WO2008013022A1

WO2008013022A1 - Cyclic olefin ring-opened copolymer and use thereof

Info

Publication number: WO2008013022A1
Application number: PCT/JP2007/062943
Authority: WO
Inventors: Nobuyuki Miyaki; Soichi Yoshida; Naoyuki Kawashima
Original assignee: Jsr Corporation
Priority date: 2006-07-25
Filing date: 2007-06-27
Publication date: 2008-01-31
Also published as: JP5304244B2; JPWO2008013022A1; TWI428364B; TW200813113A

Abstract

A cyclic olefin ring-opened copolymer comprising an essential constitutional unit (1) represented by the formula (1) and at least two other specific constitutional units. (1) It becomes possible to provide a novel norbornene ring-opened copolymer which has excellent heat resistance, processability and transparency, can be suitably used in various types of optical films and, when formed into a retardation film, can control the level of birefringence (phase difference) and wavelength dependency, an optical member, a film or a stretched film formed from the copolymer, and a polarizing plate or a liquid crystal display system using the stretched film.

Description

Specification

Cyclic olefin-based ring-opening copolymer and use thereof

Technical field

[0001] The present invention relates to a cyclic olefin-based ring-opening copolymer and its use. Specifically, the present invention uses a novel copolymer containing a specific cyclic olefin-based structural unit, an optical member obtained from the copolymer, a film, a stretched film having a positive wavelength dependency, and the stretched film. The present invention relates to a polarizing plate and a liquid crystal display device.

Background art

[0002] A cyclic olefin-based resin is excellent in transparency, heat resistance, moisture resistance, and the like, and thus is suitably used for applications such as optical films. In recent years, films made of cyclic olefin-based resins are expected to be used for polarizing plate protective films, liquid crystal substrate materials, etc. due to their relatively low birefringence, and because they have retardation stability, Expected to be used for optical compensation films such as retardation films.

[0003] For example, Patent Documents 1 to 4 describe retardation plates using a cyclic olefin-based resin film. Patent Documents 5 and 6 describe the use of a cyclic olefin-based resin film as a protective film for a polarizing plate. The polarizing plate using a cyclic olefin-based resin film can be used for liquid crystal displays. It is described to be used in

[0004] According to these conventional techniques, a retardation film made of a cyclic olefin-based resin has a function of imparting a retardation (birefringence) to transmitted light by stretching orientation. The change in the absolute value of the phase difference (birefringence) depending on the wavelength of the wavelength was not so much a problem! /.

However, at present, especially in applications such as liquid crystal displays and optical disk pickups, the phase difference of transmitted light due to the wavelength of transmitted light in a wide wavelength range such as the entire visible light range (400 to 800 nm). There is a real need to control (birefringence).

[0006] Development of a reverse wavelength dispersive stretched film and a resin thereof in which the phase difference (birefringence) of the transmitted light increases as the transmitted light becomes longer wavelength has been developed. [0007] However, it is a film using a cyclic olefin-based resin, and the phase difference (birefringence) of transmitted light becomes smaller (positive dispersion) as the transmitted light becomes longer wavelength. The development of stretched film and its resin has hardly been studied and reported, and there is known a resin that can be made into a film by extrusion, including the molding process.

[0008] For this reason, conventionally, when it is required to use a film having positive wavelength dispersion, it is necessary to use a material other than the cyclic olefin-based material. For example, a thin film such as a polycarbonate film or a polyimide polymer coating is known to have a positive wavelength dispersion of retardation, but it has a high photoelastic coefficient. When used as an optical film, it was considered as a major issue in terms of quality.

[0009] Under such circumstances, a single layer having a cyclic olefin-based resin, capable of controlling the phase difference (birefringence) of transmitted light depending on the wavelength of transmitted light, and having excellent processing characteristics in a wide wavelength range. The appearance of optical films is desired, and the appearance of resins capable of producing such optical films is demanded.

On the other hand, the applicant of the present invention has studied a cyclic olefin-based polymer suitable for an optical material. As a result, a ring-opening copolymer of a specific cyclic olefin-based monomer is excellent in transparency and heat resistance. It has also been found that the compressive force is highly soluble in solvents (see Patent Document 7).

[0011] As a result of diligent research in view of such circumstances, the present inventors have found that a specific novel norbornene-based ring-opening copolymer and its hydrogenated product have a polymerization composition and a monomer substituent. It has been found that, when a retardation film is formed, it is possible to control not only the magnitude of birefringence (retardation) but also the wavelength dispersion. It came to be completed.

