.
In addition, it has excellent characteristics of cyclic olefin-based ring-opening polymers such as heat resistance and transparency, and film forming or film stretching at a relatively low temperature such as near the glass transition temperature (hereinafter also referred to as Tg). Even when carried out, there has been a strong demand for a cyclic olefin-based ring-opening polymer suitable for uses such as a phase difference plate without causing problems such as cloudiness in the film.

Japanese Patent Laid-Open No. 1-132625 JP-A-1-132626 JP 63-218726 A JP-A-2-133413 JP 61-120816 A Japanese Patent Laid-Open No. 61-115912 JP-A-4-245202 JP-A-4-36120 JP-A-5-2108 Japanese Patent Laid-Open No. 5-64865 Japanese Patent Laid-Open No. 5-212828 JP-A-6-511117 JP-A-7-77608 JP-A-5-61026

  The present invention was made in order to address the above-mentioned problems, and can be used for a film that can satisfy advanced characteristic requirements as a phase difference plate and does not cause problems such as white turbidity even when stretched under a temperature condition near Tg. It is an object of the present invention to provide a cyclic olefin-based ring-opening polymer for molding materials, and a method for producing the same, which can be easily obtained as a retardation plate having a uniform desired retardation and having no optical axis fluctuation. . In particular, it is an object of the present invention to provide a cyclic olefin-based ring-opening polymer for a molding material that can suppress the occurrence of gel-like defects and die lines generated in a film, and a production method thereof.

The inventors of the present invention have intensively studied to eliminate defects such as yellowing of the film, occurrence of gel-like defects, and generation of die lines that occur during extrusion film formation.
It has been found that the gel and die line generated during the production of the extruded film strongly depend on the fluidity of the molten olefin-based ring-opening polymer for molding materials. The cyclic olefin-based ring-opening polymer for molding materials is a non-Newtonian fluid in the molten state, and the relationship between the shear rate and the stress exhibits nonlinearity, and the stress depends on the shear rate. Suppressing the shear rate dependence of the melt viscosity, specifically, the viscosity P1 (Pa · s) at a shear rate of 1 (s ⁻¹ ) at (glass transition temperature + 120) ° C. and a shear rate of 100 (s ^-1 ) By controlling the ratio P2 / P1 to the viscosity P2 (Pa · s) at 0.40 or more to be 0.40 or more, flow unevenness at the time of forming an extruded film is suppressed, and generation of gel and die line are suppressed. I found out that I can. The molecular weight distribution of a cyclic olefin-based ring-opening polymer for molding materials obtained from a cyclic olefin having a polar functional group and a hydrocarbon group was found to correlate with the shear rate dependence of melt viscosity. By setting the ratio to 0.5 or less, the ratio of P2 / P1 can be set to 0.40 or more, and in that case, flow unevenness, gel generation, and die line can be suppressed. As a result, it has been found that the cyclic olefin-based ring-opening polymer for molding materials has a very good extrusion film forming property and is suitable for use as a film and a phase difference plate, and has completed the present invention.

The cyclic olefin ring-opening polymer for molding materials of the present invention comprises a structural unit represented by the following structural formula (1) (hereinafter referred to as structural unit 1) and a structural unit represented by the following structural formula (2) ( Hereinafter, the molecular weight distribution (Mw / Mn) in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC) is 2.5 or less, including the structural unit 2). The melt viscosity ratio represented is 0.40 or more. Here, Mw is a weight average molecular weight, and Mn is a number average molecular weight.

構造式（１）中、ｍは０、１または２であり、Ｘは独立に−ＣＨ＝ＣＨ−および−ＣＨ₂ＣＨ₂−から選ばれる少なくとも１つの２価の基であり、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子またはハロゲン原子を表すか、酸素原子、窒素原子、イオウ原子もしくはケイ素原子を含む連結基を有していてもよい置換または非置換の炭素原子数１〜１０の炭化水素基を表すか、または極性基を表す。ただし、Ｒ¹〜Ｒ⁴の少なくとも１つが極性基であり、かつその他のＲ¹〜Ｒ⁴の少なくとも１つが炭素原子数１〜１０の炭化水素基である。

In Structural Formula (1), m is 0, 1 or 2, X is at least one divalent group independently selected from —CH═CH— and —CH ₂ CH ₂ —, and R ^{1 to} R ⁴ each independently represents a hydrogen atom or a halogen atom, or may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom, having 1 to 10 carbon atoms. Represents a hydrocarbon group or a polar group. However, at least one of R ^{1 to} R ⁴ is a polar group, and at least one of the other R ^{1 to} R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms.

数式（Ｉ）中、Ηは溶融粘度比を、Ｐ１はせん断速度が１（ｓ^-1）であるときの溶融粘度（Ｐａ・ｓ）を、Ｐ２はせん断速度が１００（ｓ^-1）であるときの溶融粘度（Ｐａ・ｓ）をそれぞれ表し、せん断速度の測定温度は走査示差熱量計で測定した成形材料用環状オレフィン系開環重合体のガラス転移温度＋１２０℃である。

In formula (I), Η is the melt viscosity ratio, P1 is the melt viscosity (Pa · s) when the shear rate is 1 (s ⁻¹ ), and P2 is the shear rate is 100 (s ⁻¹ ). The melt viscosity (Pa · s) is measured, and the measurement temperature of the shear rate is the glass transition temperature + 120 ° C. of the cyclic olefin-based ring-opening polymer for molding materials measured by a scanning differential calorimeter.

構造式（２）中、ｎは０、１または２であり、Ｘは独立に−ＣＨ＝ＣＨ−および−ＣＨ₂ＣＨ₂−から選ばれる少なくとも１つの２価の基であり、Ｒ¹¹〜Ｒ¹⁴は、それぞれ独立に、水素原子またはハロゲン原子を表すか、酸素原子、窒素原子、イオウ原子もしくはケイ素原子を含む連結基を有していてもよい置換または非置換の炭素原子数１〜１０の炭化水素基を表す。 Forming form material for the cyclic olefin ring-opening polymer of the present invention, the structural formula (1) the following structural formula as well as the structure unit represented by (2) the structural unit represented by (hereinafter referred to as structural unit 2.) It is characterized by including.

In Structural Formula (2), n is 0, 1 or 2, X is at least one divalent group independently selected from —CH═CH— and —CH ₂ CH ₂ —, and R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or a halogen atom, an oxygen atom, a nitrogen atom, sulfur atom or silicon atom may also be substituted or unsubstituted have a linking group containing 1 to 10 carbon atoms Represents a hydrocarbon group.

構造式（３）中、Ｘは独立に−ＣＨ＝ＣＨ−および−ＣＨ₂ＣＨ₂−から選ばれる少なくとも１つの２価の基であり、Ｒ⁵〜Ｒ¹⁰は、それぞれ独立に、水素原子またはハロゲン原子を表すか、酸素原子、窒素原子、イオウ原子もしくはケイ素原子を含む連結基を有していてもよい置換または非置換の炭素原子数１〜１０の炭化水素基を表すか、または極性基を表す。 Another cyclic olefin-based ring-opening polymer for molding material of the present invention is a structural unit represented by the following structural formula (3) together with the structural unit 1 and the structural unit (2) (hereinafter referred to as structural unit 3). It is characterized by including.

In Structural Formula (3), X is at least one divalent group independently selected from —CH═CH— and —CH ₂ CH ₂ —, and R ^{5 to} R ¹⁰ are each independently a hydrogen atom or Represents a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, or a polar group Represents.

The ratio of the polymer having a polystyrene-equivalent weight average molecular weight of 300,000 or more measured by GPC is 5% by weight or less based on the amount of the whole polymer. It is characterized by.
Moreover, the ratio of the polymer whose weight average molecular weight of polystyrene conversion measured by GPC is 2000 or less is 10 weight% or less with respect to the quantity of a total polymer, It is characterized by the above-mentioned.
The film of the present invention is a film obtained by molding the above cyclic olefin-based ring-opening polymer for molding material by melt extrusion molding or a solvent casting method.

The method for producing a cyclic olefin-based ring-opening polymer for molding materials of the present invention comprises a monomer that produces a structural unit 1 and a monomer that contains a monomer that produces a structural unit (2) in an organic solvent (A Or a monomer (B) containing the monomer that produces the structural unit 1, the monomer that produces the structural unit 2, and the monomer that produces the structural unit 3. In the method for producing a cyclic olefin-based ring-opening polymer for a molding material, which is ring-opening polymerized by:
Along with the ring-opening polymerization catalyst, 5 mol% or less of the terminal olefin compound is blended with respect to all the monomers blended.
In addition, the polymer obtained by the ring-opening polymerization is subjected to a hydrogenation reaction.

  The cyclic olefin-based ring-opening polymer for molding material of the present invention has a molecular weight distribution of 2.5 or less and a shear rate dependency of melt viscosity at a predetermined value, thereby causing flow unevenness and gel during film formation. Generation and die line can be suppressed. As a result, a film excellent in heat resistance and optical properties can be suitably formed. It is possible to provide a film that does not cause foreign matter defects, gels, and yellowing of the film even under heating conditions during film formation. In addition, it is possible to provide a cyclic olefin-based ring-opening polymer for molding materials that can be stretched without causing problems such as cloudiness even at a relatively low temperature near Tg. Further, by using this cyclic olefin-based ring-opening polymer for molding material, it is possible to provide a phase difference plate which is excellent in optical characteristics and heat resistance, shows a uniform phase difference and has no optical axis fluctuation. In particular, gels and die lines can be suppressed, and the appearance of the film can be improved.

It is a figure which shows the result of the melt viscosity measured by changing a shear rate.

