JP2008231318A - Resin composition, optical film, retardation film, and liquid crystal display device - Google Patents

Abstract

A resin composition having excellent transparency, heat resistance, solubility in an organic solvent, strength, and processability, and capable of arbitrarily adjusting optical properties of the film in a wide wavelength range, and a film obtained therefrom As well as its uses.
A norbornene polymer (A) having a structural unit (a) derived from a cyclic olefin monomer having a norbornene skeleton and an aromatic ring structure, and norbornene having a polar group and no aromatic ring structure A resin composition comprising a norbornene polymer (B) having a structural unit (b) derived from a cyclic olefin monomer having a skeleton and not having the structural unit (a).
[Selection figure] None

Description

  The present invention relates to a norbornene resin composition, an optical film using the composition, a retardation plate, and a liquid crystal display device. Specifically, the present invention relates to a norbornene-based resin composition that is excellent in transparency, heat resistance, solubility in an organic solvent, strength, and processability, and exhibits specific birefringence and wavelength dependency when a stretched film is produced.

  Since the cyclic olefin resin generally has a relatively small birefringence, its use for a polarizing plate protective film, a liquid crystal substrate material, an optical disk, various optical lenses, an optical fiber and the like has been studied recently. In addition, since the cyclic olefin resin exhibits appropriate birefringence by controlling the processing conditions, an optical compensation film actively utilizing this is actually used. For example, Patent Documents 1 to 4 describe retardation plates using a cyclic olefin-based resin film. Patent Documents 5 to 7 describe the use of a cyclic olefin resin film as a protective film for a polarizing plate. Furthermore, Patent Document 8 describes a liquid crystal display element substrate made of a film of a cyclic olefin resin.

  In general, a retardation film is given a function of imparting a retardation (birefringence) to transmitted light by stretching orientation. However, in many resin films, the level of transmitted light increases as the wavelength of transmitted light becomes longer. Since the absolute value of the phase difference (birefringence) tends to be small, it is very difficult to give the transmitted light a specific phase difference such as 1 / 4λ in the entire visible light region (400 to 800 nm). .

  However, at present, in applications such as reflective and transflective liquid crystal displays and optical disk pickups, a phase difference of ¼λ is actually obtained in a wide wavelength region such as the entire visible light region (400 to 800 nm). In addition, a phase difference of ½λ is required for applications such as liquid crystal projectors. In addition to this, in response to various demands, development of resins having various optical characteristics such as positive / negative of birefringence value, magnitude of absolute value thereof, magnitude of wavelength dependence of phase difference is desired. .

  For this reason, the conventional optical film made of a cyclic olefin resin cannot meet the above-mentioned high demand, and in order to achieve such optical characteristics, a plurality of films are laminated or various kinds of optical characteristics are improved for improving the optical characteristics. A coating agent is applied, or a plurality of stretched films are bonded together with orientation directions to obtain desired optical characteristics. However, the optical film obtained by such a method has problems such as high cost, low yield, and difficulty in reducing the film thickness because of complicated manufacturing processes such as cutting, film bonding, and adhesion.

Under such circumstances, the realization of a single-layer optical film having a desired retardation in a wide wavelength region is desired, and the appearance of a resin capable of producing such an optical film is strongly demanded. . Patent Document 9 shows that a film made of a specific norbornene-based ring-opening copolymer is excellent in controllability of birefringence and wavelength dispersion, but the polymer has a glass transition temperature higher than necessary, There was a problem that strength and workability were low.
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 JP 2005-36201 A

  The present invention provides a resin composition excellent in transparency, heat resistance, solubility in organic solvents, strength, and processability, and capable of arbitrarily adjusting the optical properties of the film in a wide wavelength range, and obtained therefrom. It is an object to provide a film and its use.

As a result of intensive studies on the above problems, the present inventors have found that a resin composition containing a specific norbornene-based polymer can achieve the object of the present invention.
That is, the resin composition of the present invention has a norbornene polymer (A) having a structural unit (a) derived from a cyclic olefin monomer (A) having a norbornene skeleton and an aromatic ring structure, and a polar group. A norbornene polymer (B) having a structural unit (b) derived from a cyclic olefin monomer (B) having a norbornene skeleton having no aromatic ring structure, and having no structural unit (a); It is characterized by containing.

  The norbornene polymer (A) preferably has a structural unit represented by the following formula (1).

（式（１）中、ａは０または１を表し、Ｒは、それぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜３０の炭化水素基；または極性基を表す。Ｘは−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−を表す。複数存在するＸは同一でも異なっていてもよい。）
前記ノルボルネン系重合体（Ｂ）は、下記式（２）で表される構造単位を有することが好ましい。

(In formula (1), a represents 0 or 1, and each R may independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, X represents —CH═CH— or —CH ₂ CH ₂ —, and a plurality of X may be the same or different. Good.)
The norbornene polymer (B) preferably has a structural unit represented by the following formula (2).

（式（２）中、ａは０または１を表し、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜３０の炭化水素基；または極性基を表す。ただし、Ｒ¹〜Ｒ⁴の少なくとも１つは極性基である。Ｘは独立に、−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−を表す。複数存在するＸは同一でも異なっていてもよい。）
また、本発明の樹脂組成物は、該樹脂組成物全量中にノルボルネン系重合体（Ａ）を７０重量％以上、１００重量％未満含有することが好ましい。

(In the formula (2), a represents 0 or 1, and R ^{1 to} R ⁴ each independently have a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, wherein at least one of R ^{1 to} R ⁴ is a polar group, X is independently —CH ═CH— or —CH ₂ CH ₂ —, wherein a plurality of X may be the same or different.
Moreover, it is preferable that the resin composition of this invention contains a norbornene-type polymer (A) 70weight% or more and less than 100 weight% in this resin composition whole quantity.

The film of the present invention is formed from the resin composition.
The retardation film of the present invention is formed from the resin composition.
The liquid crystal display device of the present invention is manufactured using the film.

  The liquid crystal display device of the present invention is produced using the retardation film.

  The present invention is a resin composition having excellent transparency, heat resistance, solubility in an organic solvent, strength and processability, and having specific birefringence and wavelength dependency, an optical film using the composition, and a retardation Board can be provided.

Hereinafter, the present invention will be specifically described.
In the present specification, the term birefringence is used in the ordinary sense. Further, the value of birefringence (this is referred to as Δn) is a stretched film in which a film formed from a polymer is uniaxially or biaxially stretched and the polymer molecular chains are oriented in one direction. x-axis larger direction) of the draw ratio in biaxial stretching, the in-plane direction perpendicular to the y-axis, the refractive index of the x-axis direction n _x, the refractive index of the Y-axis direction as n _y contrast, the following formula:
Δn = n _x -n _y
The absolute value is different depending on the wavelength of incident light.

And positive (or negative) birefringence means the property of the stretched film when Δn is positive (or negative).
Next, the retardation (hereinafter referred to as “Re”) is the following formula:
Re = Δn × d
(In the formula, d is the optical path length (nm) of transmitted light, and is usually the thickness of the stretched film.)
The absolute value varies depending on the wavelength of incident light. Further, “the phase difference is ¼λ” means that a phase difference corresponding to ¼ of the incident light wavelength (λ) is developed.