Patent Document 1: Japanese Patent Laid-Open No. 4-245202

Patent Document 2: JP-A-4-36120

Patent Document 3: Japanese Patent Laid-Open No. 5-2108

Patent Document 4: Japanese Patent Laid-Open No. 5-64865

Patent Document 5: JP-A-5-212828

Patent Document 6: JP-A-6-51117 Patent Document 7: Japanese Unexamined Patent Publication No. 2003-165828

Disclosure of the invention

Problems to be solved by the invention

[0012] The present invention is excellent in heat resistance and cacheability, excellent in transparency, and can be suitably used for optical film applications. When a retardation film is formed, the birefringence (phase difference) is large. And a novel norbornene-based ring-opening copolymer capable of controlling the wavelength dependence, an optical member capable of obtaining the copolymer force, a film suitably used as an optical film, and a stretched film having positive wavelength dispersion Another object of the present invention is to provide a polarizing plate and a liquid crystal display device using the stretched film.

Means for solving the problem

[0013] The cyclic olefin-based ring-opening copolymer of the present invention,

A structural unit (1) represented by the following formula (1):

A group force consisting of a structural unit (2) represented by the following formula (2) and a structural unit (3) represented by the following formula (3):

It is characterized by having.

[0014] [Chemical 1]

(In the formula (1), a and b represent 0 or 1, and! ^-And a plurality of R ⁷ are independently hydrogen atom; halogen atom; oxygen atom, sulfur atom, nitrogen atom or key atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group Or represents a polar group. X represents CH = CH or —CH 2 CH 3. )

[0016] [Chemical 2]

(In formula (2), a represents 0 or 1, and I ^ to R ⁴ each independently include a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a key atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group; or a polar group, X represents CH = CH or —CH 2 CH—, and a plurality of X are present. Same or different

twenty two

May be. )

[0018] [Chemical 3]

(In the formula (3), a represents 0 or 1, and R ¹ and R ² each independently include a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a key atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group; or a polar group, X represents CH = CH or —CH 2 CH—, and a plurality of X are present. Same or different

twenty two

You may go on. Y is one CH = CH, one CH CH—, or

twenty two

[0020] [Chemical 4]

[0021] )

Such a cyclic olefin-based ring-opening copolymer of the present invention is such that the total of a plurality of X in the formulas (1), (2) and (3) is 100 mol%, and 80 mol% or more of X is —CH CH

2 is preferably a group represented by

[0022] The cyclic olefin-based ring-opening copolymer of the present invention contains 5 to 50 mol% of the structural unit (1) in 100 mol% of the total amount of the structural units (1), (2) and (3). I prefer that.

In the cyclic olefin-based ring-opening copolymer of the present invention, R ¹ and R ² in the formula (2) are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, and R ⁴ is hydrogen. It is preferred to have the structural unit (2), which is an atom, an alkoxy carbo yl group or a phenyl group! /.

[0024] The cyclic olefin-based ring-opening copolymer of the present invention has at least one structural unit (2) selected from structural units represented by the following formulas (2-1) to (2-5). Is preferred.

[0025] [Chemical 5]

… (twenty two)

[0026] [6]

(In formulas (2-1) to (2-5), X is as defined in general formula (2).)

The cyclic olefin-based ring-opening copolymer of the present invention preferably has at least one structural unit (3) that is selected from the structural unit forces represented by the following formulas (3-1) to (3-3). ,.

[0028] [Chemical 7]

(3-1)

[0029] [Yi 8]

[0030] (In formulas (3-1) to (3-3), X is as defined in general formula (3).)

The cyclic olefin-based ring-opening copolymer of the present invention preferably has an extrapolated glass transition initiation temperature of 110 to 170 ° C. measured according to Japanese Industrial Standard K7121. The logarithmic viscosity measured at a sample concentration of 0.5 g / dL and a temperature of 30 ° C. in black mouth form is preferably 0.4 to 0.8 dLZg.

[0031] The optical component of the present invention is obtained by molding the cyclic olefin-based ring-opening copolymer of the present invention.

[0032] The film of the present invention is obtained by forming the cyclic olefin-based ring-opening copolymer of the present invention by a casting method or an extrusion method.

[0033] The stretched film of the present invention is formed by forming a film of the cyclic olefin-based ring-opening copolymer of the present invention by a casting method or an extrusion method, and stretching the film.

[0034] The stretched film of the present invention preferably satisfies the optical properties of the following formulas (a), (b) and (c).

[0035] Re550> 0---(a)

Re450 / Re550> 1. 022 ••• (b)

Re650 / Re550 <0. 990---(c)

(In the above formulas (a) to (c), Re450, Re550, and Re650 represent in-plane retardations at wavelengths of 450 nm, 550 ηm, and 650 nm, respectively.)