式（１'）において、ｍ、Ｒ¹〜Ｒ⁴は式（１）のＲ¹〜Ｒ⁴と同じである。
構造式（１）あるいは式（１'）におけるＲ¹〜Ｒ⁴で表されるハロゲン原子としては、フッ素原子、塩素原子および臭素原子が挙げられる。
置換または非置換の炭素原子数１〜１０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基などのアルキル基；シクロペンチル基、シクロヘキシル基などのシクロアルキル基；ビニル基、アリル基、プロペニル基などのアルケニル基などが挙げられる。
これらの置換または非置換の炭化水素基は直接環構造に結合していてもよいし、あるいは酸素原子、窒素原子、イオウ原子もしくはケイ素原子を含む連結基（ｌｉｎｋａｇｅ)を介して結合していてもよい。連結基としては、例えば炭素原子数１〜１０の２価の炭化水素基（例えば、−（ＣＨ₂）_q−（式中、ｑは１〜１０の整数）で表されるアルキレン基）；酸素、窒素、イオウまたはケイ素を含む連結基（例えば、カルボニル基(−ＣＯ−)、オキシカルボニル基(−Ｏ（ＣＯ）−)、スルホン基(−ＳＯ₂−)、エーテル結合(−Ｏ−)、チオエーテル結合(−Ｓ−)、イミノ基(−ＮＨ−)、アミド結合(−ＮＨＣＯ−，−ＣＯＮＨ−)、シロキサン結合(−ＯＳｉ（Ｒ¹⁵）₂−（式中、Ｒ¹⁵はメチル、エチルなどのアルキル基）)などが挙げられ、これらの複数を含む連結基であってもよい。 The cyclic olefin ring-opening polymer for molding materials of the present invention contains the structural unit 1 described above. This structural unit 1 is obtained by ring-opening polymerization of a cyclic olefin monomer represented by the following formula (1 ′).

In the formula (1 '), m, R 1 ~R 4 is the same as R ¹ to R ⁴ of formula (1).
Examples of the halogen atom represented by R ^{1 to} R ⁴ in Structural Formula (1) or Formula (1 ′) include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group, allyl group, Examples include alkenyl groups such as propenyl groups.
These substituted or unsubstituted hydrocarbon groups may be directly bonded to the ring structure, or may be bonded via a linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom. Good. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by — (CH ₂ ) _q — (wherein q is an integer of 1 to 10)); oxygen , A linking group containing nitrogen, sulfur or silicon (for example, a carbonyl group (—CO—), an oxycarbonyl group (—O (CO) —), a sulfone group (—SO ₂ —), an ether bond (—O—), Thioether bond (—S—), imino group (—NH—), amide bond (—NHCO—, —CONH—), siloxane bond (—OSi (R ¹⁵ ) ₂ — (wherein R ¹⁵ is methyl, ethyl, etc.) And a linking group containing a plurality of them may be used.

  Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, and a triorganosilyl group. Amino group, acyl group, alkoxysilyl group, sulfonyl group, carboxyl group, and the like. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, and an aryl such as a benzoyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, Biphenylyloxycarbonyl group and the like; examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethylsilyl group, Such Riechirushiriru group and the like; examples of the amino group include primary amino group, the alkoxysilyl group, for example trimethoxysilyl groups, such as triethoxysilyl group.

At least one of R ^{1 to} R ⁴ in the structural formula (1) or the formula (1 ′) is the polar group, and at least one of the other R ^{1 to} R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms. It is.

Specific examples of the cyclic olefin monomer represented by the formula (1 ′) include, for example, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- Methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-6-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-6- Phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (hereinafter referred to as DNM), 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-n-propoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene etc. can be mentioned, but it is not limited to these examples.

In the present invention, the polar group in the monomer represented by the formula (1 ′) that generates the structural unit 1 is preferably a group represented by the following formula (4). That is, it is preferable that at least one of R ^{1 to} R ^{4 in} the above structural formula (1) or the above formula (1 ′) is a group represented by the following formula (4).

-(CH ₂ ) _p COOR ¹⁶ (4)

In Formula (4), p is 0 or an integer of 1 to 5, and R ¹⁶ is a hydrocarbon group having 1 to 15 carbon atoms.
In the above formula (4), the smaller the value of p and the smaller the number of carbon atoms in R ¹⁶ , the higher the glass transition temperature of the resulting polymer and the better the heat resistance. That is, p is usually 0 or an integer of 1 to 5, preferably 0 or 1, and R ¹⁶ is usually a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 3 carbon atoms. It is an alkyl group.
Furthermore, in the structural formula (1), when an alkyl group is further bonded to the carbon atom to which the polar group represented by the above formula (4) is bonded, the resulting polymer has heat resistance and water absorption (wetness). ) It is preferable in order to balance the sex. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

式（２'）において、ｎ、Ｒ¹¹〜Ｒ¹⁴は構造式（２）と同じである。
構造式（２）あるいは式（２'）におけるＲ¹¹〜Ｒ¹⁴で表されるハロゲン原子としては、フッ素原子、塩素原子および臭素原子が挙げられる。
置換または非置換の炭素原子数１〜１０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基などのアルキル基；シクロペンチル基、シクロヘキシル基などのシクロアルキル基；ビニル基、アリル基、プロペニル基などのアルケニル基などが挙げられる。
これらの置換または非置換の炭化水素基は直接環構造に結合していてもよいし、あるいは酸素原子、窒素原子、イオウ原子もしくはケイ素原子を含む連結基（ｌｉｎｋａｇｅ)を介して結合していてもよい。連結基としては、例えば炭素原子数１〜１０の２価の炭化水素基（例えば、−（ＣＨ₂）_q−（式中、ｑは１〜１０の整数）で表されるアルキレン基）；酸素、窒素、イオウまたはケイ素を含む連結基（例えば、カルボニル基(−ＣＯ−)、オキシカルボニル基(−Ｏ（ＣＯ）−)、スルホン基(−ＳＯ₂−)、エーテル結合(−Ｏ−)、チオエーテル結合(−Ｓ−)、イミノ基(−ＮＨ−)、アミド結合(−ＮＨＣＯ−，−ＣＯＮＨ−)、シロキサン結合(−ＯＳｉ（Ｒ¹⁵）₂−（式中、Ｒ¹⁵はメチル、エチルなどのアルキル基）)などが挙げられ、これらの複数を含む連結基であってもよい。 Molding material for the cyclic olefin ring-opening polymer of the present invention, Ru copolymer der containing the structural unit 1 and the following structural units 2.
The structural unit 2 is obtained by ring-opening polymerization of a cyclic olefin monomer represented by the following formula (2 ′).

In the formula (2 ′), n and R ^{11 to} R ¹⁴ are the same as in the structural formula (2).
Examples of the halogen atom represented by R ^{11 to} R ¹⁴ in Structural Formula (2) or Formula (2 ′) include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group, allyl group, Examples include alkenyl groups such as propenyl groups.
These substituted or unsubstituted hydrocarbon groups may be directly bonded to the ring structure, or may be bonded via a linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom. Good. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by — (CH ₂ ) _q — (wherein q is an integer of 1 to 10)); oxygen , A linking group containing nitrogen, sulfur or silicon (for example, a carbonyl group (—CO—), an oxycarbonyl group (—O (CO) —), a sulfone group (—SO ₂ —), an ether bond (—O—), Thioether bond (—S—), imino group (—NH—), amide bond (—NHCO—, —CONH—), siloxane bond (—OSi (R ¹⁵ ) ₂ — (wherein R ¹⁵ is methyl, ethyl, etc.) And a linking group containing a plurality of them may be used.

Specific examples of the cyclic olefin monomer represented by the formula (2 ′) include bicyclo [2.2.1] hept-2-ene (hereinafter referred to as NB) and tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] -dodec- ³ -ene, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . ^0,14 ] hept-4-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-bicyclo [2.2.1] hept-2-ene and the like. However, it is not limited to these examples. Of these, NB is particularly preferably used.

式（３’）中、Ｒ⁵〜Ｒ¹⁰は、構造式（３）のＲ⁵〜Ｒ¹⁰と同じである。
構造式（３）あるいは式（３'）におけるＲ⁵〜Ｒ¹⁰として表されるハロゲン原子、酸素原子、窒素原子、イオウ原子もしくはケイ素原子を含む連結基を有していてもよい置換または非置換の炭素原子数１〜１０の炭化水素基、および極性基は、上記構造式（１）に関して述べたものと同じである。 The cyclic olefin ring-opening polymer for molding material of the present invention can be a copolymer containing the structural unit 3.
The structural unit 3 is obtained by ring-opening polymerization of a cyclic olefin monomer represented by the following formula (3 ′).

In formula (3 ′), R ^{5 to} R ¹⁰ are the same as R ^{5 to} R ¹⁰ in structural formula (3).
Substituted or unsubstituted which may have a linking group containing a halogen atom, oxygen atom, nitrogen atom, sulfur atom or silicon atom represented by R ^{5 to} R ¹⁰ in Structural Formula (3) or Formula (3 ′) The hydrocarbon group having 1 to 10 carbon atoms and the polar group are the same as those described for the structural formula (1).

As such a cyclic olefin monomer (3 ′), specifically, for example,
Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 8-methyl-tricyclo [4. 3.0.1 ^2,5 ] dec-3-ene, 7-ethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 7-isopropyl-tricyclo [4.3.0. 1 ^2,5 ] dec-3-ene, 7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 7-phenyl-tricyclo [4.3.0.1 ^2,5 Deca-3-ene, 7,7-dimethyl-tricyclo [4.3.0.1 ^2,5 ] Dec-3-ene, 7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 7-methyl-8-ethyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene, 7-methoxycarbonyl - tricyclo [4.3. .1 ^2,5] dec-3-ene, 8-methoxycarbonyloxy - tricyclo [4.3.0.1 ^2,5] dec-3-ene, 7-phenoxycarbonyl - tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 7-methyl-7-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 8-methyl-8-methoxycarbonyl-tricyclo [4 .3.0.1 ^2,5 ] dec-3-ene, 7-fluoro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 8-fluoro-tricyclo [4.3.0 .1, ^2,5 ] dec-3-ene, 7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 8-chloro-tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene, 7,7-difluoro - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene, 7,8-difluoro - Rishikuro [4.3.0.1 ^{2, 5]} dec-3-ene, 7,8-dichloro - can be exemplified tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene However, it is not limited to these examples.

The structural unit 3 is a ring-opened cyclic olefin monomer represented by the following formula (3 ″) (wherein R ^{5 to} R ⁷ and R ⁹ are the same as in the structural formula (3)). It can also be obtained by polymerizing and then hydrogenating the five-membered ring.

As such a cyclic olefin monomer (3 ″), specifically, for example, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (hereinafter referred to as DCP). ), 7-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, 8-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7- Diene, 9-methyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, 7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3, 7-diene, 7-ethyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, 7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] deca-3, 7-diene, 7-phenyl - tricyclo [4.3.0.1 ^{2, 5]} deca-3,7-diene, 7- (4-biphenyl) - tricyclo [4.3. .1 ^2,5] deca-3,7-diene, 7-methoxycarbonyl - tricyclo [4.3.0.1 ^2,5] deca-3,7-diene, 7-phenoxycarbonyl - tricyclo [4.3 .0.1 ^2,5 ] deca-3,7-diene, 7-methyl-7-methoxycarbonyl-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, 7-fluoro- Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, 7,8-difluoro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, 7- Examples include chloro-tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, but are not limited to these examples. Of these, DCP is particularly preferably used in the present invention.