And the wavelength dependence of the phase difference means the correlation between the value of Re and the wavelength of incident light,
“The phase dependence of the phase difference is large” means that the difference between the absolute value of Re for short-wavelength incident light and the absolute value of Re for long-wavelength incident light is large. “Normal wavelength dispersion” means the characteristic that the phase difference decreases as the incident light wavelength becomes longer, and “Reverse wavelength dispersion” means that the incident light wavelength becomes longer. This means the characteristic that the phase difference becomes large.

<Resin composition>
The resin composition of the present invention includes a norbornene polymer (A) having a structural unit (a) derived from a cyclic olefin monomer (A) having a norbornene skeleton and an aromatic ring structure, a polar group and an aromatic Containing a norbornene polymer (B) having a structural unit (b) derived from a cyclic olefin monomer (B) having a norbornene skeleton having no ring structure and having no structural unit (a) is doing. The resin composition of the present invention contains a norbornene polymer (A) of 70% by weight or more and less than 100% by weight, preferably 90% by weight or more and less than 100% by weight.

[Norbornene polymer (A)]
Cyclic olefin monomer (A)
The cyclic olefin monomer (A) is a compound having a norbornene skeleton and an aromatic ring structure. The cyclic olefin monomer (A) may have only one aromatic ring structure in the molecule, or may have two or more. In the present invention, a cyclic olefin monomer having one or two aromatic ring structures in the molecule is preferably used.

  As the cyclic olefin monomer (A), for example, one or more selected from the group consisting of compounds represented by the following formulas (1-1) to (1-4) are used.

（式（１−１）〜（１−４）中、ａは０または１を表し、ｂは０から４の整数を表し、ｃは０から６の整数を表し、複数存在するＲは、それぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜３０の炭化水素基；または極性基を表す。）
ここで、前記式（１−１）〜（１−４）中のＲについて説明する。

(In the formulas (1-1) to (1-4), a represents 0 or 1, b represents an integer of 0 to 4, c represents an integer of 0 to 6, and a plurality of R's each represent Independently, a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; or a polar group Represents.)
Here, R in the formulas (1-1) to (1-4) will be described.

As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.
Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; Groups, alkylidene groups such as propylidene groups; aromatic groups such as phenyl groups, naphthyl groups, anthracenyl groups, and the like. A hydrogen atom bonded to a carbon atom in these groups may be substituted with, for example, a halogen atom such as fluorine, chlorine or bromine, a phenylsulfonyl group, a cyano group or the like.

The substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. 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 ) _m — (wherein m is an integer of 1 to 10)); A linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom (for example, a carbonyl group (—CO—), a carbonyloxy group (—COO—), a sulfonyl group (—SO ₂ —), a sulfonyloxy group (—SO ₂ ). ₂ -O-), an ether bond (-O-), thioether bond (-S-), an imino group (-NH-), amide bond (-NHCO-), siloxane bond (-Si (R) ₂ O-) (Wherein, R is an alkyl group such as a methyl group or an ethyl group); or a combination of two or more of these groups.

Examples of polar groups include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, alkylcarbonyloxy groups, arylcarbonyloxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, cyano groups, nitro groups, amide groups, imino groups ( ═NH), triorganosiloxy group, triorganosilyl group, amino group, acyl group, alkoxysilyl group, sulfino group (—SO ₂ H), carboxyl group and the like.

  More specifically, examples of the alkoxy group include methoxy group and ethoxy group; examples of the alkylcarbonyloxy group include acetoxy group and propionyloxy group; and examples of the arylcarbonyloxy group include 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, and a fullyl group. Examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethylsilyl group. Examples of the amino group, for example, primary amino group or the like; group, triethylsilyl group, etc. Examples of the alkoxysilyl group, for example, trimethoxysilyl groups, triethoxysilyl group, and the like.

In the compounds represented by the formulas (1-1) to (1-4), R is preferably a hydrogen atom, a halogen atom, a methoxy group, an ethoxy group, or a phenoxy group.
Preferable specific examples of the compound represented by the formula (1-1) include the following.

前記式（１−２）で表される化合物の好ましい具体例としては、例えば以下のものが挙げられる。

Preferable specific examples of the compound represented by the formula (1-2) include the following.

前記式（１−３）で表される化合物の好ましい具体例としては、例えば以下のものが挙げられる。

Preferable specific examples of the compound represented by the formula (1-3) include the following.

前記式（１−４）で表される化合物の好ましい具体例としては、例えば以下のものが挙げられる。

Preferable specific examples of the compound represented by the formula (1-4) include, for example, the following.

本発明では、これらの環状オレフィン系モノマー（Ａ）のうち、好ましくは、前記式（
１−１）〜（１−４）で表される化合物よりなる群から選ばれる一種以上が用いられ、より好ましくは、前記式（１−１）で表される化合物よりなる群から選ばれる一種以上が用いられる。

In the present invention, among these cyclic olefin monomers (A), preferably the above formula (
One or more selected from the group consisting of compounds represented by 1-1) to (1-4) is used, more preferably one selected from the group consisting of compounds represented by the formula (1-1). The above is used.

In the present invention, the cyclic olefin-based monomer (A) may be used singly or in combination of two or more, but is more preferably used singly.
Other copolymerizable monomers The norbornene polymer (A) used in the present invention may be a (co) polymer obtained by polymerizing only one or more of the above-mentioned cyclic olefin monomers (A). However, it may be a copolymer obtained by copolymerizing a cyclic olefin monomer (A) and a copolymerizable monomer other than the cyclic olefin monomer (A) as necessary. By using another copolymerizable monomer, the glass transition temperature of the cyclic olefin copolymer can be controlled. Examples of other copolymer monomers include cyclic olefins such as cyclobutene, cyclopentene, cyclooctene, and cyclododecene; and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene. The copolymerizable monomers can be used singly or in combination of two or more.
Norbornene polymer (A)
The norbornene polymer (A) used in the present invention is a ring-opening (co) polymerization or addition (co) polymerization of the above-mentioned cyclic olefin monomer (A) and, if necessary, other copolymerizable monomers. And it can manufacture by hydrogenating as needed, and all of these can be used.

  As the norbornene polymer (A) used in the invention, the cyclic olefin monomer (A) is subjected to ring-opening polymerization alone or ring-opening copolymerization with other copolymerizable monomers, and hydrogenated as desired. The (co) polymer produced by this is preferably used. In the present invention, a polymer having a structural unit represented by the following general formula (1) is particularly preferably used.

（式（１）中、ａは０または１を表し、Ｒは、それぞれ独立に、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜３０の炭化水素基；または極性基を表す。Ｘは−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−を表す。複数存在するＸは同一でも異なっていてもよい。）
本発明で用いられるノルボルネン系重合体（Ａ）は、全構造単位１００モル％中、構造単位（ａ）を１０〜５０ｍｏｌ％の範囲で含んでいることが好ましく、構造単位（ａ）を２０〜３５ｍｏｌ％の範囲で含んでいることがさらに好ましい。

(In formula (1), a represents 0 or 1, and each R may independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, X represents —CH═CH— or —CH ₂ CH ₂ —, and a plurality of X may be the same or different. Good.)
The norbornene polymer (A) used in the present invention preferably contains 10 to 50 mol% of the structural unit (a) in 100 mol% of all structural units, and 20 to 20 of the structural unit (a). More preferably, it is contained in the range of 35 mol%.