The polarizing plate or the liquid crystal display device of the present invention includes the stretched film of the present invention. It is a feature.

The invention's effect

[0036] According to the present invention, the film has excellent heat resistance and cacheability, excellent transparency, and can be suitably used for optical film applications. When a retardation film is formed, birefringence (retardation) is reduced. Novel norbornene-based ring-opening copolymer capable of controlling size and wavelength dispersion, optical member obtained from the copolymer, film suitably used as an optical film, and positive wavelength dispersion A stretched film that can be suitably used as a retardation film, a polarizing plate using the stretched film, and a liquid crystal display device can be provided.

[0037] The cyclic olefin-based ring-opening copolymer according to the present invention is very useful as an optical material, and includes an optical disk, a magneto-optical disk, an optical lens (FΘ lens, pickup lens, laser printer lens, camera, etc. Lenses, etc.), eyeglass lenses, optical film Z 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, optical fiber, light guide plate, optical card, optical mirror, IC, LSI, LED encapsulant, etc. Very high precision optical design is required Application to optical materials is possible.

[0038] In particular, the cyclic olefin-based ring-opening copolymer according to the present invention can be used for optical film applications, and is suitable for production of a film formed by a casting method or an extrusion method, and a stretched film obtained by stretching the film. ing. The stretched film is suitable as a retardation film and can be suitably used for applications such as a polarizing plate and a liquid crystal display device.

Brief Description of Drawings

FIG. 1 shows an infrared absorption (IR) spectrum of the hydrogenated ring-opening copolymer (D) obtained in Example 1.

FIG. 2 shows the ¹ H-NMR spectrum of the hydrogenated ring-opening copolymer (D) obtained in Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

[0040] The present invention will be specifically described below. [0041] In the present specification, the term birefringence is used in the ordinary sense. Also, the value of birefringence (this is assumed to be Δη) is a stretched film in which a film formed from a polymer is uniaxially, biaxially, or biaxially stretched and the polymer molecular chains are oriented in one direction. The stretching direction (the direction in which the stretching ratio is large in biaxial stretching and the shrinking direction in biaxial stretching) is the X axis, and the vertical direction in the plane is the y axis, and the refractive index in the X axis direction is n, When the refractive index in the y-axis direction is n, the following formula:

Δ η = η— η

The absolute value is different depending on the wavelength of incident light.

[0042] The positive (or negative) birefringence means the property of the stretched film when Δn is positive (or negative).

[0043] Next, the phase difference (Retardation, which is referred to as Re) is the following formula:

Re = Δ ηΧ ά (where d is the optical path length (nm) of transmitted light, and is usually the thickness of the stretched film), and is a positive to negative value, and its absolute value The value depends on the wavelength of the incident light. In addition, “the phase difference is 1Z4” means that a phase difference corresponding to 1Z4 of the incident light wavelength (λ) is developed.

[0044] The wavelength dispersion of the phase difference means the correlation between the value of Re and the wavelength of the incident light, and "the wavelength dispersion of the phase difference is large" means the Re of the incident light having a short wavelength. This means that the difference between the absolute value and the absolute value of Re for long-wavelength incident light is large. In addition, “reverse wavelength dispersion” means a characteristic in which the phase difference increases as the incident light wavelength becomes longer, and “positive wavelength dispersion” means that the incident light wavelength becomes shorter as the incident light wavelength becomes shorter. It means the characteristic that the phase difference becomes large.

The cyclic olefin-based ring-opening copolymer of the present invention contains the structural unit (1) represented by the formula (1) as an essential structural unit, and the structural unit represented by the formula (2) (2 ) And at least two structural units selected from the group force consisting of the structural unit (3) represented by the formula (3) as essential structural units. The cyclic olefin-based ring-opening copolymer of the present invention may be composed of only these structural units (1) and structural units (2) and Z or (3). You may have a structural unit of! [0046] Here, represented by Ri to R ⁷ in the formula (1) and I ^ to R ⁴ in the formulas (2) and (3), a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, nitrogen A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an atom or a key atom; or a polar group will be described.

[0047] Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

[0048] Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as a methyl group, an ethyl group, and a propyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; An alkenyl group such as a group; an alkylidene group such as an ethylidene group or a propylidene group; an aromatic group such as a phenyl group, a naphthyl group or an anthracenyl group. 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 phenolsulfol group, a cyano group or the like.