In the present invention, structural units 1, the combination of the structural units 2 and structural units 3, the combination of the structural unit 1 and the structural unit 2, a combination of structural units 1 and the structural unit 2 and structural units 3 preferred.
In the present invention, structural units other than the structural unit 1, the structural unit 2 and the structural unit 3 can be combined within a range that does not impair the object of the present invention. 2 and structural unit 3 are preferred.
The ratio in the case of the combination of the structural unit 1 and the structural unit 2 is 80 to 99.5 parts by weight, preferably 90 to 99 parts by weight, when the total of these structural units is 100 parts by weight. The structural unit 2 is in the range of 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight .
The proportion of the combination of the structural unit 1 and the structural unit 2 and the structural unit 3, when the sum of these structural units is 100 parts by weight, structural units 1 50 to 90 parts by weight, preferably 50 to 80 The weight unit and the structural unit 2 are 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, and the structural unit 3 is 9.5 to 40 parts by weight, preferably 9.5 to 30 parts by weight.
The glass transition temperature can be adjusted by copolymerizing the structural unit 3, but if it exceeds 40 parts by weight, the filtration performance of the resulting polymer in the solution may deteriorate. For this reason, by using a small amount of the cyclic olefin monomer represented by the formula (2 ′) as a copolymerization monomer together with the cyclic olefin monomer represented by the formula (3 ′), filtration is performed. A polymer having an objective glass transition temperature and excellent extrudability can be obtained without reducing the performance.

  In the present invention, the monomer that generates the structural unit 1 is preferably DNM, the monomer that generates the structural unit 2 is preferably NB, and the monomer that generates the structural unit 3 is Is preferably DCP.

  In the present invention, in addition to the cyclic olefin monomer represented by the above formula (1 ′), formula (2 ′), formula (3 ′), and formula (3 ″), the object of the present invention is not impaired. Examples of other monomers that can be used in a small amount within the range include cycloolefin monomers such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene. In addition, in the presence of an unsaturated hydrocarbon polymer having an olefinically unsaturated bond in the main chain such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, polynorbornene, etc. It can also be formed by ring-opening copolymerization of a cyclic olefin monomer, and when it has such a structural unit, the impact resistance of the polymer of the present invention tends to be improved.

  The cyclic olefin-based ring-opening polymer of the present invention has a polystyrene-equivalent molecular weight distribution Mw / Mn measured by GPC of 2.5 or less, preferably 1.1 to 2.4. When the molecular weight distribution Mw / Mn exceeds 2.5, moldability is lowered, and gel and die line are generated.

Moreover, as a molecular weight of the cyclic olefin ring-opening polymer of this invention, it is preferable that the weight average molecular weight (Mw) of polystyrene conversion measured by GPC is the range of 10,000-100,000 normally.
Moreover, it is preferable that the ratio of the polymer whose weight average molecular weight is 300,000 or more is 5 weight% or less with respect to the quantity of all the polymers.
Furthermore, the ratio of the polymer having a weight average molecular weight of 2000 or less is preferably 10% by weight or less with respect to the total amount of the polymer.
When the ratio of the polymer having a weight average molecular weight of 2000 or less exceeds 10% by weight, the strength of the obtained film may be low. On the other hand, when the ratio of the polymer of 300,000 or more exceeds 5% by weight, the solution viscosity becomes too high, and the productivity and processability of the polymer of the present invention may be deteriorated.

The cyclic olefin ring-opening polymer of the present invention has a melt viscosity ratio represented by the above formula (I) of 0.40 or more.
FIG. 1 shows the results of the melt viscosity measured for the polymers obtained in Example 1, Example 2 and Comparative Example 1 described later by changing the shear rate. FIG. 1 is a logarithmic scale with melt viscosity on the vertical axis and shear rate on the horizontal axis. The melt viscosity measurement method and conditions are the same as those described later.
As shown in FIG. 1, in the case of Example 1 and Example 2 in which the molecular weight distribution Mw / Mn is 2.5 or less, compared to Comparative Example 1 in which the molecular weight distribution Mw / Mn exceeds 2.5, the shear of the melt viscosity Speed dependence is small.
When the melt viscosity has a small shear rate dependency, flow unevenness, gel generation, and die line can be suppressed during molding of the cyclic olefin-based ring-opening polymer.

  Tg of the cyclic olefin ring-opening polymer of the present invention is usually 110 to 250 ° C, preferably 115 to 220 ° C, and more preferably 120 to 200 ° C. A Tg of 110 ° C. or higher is preferable because of excellent heat resistance. When Tg is less than 110 ° C., the heat distortion temperature becomes low, which may cause a problem in heat resistance, and there may be a problem that a change in optical properties due to temperature in the obtained film becomes large. is there. On the other hand, when Tg exceeds 250 ° C., the processing temperature becomes too high during the stretching process, and the polymer may be thermally deteriorated.

  Further, the cyclic olefin ring-opening polymer of the present invention has a differential differential scanning calorimetry curve (DSC curve) showing a single peak, and a Tg distribution which is the rising temperature width of the peak is 40 ° C. or less, preferably 35 ° C. or less. It is preferable to have such a narrow distribution. In addition, the differential differential scanning calorific value curve used in the present invention is obtained when measured in a nitrogen atmosphere at a heating rate of 20 ° C./min. The peak rising temperature width is the width between the inflection points where the peak rises from the baseline. Furthermore, the Tg of the cyclic olefin-based ring-opening polymer is plotted on the differential scanning calorimetry curve with the maximum differential peak temperature (point A) of differential differential scanning calorie and the temperature (point B) of −20 ° C. from the maximum peak temperature, It is obtained as the intersection of the tangent line on the baseline starting from point B and the tangent line starting from point A.

  Additives such as known antioxidants and ultraviolet absorbers are added to the cyclic olefin-based ring-opened polymer of the present invention in order to improve heat deterioration resistance and light resistance within a range not impairing the effects of the present invention. be able to. For example, at least one compound selected from the group consisting of the following phenol compounds, thiol compounds, sulfide compounds, disulfide compounds, and phosphorus compounds is 0.01 to 100 parts by weight with respect to 100 parts by weight of the polymer of the present invention. By adding 10 parts by weight, the heat deterioration resistance can be improved.

Phenolic compounds:
Examples of phenolic compounds include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol-bis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -3,5-triazine, penta Erythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N-hexamethylenebis 3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) Benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, and the like. Preferably, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], particularly preferably octadecyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate] and the like.

Thiol compounds:
Examples of thiol compounds include alkyl mercaptans such as t-dodecyl mercaptan and hexyl mercaptan, 2-mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1-methyl-2- (methylmercapto) benzimidazole, and 2-mercapto. -1-methylbenzimidazole, 2-mercapto-4-methylbenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5,6-dimethylbenzimidazole, 2- (methylmercapto) benzimidazole, 1- Examples include methyl-2- (methylmercapto) benzimidazole, 2-mercapto-1,3-dimethylbenzimidazole, mercaptoacetic acid, and the like.
Sulfide compounds:
Examples of sulfide compounds include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis (4-methyl-6-t- Butylphenol), 2,4-bis (n-octylthiomethyl) -6-methylphenol, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'- Examples thereof include thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), and ditridecyl 3,3′-thiodipropionate.
Disulfide compounds:
Disulfide compounds include bis (4-chlorophenyl) disulfide, bis (2-chlorophenyl) disulfide, bis (2,5-dichlorophenyl) disulfide, bis (2,4,6-trichlorophenyl) disulfide, bis (2-nitro Phenyl) disulfide, ethyl 2,2′-dithiodibenzoate, bis (4-acetylphenyl) disulfide, bis (4-carbamoylphenyl) disulfide, 1,1′-dinaphthyl disulfide, 2,2′-dinaphthyl disulfide, 1,2′-dinaphthyl disulfide, 2,2′-bis (1-chlorodinaphthyl) disulfide, 1,1′-bis (2-chloronaphthyl) disulfide, 2,2′-bis (1-cyanonaphthyl) Disulfide, 2,2′-bis (1-acetylnaphthyl) disulfide, Lauryl-3,3'-thiodipropionate and the like.
Phosphorus compounds:
Examples of phosphorus compounds include tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,6 -Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and the like.

  Further, benzophenone compounds such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, benzotriazole compounds such as N- (benzyloxycarbonyloxy) benzotriazole, 2-ethyloxanilide, 2-ethyl By adding 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, of an oxanilide compound such as -2'-ethoxyoxanilide to 100 parts by weight of the polymer of the present invention, light resistance Can be improved.

The cyclic olefin-based ring-opening polymer of the present invention is added in order to prevent the ring-opening polymer from being thermally deteriorated due to the heat history during melt extrusion when it is formed into a film or the like by melt extrusion. Choosing an antioxidant is an important technical factor. That is, when the film obtained by melt extrusion is stretched, in order not to reduce the retardation, or to reduce the degree of decrease as much as possible, than the Tg of the cyclic olefin ring-opening polymer to be melt-extruded. It is preferable to use a hindered phenol compound having a melting point in the temperature range of + 20 ° C. to Tg + 130 ° C., preferably Tg + 30 ° C. to Tg + 130 ° C. as an antioxidant.
If the melting point is less than + 20 ° C. than the Tg of the cyclic olefin-based ring-opening polymer to be melt-extruded, even if a hindered phenol-based compound is used, if the addition amount is increased, the phase difference is greatly reduced. Sometimes. On the other hand, if the melting point exceeds + 130 ° C. above the Tg of the cyclic olefin ring-opening polymer that is melt-extruded, the antioxidant may not be dissolved during processing, which may cause film defects such as fish eyes and foreign matters. In addition, even when the melting point is Tg + 20 ° C. to Tg + 130 ° C. of the cyclic olefin ring-opening polymer, when a compound other than the hindered phenol compound is used as an antioxidant, a reduction in retardation is observed. There is.