The norbornene polymer (A) used in the present invention has an extrapolated glass transition start temperature measured according to Japanese Industrial Standard K7121, preferably 155 to 200 ° C., more preferably 16
A temperature of 0 to 190 ° C., more preferably 165 to 180 ° C., is desirable because it has sufficient heat resistance and excellent moldability that enables melt molding such as extrusion molding.

Further, the norbornene-based polymer (A) used in the present invention has a logarithmic viscosity measured in a chloroform at a sample concentration of 0.5 g / dl and a temperature of 30 ° C. using an Ubbelohde viscometer, preferably 0.2. -5 dl / g, more preferably 0.3 to 3 dl / g, still more preferably 0.4 to 0.8 dl / g. Moreover, in the measurement of the average molecular weight by gel permeation chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion value), the number average molecular weight (Mn) of the norbornene polymer (A) is usually 1,000 to 500,000. The weight average molecular weight (Mw) is usually 5,000 to 2,000,000, preferably 10,000 to 2,000 to 300,000, more preferably 5,000 to 300,000. It is desirable that it is 1,000,000, more preferably 30,000 to 500,000.

In the present invention, the logarithmic viscosity (ηinh) is less than 0.2, the number average molecular weight (Mn) is less than 1,000, or the weight average molecular weight (Mw) is less than 5,000. The strength of the molded product obtained from the norbornene polymer (A) used may be significantly reduced. On the other hand, the logarithmic viscosity (ηinh) is 5 dl / g or more, the number average molecular weight (Mn) is 500,000 or more, or the weight average molecular weight (Mw) is 2,000,000 or more. The melt viscosity or solution viscosity of the norbornene polymer (A) may become too high, making it difficult to obtain a desired molded product.

[Norbornene polymer (B)]
Cyclic olefin monomer (B)
The cyclic olefin monomer (B) is not particularly limited as long as it is a compound having a norbornene skeleton having a polar group and no aromatic ring structure, and is represented by the following formula (2-1). It is a compound.

（式（２−１）中、Ｒ¹〜Ｒ⁶は、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜３０の炭化水素基；または極性基を表す。ただし、Ｒ¹〜Ｒ⁶の少なくとも１つが極性基（またはハロゲン原子）である。また、Ｒ³〜Ｒ⁶ のうち任意の２つが互いに結合して、
芳香環以外の環を形成してもよい。ｍは０または正の整数であり、ｐは０または正の整数である。）
式（２−１）において、ｐ＝０、ｍが０または１であり、Ｒ⁵およびＲ⁶が水素原子である場合が好ましい。

(In formula (2-1), R ^{1 to} R ⁶ are a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A hydrocarbon group having 1 to 30 atoms; or a polar group, provided that at least one of R ^{1 to} R ⁶ is a polar group (or a halogen atom), and any two of R ^{3 to} R ⁶ are Combined with each other,
Rings other than aromatic rings may be formed. m is 0 or a positive integer, and p is 0 or a positive integer. )
In formula (2-1), it is preferable that p = 0, m is 0 or 1, and R ⁵ and R ⁶ are hydrogen atoms.

As the polar group, like the polar groups described in formulas (1-1) to (1-4), a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylcarbonyloxy group, an arylcarbonyloxy group, and an alkoxycarbonyl group. , Aryloxycarbonyl group, cyano group, nitro group,
Amide group, an imino group (= NH), triorganosiloxy groups, triorganosilyl groups, amino group, an acyl group, an alkoxysilyl group, a sulfino group (-SO ₂ H), a carboxyl group.

Among the cyclic olefin monomers (B) used in the present invention, any one or more of R ^{3 to} R ⁶ has a polar group represented by the following formula (3), and the glass transition This is preferable in that a resin composition having a high temperature (hereinafter also referred to as “Tg”) and a low hygroscopic property is obtained.

^{_{- (CH 2) n COOR 7}} (3)
(Wherein, R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, n is an integer from 0 to 5.)
In the above formula (3), R ⁷ is preferably an alkyl group.

  Moreover, since the Tg of the obtained resin composition becomes higher as the value of n is smaller, the cyclic olefin monomer (B) in which n is 0 is particularly preferred in terms of easy synthesis.

In the above formula (2-1), R ³ or R ⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 2 carbon atoms. Particularly preferred is a methyl group. Furthermore, it is preferable that this alkyl group is bonded to the same carbon atom as the carbon atom to which the polar group represented by the above formula (3) is bonded.

In addition, the cyclic olefin monomer (B) in which m is 1 in the above formula (2-1) is preferable in that a resin composition having a higher Tg is obtained.
As a specific example of the cyclic olefin monomer (B) represented by the above formula (2m),
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8 methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8-methyl-8-ethoxycarbonyl tetracyclo [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]
-3-dodecene,
8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
-3-dodecene,
8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-
En,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoroisopropyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-fluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene,
8 difluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8 pentafluoroethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-methyl-8-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene,
8,8,9- trifluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9- tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -
3-dodecene,
8,8,9,9- tetrafluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9,9- tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-Difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^{2
, 5.1 7,10} ] -3-dodecene,
8,8,9- trifluoro-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8,8,9- trifluoro-9-pentafluoro propoxy tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8-Chloro -8,9,9- trifluoro tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.
4.0.1, ² , ^5.1,10 ] -3-dodecene.

Among these cyclic olefin monomer (B), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-ethylidene tetracyclo [ 4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene, 8-ethyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene, pentacyclo [7.4.0.1 ^2,5. 1 ^{9,12.0 8,13} ] -3-pentadecene is preferable in that a resin composition having excellent heat resistance can be obtained.

Other copolymerizable monomer / unsaturated double bond-containing compound The norbornene polymer (B) used in the present invention is obtained by polymerizing only one or more cyclic olefin monomers (B). A copolymer may be used, but it may be a copolymer obtained by copolymerizing a cyclic olefin monomer (B) and a copolymerizable monomer other than the cyclic olefin monomer (B) as necessary. As the other copolymer monomer, for example, a cycloolefin having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms is preferably used, and specific examples thereof include cyclobutene, cyclopentene, cycloheptene, cyclooctene, and tricyclo [5. 2.1.0 ^2,6 ] -3-decene, 5-ethylidene-2-norbornene, dicyclopentadiene and the like.

  The use ratio of the cyclic olefin monomer (B) and the unsaturated double bond-containing compound is such that the cyclic olefin monomer (B): copolymerizable cyclic monomer or unsaturated double bond-containing compound is 80 by weight. : It is preferable that it is 20-100: 0, More preferably, it is 89: 11-100: 0.

  When the use ratio of the unsaturated double bond-containing compound is excessive, the Tg of the resulting copolymer is lowered, and as a result, the heat resistance of the resin is lowered, so that a sheet having high heat resistance can be obtained. It becomes difficult.

Norbornene polymer (B)
The norbornene polymer (B) used in the present invention has a structural unit represented by the following general formula, and the cyclic olefin monomer (B) is used alone or in combination of two or more, or the cyclic olefin monomer (B) ) And other copolymerizable monomers, used as a polymerization or copolymerization monomer to hydrogenate double bonds in the main chain after addition (co) polymerization, ring-opening (co) polymerization, or ring-opening (co) polymerization Obtained.