[0049] The above 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, (CH 3) (wherein m is 1

An alkylene group represented by an integer of 2 m to 10); a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom (for example, a carbo group (one CO 2), a carbo-loxy group (one COO ), Sulfo-lole group (—SO—), sulfo-loxy group (one SO—O), ether bond (—O),

twenty two

One-tel bond (S), imino group (NH), amide bond (NHCO), siloxane bond (-Si (R) O) (wherein R is an alkyl group such as a methyl group or an ethyl group); Or this

2

A combination of two or more of these is listed.

[0050] Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group, a alkoxy group, an aryl carboxy group, an alkoxy carbo group, an aryl carboxy group, and a cyan group. Nitro group, amide group, imino group (= NH), triorganosiloxy group, triorganosilyl group, amino group, acyl group, alkoxysilyl group, sulfino group (—SO 2 H), carboxyl group and the like.

2

[0051] More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the alkylcarboxoxy group include a acetooxy group and propio- Examples of the arylcarbonyl group include a benzoyloxy group; examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; Examples of the -l group include a phenoxycarbol group, a naphthyloxycarbonyl group, a fluorocarbonyl group, a biphenyloxycarbol group, and the like; examples of the triorganosiloxy group include: Examples include trimethylsiloxy group and triethylsiloxy group; examples of triorganosilyl group include trimethylsilyl group and triethylsilyl group; examples of amino group include primary amino group and the like; alkoxy Examples of the silyl group include a trimethoxysilyl group and a triethoxysilane. Group, and the like.

[0052] In the cyclic olefin-based ring-opening copolymer of the present invention, as the structural unit (2), the above formula

In (2), when a is 0 or 1, when a is 0, R ¹ and R ² are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom, an alkoxycarbonyl group Or the structural unit which is a phenyl group is preferable. As the structural unit (2), structural units represented by the following formulas (2-1) to (2-5) are particularly preferable.

[0053] [Chemical 9]

… (2-2)

[0054] [Chemical 10]

… (twenty three )

[0055] [Chemical 11]

[0056] In the above formulas (2-1) to (2-5), X is as defined in the general formula (2), and CH = CH-or-CH CH-, It may be the same or different.

twenty two

[0057] In the cyclic olefin-based ring-opening copolymer of the present invention, as the structural unit (3), when the a in the formula (3) is 0 or 1, and a is 1, R ¹ and R ² is preferably a structural unit in which a hydrogen atom is present. A structural unit in which a is 0 is more preferable. Examples of the structural unit (3) include structural units represented by the following formulas (3-1), (3-2), and (3-3).

[0058] [Chemical 12]

[0059] [Chemical 13]

[0060] In the above formulas (3-1) to (3-3), X is as defined in the general formula (3), and CH = CH-or-CH CH-, It may be the same or different.

twenty two

In the cyclic olefin-based ring-opening copolymer of the present invention, as described above, X in the structural units (1), (2) and (3) is CH = CH or —CH 2 CH—. There are multiple X

twenty two

Identical or different. That is, the cyclic olefin-based ring-opening copolymer of the present invention is a copolymer obtained by ring-opening copolymerization of a cyclic olefin-based monomer capable of forming the structural units (1), (2) and (3). It may be further hydrogenated. A copolymer obtained by copolymerizing a cyclic olefin-based monomer is in the state of an olefinically unsaturated group represented by CH = CH. From the viewpoint of heat resistance stability, It is preferable that the hydrogenation is carried out and the X is converted to a group represented by —CH 2 CH 1.

twenty two

. In the cyclic olefin-based copolymer of the present invention, the total of X in the structural units (1), (2) and (3) is 100 mol%, usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol%. % Or more is preferably CH 2 CH—. X is one CH CH-

The higher the ratio of 2 2 2 2, that is, the higher the hydrogen transfer rate of the copolymer, the more stable the copolymer and the more preferable coloring and deterioration due to heat and oxygen are suppressed.

[0062] In the structural unit (3), Y in the formula (3) is CH = CH-, -CH CH-, or

twenty two

[0063] [Chemical 14]

[0064] is a structural unit represented by CH CH-, or

twenty two

[0065] [Chemical 15]

[0066] A structural unit represented by

[0067] The cyclic olefin-based ring-opening copolymer of the present invention has the structural unit (1) as an essential structural unit, and at least two kinds of group forces consisting of the structural units (2) and (3) are also selected. Having a structural unit of That is, one or more of the structural units (1) and two or more of the structural units (2) may be included, or two or more of the structural units (3) may be included. Further, it may have one or more of the structural units (2) and one or more of the structural units (3).