Specific examples of the antioxidant preferably used when the cyclic olefin ring-opening polymer of the present invention is formed by melt extrusion include, for example, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tris- (3,5-di) -T-butyl-4-hydroxybenzyl) -isocyanate, tris (2,4-di-t-butylphenyl) phosphite, and the like, but the present invention is not limited to these examples. However, it may be unsuitable depending on the Tg of the cyclic olefin ring-opening polymer to be melt-extruded. In addition, as long as the effect of this invention is not impaired, these may be used in combination and may be used independently.
The amount of these antioxidants to be added is generally 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, and more preferably 0.1 to 100 parts by weight of the cyclic olefin-based ring-opening polymer. 1 to 1.5 parts by weight. When the addition amount of the antioxidant is less than 0.01 parts by weight, a gel is likely to be generated in the resin during the extrusion process, and as a result, it may be recognized as a defect on the obtained film. There is not preferable. On the other hand, if the amount of the additive exceeds 5 parts by weight, it may cause the generation of eyes and the like during processing, which is not preferable because it causes die lines, fish eyes on the film, and burns.
These antioxidants may be added when the cyclic olefin ring-opening polymer is produced, or may be blended together with the pellets of the cyclic olefin ring-opening polymer during melt extrusion.
In addition, when the cyclic olefin-based ring-opening polymer of the present invention is molded by melt extrusion, addition of the above-mentioned antioxidants such as a lubricant, an ultraviolet absorber, a dye or a pigment within a range not impairing the effects of the present invention An agent can be used. Of course, even in this case, in the case of an additive having a melting point, the melting point is preferably in the range of the melting point of the essential antioxidant of the present invention.

  When the cyclic olefin-based ring-opening polymer of the present invention is used particularly for the production of films and sheets, the production of retardation plates, etc., it is preferable that the amount of foreign matter / gel contained in the polymer is as small as possible. When there are a lot of foreign objects and gels, fish-eye defects and die lines occur in the extruded film obtained by melt molding, resulting in a film with insufficient surface accuracy, especially for use in optical applications. Sometimes.

The cyclic olefin-based ring-opening polymer of the present invention can be formed into a film by molding by the melt extrusion molding and solvent casting methods described below.
Melt extrusion method:
Hereinafter, although an example is given and demonstrated about facilities, such as an extruder used by this invention, this invention is not limited to these examples.
In the melt extrusion method of the present invention, usually, before the cyclic olefin ring-opening polymer is charged into the extruder, moisture, gas (oxygen, etc.), residual solvent contained in the cyclic olefin ring-opening polymer The cyclic olefin-based ring-opening polymer is dried at an appropriate temperature of Tg or less for the purpose of removing the above in advance.
The dryer used for drying is not particularly limited. Usually, a hot-air circulating dryer, a dehumidifying dryer, a vacuum dryer, an inert gas circulating dryer such as nitrogen is used, and a cyclic olefin ring-opening is used. In view of efficiently removing volatile components or dissolved oxygen of the polymer, it is particularly preferable to use an inert gas circulation dryer or a vacuum dryer. In order to suppress moisture absorption and oxygen absorption in the hopper, it is also preferable to seal the hopper with an inert gas such as nitrogen or argon, or to use a vacuum hopper that can be kept under reduced pressure. Furthermore, the extruder cylinder may be provided with a vent function to remove volatile components generated during melt extrusion and a function to seal with an inert gas such as nitrogen or argon in order to push the deterioration of the polymer due to oxygen contamination. preferable.

As an extrusion molding method, the cyclic olefin-based ring-opening polymer is melted by an extruder, supplied in a fixed amount by a gear pump, impurities are removed by filtration with a metal filter, and the film shape is formed by a die, A method is generally used in which a film is cooled using a take-up machine and taken up using a take-up machine.
As an extruder used for extrusion molding, any of a single screw, a twin screw, a planetary type, a kneader, a Banbury mixer type and the like may be used, but a single screw extruder is preferably used. In addition, there are vent type, tip dull mage type, double flight type, full flight type, etc. as extruder screw shape, and compression type includes slow compression type, quick compression type, etc., but full flight type slow compression. Type is preferred.
Regarding gear pumps used for metering, there are internal lubrication systems in which the cyclic olefin-based ring-opening polymer returned from the downstream side between the gears enters the system and external lubrication systems that are discharged to the outside, but thermal stability In the case of a cyclic olefin-based ring-opening polymer having a poor value, an external lubrication method is preferred. As for the gear teeth of the gear pump, the helical type is more preferable than the direction parallel to the shaft from the viewpoint of stabilization of measurement.

  Regarding the filter used for filtering foreign matter, there are leaf disc type, candle filter type, leaf type, screen mesh, etc., but leaf disc type with relatively small residence time distribution and large filtration area. Are preferred. Examples of the filter element include a metal fiber sintered type, a metal powder sintered type, and a metal fiber / powder laminated type.

The shape of the center pole of the filter includes external flow type, hexagonal column internal flow type, cylindrical internal flow type, etc., but any shape can be selected as long as the retention part is small, The external flow type is preferable.
The melted cyclic olefin-based ring-opening polymer is discharged from a die, and is solidified in close contact with a cooling drum to be formed into a target film. Regarding the die shape, it is essential to make the flow of the cyclic olefin-based ring-opening polymer inside the die uniform. In order to maintain the uniformity of the film thickness, the pressure distribution inside the die near the die outlet is It is essential to be constant in the width direction. In addition, the flow rate of the cyclic olefin-based ring-opening polymer in the width direction is substantially constant, and the fineness of the flow rate at the die outlet is constant within a range that can be adjusted by the lip opening. It is a requirement to get. In order to satisfy the above conditions, the coat hanger type is preferable for the manifold shape, and the straight manifold, fishtail type and the like are not preferable because the flow rate distribution in the width direction is likely to occur.

  Further, in order to make the thickness distribution of the film uniform, it is important to make the temperature distribution at the die exit constant in the width direction, and the temperature distribution is preferably ± 1 ° C. or less, more preferably ± 0.5 ° C. or less. When temperature unevenness occurs in the width direction exceeding ± 1 ° C., a difference in melt viscosity of the cyclic olefin-based ring-opening polymer occurs, resulting in thickness unevenness, stress distribution unevenness, etc. Undesirably, phase difference unevenness is likely to occur.

  Further, the lip opening amount of the die outlet (hereinafter referred to as “lip gap”) is usually 0.05 to 1 mm, preferably 0.3 to 0.8 mm, more preferably 0.35 to 0. 0.7 mm. When the lip gap is less than 0.05 mm, the pressure of the cyclic olefin ring-opening polymer inside the die becomes too high, and the cyclic olefin ring-opening polymer tends to cause resin leakage from a place other than the lip of the die. Therefore, it is not preferable. On the other hand, when the lip gap exceeds 1 mm, it is difficult to increase the pressure of the cyclic olefin-based ring-opening polymer of the die.

Examples of methods for tightly solidifying the film extruded from the die include a nip roll method, an electrostatic application method, an air knife method, a vacuum chamber method, a calendar method, and the like, and an appropriate method is selected according to the film thickness and application. Is done.
Various surface treatments are preferably performed on the surface of the cooling roll for solidifying the film extruded from the die as well as the extruder cylinder and the inner surface of the die. These surface treatments prevent the adhesion of the extruded film to the roll surface and prevent the occurrence of uneven thickness of the film. Also, the surface accuracy of the cooling roll is increased, and the surface hardness is high, so that the film is not easily damaged. Even if it manufactures, it is preferable at the point which can maintain the film surface precision stably and can manufacture a film without a thickness spot.

Examples of the material of the extruder (cylinder, screw, etc.) and the die include, but are not limited to, SCM steel and stainless steel such as SUS. Also, the inner surface of the extruder cylinder, the die and the screw surface of the extruder are plated with chromium, nickel, titanium, etc., and PVD (Physical Vapor Deposition) method, etc., TiN, TiAlN, TiCN, CrN, DLC It is preferable to use a material in which a film such as (diamond-like carbon) is formed, a tungsten-based material such as WC, a material sprayed with a ceramic such as cermet, or a material whose surface is nitrided. Such a surface treatment is preferable in that a uniform molten state of the polymer can be obtained because the coefficient of friction with the cyclic olefin ring-opening polymer is small.

  In the present invention, the cyclic olefin-based ring-opening polymer temperature (extruder cylinder temperature) for producing a melt-extruded film is usually 200 to 350 ° C, preferably 220 to 320 ° C. If the cylinder temperature is less than 200 ° C, the polymer cannot be melted uniformly. On the other hand, if the temperature exceeds 350 ° C, it is difficult to produce a high-quality film with excellent surface properties due to thermal degradation of the polymer during melting. become. Furthermore, it is particularly preferable that the temperature is within the above-mentioned temperature range and within the range of Tg + 120 ° C. to Tg + 160 ° C. with respect to the glass transition temperature (Tg) of the polymer. For example, if the Tg of the polymer is 130 ° C., a particularly preferable temperature range for film production is 250 ° C. to 290 ° C.

The shear rate during melt extrusion is usually ^{1 to} 500 s ⁻¹ , preferably 2 to 350 s ⁻¹ , more preferably 5 to 200 s ⁻¹ . The shear rate is less than 1s ^-1 during extrusion, it is impossible to uneven thickness can not be uniformly melted polymer to obtain a small extruded film, whereas, if more than 500 s ^-1, shearing force is too large As a result, the polymer and additives are decomposed and deteriorated, and defects such as foaming, die lines and deposits may occur on the surface of the extruded film.

In the present invention, the thickness of the melt-extruded film is usually 10 to 800 μm, preferably 20 to 500 μm, more preferably 40 to 500 μm. When the thickness is less than 10 μm, it may be difficult to perform post-processing such as stretching due to insufficient mechanical strength. On the other hand, when the thickness exceeds 800 μm, a film having uniform thickness and surface properties is produced. In addition to being difficult, it may be difficult to wind up the resulting film.
The thickness distribution of the raw film of the present invention obtained by the melt extrusion method is usually within ± 5%, preferably within ± 3%, more preferably within ± 1% of the average value. When the thickness distribution exceeds ± 5%, retardation unevenness may easily occur when a retardation film is formed to form a retardation film.

Solvent casting method:
As the solvent casting method, for example, by dissolving or dispersing the cyclic olefin-based ring-opening polymer of the present invention in a solvent, a film-forming solution containing the polymer of the present invention at an appropriate concentration is prepared. The film-forming solution is cast by pouring or coating on a suitable carrier, whereby a liquid phase of the film-forming solution is formed on the carrier, and then the solvent is removed from the liquid layer by drying or the like. A preferred method is to carry out and peel the resulting film from the carrier.