（式中、Ｒ¹〜Ｒ⁶は、水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を含む連結基を有してもよい、置換もしくは非置換の炭素原子数１〜３０の炭化水素基；または極性基を表す。ただし、Ｒ¹〜Ｒ⁶の少なくとも１つが極性基（またはハロゲン原子）である。また、Ｒ³〜Ｒ⁶ のうち任意の２つが互いに結合して、芳香環以外
の環構造を形成してもよい。ｍは０または正の整数であり、ｐは０または正の整数である。Ｘは独立に、−ＣＨ＝ＣＨ−または−ＣＨ₂ＣＨ₂−を表す。複数存在するＸは同一でも異なっていてもよい。）
前記式中において、ｐ＝０、ｍが０または１であり、Ｒ⁵およびＲ⁶は水素原子である場合が好ましい。

(In the formula, R ^{1 to} R ⁶ are each a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, which may have a linking group having 1 to 30 substituted or unsubstituted carbon atoms. Or a polar group, provided that at least one of R ^{1 to} R ⁶ is a polar group (or a halogen atom), and any two of R ^{3 to} R ⁶ are bonded to each other; A ring structure other than an aromatic ring may be formed, m is 0 or a positive integer, p is 0 or a positive integer, X is independently —CH═CH— or —CH ₂ CH ₂ —. A plurality of X may be the same or different.)
In the above formula, it is preferable that p = 0, m is 0 or 1, and R ⁵ and R ⁶ are hydrogen atoms.

  The norbornene-based polymer (B) used in the present invention preferably contains the structural unit (b) in the range of 60 to 100 mol% in 100 mol% of all structural units, and the structural unit (b) is 75 to 75 mol%. More preferably, it is contained in the range of 100 mol%.

The norbornene polymer (B) used in the present invention preferably has an intrinsic viscosity (η _inh ) measured in chloroform at 30 ° C. of 0.2 to 5 dl / g.
The norbornene polymer (B) has an average molecular weight of 8,000 to 100,000 in terms of polystyrene number average molecular weight (Mw) measured by gel permeation chromatography (GPC), and a weight average molecular weight (Mw). ) Is preferably in the range of 20,000 to 300,000.

Furthermore, the extrapolated glass transition start temperature measured according to the Japanese Industrial Standard K7121 for cyclic olefin resins is preferably 130 ° C. or higher.
Moreover, the cyclic olefin resin film used in the present invention may be formed from a resin composition containing the norbornene polymer (B). In addition to the norbornene-based polymer (B), various additives that can be blended in resins such as resin components other than cyclic olefin-based resins, stabilizers and processability improvers can be blended in the resin composition.

[Polymerization method]
The above-described norbornene polymers (A) and (B) can be produced by the following method using the respective monomers described above.

Polymerization method In the present invention, polymerization is started by using a part of the total amount of monomers until the end of the reaction (initial polymerization monomer) and a polymerization catalyst, and the remaining monomer is supplied during the polymerization reaction. I do. In the present invention, the amount of the monomer used as the initial polymerization monomer is preferably at least 5% by weight of the total monomer amount, more preferably 10 to 95% by weight, and further preferably 20 to 90% by weight. When the amount of the initial polymerization monomer is less than 5% by weight, the structure in the polymer is unevenly distributed, so that the effect of the present invention cannot be obtained. The temperature of the monomer solution when starting the initial polymerization is preferably 30 to 200 ° C, more preferably 50 to 180 ° C. When the temperature is lower than 30 ° C, the yield of the polymer may be lowered, and when it exceeds 200 ° C, it may be difficult to control the molecular weight.

  The polymerization reaction in the present invention is an exothermic reaction, and when the polymerization catalyst is added, the temperature of the polymerization solution starts to rise. The remaining monomer is preferably added when the temperature rise of the initial polymerization reaction solution becomes small. Specifically, it is preferable to add the monomer residue at a time of 0.1 to 10 ° C./min, more preferably 0.1 to 7 ° C./min, and further preferably 0.1 to 5 ° C. It is.

  The addition of the remaining monomer may be performed only once, or may be performed sequentially in a plurality of divided portions, and is preferably performed only once when the temperature rise of the initial polymerization reaction solution becomes small. The addition of the remaining monomer is preferably performed by a method that does not cause a sudden change in the monomer concentration, and a method such as dropping is preferably employed.

  In the present invention, it is preferable that the remaining monomer added during the polymerization reaction contains a large amount of highly copolymerizable monomers among the copolymerizable monomer components. In the present invention, the residual monomer is preferably a monomer having a high content of the cyclic olefin monomer (B), and the residual monomer is preferably only the cyclic olefin monomer (B).

Polymerization Catalyst A polymerization catalyst that can be suitably used to produce the norbornene-based polymers (A) and (B) used in the present invention includes a ring-opening polymerization catalyst used when a cyclic olefin such as norbornene is polymerized. Both addition polymerization catalysts can be used.

For example, as a catalyst for ring-opening copolymerization,
(I) A catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) is preferably used. Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V and Ti, and (b) an alkali metal element (for example, Li, Na, K), alkaline earth. Group metal elements (eg, Mg, Ca), Group 12 elements (eg, Zn, Cd, Hg), Group 13 elements (eg, B, Al), Group 14 elements (eg, Si, Sn, Pd) And a metathesis catalyst comprising a combination with at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond. In order to enhance the activity of the catalyst, the additive (c) described later may be added.

Specific examples of the component (a) include, for example, WCl ₆ , MoCl ₅ , ReOCl ₃ , VO.
Examples include compounds described in JP-A-1-240517 such as Cl ₃ and TiCl ₄ . These can be used singly or in combination of two or more.

Specific examples of the component (b) include, for example, n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , ( Examples thereof include compounds described in JP-A-1-240517 such as C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like. These can be used singly or in combination of two or more.

Examples of the additive for the component (c) include alcohols, aldehydes, ketones,
Amines and the like can be preferably used, and further, compounds described in JP-A-1-240517 can be used. These can be used singly or in combination of two or more.

  The amount of the metathesis catalyst formed by combining the component (a) and the like is such that “(a) of the component (a) and all monomers (the total of the above-described monomers and other copolymerizable monomers, the same applies hereinafter) The molar ratio of “component: all monomers” is usually in the range of 1: 500 to 1: 500,000, preferably in the range of 1: 1,000 to 1: 100,000. Further, the ratio of the component (a) to the component (b) is such that the metal atom (mole) ratio of “(a) :( b)” is usually 1: 1 to 1:50, preferably 1: 2. It is in the range of ˜1: 30. When the additive (c) is added to the metathesis catalyst, the ratio of the component (a) to the component (c) is such that the molar ratio of “(c) :( a)” is usually 0.005: 1 to The range is 15: 1, preferably 0.05: 1 to 7: 1.

As other catalysts,
(II) A metathesis catalyst composed of a transition metal-carbene complex or a metallacyclobutane complex of Groups 4 to 8 of the periodic table can be used.

Specific examples of the catalyst (II), for example, W (= N-2,6- C 6 H 3 i Pr 2) (= CH t Bu) (O t Bu) 2, Mo (= N-2, 6-C ₆ H ₃ ⁱ Pr ₂ ) (= CH ^t Bu) (O ^t
_{Bu) 2, Ru (= CHCH} = CPh 2) (PPh 3) 2 Cl 2, Ru (= CHPh 2) [P (C 6 H 11) 3] 2 Cl 2 , and the like. These can be used singly or in combination of two or more.

  The amount of the catalyst (II) used is such that the molar ratio of “catalyst (II): total monomer” is usually 1: 500 to 1: 50,000, preferably 1: 100 to 1: 10,000. It is a range.