[0068] In the cyclic olefin-based ring-opening copolymer of the present invention, the proportion of the structural unit (1) is 5 to 50 mol% in the total amount of 100 mol% of the structural units (1), (2) and (3). It is more preferable that the proportion of the structural unit (1) is preferably in the range of 7 to 50 mol%. The higher the proportion of structural units (1), the higher the retardation development. However, when it is higher than 50 mol%, the solubility of the resulting polymer in common organic solvents is significantly reduced, and the transparency of the film is reduced. The properties are also significantly reduced. On the other hand, when the proportion of the structural unit (1) is less than 5 mol%, the resulting polymer strength may have a significant decrease in the effect of developing positive wavelength dispersion in the obtained stretched film.

[0069] In the cyclic olefin-based ring-opening copolymer of the present invention, the total of the structural units (1), (2) and (3) is 70 mol% or more, preferably 80 mol% or more in all the structural units. It is desirable that there be. As structural units other than the structural units (1), (2) and (3), ring-opening polymerization of cyclic olefin-based monomers other than the monomers (1), (2) and (3) described later is carried out. Examples of the structural unit to be formed.

[0070] The cyclic olefin-based ring-opening copolymer of the present invention has an extrapolated glass transition initiation temperature measured according to Japanese Industrial Standard CiIS) K7121, preferably 110 to 170 ° C, more preferably 115 to 165 ° C, It is preferably 120 to 160 ° C, has sufficient heat resistance, and Excellent moldability that enables melt molding such as extrusion molding.

[0071] Further, the cyclic olefin-based ring-opening copolymer of the present invention is a logarithm measured at a sample concentration of 0.5 g / dL at a temperature of 30 ° C in a black mouth form using a Ubbelohde viscometer. The viscosity is preferably 0.4 to 0.80 dL / g, more preferably 0.42 to 0.70 dL / g, and still more preferably 0.42 to 0.65 dLZg. In addition, 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 ring-opening polymer is usually 1,000 to 500,000, preferably 2000 The weight average molecular weight (Mw) is usually from 5,000 to 2,000,000, preferably from 10,000 to 1,000,000, and more preferably from 30,000 to 500,000.

[0072] When the logarithmic viscosity (7? Inh) is less than 0.4, the number average molecular weight (Mn) is less than 1000, or the weight average molecular weight (Mw) is less than 000, The strength of the molded product in which the norbornene-based ring-opening polymer strength of the invention can also be obtained may be significantly reduced. On the other hand, if the logarithmic viscosity (7? Inh) is 0.81 or more, the number average molecular weight (Mn) is 500,000 or more, or the weight average molecular weight (Mw) is 2 million or more, Since the melt viscosity or solution viscosity of the ring-opening polymer is increased, it may be difficult to obtain a desired molded product such as a sheet, film, or optical component.

Such a cyclic olefin-based ring-opening copolymer of the present invention can be produced, for example, as follows.

[0073]

, Monomer

The cyclic olefin-based ring-opening copolymer of the present invention comprises a monomer (lm) represented by the following formula (lm), a monomer (2m) represented by the following formula (2m), and the following formula (3m ) Can be produced by ring-opening copolymerization and hydrogenation as desired. .

[0074] [Chemical 16]

(Lm)

[0075] (In the formula (lm), a, b and ˜1 ^ ⁷ are as defined for the formula (1).)

[0076] [Chemical 17]

(2 m)

[0077] [Chemical 18]

(In the formulas (2m) and (3m), a, Y and ˜ are as defined for the formula (2) or (3).)

In the cyclic olefin-based ring-opening polymer of the present invention, the structural unit (1) is from the monomer (lm), the structural unit (2) is from the monomer (2m), and the structural unit (3) is from the monomer (3m). ) Are derived from each.

[0079] The monomer (lm) for deriving the structural unit (1) is a acenaphthylene or derivative thereof and It can be produced by performing Diels-Alder type reaction using oral pentagen or a derivative thereof as a raw material. Examples of such a monomer (lm) include the following.

[Chemical 19]

[0085] Because it is readily available, it is also preferred because it also controls the extrapolated glass transition temperature. In addition, the mutual configuration of the above compound with the norbornene ring and the isenaphten ring is not particularly limited, and may be an endo isomer, an exo isomer, or an endo exo isomer mixture.