In the preparation of the film forming solution by the solvent casting method, the concentration of the polymer of the present invention is usually 0.1 to 70% by weight, preferably 1 to 50% by weight, more preferably 10 to 35% by weight. . When this concentration is too small, it becomes difficult to obtain a film having a required thickness, and when the solvent is removed by drying, foaming or the like is likely to occur with evaporation of the solvent, and surface smoothness is obtained. It may be difficult to obtain a good film. On the other hand, if this concentration is excessive, the viscosity of the film-forming solution becomes too high, and it may be difficult to obtain a film having a uniform thickness and surface condition.
The viscosity of the film-forming solution is usually 1 to 1,000,000 (mPa · s), preferably 10 to 100,000 (mPa · s), more preferably 100 to 80,000 (mPa · s) at room temperature. s), particularly preferably 1000 to 60,000 (mPa · s).
Solvents used for the preparation of the film forming liquid include aromatic solvents such as benzene, toluene and xylene, cellosolve solvents such as methyl cellosolve, ethyl cellosolve and 1-methoxy-2-propanol, diacetone alcohol, acetone and cyclohexanone. Ketone solvents such as methyl ethyl ketone, 4-methyl-2-pentanone, cyclohexanone, ethyl cyclohexanone and 1,2-dimethylcyclohexane, ester solvents such as methyl lactate and ethyl lactate, 2,2,3,3-tetrafluoro- Examples thereof include halogen-containing solvents such as 1-propanol, methylene chloride and chloroform, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as 1-pentanol and 1-butanol.

Also in addition to the above solvent, SP value (solubility parameter) of usually 10 to 30 (MPa ^1/2), preferably 10 to 25 (MPa ^1/2), more preferably 15-25 (MPa ^1/2 ), And particularly preferably, by using a solvent in the range of 15 to 20 (MPa ^1/2 ), a film having good surface state uniformity and optical properties can be obtained.
Said solvent can be used individually or in combination of 2 or more types. When two or more solvents are used in combination, the SP value of the obtained mixed solvent is preferably within the above range. Here, the SP value of the mixed solvent can be determined from the SP value of each solvent and the weight ratio thereof. For example, in a mixed solvent obtained from two kinds of solvents, the weight fraction of each solvent is set to W1 and When W2 is set and SP values are SP1 and SP2, the SP value of the mixed solvent can be calculated by the formula: SP value = W1 · SP1 + W2 · SP2.

The temperature for dissolving or dispersing the cyclic olefin-based ring-opening polymer of the present invention in a solvent may be room temperature or high temperature, and the film-forming solution in which the polymer of the present invention is uniformly dissolved or dispersed by sufficiently stirring. Is obtained.
Moreover, coloring agents, such as dye and a pigment, can be suitably added to a film formation liquid as needed, and thereby a colored film can be obtained.
Moreover, you may add a leveling agent to a film formation liquid for the purpose of improving the surface smoothness of the film obtained. As such leveling agents, various ones can be used as long as they are general, and specific examples thereof include fluorine-based nonionic surfactants, special acrylic resin-based leveling agents, silicone-based leveling agents, and the like. .
As a carrier for forming the liquid layer of the film forming liquid, a metal drum, a steel belt, a polyester film made of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a polytetrafluoroethylene belt, or the like may be used. it can.

As a method for applying the film forming liquid, a method using a die or a coater, a spray method, a brush coating method, a roll coating method, a spin coating method, a dipping method, or the like can be used.
Moreover, the thickness and surface smoothness of the film obtained can also be controlled by repeatedly applying the film forming liquid.
When a polyester film is used as the carrier, a surface-treated film may be used. Here, as a surface treatment method, a commonly-used hydrophilic treatment method, for example, a method of forming a layer made of these resins by coating or laminating an acrylic resin or a sulfonate group-containing resin. Or the method etc. which improve the hydrophilic property of the film surface by corona discharge treatment etc. are mentioned.
In addition, as a carrier, for example, a metal drum, a steel belt, a polyester film, or the like that has been subjected to sand mat treatment or emboss treatment to form irregularities, the resulting film surface has irregularities on the carrier surface. Is transferred, whereby a film having a light diffusion function can be produced. Of course, it is also possible to impart a light diffusion function to the film by subjecting the film to a sand mat treatment.

In the solvent casting method, a specific method for removing the solvent in the liquid layer is not particularly limited, and a commonly used drying treatment method, for example, a method of passing through a drying furnace with a large number of rollers is used. However, if bubbles are generated as the solvent evaporates in the drying step, the properties of the resulting film are significantly reduced. To avoid this, the drying step is divided into a plurality of steps of two or more steps. It is preferable to control the temperature or the air volume at.
The amount of residual solvent in the film thus obtained is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. Here, when the amount of residual solvent in the film exceeds 10% by weight, the dimensional change with time becomes large when the film is actually used, which is not preferable. Further, the residual solvent lowers the glass transition temperature and lowers heat resistance, which is not preferable.
In addition, in order to perform the extending | stretching process mentioned later suitably, it may be necessary to adjust the residual solvent amount in a film suitably within the said range. Specifically, the amount of residual solvent in the film is usually 10 to 0.1% by weight, preferably 5 to 0.1% by weight, in order to stably and uniformly express the phase difference in the film by the stretching and orientation treatment. More preferably, it may be 1 to 0.1% by weight. By leaving a trace amount of solvent in the film, the stretching and orientation treatment may be facilitated or the retardation may be easily controlled.

The thickness of the film of the present invention obtained by the solvent casting method is usually 0.1 to 3,000 μm, preferably 0.1 to 1,000 μm, more preferably 1 to 500 μm, and most preferably 5 to 300 μm. When this thickness is too small, it becomes difficult to actually handle the film. On the other hand, when this thickness is excessive, it becomes difficult to wind in a roll shape.
The thickness distribution of the film of the present invention obtained by the solvent casting method is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3% relative to the average value. It is. Further, the variation rate of the thickness per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less. By controlling the thickness distribution of the film within the above range, the occurrence of retardation unevenness can be prevented when the film is stretched and oriented.

The film of the present invention has a function of giving a phase difference to transmitted light by subjecting the molecular chains of the polymer of the present invention forming the film to regular orientation in a certain direction by performing a stretching process (stretch orientation treatment). It can be set as an optical film (retardation film).
Here, “regularly oriented” means that when a normal polymer is formed into a film by a melt extrusion method or a solvent casting method, it depends on the magnitude of distortion of the film generated in the process, The molecular chains of the polymer are in a random state without facing a specific direction, whereas the molecular chains of the polymer are regularly oriented in a uniaxial direction, biaxial direction or thickness direction of the plane of the film. Means that. The degree of regularity of the orientation of the polymer varies and can be controlled by the stretching conditions.
In other words, the horizontal uniaxial stretching method using the tenter method, the compression stretching method between rolls, the longitudinal uniaxial stretching method using two sets of rolls with different circumferences, or the biaxial stretching method combining horizontal uniaxial and longitudinal uniaxial, stretching by the inflation method The law etc. can be used.
When the uniaxial stretching method is used, the stretching speed is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, and more preferably 100 to 1,000% / min. Yes, particularly preferably 100 to 500% / min.

  As the biaxial stretching method, a method of stretching in two directions intersecting each other at the same time or a method of stretching in a direction different from the first stretching direction after uniaxial stretching can be used. In these methods, the intersecting angle between the two stretching axes is not particularly limited because it is determined according to the desired characteristics, but is usually in the range of 120 to 60 degrees. The stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, and more preferably 100 -1,000% / min, particularly preferably 100-500% / min.

The processing temperature in the stretching process is not particularly limited, but when the glass transition temperature of the polymer used is Tg, it is usually in the range of Tg-5 ° C to Tg + 20 ° C, preferably Tg to Tg + 10 ° C. Is desirable. By setting the treatment temperature within the above range, it is possible to suppress the occurrence of high phase difference and phase difference unevenness, and it is preferable because the control of the refractive index ellipsoid becomes easy.
In addition, even if it carries out an extending | stretching process in the temperature range which concerns, as long as the cyclic olefin type ring-opening polymer of this invention is used, problems, such as cloudiness, will not arise in the phase difference plate obtained. This is presumably because the polymer of the present invention has a relatively small Tg distribution and is plasticized substantially uniformly by heating in the vicinity of Tg. Conversely, in the case of a cyclic olefin-based ring-opening polymer having a large Tg distribution, even when heated in the vicinity of Tg, it is not uniformly plasticized and there is a partially unplasticized part. It is thought that this causes.

The draw ratio is not particularly limited because it is determined according to the desired properties such as retardation, but is usually 1.01 to 10 times, preferably 1.03 to 5 times, more preferably 1.03 to 3 times. It is.
In the case of the cyclic olefin ring-opening polymer of the present invention, since it can be stretched in the vicinity of Tg, it is possible to apply a high stress to the film even at a low magnification, and thus a high retardation can be obtained. In addition, when the draw ratio is relatively low as described above, it is possible to easily produce a retardation plate without transparency and optical axis deviation. When the stretch ratio is excessive, it may be difficult to control the phase difference and the optical axis.

Although the stretched film may be cooled as it is at room temperature, it is kept in a temperature atmosphere of about Tg-100 ° C. to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes. It is also preferable to heat-set and then cool to room temperature, whereby a retardation plate having stable retardation characteristics with little change over time in the retardation of transmitted light is obtained.
The retardation plate obtained as described above gives a retardation to transmitted light due to the orientation of molecules by stretching. This retardation is determined by the stretching ratio or the thickness of the film before stretching. It is possible to control by adjusting. For example, as for the draw ratio, even if the film has the same thickness before drawing, the absolute value of the retardation of transmitted light tends to increase as the draw ratio increases. A film that imparts a retardation to transmitted light can be obtained. As for the thickness of the film before stretching, even if the stretching ratio is the same, the larger the thickness of the film before stretching, the greater the absolute value of the phase difference given to transmitted light. By changing the thickness of the retardation plate, it is possible to obtain a retardation plate that imparts a desired retardation to transmitted light.