The catalysts (I) and (II) may be used in combination.
Moreover, as a catalyst which performs addition copolymerization, at least 1 type chosen from the titanium compound, the zirconium compound, and the vanadium compound, and the organoaluminum compound as a co-catalyst are used.

  Here, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride.

Furthermore, as a vanadium compound, general formula VO (OR) _a X _b or V (OR) _c X _d
[Wherein R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3, ≦ (c + d) ≦ 4. ]
Or an electron-donating adduct of these compounds.

  Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

Furthermore, as the organoaluminum compound as the promoter, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

  In the above, for example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atom to vanadium atom (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. Range.

Molecular weight regulator The molecular weight of the norbornene polymers (A) and (B) used in the present invention can be adjusted by adjusting the polymerization temperature, the type of catalyst, the type of solvent, etc. It is preferable to adjust by making the agent coexist in the copolymerization reaction system. As the molecular weight regulator, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and other α-olefins and styrene are preferable. Of these, 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used singly or in combination of two or more. The amount of the molecular weight regulator used is usually 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per mol of all monomers.

Polymerization reaction solvent Examples of the solvent used in the copolymerization reaction (that is, a solvent that dissolves a monomer, a polymerization catalyst, a molecular weight regulator, etc.) include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, Compounds such as halogenated alkanes and aryl halides such as chloroform and tetrachloroethylene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate and methyl propionate; dibutyl ether and tetrahydro Emissions, include ethers such as dimethoxyethane, aromatic hydrocarbons are preferred among these. These can be used singly or in combination of two or more. The polymerization reaction solvent is used in such an amount that the weight ratio of “solvent: total monomer” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. Is desirable.

Hydrogenation The norbornene-based polymer obtained by the above copolymerization has a structure of an olefinically unsaturated group when produced by ring-opening polymerization. Although this polymer can be used as it is, it can be obtained as a hydrogenated polymer (hydrogenated product) by hydrogenating the olefinically unsaturated group in order to further improve the heat stability. preferable. However, the hydrogenated product referred to in the present invention is a product obtained by hydrogenating the olefinically unsaturated group produced by copolymerization, and is an intracyclic conjugated group in an aromatic skeleton such as a benzene ring derived from a monomer structure. The double bond is preferably substantially not hydrogenated.

  The hydrogenation rate of the norbornene polymers (A) and (B) of the present invention is 80 moles or more, preferably 85 moles or more when the number of moles of olefinically unsaturated bonds present before hydrogenation is 100. More preferably, it is 90 mol or more. The higher the hydrogenation rate, the more preferable the occurrence of coloring and deterioration of the norbornene polymer under high temperature conditions.

  The hydrogenation reaction is desirably carried out under the condition that the intracyclic conjugated double bond in the aromatic ring skeleton is not substantially hydrogenated. For example, a hydrogenation reaction catalyst is added to a polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is usually added thereto, and usually 0 to 200 ° C., preferably 50 to The reaction can be carried out at 200 ° C.

  As the hydrogenation reaction catalyst, those used for the usual hydrogenation reaction of olefinic compounds can be used, and heterogeneous catalysts and homogeneous catalysts are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. Examples of homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. These catalysts may be in the form of powder or granules. In addition, this hydrogenation reaction catalyst can be used singly or in combination of two or more.

These hydrogenation reaction catalysts need to be added in an amount so that the intraconjugated conjugated double bond in the aromatic ring skeleton is not substantially hydrogenated. The "reaction catalyst" is usually used at a ratio of 1: 1 x ^10-6 to 1: 2.

<Optical film and manufacturing method thereof>
The resin composition of the present invention can be suitably molded into a desired shape by any of melt molding such as extrusion molding and injection molding and molding by a solution casting method (cast method). Therefore, it is preferable to form a film by a solution casting method.

  The physical properties of the resin composition of the present invention can be controlled by the copolymer composition ratio and the amount of the molecular weight regulator used, but various additives are added within the range not losing the characteristics of the resin composition of the present invention. May be. In addition, various known additives can be added to the norbornene-based polymer used in the present invention for other purposes.

Examples of the additive include 2,6-di-tert-butyl-4-methylphenol,
2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythritol tetrakis [3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, octadecyl, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "- (Mesitylene-2,4,6-triyl) phenolic and hydroquinone antioxidants such as tri-p-cresol; tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, And phosphorous antioxidants such as tris (2,4-di-tert-butylphenyl) phosphite, one or two of these antioxidants. By adding the above, it is possible to improve the oxidation degradation resistance of the ring-opening copolymer, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-methylenebis. Light resistance can be improved by adding an ultraviolet absorber such as [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]]. Furthermore, additives such as a lubricant can be added for the purpose of improving processability, and these additives can be used alone or in combination of two or more.

  The resin composition of the present invention can be molded into a desired shape, but is excellent in optical characteristics, and thus is useful for various optical materials. Especially, shaping | molding into a film or a sheet | seat (in this invention, these are named generically and a film) is preferable, and can use it suitably for the use of various optical films.

Solution Casting Method As the solution casting method (solvent casting method), the resin composition of the present invention is dissolved or dispersed in a solvent to prepare a film forming solution containing the resin composition at an appropriate concentration. If necessary, the film-forming solution is filtered and cast by pouring or coating the filtrate on a suitable carrier to form a liquid phase of the film-forming solution on the carrier, followed by drying or the like. A preferred method is to remove the solvent from the liquid phase and peel the resulting film from the carrier.

  In the preparation of the film forming solution, the concentration of the resin composition 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 low, it becomes difficult to obtain a film having a desired thickness, and when the solvent is removed by drying, foaming or the like tends to occur with evaporation of the solvent, and the surface smoothness is improved. It may be difficult to obtain a good film. On the other hand, when 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.

  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, 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- Listed are 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. Door can be.

  In the present invention, examples of the solvent for dissolving or dispersing the resin composition include those having a boiling point of 10 ° C. or higher and 150 ° C. or lower, preferably 20 ° C. or higher and 50 ° C. or lower, more preferably 30 ° C. or higher and 50 ° C. or lower.

Also in addition to the above solvent, SP value (solubility parameter), usually 10 to 30 (MPa ^1/2), preferably 10 to 25 (MPa ^1/2), more preferably 15-25 (MPa ^1/2
), Particularly preferably by using a solvent in the range of 15 to 20 (MPa ^1/2 ), a film with 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. In addition, SP value of mixed solvent can be calculated | required from SP value of each solvent, and those weight ratios, for example, in the mixed solvent obtained from 2 types of solvents, let the weight fraction of each solvent be W1 and W2, When the SP value is SP1 and SP2, it can be calculated by the formula: SP value = W1 · SP1 + W2 · SP2.

  The temperature at which the resin composition of the present invention is dissolved or dispersed in a solvent may be room temperature or high temperature. By sufficiently stirring, a solution in which the resin composition is uniformly dissolved or dispersed can be obtained. A film forming liquid is obtained by filtering this. That is, it is possible to obtain a uniform filtrate that does not contain a partially gelled product by filtration. In the present invention, this filtrate is preferably used as a film-forming liquid. When such a film forming liquid is used, the formed film does not show foreign matters or does not partially differ in thickness, and is excellent in surface smoothness.