[0086] Examples of the monomer (2m) for deriving the structural unit (2) include the following. Bicyclo [2. 2. 1] hept

[0087] [Chemical 23]

[0088] 5-Methylbicyclo [2. 2. 1] Hepto-2-ene

[0089] [Chemical 24]

[0090] 5-Ethylbicyclo [2.2.1] hept

[0091] [Chemical 25]

[0092] 5-Butylbicyclo [2.2.1] hept

[0093] [Chemical 26]

[0094] 5—Phenolbicyclo [2. 2. 1] Heptou 2—Yen

[0095] [Chemical 27]

2. 1 1 Heptou 2—Yen

[0098] 5— (Naphthalene-2-yl) bicyclo [2.2.1] hepto-2-ene

[0099] [Chemical 29]

[0100] 5— (Naphthalenyl) bicyclo [2. 2. I I Hepto-2-en [0101] [Chemical 30]

2. 1 ”Heptou 2—Yen

[0104] 5— (Cyclohexene 4-. 2. 1 ”hept-2-ene

[0105] [Chemical 32]

[0106] 5-Methoxycarbo-bibicyclo [2. 2. 1] hepto-2-en

[0107] [Chemical 33]

COO e

[0108] 5-Ethoxycarbo-bibicyclo [2.2.1] hepto-2-en

[0109] [Chemical 34]

COOEt

[0110] 5-Butoxycarborubicyclo [2. 2. 1] hepto-2-en

[0111] [Chemical 35]

COOBu

[0112] 5-. 2. 1] Heptou 2-Yen

[0113] [Chemical 36]

[0114] 5-Methinole-5-methoxycarborubicyclo [2.2.1] hepto-2-en [0115] [Chemical 37]

[0116] 5-Methyl-5 ethoxycarbo-bicyclo [2.2.1] hepto-2-ene [0117] [Chemical 38]

[0118] 5-Methinore-5-phenoxycarbo-bibicyclo [2.2.1] hepto-2-en [0119] [Chemical 39]

[0120] 5 Fluorobicyclo [2.2.1] Heptou 2

[0121] [Chemical 40]

[0122] 5— “!. 2. 1] Heptou 2—Yen

[0123] [Chemical 41]

[0124] Tetracyclo [4. 4. 0. I ² ' ⁵ · 1 ⁷ . ] 3 Dodecene

[0125] [Chemical 42]

[0126] 8-phenyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] -3-Dodecene

[0127] [Chemical 43]

[0128] 8-Methoxycarbonyltetracyclo [4.

[0129] [Chemical 44]

[0130] 8-Ethoxycarbonyltetracyclo [4.

[0131] [Chemical 45]

COOEt

[0132] 8— n-propoxycarborutetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] — 3-dodecene [0133] [Chem 46]

[0134] 8—Isopropoxycarborutetracyclo [4. 4. 0. I ² ' ^5. ".] — 3-Dodecene [0135] [Chemical 47]

[0136] 8— n-Butoxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. l ⁷ ] — 3-dodecene [0137] [Chemical 48]

1) 1 /

[0138] 8-Fuenokishikarubo - Rutetorashikuro ^{^{[4. 4. 0. I 2,5 '10}} .] - 3- dodecene [0139] [Formula 49]

[0140] 8— (1-Naphoxy) carbonyltetracyclo [4. 4. 0. I ² ' ^5. 1 ⁷ ' ^ω ] — 3 Dodecene [0141] [Chemical 50]

[0142] 8— (2 Naphthoxy) carbonyltetracyclo [4. 4. 0. I ² ' ^5. L ⁷ ' ¹⁰ ] — 3 Dodecene [0143] [Chemical 51]

2,5 7,1

[0144] 8— (4-Ferfenoxy) carbonyltetracyclo [4. 4. 0. '] 1 3-Dodecene

[0145] [Chemical 52]

[0146] 8-Methyl 8-methoxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] —3 Dodecene [0147] [Chemical 53]

[0148] 8-Methyl 8 ethoxycarbotetracyclo [4. 4. 0. I ² ' ^5. L ⁷ ' ¹⁰ 1-3 Dodecene [0149] [Chem 54]

COOEt

ji Me [0150] 8—Methinore-8— n—Propoxycarborutetracyclo [4. 4. 0. I ² ' ^5. L ⁷ ' ^lu ] — 3 dedecene

[0151] [Chemical 55]

COO "Pr

Me

[0152] 8-Methyleno-8-isopropoxycarborutetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹ "] — 3 dedecene

[0153] [Chemical 56]

[0154] 8-Mechinore --8-n-butoxycarbonyl - Rutetorashikuro ^{[4. 4. 0. I 2 '.} 5 I 7' ^one one 3 dodecene

[0155] [Chemical 57]

. COO¾u

Me

[0156] 8-Methinole-8 phenoxycarborutetracyclo [4. 4. 0. I ² ' ^5. l ⁷ ' ^lu ] — 3 dodecene

[0157] [Chemical 58]