In the retardation plate obtained as described above, the value of the phase difference given to the transmitted light is determined depending on the use and is not uniquely determined. However, the liquid crystal display element or the electroluminescence display element is used. Or when using for the wavelength plate of a laser optical system, it is desirable that it is 1-10,000 nm normally, Preferably it is 10-2,000 nm, More preferably, it is 15-1,000 nm.
Further, the phase difference of light transmitted through the film is preferably highly uniform. Specifically, the variation at a light wavelength of 550 nm is usually ± 20% or less, preferably ± 10% or less, more preferably. It is desirable that it be ± 5% or less. When the variation of the phase difference exceeds ± 20%, when used in a liquid crystal display element or the like, color unevenness may occur, resulting in a problem that the performance of the display body is degraded. Similarly, the variation of the optical axis is usually ± 2.0 degrees or less, preferably ± 1.0 degrees or less, more preferably ± 0.5 degrees or less.

The retardation plate can be used alone or in a laminate of two or more or bonded to a transparent substrate or the like. Moreover, it can also be laminated | stacked and used for another film, a sheet | seat, and a board | substrate.
When laminating a film or the like, a pressure-sensitive adhesive or an adhesive can be used. As the pressure-sensitive adhesive and adhesive, those having excellent transparency are preferably used. Specific examples thereof include natural rubber, synthetic rubber, vinyl acetate / vinyl chloride copolymer, polyvinyl ether, acrylic resin, and modified polyolefin. Adhesives such as resins, curable adhesives in which curing agents such as isocyanato group-containing compounds are added to the resins having functional groups such as hydroxyl groups and amino groups, polyurethane-based dry laminate adhesives, and synthetic rubber adhesives Agents, epoxy adhesives and the like.
In addition, a pressure-sensitive adhesive layer or an adhesive layer can be laminated in advance on the retardation plate in order to improve the workability of lamination with other films, sheets, substrates, and the like. In the case where the pressure-sensitive adhesive layer or the adhesive layer is laminated, the pressure-sensitive adhesive or the adhesive as described above can be used as the pressure-sensitive adhesive or the adhesive.

The cyclic olefin ring-opening polymer for molding materials of the present invention can be produced by polymerizing the above cyclic olefin monomer in the presence of a ring-opening polymerization catalyst in an organic solvent.
Examples of the single component ring-opening polymerization catalyst include titanium compounds such as biscyclopentadienyl-3,3-dimethyltitanacyclobutane and biscyclopentadienyl-3-t-butyltitanacyclobutane, and W (OR ¹⁷ ). ₂ (= NAr) (= CH (C (CH ₃ ) ₂ R ¹⁸ ), W (CO) ₄ (= C (OMe) (CH ₂ CH ₂ CH═CH ₂ ), W (Br) ₂ (OCH ₂ ( t-Bu)) ₂ (= CH (t-Bu)) and other tungsten compounds, Mo (OR ¹⁹ ) ₂ (= NAr) (= CH (C (CH ₃ ) ₂ R ²⁰ ) and other molybdenum compounds, Ruthenium-based first generation Grubbs catalysts such as RuCl ₂ [PPh ₃ ] ₂ (= CHCO ₂ Et), RuCl ₂ [PCy ₃ ] ₂ (= CHCH = CPh ₂ ), RuCl ₂ [PCy ₃ ] ₂ (= CHPh), Benzylidene (1,3-bis (2,4,6-to Second generation Grubbs catalyst such as (Rimethylphenyl) -2-imidazolidinylidene) dichloro (tricyclohexylphosphine) ruthenium, Ta (OAr) ₃ (= CH (t-Bu)), Ta (SAr ′) ₃ (= CH (T-Bu)), etc., where R ^{17 to} R ²⁰ represent a hydrocarbon group or a halogenated hydrocarbon group, and Ar and Ar ′ represent an aromatic substituent. .
As the single-component ring-opening polymerization catalyst, a single-component ring-opening polymerization catalyst containing Ru is preferable.
The amount of the single-component ring-opening polymerization catalyst used is usually 1 / 1,000,000 to 10,000,000 / mole, preferably 10,000 / mole, per 1 mol of the total amount of monomers. The range is from mol to 1 / 1,000,000 mol.

As the multi-component catalyst, (a) tungsten compound, (b) organoaluminum compound, (c) alcohol compound, (d) ketone compound, (e) nitrile compound, (f) ether compound, (g) ester compound Examples thereof include a ring-opening polymerization catalyst system comprising a combination, which essentially includes the components (a) and (b) and includes one or more selected from the components (c) to (g).
The (a) a tungsten compound, for _{example, WCl 6, WCl 5, WCl} 4, WCl 2, WBr 6, WBr 4, WBr 2, WF 6, WF 4, WI 6, WI 4 halogenated and tungsten; WOCl ₄ Tungsten oxyhalides such as WBr ₄ , WOF ₄ ; tungsten oxides or aryloxygenated tungsten such as W (OC ₆ H ₅ ) ₆ ; partially halogenated alkoxylated tungsten such as WCl ₂ (OC ₆ H ₅ ) ₄ or Partially chlorinated aryloxylated tungsten; W (CO) ₃ (CH ₃ CN) ₃ , W (OC ₂ H ₅ ) ₂ Cl ₃ , (CO) ₅ WC (OCH ₃ ) (CH ₃ ), (CO) ₅ WC _{(OC 2 H 5) (CH} 3), (CO) 5 WC (OC 2 H 5) (C 4 H 5) ( partial) carbonylation, such as (partially) chlorination, (partial) halogen , (Partial) alkoxylation, or (partial) tungsten compounds aryloxy, etc.; and the like.
Among these tungsten compounds, polymerization activity is high, and preferred compounds include halogenated or partially alkoxylated (or aryloxylated) and halogenated tungsten compounds such as WCl ₆ and W (OC ₂ H ₅ ) ₂ Cl ₃ . Is mentioned. These tungsten compounds are particularly preferable in that they have high polymerization activity and are easy to obtain a high molecular weight ring-opening polymer and a hydrogenated product thereof. These tungsten compounds can be used alone or in combination of two or more. The amount used is usually in the range of 0.001 to 10 mol, preferably 0.005 to 0.01 mol, per 100 mol of the total amount of monomers.

  (B) The organoaluminum compound is used as a promoter. Of the organoaluminum compounds, trialkylaluminum is preferred. Preferred organoaluminum compounds include, for example, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, It is not limited to these. These organoaluminum compounds can be used alone or in combination of two or more. The amount of the organoaluminum compound used is appropriately selected according to the reaction conditions, but is usually from 1: 0.1 to 1:10, preferably from 1: 0.3 to the metal atom ratio of tungsten compound: organoaluminum compound. The range is 1: 5, more preferably 1: 0.5 to 1: 2.

(C) The alcohol compound can be used as a metathesis polymerization activity modifier (reaction modifier).
Examples of the alcohol compound include ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, hexanol, octanol, decanol, cyclopentanol, cyclohexanol, phenol, and benzyl alcohol. Among these, propanol, isopropanol, butanol, isobutanol, pentanol, phenol and the like are preferable.
These alcohol compounds can be used alone or in combination of two or more. The amount of the alcohol compound used is appropriately selected according to the reaction conditions, but is usually 1: 0 to 1: 100, preferably 1: 0 to 1:10, more preferably, in the molar ratio of metathesis polymerization catalyst: alcohol compound. Is in the range of 1: 0 to 1: 6. Since the alcohol compound has the effect of reducing the polymerization activity of the metathesis polymerization catalyst, it is necessary to select the amount of the alcohol compound used according to the type of the metathesis polymerization catalyst. In addition, since the organoaluminum compound and the alcohol compound of the reaction activator are easily reacted and alkoxylated, an organoaluminum compound partially alkoxylated in advance is used, and an organoaluminum compound that is not alkoxylated And adding an alcohol compound to the reaction system and using it have the same effect. The reaction regulator may be added separately from the ring-opening polymerization catalyst, or both may be used in advance.

At least one compound selected from the group consisting of (d) a ketone compound, (e) a nitrile compound, (f) an ether compound, and (g) an ester compound can be present in the reaction system as a reaction regulator.
(D) The ketone compound is a compound represented by the formula R ²¹ —C (═O) —R ²² , and R ²¹ and R ²² are hydrocarbon groups such as an alkyl group and an aryl group. The number of carbon atoms of the alkyl group is usually 1-20, preferably 1-10. As the aryl group, a phenyl group is preferable. Preferable specific examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl phenyl ketone and the like.
(E) The nitrile compound is a compound represented by the formula R ²³ CN, and R ²³ is a hydrocarbon group such as an alkyl group or an aryl group. As an alkyl group, a C1-C20, Preferably 3-15, More preferably, 4-10 alkyl group is mentioned. Preferred examples of the alkyl group include i-propyl group, t-butyl group, n-pentyl group, t-pentyl group, hexyl group, heptyl group, octyl group and the like. Examples of the aryl group include a phenyl group, an alkyl-substituted phenyl group (for example, a tolyl group and a xylyl group), a naphthyl group, and an alkyl-substituted naphthyl group. Preferable specific examples of nitrile include t-butyl nitrile, benzonitrile and the like.
(F) The ether compound is a compound represented by the formula R ²⁴ OR ²⁵ , and R ²⁴ and R ²⁵ are hydrocarbon groups such as an alkyl group and an aryl group. The number of carbon atoms of the alkyl group is usually 1-20, preferably 1-10. As the aryl group, a phenyl group is preferable.
Specific examples of the ether include dimethyl ether, diethyl ether, methyl ethyl ether, methyl phenyl ether, isopropyl ether and the like.
(G) The ester compound is a compound represented by the formula R ²⁶ COOR ²⁷ , and R ²⁶ and R ²⁷ are hydrocarbon groups such as an alkyl group and an aryl group. The number of carbon atoms of the alkyl group is usually 1-20, preferably 1-10. As the aryl group, a phenyl group is preferable. Specific examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, methyl benzoate, ethyl benzoate Etc.
The above (d) ketone compound, (e) nitrile compound, (f) ether compound and / or (g) ester compound can be used alone or in combination of two or more as a reaction modifier. Although the usage-amount of a reaction regulator is suitably selected according to reaction conditions, it is 0.001-10 mol normally with respect to the total amount of monomers of 100 mol, Preferably it is 0.005-5 mol, More preferably The range is 0.01 to 2 mol.