The film formed as described above usually becomes an optical film through a drying process.
The specific method for removing the solvent in the film-forming solution applied to the carrier is not particularly limited, and a commonly used drying treatment method, for example, a method of passing through a drying furnace by a number of rollers, etc. Can be used. If bubbles are generated as the solvent evaporates in the drying process, the film characteristics will be significantly reduced. The drying process is divided into two or more steps, and the generation of bubbles is avoided by controlling the temperature or air volume in each step. It is preferable to do.

  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. When the residual solvent amount 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 the heat resistance, which is not preferable.

  In addition, in order to perform the extending | stretching process mentioned later suitably, it is necessary to adjust the residual solvent amount in a film suitably within the said range. Specifically, in order to stably and uniformly express the phase difference in the film by stretching and orientation treatment, the amount of residual solvent in the film is usually 10 to 0.1% by weight, preferably 5 to 0.1% by weight. More preferably, it should be 1 to 0.1% by weight. If a trace amount of solvent remains in the film, the stretching and orientation treatment is facilitated, or the retardation is easily controlled.

  The thickness of the optical film formed by the solution casting method is usually 0.1 to 3,000 μm, preferably 0.1 to 1,000 μm, more preferably 1 to 500 μm, and particularly preferably 5 to 300 μm. When this thickness is too small, it becomes difficult to handle the film in practice. On the other hand, when this thickness is excessive, it becomes difficult to wind in a roll shape.

  The thickness distribution of the optical film formed by the solution casting method is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3% with respect 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.

  The optical film thus formed has excellent transparency, small surface roughness, excellent surface smoothness, little optical unevenness, and is suitably used for optical applications such as various protective films as it is. be able to. Further, it can be further stretched. In the case of producing a stretched film used as a retardation plate or the like, by using this optical film, it is possible to prevent the occurrence of retardation unevenness when performing a stretching orientation treatment.

Stretching The above-mentioned unstretched optical film of the present invention is subjected to stretching processing (stretch orientation treatment), whereby the molecular chains of the copolymer of the present invention forming the film are regularly oriented in a certain direction, and transmitted light It can be set as the optical film (retardation film) which has the function to give phase difference to.

  Here, “regularly oriented” means that in an unstretched film, the molecular chain of the polymer compound (polymer) in the film is in a random state without facing a specific direction, whereas the polymer compound Means that the molecular chains are regularly oriented in a uniaxial direction, biaxial direction or thickness direction of the plane of the film. The degree of regularity of the orientation of the polymer compound varies and can be controlled by the stretching conditions.

  Specific examples of the stretching method include known uniaxial stretching methods and biaxial stretching methods. 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 method 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, 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 and a method of stretching in a direction different from the initial 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, more preferably 100. -1,000% / min, particularly preferably 100-500% / min.

  The processing temperature in the stretching process is not particularly limited. When the glass transition temperature of the norbornene polymer (A) in the resin composition constituting the film is Tg, the processing temperature is usually (Tg-5) to ( Tg + 20) ° C., preferably in the range of Tg to (Tg + 10) ° C. 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 control of the refractive index ellipsoid is facilitated.

  In addition, even if it stretches in such a temperature range, since the specific resin composition is used in this invention, problems, such as cloudiness, do not arise in the obtained optical film. This is because the Tg distribution of the norbornene-based polymer (A) in the resin composition used in the present invention is relatively small, and preferably the Tg distribution of the entire resin composition is relatively small. This is thought to be due to plasticizing substantially uniformly. On the other hand, when a cyclic olefin-based ring-opening copolymer having a large Tg distribution is included, since it is not uniformly plasticized only by heating to the vicinity of Tg, there is a part in an unplasticized state. Is considered to cause white turbidity during stretching.

  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 present invention, since the resin composition containing the norbornene-based polymer (A) is used, the film can be stretched in the vicinity of its Tg, so that a high stress can be applied to the film even at low magnification. The optical film which has can be manufactured. When the draw ratio is relatively low, a retardation film without transparency and optical axis deviation can be easily produced. On the other hand, when the draw ratio is excessive, it may be difficult to control the phase difference and the optical axis.

  The stretched film may be cooled as it is at room temperature, but it is at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes in a temperature atmosphere of about (Tg-100) to Tg ° C. It is preferable to hold and heat set, and then cool to room temperature, whereby an optical film having a stable retardation characteristic can be obtained with little change over time in the retardation of transmitted light.

The optical film of the present invention obtained by stretching as described above gives a retardation to transmitted light when molecules are oriented by stretching. This retardation is determined by the stretching ratio or the thickness of the film before stretching. It is controlled by adjusting etc. 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 optical film, an optical film that imparts a desired phase difference to the transmitted light can be obtained.

<Application>
In the stretched optical film of the present invention obtained by stretching as described above, the retardation value given to the transmitted light is determined by its use, and is not uniquely determined. When used for a wavelength plate of a liquid crystal display element, an electroluminescence display element or a laser optical system, it is usually 1 to 10,000 nm, preferably 10 to 2,000 nm, and more preferably 15 to 1,000 nm.

  The phase difference of the 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 ±. 5% or less. When the dispersion of the phase difference exceeds the range of ± 20%, when used in a liquid crystal display element or the like, color unevenness or the like may occur, resulting in a problem that the performance of the display body is degraded. Similarly, the variation in the optical axis is usually ± 2.0 degrees or less, preferably ± 1.0 degrees or less, more preferably ± 0.5 degrees or less.

  The stretched optical film of the present invention can be used as a retardation plate (retardation film) alone or in a laminate of two or more or bonded to a transparent substrate. 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 and an adhesive can be used. As such 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 isocyanate 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 and epoxy adhesives.

  In addition, an adhesive layer or an adhesive layer can be previously laminated on the retardation plate in order to improve the workability of lamination with other films, sheets, substrates, and the like. When laminating the pressure-sensitive adhesive layer or the adhesive layer, the pressure-sensitive adhesive or adhesive as described above can be used.

  When the optical film of the present invention is used in a liquid crystal display device, the display characteristics of the liquid crystal display device can be further improved. Examples of the liquid crystal display device include various liquid crystal display devices such as a mobile phone, a digital information terminal, a pager, navigation, an in-vehicle liquid crystal display, a liquid crystal monitor, a light control panel, a display for OA equipment, and a display for AV equipment. .

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. Moreover, room temperature is 25 degreeC.

The measuring method of various physical property values in the present invention is shown below.
・ Glass transition temperature (Tg)
Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., trade name: DSC6200), an extrapolated glass transition start temperature (hereinafter simply referred to as “glass transition temperature (Tg)”) was determined according to Japanese Industrial Standard K7121.
Weight average molecular weight and molecular weight distribution Polystyrene equivalent weight average molecular weight (Mw) using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, trade name: HLC-8020) and tetrahydrofuran (THF) as a solvent. The molecular weight distribution (Mw / Mn) was measured. The Mn is a number average molecular weight.
Polymer molecular structure ¹ H-NMR was measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorber (NMR) (manufactured by Bruker, trade name: AVANCE500), and the copolymer composition ratio and hydrogenation rate Was calculated.
・ Evaluation of phase difference and birefringence A toluene or methylene chloride solution (concentration 25%) of a ring-opening polymer was cast on a smooth glass plate, and after drying, a thickness of 100 μm and a residual solvent of 0.5 to 0.8% A colorless and transparent film was obtained. The film was uniaxially stretched 1.2 to 2.0 times at a temperature 5 to 10 ° C. higher than the glass transition temperature (Tg) of the film. The retardation and birefringence values of the stretched film were measured using a retardation measuring device (manufactured by Oji Scientific Instruments, trade name: KOBRA21DH).
-Logarithmic viscosity Using a Ubbelohde viscometer, the sample concentration in chloroform is 0.5 g / dL, and the temperature is 30.
Measured at ° C.
-Tearing strength It measured using the Elmendorf tear test apparatus 3200 type | mold made by Toyo Seiki Seisakusho.
-Residual solvent amount A sample was dissolved in toluene and measured using GC-14B gas chromatography manufactured by Shimadzu Corporation.