[0158] 8-Methyl 8-- (1-Naphthoxy) carborutetracyclo [4. 4. 0. Ϋ 'l ⁷ ' ¹⁰ ] — 3 Dodecene

[0159] [Chemical 59]

Naphthoxy) carbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] — 3—

Phenolphenoxy) Carbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ '

[0164] 8-Fluorotetracyclo [4. 4. 0. l ² '. I ⁷ ' ¹⁰ ] —3-Dodecene

[0165] [Chemical 62]

[0166] 8-Fluoromethyltetracyclo [4. 4. 0. 'I ⁷ ' ¹⁰ ] — 3-Dodecene

[0167] [Chemical 63]

[0168] 8-triflate Ruo Russia methyl tetracyclo ^{^{[4. 4. 0. I 2 '5}} .丄^7' ^1. ] —3—Dodecene

[0169] [Chemical 64]

[0170] 8—Pentafluoroethyl tetracyclo [4. 4. 0. I ² ' ^5. 1 ⁷ ' ^{1 ()} Ί— 3-Dodecene

[0171] [Chemical 65]

[0172] 8, 8—Difluoroteracyclo [4. 4. 0. 1 '] —3-Dodecene

[0173] [Chemical 66]

[0174] 8,8-Bis (trifluoromethyl) tetracyclo [4. 4. 0. I ² ' ^5. l ⁷ ' ¹⁰ ] -3-Dodecene

[0175] [Chemical 67]

[0176] As the monomer (2m), among these, R ¹ and R ² in the formula (2m) are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, and R ⁴ is hydrogen. Of these, compounds which are atoms, alkoxy carbo yl groups or phenyl groups are preferred.

[0177] [Chemical 68]

[0178] At least one selected from the compound forces represented by [0178] is preferably used.

[0179] Examples of the monomer (3m) for deriving the structural unit (3) include the following:

be able to.

Pentacyclo ^{^{[6. 5. 1. I 3 '6}} 0 2.' 7 0 9 '13.] - 4- pentadecene

[0180] [Chem 69]

[0181] Tricyclo [5. 2. 1. 0 ² ' ⁶ ] — 8-Decene [0182] [Chemical 70]

[0183] Tricyclo [5. 2. 1. 0 ² ' ⁶ ] —Deca 3, 8—Gen

[0184] [Chemical 71]

[0185] [Chemical 72]

[0187] As the monomer (3m), among these,

[0188] [Chemical 74]

, And Z or

[0189] It is preferable.

[0190] In producing the cyclic olefin-based ring-opening copolymer according to the present invention, the monomer (1 m), the monomer (2m) and the monomer (3m) force are selected from two kinds of monomers. It is preferable to use a monomer. When one monomer selected from monomers (2m) and (3m) is used, it is difficult to achieve both polymer properties (glass transition temperature) and film optical properties (phase difference development). The ability to control the glass transition temperature, that is, the processability, even with a copolymer of monomer (lm) and one monomer selected from monomer (2m) and monomer (3m) this In the copolymerization system of these two types of monomers, the optical properties are determined when the copolymerization composition ratio at which the desired glass transition temperature is obtained, and the glass transition temperature and the optical properties can be controlled simultaneously. Have difficulty. Therefore, it is preferable to use two monomers selected from the monomer (2m) and the monomer (3m), and the glass transition temperatures of the homopolymers of these two monomers are different from each other. It is preferable. By using the monomer (lm) and two types of monomer (2m) and monomer (3m) force, the phase difference can be controlled by the monomer (lm) content. It is possible to control the glass transition temperature by the content of the two monomers, which are also selected for wavelength dispersion, monomer (2m) and monomer (3m) forces.

[0191] The total amount of monomer (lm), monomer (2m) and monomer (3m) in the monomer composition is 10 Omol%, and the monomer (lm) is 5 to 50 mol% The range of 10 to 50 mo 1% is more preferable. By using the monomer (lm) at such a copolymerization ratio, the resulting cyclic olefin-based ring-opening copolymer of the present invention has optical characteristics such as refractive index anisotropy and wavelength dispersion, In addition, physical properties such as glass transition temperature can be easily controlled without problems.

[0192] In addition to the above-mentioned monomer (lm), monomer (2m) and monomer (3m), the monomer yarn and composition may have other properties as long as the object of the present invention is not impaired. It may contain a copolymerizable monomer. Examples of the copolymerizable monomer include cyclic olefins such as cyclobutene, cyclopentene, cyclootaten, and cyclododecene; and non-conjugated cyclic polyenes such as 1,4-cyclooctene and cyclododecatriene. The copolymerizable monomers can be used singly or in combination of two or more. In the present invention, the copolymerizable monomer in the monomer composition is preferably 30 mol% or less, more preferably 20 mol% or less.