When polymerizing the cyclic olefin ring-opening polymer for molding materials of the present invention, it is preferable to add a terminal olefin compound as a molecular weight regulator together with the ring-opening polymerization catalyst. Examples of the terminal olefin compound include α-olefins such as ethylene, 1-propene, 1-butene, 1-hexene, 1-pentene, 1-hexene and 1-heptene, vinyl ether, thiovinyl ether, vinyl acetate and the like.
The addition amount of the terminal olefin compound is 5 mol% or less with respect to all the monomers to be blended.
The organic solvent for the ring-opening polymerization reaction is preferably an aliphatic hydrocarbon such as n-pentane, hexane or heptane; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or decalin; an aromatic hydrocarbon such as benzene or toluene; Or these halides (chloroform, dichloroethane, etc.).

Ring-opening polymerization can be carried out according to a conventional method. That is, it can be carried out by so-called batch polymerization or continuous polymerization.
An example of a specific method of ring-opening copolymerization will be described. Under a nitrogen or argon atmosphere, an organic solvent and a cyclic olefin system represented by the formula (1 ′) which is an essential monomer are contained in a reaction vessel. The monomer component and the cyclic olefin monomer represented by the formula (2 ′) which is an arbitrary monomer and / or the formula (3 ′) or the formula (3 ″) which is an arbitrary monomer And a molecular weight regulator used as necessary, and the polymerization system is set to a temperature in the range of -20 ° C to 100 ° C. Next, a polymerization catalyst is added to this polymerization system, and polymerization is carried out in the range of -20 ° C to 120 ° C. The addition amount of the polymerization catalyst is preferably such that the monomer component is 100 to 100,000 mol per gram atom of the transition metal atom in the polymerization catalyst. The polymerization method may be a batch method or a continuous method. In addition, the cyclic olefin monomer component and any of the molecular weight regulators used as needed are supplied to the reaction vessel to start the polymerization, and during the polymerization process, other monomers are put into the reaction vessel. By supplying stepwise or continuously, it is possible to obtain a cyclic olefin-based ring-opening copolymer in which the proportion of each structural unit is changed in a gradient or each structural unit is unevenly distributed in a block shape. .

  In order to obtain a resin having a molecular weight distribution of 2.4 or less, the smaller the amount of the molecular weight regulator, the better. The active species of the polymerization catalyst is greatly different in reactivity to the cyclic olefin monomer component and reactivity to the molecular weight regulator. Since the reactivity to the cyclic olefin monomer is relatively high, the ratio of the cyclic olefin monomer to the molecular weight regulator is greatly changed between the end of polymerization and the initial stage of polymerization. In order to reduce this difference in the ratio, the smaller the amount of molecular weight regulator used, the better. Further, by performing continuous polymerization, the amount of the molecular weight regulator can be further reduced, and a resin having a narrower molecular weight distribution can be obtained.

The cyclic olefin-based ring-opening polymer for molding material of the present invention is preferably hydrogenated in the presence of a hydrogenation catalyst.
The hydrogenation rate of the olefinically unsaturated bond is usually 80 mol% or more, preferably 90 mol% or more, and more preferably 95 mol% or more. The hydrogenation reaction in the present invention is as described above for olefinic unsaturated bonds in the molecule, and when the cyclic olefin ring-opening polymer of the present invention has an aromatic group, the aromatic group May have an advantageous effect on optical properties such as refractive index and heat resistance, and thus does not necessarily need to be hydrogenated.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, Examples 1-4, 6, and 11 are reference examples. In the following, parts or% are based on weight unless otherwise specified.

Various physical properties were measured or evaluated as follows.
Glass transition temperature (Tg):
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature increase rate was measured at 20 ° C. per minute under a nitrogen stream. Tg is the tangent on the baseline starting from point B, with the differential peak scanning calorie maximum peak temperature (point A) and the temperature at −20 ° C. from the maximum peak temperature (point B) plotted on the differential scanning calorimetry curve. And the intersection of the tangent starting from point A.

測定された複素粘性率から、数式（III）で表されるＣｏｘ−Ｍｅｒｚ経験式に従い、ずり粘度を計算した。

次に、各温度で求めたずり粘度のデータから、温度時間換算則に従い２５０℃でのマスターカーブを作成し、ＷＬＦ式により、Ｔｇ＋１２０℃での粘度を算出した（高分子刊行会 日本レオロジー学会編 講座・レオロジー）。
Ｔｇ＋１２０℃での粘度から、数式（IV）で表されるＣｒｏｓｓ式を用いてフィッティングし、ずり速度１（ｓ^-1）およびずり速度１００（ｓ^-1）での粘度を算出した。

Measurement of melt viscosity dependence on shear rate:
A 1 mm thick plate was produced from the synthesized polymer using a vacuum press. The production conditions were a press at 30 MPa for 15 minutes under a temperature of + 120 ° C. higher than Tg under vacuum. A circular sample having a diameter of 20 mm was cut out from the obtained 1 mm plate with a nipper and used for evaluation.
The dynamic viscoelasticity measurement was performed using MR-500 manufactured by UBM Co., Ltd. The cone plate used was 20 mmφ2 °. Measurement temperature is 210 degreeC, 230 degreeC, 250 degreeC, 270 degreeC, 290 degreeC. The measurement of the complex viscosity was performed with the measurement mode being dynamic, frequency dispersion (18-0.01 Hz), and the strain being 0.3 deg.
At each temperature, the complex viscosity expressed by the formula (II) is obtained.

The shear viscosity was calculated from the measured complex viscosity according to the Cox-Merz empirical formula represented by Formula (III).

Next, from the shear viscosity data obtained at each temperature, a master curve at 250 ° C. was created according to the temperature time conversion rule, and the viscosity at Tg + 120 ° C. was calculated by the WLF equation (Polymer Publishing Society, Japan Society of Rheology) (Course / Rheology).
From the viscosity at Tg + 120 ° C., fitting was performed using the Cross equation represented by Formula (IV), and the viscosity at a shear rate of 1 (s ⁻¹ ) and a shear rate of 100 (s ⁻¹ ) was calculated.

Weight average molecular weight:
Using a HLC-8020 GPC apparatus manufactured by Tosoh Corporation, polystyrene-converted weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured with a tetrahydrofuran (THF) solvent. Mn represents a number average molecular weight. Moreover, the sample insoluble in THF solvent measured the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polystyrene conversion with the tetrahydrofuran (THF) solvent using the HLC-8020 GPC apparatus by Tosoh Corporation. Mn represents a number average molecular weight.
Gel-like defects in the film:
Point defects were identified by 1 m ² reflection inspection, and the number of gels of 200 μm or more was detected. A three-wavelength fluorescent lamp was used as the light source, and defects were determined visually.

Example 1
Under a nitrogen atmosphere, 25.0 kg of DNM was used as a monomer in a 100 L reactor, 151 g of 1-butene as a molecular weight regulator and 37.5 kg of toluene were charged and heated to 100 ° C. Methanol-modified aluminum (methanol (represented by MeOH in Table 1) 0.069 g and triethylaluminum (represented by Et ₃ Al in Table 1) 1.23 g) was added to the heated solution. Further, 2.13 g of tungsten hexachloride (represented by WCl ₆ in Table 1) was added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
An additional 200 parts of toluene was added to a toluene solution containing 100 parts by weight of the obtained polymer. Next, 1 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX1076) as a reaction modifier and RuHCl (CO) [P (C ₆ H ₅ )] After 0.06 part of ₃ was added and heated to 155 ° C., hydrogen gas was charged into the reactor, and the pressure was adjusted to 10 MPa. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa. After completion of the reaction, 100 parts by weight of toluene, 3 parts by weight of distilled water, 0.72 parts by weight of lactic acid and 0.00214 parts by weight of hydrogen peroxide were added and heated at 60 ° C. for 30 minutes. Thereafter, 200 parts by weight of methanol was added and heated at 60 ° C. for 30 minutes. When this was cooled to 25 ° C., it was separated into two layers. After removing 500 parts by weight of the supernatant, 350 parts by weight of toluene and 3 parts by weight of water were added again and heated at 60 ° C. for 30 minutes, and then 240 parts by weight of methanol was added and heated at 60 ° C. for 30 minutes and cooled to 25 ° C. After removing 500 parts by weight of the supernatant separated into two layers, 350 parts by weight of toluene and 3 parts by weight of water were added and heated at 60 ° C. for 30 minutes, then 240 parts by weight of methanol was added and heated at 60 ° C. for 30 minutes for 25 minutes. Cooled to 0 ° C. and separated into two layers. Finally, after removing 500 parts by weight of the supernatant, the remaining polymer solution was filtered at a temperature of 50 ° C. with 2.0 μm, 1.0 μm and 0.2 μm filters connected in series. Thereafter, the polymer solution was concentrated to a solid content concentration of 55%, subjected to desolvation treatment at 250 ° C., 4 torr, and a residence time of 1 hour, and passed through a 10 μm polymer filter to obtain a polymer (1). The polymer solution before the solvent removal treatment was continuously filtered and the change in filtration rate with time was followed. As a result, the filter was not clogged even after 1000 hours, and the filtration rate did not decrease.
The physical property evaluation results of the obtained polymer are shown in Table 1. Moreover, the obtained polymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.
In Table 1, “Batch” as the polymerization condition is a method for charging monomers simultaneously, and “Increment” is a method for continuously charging monomers.