<Synthesis Example 1>
39.0 g (1.03 mol) of lithium aluminum hydride was dispersed in 1000 mL of tetrahydrofuran (THF), and 100 g (0.61 mol) of hymic anhydride dissolved in 600 mL of tetrahydrofuran was heated to a reaction solution temperature of 35 ° C. or lower. It was dripped while adjusting. After completion of the dropwise addition, the reaction temperature was raised to room temperature and reacted for 20 hours. After the reaction, the reaction mixture was ice-cooled and water (171 mL) was added, followed by 15% aqueous sodium hydroxide (39 mL).

  Next, the precipitate was separated by filtration, 400 mL of water was added to the filtrate, and the mixture was extracted three times with 300 mL of diethyl ether and twice with 400 mL of ethyl acetate. The extract was dried over anhydrous magnesium sulfate, concentrated and dried to obtain 83 g of white solid 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene (yield 88%). It was.

  99 g (0.51 mol) of p-toluenesulfonyl chloride was dissolved in 129 mL of tetrahydrofuran and cooled to 8 ° C. In this solution, 36 g (0.234 mol) of 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene dissolved in 162 mL of pyridine was adjusted so that the reaction temperature was 10 ° C. or less. It was added dropwise while adjusting the temperature. After completion of the dropwise addition, the reaction temperature was raised to room temperature and reacted for 20 hours. After the reaction, 900 mL of water was added and extracted once with 900 mL of ethyl acetate. The extract was washed once with 600 mL of 0.1N hydrochloric acid and once with 600 mL of water, and dried over anhydrous magnesium sulfate. After concentration and drying, 66 g of white solid 5,6-di (p-toluenesulfonyloxymethyl) bicyclo [2.2.1] hept-2-ene was purified by silica gel column chromatography using methylene chloride as a developing solvent. (Yield 63%) was obtained.

36 g (0.217 mol) of fluorene was dissolved in 380 mL of tetrahydrofuran and cooled to −60 ° C. 270 mL (0.432 mol) of 1.6 mol / L n-butyllithium / n-hexane solution was gradually added while adjusting the temperature so that the temperature of the solution was −50 ° C. or lower, and the reaction was allowed to proceed for about 1 hour. To this, 50 g (0.108 mol) of 5,6-di (p-toluenesulfonyloxymethyl) bicyclo [2.2.1] hept-2-ene dissolved in 1200 mL of tetrahydrofuran is brought to a reaction temperature of −50 ° C. or lower. The solution was added dropwise while adjusting the temperature. After completion of the dropwise addition, the reaction temperature was raised to room temperature and the reaction was allowed to proceed for 15 hours. Thereafter, 140 mL of brine was added and stirred, and then tetrahydrofuran was distilled off under reduced pressure. After adding 300 mL of water to the residue and extracting 3 times with 300 mL of cyclohexane, the extract was washed 3 times with 1000 mL of water and dried over anhydrous magnesium sulfate. After concentration and drying, the product was purified by silica gel column chromatography using methylene chloride as a developing solvent to obtain a yellow solid. The crude material was recrystallized from methanol, spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] [3] decene] of white needles represented by the following structural formula 11g (yield: 36%).

単量体として合成例１で得られたスピロ［フルオレン−９,８'−トリシクロ［４.３.０.１^2.5］[３]デセン］（以下、「単量体Ａ」という。）３０ｇ（０．１０５５ｍｏｌ）、下記式（Ｂ）で表される８−メトキシカルボニル−８−メチルテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン（以下、「単量体Ｂ」という。）６６ｇ（０．２８４１ｍｏｌ）、下記式（Ｃ）で表されるビシクロ［２．２．１］ヘプト−２−エン（以下、「単量体Ｃ」という。）４ｇ（０．０４２５ｍｏｌ）、分子量調節剤として１−へキセン５１ｇ（０．０６０５ｍｏｌ）、およびトルエン２５０ｇを窒素置換した反応容器に仕込み、８０℃に加熱した。これにトリエチルアルミニウムのトルエン溶液（トリエチルアルミニウム濃度０．６１ｍｏｌ／Ｌ）０．５７ｍＬおよびメタノール変性ＷＣｌ₆のトルエン溶液（メタノール変性ＷＣｌ₆濃度０．０２５ｍｏｌ／Ｌ）１．７３ｍＬを加え、８０℃のオイルバス浴条件下で１時間反応させることにより重合体を得た。

30 g of spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] [3] decene] (hereinafter referred to as “monomer A”) obtained in Synthesis Example 1 as a monomer. 0.1055 mol), 8-methoxycarbonyl-8-methyltetracyclo represented by the following formula (B) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (hereinafter referred to as “monomer B”) 66 g (0.2841 mol), bicyclo [2.2.1] hept-2-ene represented by the following formula (C) (Hereinafter referred to as “monomer C”) 4 g (0.0425 mol), 1-hexene 51 g (0.0605 mol) as a molecular weight regulator, and 250 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. did. This triethylaluminum in toluene solution (triethyl aluminum concentration 0.61 mol / L) 0.57 mL and toluene solution of methanol-modified WCl ₆ (methylated WCl ₆ concentration 0.025 mol / L) 1.73 mL was added, 80 ° C. oil A polymer was obtained by reacting for 1 hour under bath bath conditions.

ここで得られた重合体溶液をオートクレーブに入れ、さらにトルエンを１５０ｇ加えた。水素添加反応触媒としてＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．０４０ｇ添加し、水素ガスを１０ＭＰａのゲージ圧となるように添加し、 １６０〜１６５℃に加熱して
３時間反応させた。反応終了後、多量のメタノールに沈殿させることにより水素添加体を回収し、１００℃の真空乾燥機で１２時間乾燥した。得られた水素添加体の重量平均分子量（Ｍｗ）＝８３，２３７、分子量分布（Ｍｗ／Ｍｎ）＝４．３３であり、対数粘度（ηinh）＝０．６１、補外ガラス転移開始温度（Ｔｇ）＝１６８．０℃、収量８０ｇ（収率８０％）であった。ＮＭＲ測定により求めたこの水素添加体の水素添加率は９９．８％であり、芳香環残存率は１００％であった。また、ＮＭＲにより求めた単量体Ａ、単量体Ｂ、および単量体Ｃ由来の構造単位含有率(共重合組成比)はそれぞれ２１、７１、および８重量％であった。

The polymer solution obtained here was put into an autoclave, and 150 g of toluene was further added. As a hydrogenation reaction catalyst, 0.040 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ is added, hydrogen gas is added so as to have a gauge pressure of 10 MPa, heated to 160 to 165 ° C. and 3 Reacted for hours. After completion of the reaction, the hydrogenated product was recovered by precipitation in a large amount of methanol and dried in a vacuum dryer at 100 ° C. for 12 hours. The resulting hydrogenated product had a weight average molecular weight (Mw) = 83,237, molecular weight distribution (Mw / Mn) = 4.33, logarithmic viscosity (ηinh) = 0.61, extrapolated glass transition start temperature (Tg ) = 168.0 ° C., yield 80 g (yield 80%). The hydrogenation rate of this hydrogenated product determined by NMR measurement was 99.8%, and the aromatic ring residual rate was 100%. Moreover, the structural unit content rate (copolymerization composition ratio) derived from monomer A, monomer B, and monomer C determined by NMR was 21, 71, and 8% by weight, respectively.

<Synthesis Example 2>
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
250 parts of 3-dodecene (specific monomer), 18 parts of 1-hexene (molecular weight regulator) and 750 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel, and this solution was charged. Heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / L) as a polymerization catalyst and tungsten hexachloride modified with tert-butanol and methanol (tert-butanol: methanol: tungsten) were added to the solution in the reaction vessel. = 0.35 mol: 0.3 mol: 1 mol) of toluene solution (concentration 0.05 mol / l) was added and 3.7 parts of the solution was heated and stirred at 80 ° C. for 3 hours to open the ring. Polymerization reaction was performed to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of hydrogen gas pressure of 100 kg / cm ² and reaction temperature of 165 ° C.

After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter referred to as “copolymer B1”).
About the copolymer thus obtained,
^The hydrogenation rate measured using ¹ H-NMR is 99.9%,
The glass transition temperature (Tg) measured by DSC method is 165 ° C.
The number average molecular weight (Mn) in terms of polystyrene measured by GPC method is 32,000, the weight average molecular weight (Mw) is 137,000, the molecular weight distribution (Mw / Mn) is 4.29,
Saturated water absorption at 23 ° C is 0.3%,
The logarithmic viscosity in chloroform at 30 ° C. was 0.78 dl / g.

<Synthesis Example 3>
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
Similar to Synthesis Example 2, except that 227 parts of 3-dodecene and 23 parts of bicyclo [2.2.1] hept-2-ene were used and the addition amount of 1-hexene was 12 parts. A coalescence (hereinafter referred to as “copolymer B2”) was obtained.

About the polymer thus obtained,
^The hydrogenation rate measured using ¹ H-NMR is 99.9%,
Tg measured by DSC method is 133 ° C.
Mn in terms of polystyrene measured by GPC method was 21,000, Mw was 70,000, Mw / Mn was 3.33,
The saturated water absorption at 23 ° C. is 0.18%,
The logarithmic viscosity in chloroform at 30 ° C. was 0.60 dl / g.

<Synthesis Example 4>
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
Similar to Synthesis Example 2, except that 215 parts of 3-dodecene and 35 parts of bicyclo [2.2.1] hept-2-ene were used and the addition amount of 1-hexene was 30 parts. A coalescence (hereinafter referred to as “copolymer B3”) was obtained.

About the polymer thus obtained,
^The hydrogenation rate measured using ¹ H-NMR is 99.9%,
Tg measured by DSC method is 125 ° C.
Mn in terms of polystyrene measured by GPC method is 46,000, Mw is 190,000, Mw / Mn is 4.15,
The saturated water absorption at 23 ° C. is 0.18%,
The logarithmic viscosity in chloroform at 30 ° C. was 0.53 dl / g.

[Reference Example 1] [Example 1]
Using a dry resin of the copolymer (A) and copolymer (B1) obtained in Synthesis Examples 1 and 2, a 10% methylene chloride solution was used as copolymer (A) / copolymer (B1) = 100 / It was produced at a ratio of 0 (Reference Example 1), 99/1, 95/5, 90/10, and 70/30 (Example 1). The resulting solution was filtered under reduced pressure (filter agent: GA200 manufactured by ADVANTEC), and cast into a smooth glass bath (inner dimensions: width 260 × depth 380 × depth 5 mm). After peeling this film from the bathtub, it was dried with a vacuum dryer at 100 ° C. for 12 hours to obtain a film. The amount of residual solvent in the obtained film was 500 ppm. The tear strength of this film was 50 gf.

  This film was cut into a width of 10 × 70 mm in length, and a stretched tester equipped with a thermostatic layer was heated and stretched under the conditions shown in Table 1 to create a stretched film. The retardation of the obtained film (R480, R550, R650) was measured. Here, R480, R550, and R650 represent phase differences at wavelengths of 480, 550, and 650 nm, respectively. The results are shown in Table 1.

[Example 2]
Using a dry resin of the copolymer (A) and copolymer (B2) obtained in Synthesis Examples 1 and 3, a 10% methylene chloride solution was used as copolymer (A) / copolymer (B2) = 99/1. , 95/5, 90/10, and 70/30. The results are shown in Table 1.

[Example 3]
Using a dry resin of copolymer (A) and copolymer (B3) obtained in Synthesis Examples 1 and 4, 10% methylene chloride solution was copolymer (A) / copolymer (B3) = 99 / The same procedure as in Example 1 was performed except that the samples were manufactured at ratios of 1, 95/5, 90/10, and 70/30. The results are shown in Table 1.

  The cyclic olefin polymer of the present invention is useful as an optical material, such as an optical disk, a magneto-optical disk, an optical lens (Fθ lens, pickup lens, laser printer lens, camera lens, etc.), spectacle lens, optical film / sheet ( Display film, retardation film, polarizing film, polarizing plate protective film, diffusion film, antireflection film, liquid crystal substrate, EL substrate, electronic paper substrate, touch panel substrate, PDP front plate, etc.), transparent conductive film substrate, Applications to optical materials that require high-precision optical design, such as optical fibers, light guide plates, optical cards, optical mirrors, ICs, LSIs, and LED sealing materials, are possible. The retardation film of the present invention is particularly useful as a member for polarizing plates or liquid crystal display devices.

Claims (8)

A norbornene polymer (A) having a structural unit (a) derived from a cyclic olefin monomer (A) having a norbornene skeleton and an aromatic ring structure;
A norbornene polymer having a structural unit (b) derived from a cyclic olefin monomer (B) having a norbornene skeleton having a polar group and no aromatic ring structure, and having no structural unit (a) A resin composition comprising (B). The said norbornene-type polymer (A) has a structural unit represented by following formula (1), The resin composition of Claim 1 characterized by the above-mentioned.

(In formula (1), a represents 0 or 1, and each R may independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, X represents —CH═CH— or —CH ₂ CH ₂ —, and a plurality of X may be the same or different. Good.) The said norbornene-type polymer (B) has a structural unit represented by following formula (2), The resin composition of Claim 1 or 2 characterized by the above-mentioned.

(In the formula (2), a represents 0 or 1, and R ^{1 to} R ⁴ each independently have a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, wherein at least one of R ^{1 to} R ⁴ is a polar group, X is independently —CH ═CH— or —CH ₂ CH ₂ —, wherein a plurality of X may be the same or different.   The resin composition according to any one of claims 1 to 3, wherein the norbornene polymer (A) is contained in the total amount of the resin composition by 70 wt% or more and less than 100 wt%.   A film formed from the resin composition according to claim 1.   A retardation film formed from the resin composition according to claim 1.   A liquid crystal display device produced using the film according to claim 5.   A liquid crystal display device produced using the retardation film according to claim 6.