Example 2
Under a nitrogen atmosphere, DNM 2.5 kg was used as a monomer in a 100-L reactor, 90.6 g of 1-butene as a molecular weight regulator, and 37.5 kg of toluene were charged and heated to 100 ° C. Methanol-modified aluminum (0.138 g of methanol and 2.46 g of triethylaluminum was reacted) was added to the heated solution, and 8.53 g of tungsten hexachloride was further added to initiate the polymerization reaction. One minute after the start of polymerization, 22.5 kg of DNM was added dropwise to the reaction solution over 20 minutes while maintaining the internal temperature at 40 ° C. After completion of the dropwise addition of DNM, a polymerization reaction was carried out for 30 minutes.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained polymer are shown in Table 1. The obtained polymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 3
Under a nitrogen atmosphere, 25.0 kg of DNM was used as a monomer in a 100 L reactor, 151 g of a molecular weight regulator, 37.5 kg of toluene, and 37.5 kg of toluene were charged and heated to 100 ° C. 0.069 g of methanol was added to the heated solution, and 1.97 g of triisobutylaluminum was further added. Thereafter, 2.13 g of tungsten hexachloride was added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained polymer are shown in Table 1. The obtained polymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 4
Under a nitrogen atmosphere, 25.0 kg of DNM was used as a monomer in a 100 L reactor, 151 g of a molecular weight regulator, 37.5 kg of toluene, and 37.5 kg of toluene were charged and heated to 100 ° C. Ether-modified aluminum (0.535 g of dihexyl ether and 2.63 g of triisobutylaluminum) was added to the heated solution, and 2.84 g of tungsten hexachloride was further added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained polymer are shown in Table 1. The obtained polymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 5
Under a nitrogen atmosphere, 22.5 kg of DNM, 2.50 kg of NB, 173 g of a molecular weight regulator, 173 g and 37.5 kg of toluene were charged in a 100 L reactor and heated to 100 ° C. Methanol-modified aluminum (0.079 g of methanol and 2.26 g of triisobutylaluminum was reacted) was added to the heated solution, and 2.45 g of tungsten hexachloride was further added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
In addition, the monomer seed | species shown in Table 1 is the kind of monomer mix | blended, and its weight ratio.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 6
Under a nitrogen atmosphere, a 100-L reactor was charged with 22.5 kg of DNM, 2.50 kg of NB, 162 g of a molecular weight regulator, 37.5 kg of toluene, and heated to 100 ° C. Methanol-modified aluminum (0.074 g of methanol and 2.30 g of triisobutylaluminum) was added to the heated solution, and 2.45 g of tungsten hexachloride was further added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 7
Under a nitrogen atmosphere, 17.8 kg of DNM, 6.25 kg of DCP, 1.00 kg of NB, 1-butene as a molecular weight regulator, 188 g, and 37.5 kg of toluene were charged into a 100 L reactor and heated to 100 ° C. Methanol-modified aluminum (0.086 g of methanol and 2.46 g of triisobutylaluminum) was added to the heated solution, and 2.66 g of tungsten hexachloride was further added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 8
In a 100 L reactor under a nitrogen atmosphere, 16.8 kg (72.1 mol) of DNM, 6.25 kg (47.3 mol) of DCP, 2.00 kg (21.24 mol) of NB, and 197 g (3 of molecular weight regulator) .51 mmol), and 37.5 kg of toluene were charged and heated to 100 ° C. Methanol-modified aluminum (0.090 g (2.81 mmol) of methanol and 2.58 g (14.1 mmol) of methanol) was added to the heated solution, and 2.79 g (7 of tungsten hexachloride) was added. 0.03 mmol) was added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 9
Under a nitrogen atmosphere, a 100 L reactor was charged with 1.68 kg of DNM, 0.625 kg of DCP, 0.20 kg of NB, 1-butene as a molecular weight regulator, 118 g of 37.5 kg of toluene, and heated to 100 ° C. Methanol-modified aluminum (a mixture of 0.180 g of methanol and 5.16 g of triisobutylaluminum) was added to the heated solution, and 11.2 g of tungsten hexachloride was further added to initiate the polymerization reaction. One minute after the initiation of polymerization, 15.1 kg (64.9 mol) of DNM, 5.63 kg (42.5 mol) of DCP, and 1.80 kg (19.1 mol) of NB were added dropwise to the reaction solution over 20 minutes. After completion of the dropping, a polymerization reaction was carried out for 30 minutes.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 10
Under a nitrogen atmosphere, a 100 L reactor was charged with 1.9 kg of DNM, 0.50 kg of DCP, 0.10 kg of NB, 110 g of a molecular weight regulator, 37.5 kg of toluene, and heated to 100 ° C. Methanol-modified aluminum (0.167 g of methanol and 4.77 g of triisobutylaluminum was reacted) was added to the heated solution, and 10.3 g of tungsten hexachloride was further added to initiate the polymerization reaction. One minute after the start of polymerization, 17.1 kg of DNM, 4.50 kg of DCP, and 0.9 kg of NB were added dropwise to the reaction solution over 20 minutes. After completion of the dropping, a polymerization reaction was carried out for 30 minutes.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 11
Under a nitrogen atmosphere, 25.0 kg of DNM was used as a monomer in a 100 L reactor, 90.6 g of 1-butene as a molecular weight regulator and 37.5 kg of toluene were charged and heated to 100 ° C. 1.83 g of benzylidene (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (tricyclohexylphosphine) ruthenium (Grubbs 2nd generation catalyst) was added to the heated solution, and polymerization was performed. The reaction was started. The polymerization reaction was carried out for 30 minutes after adding the Grubbs 2nd generation catalyst.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained polymer are shown in Table 1. The obtained polymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Example 12
Under a nitrogen atmosphere, 16.8 kg of DNM, 6.25 kg of DCP, 2.00 kg of NB, 118 g of a molecular weight regulator, 37.5 kg of toluene were charged in a 100 L reactor and heated to 100 ° C. 2.39 g of benzylidene (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (tricyclohexylphosphine) ruthenium (Grubbs 2nd generation catalyst) was added to the heated solution and polymerized. The reaction was started. The polymerization reaction was carried out for 30 minutes after adding the Grubbs 2nd generation catalyst.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Comparative Example 1
Under a nitrogen atmosphere, 17.8 kg of DNM, 6.25 kg of DCP, 1.00 kg of NB, 1356 g of a molecular weight regulator, 1356 g of toluene and 37.5 kg of toluene were charged into a 100 L reactor and heated to 100 ° C. A solution obtained by reacting 10.7 g of triethylaluminum was added to the heated solution, and further modified tungsten hexachloride (2.66 g of tungsten hexachloride) was added to initiate a polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of the modified tungsten hexachloride.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

Comparative Example 2
In a 100 L reactor under a nitrogen atmosphere, DCP 2.50 kg, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 )] Dodec-4-ene (DMON) 22.5 kg, 223 g of a molecular weight regulator 1-butene, and 37.5 kg of toluene were charged and heated to 100 ° C. 0.102 g of methanol was added to the heated solution, and 2.92 g of triisobutylaluminum was further added. Thereafter, 3.16 g of tungsten hexachloride was added to initiate the polymerization reaction. A polymerization reaction was carried out for 30 minutes after the addition of tungsten hexachloride.
Subsequent hydrogenation, decatalysis, filtration, and finishing steps were carried out in the same manner as in the method described in Example 1, and no problems in the process occurred. The physical property evaluation results of the obtained copolymer are shown in Table 1. The obtained copolymer was formed into a film by melt extrusion to obtain an extruded film having a thickness of 130 μm.

  As shown in Table 1, the resins described in Examples 1 to 12 have a characteristic that the number of gel defects during film formation is remarkably small as compared with Comparative Example 1 which is a sample having a wide molecular weight distribution. Moreover, it became clear that there are few gel defects at the time of film forming compared with the comparative example 2 which does not have a polar group in a structural unit. Further, these resins having a narrow molecular weight distribution are less dependent on the shear rate of the melt viscosity. Therefore, it is thought that the gel defect at the time of film formation decreased.

  The cyclic olefin-based ring-opening polymer for molding materials of the present invention is excellent in heat resistance and can be suitably used in general optical applications as a resin having few defects during molding processing, and particularly suitably used in optical film applications. be able to.

Claims (7)

The molecular weight distribution Mw / Mn in terms of polystyrene measured by gel permeation chromatography is 2.5 or less, including the structural unit represented by the following structural formula (1) and the structural unit represented by the following structural formula (2). A cyclic olefin-based ring-opening polymer for molding materials, wherein the melt viscosity ratio represented by the following formula (I) is 0.40 or more.

In (Formula (1), m is 0, 1 or 2, X is -CH = CH- and -CH ₂ CH ₂ independently - at least one divalent group selected from, R ¹ ~ R ⁴ each independently represents a hydrogen atom or a halogen atom, or may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, or a substituted or unsubstituted carbon atom having 1 to 10 carbon atoms. Or a polar group, provided that at least one of R ^{1 to} R ⁴ is a polar group, and at least one of the other R ^{1 to} R ⁴ is a carbon atom having 1 to 10 carbon atoms. It is a hydrogen group.)

(In the structural formula (2), n is 0, 1 or 2, X is -CH = CH- and -CH ₂ CH ₂ independently - at least one divalent group selected from, R ¹¹ ~ R ¹⁴ each independently represents a hydrogen atom or a halogen atom, or may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. Represents a hydrocarbon group of

(In Formula (I), Η is the melt viscosity ratio, P1 is the melt viscosity (Pa · s) when the shear rate is 1 (s ⁻¹ ), and P2 is the shear rate is 100 (s ⁻¹ ). Representing melt viscosity (Pa · s) at a certain time, the measurement temperature of the shear rate is the glass transition temperature of the cyclic olefin-based ring-opening polymer for molding material measured by a scanning differential calorimeter + 120 ° C.) Following structural formula (3), characterized in that it comprises a structural unit represented by claim 1 Symbol mounting molding material for the cyclic olefin ring-opening polymer of.

(In the structural formula (3), X is -CH = CH- and -CH ₂ CH ₂ independently - at least one divalent group selected from, R ⁵ to R ¹⁰ are independently a hydrogen atom Or a halogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, or polar Represents a group.) Ratio of the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography over 300,000 of the polymer relative to the amount of total polymer, according to claim 1 or claim, wherein more than 5% by weight Item 3. A cyclic olefin-based ring-opening polymer for a molding material according to Item 2 . The ratio of a polymer having a polystyrene-reduced weight average molecular weight of 2000 or less measured by gel permeation chromatography is 10% by weight or less based on the total amount of the polymer. molding material for the cyclic olefin ring-opening polymer according to any one of 3. A film obtained by molding a polymer by melt extrusion molding or a solvent casting method, wherein the polymer is a cyclic olefin ring-opening polymer for molding materials according to any one of claims 1 to 4. A film characterized by being. Monomer (A) containing the monomer that generates the structural unit represented by the structural formula (1) and the monomer that generates the structural unit represented by the structural formula (2 ), or the structure A monomer that generates a structural unit represented by formula (1), a monomer that generates a structural unit represented by structural formula (2), and a structural unit represented by structural formula (3). The cyclic olefin ring-opening for molding materials according to any one of claims 1 to 4 , wherein the monomer (B) containing the monomer to be formed is subjected to ring-opening polymerization with a ring-opening polymerization catalyst in an organic solvent. In the method for producing a polymer,
The manufacturing method of the cyclic olefin type ring-opening polymer for molding materials characterized by mix | blending 5 mol% or less of terminal olefin compounds with respect to all the monomers mix | blended with the said ring-opening polymerization catalyst. The method for producing a cyclic olefin-based ring-opening polymer for molding materials according to claim 6 , wherein a hydrogenation reaction is performed on the polymer obtained by the ring-opening polymerization.

Images