[0193] Ring-opening polymerization catalyst

Examples of the catalyst for ring-opening polymerization that can be suitably used for producing the cyclic olefin-based ring-opening copolymer of the present invention include:

The catalyst described in (I) Olefin Metathesis and Metathesis Polymerization (KJ IVIN, JCMOL, Academic Press 1997) is preferably used. Examples of such a catalyst include (a) at least one compound selected from W, Mo, Re, V, and Ti, and (b) Al. Potassium metal elements (eg Li, Na, K), alkaline earth metal elements (eg Mg, Ca), Group 12 elements (eg Zn, Cd, Hg), Group 13 elements (eg B, A1), Group 14 elements (eg, Si, Sn, Pd), etc., having at least one element carbon bond or element hydrogen bond in combination with at least one selected element Powerful metathesis catalysts. In order to enhance the activity of the catalyst, the additive (c) described later may be added.

[0194] Specific examples of the component (a) include WC1, MoCl, ReOCl, VOC1, and TiCl.

6 5 3 3 4 The compounds described in Japanese Patent Publication No. 240517 are listed. These can be used singly or in combination of two or more.

[0195] Specific examples of the component (b) include n—C H Li, (C H) Al, (C H) A1C1, and (C H).

4 9 2 5 3 2 5 2 2 5 1.

A1C1, (C H) A1C1, methylalumoxane, LiH, etc. JP-A-1-240517

5 1.5 2 5 2

And the compounds described in the above. These can be used alone or in combination of two or more.

[0196] As the additive of the component (c), alcohols, aldehydes, ketones, amines and the like can be preferably used, and further, compounds described in JP-A-1-240517 are used. can do. These can be used singly or in combination of two or more.

[0197] The amount of the metathesis catalyst formed by combining the above component (a) and the like is the amount of the above component (a), all monomers (the above-mentioned monomers (lm), (2m), (3m) and others The specific molar ratio of “(a) component: total monomers” is usually in the range of 1: 500 to 1: 500, 00, preferably The range is 1: 1 000-1: 100,000. Furthermore, 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. If this metathesis catalyst to the (c) additive is added Caro, the molar ratio of the proportion of the component (a) and component (c), "(Ji) :( _&)", typically 0.005: 1 ~ 15: 1, preferably in the range of 0.05: 1 to 7: 1.

[0198] As other catalysts,

(II) Metathesis catalysts composed of Group 4 to Group 8 transition metal carbene complexes, metallacyclobutane complexes, and the like can be used. [0199] Specific examples of the catalyst (Π) include W (= N— 2, 6-CH 'Pr) (= ΟΗ¾ιι) (O'Bu)

6 3 2 2

, Mo (= N- 2, 6-C H) (= ΟΗ ιι) (O'Bu), Ru (= CHCH = CPh) (PPh

6 3 2 2 2 3

) CI, Ru (= CHPh) [P (C H)] CI, and the like. These can be used alone or in combination

2 2 2 6 11 3 2 2

A combination of the above can also be used.

[0200] The amount of the catalyst (Π) used is such that the molar ratio of “catalyst (Π): total monomer” is usually 1: 500 to 1: 50,000, preferably 1: 100 to The range is 1: 10,000.

[0201] The above catalysts (I) and (i) may be used in combination.

[0202], Molecular weight regulator

The molecular weight of the cyclic olefin-based ring-opening copolymer according to the present invention can be adjusted by adjusting the polymerization temperature, the type of catalyst, the type of solvent, and the like. It is preferable to adjust by making it coexist in the polymerization reaction system. As molecular weight regulators, 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 preferred. 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 0.005-0. 6 mol, preferably 0.02-0.5 mol, per mol of all monomers.

[0203], Ring-opening polymerization reaction solvent

Examples of the solvent used in the ring-opening copolymerization reaction (that is, the solvent that dissolves the monomer, the ring-opening polymerization catalyst, the molecular weight regulator, etc.) include, for example, pentane, hexane, heptane, octane, nonane, decane. Alkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, etc .; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride , Dichloroethane, hexamethylene dibuamide, black benzene, chlorophenol, tetrachloroethylene, halogenated alkanes such as ethylene, halogenated aryl, etc .; saturated carboxylic acids such as ethyl acetate, η-butyl acetate, isobutyl acetate, methyl propionate, etc. Esters: Dibutyl ether, Tetrahi Examples include ethers such as drofuran and dimethoxyethane. Among these, aromatic hydrocarbons are preferable. These can be used alone or in combination of two or more. Can be used together. The amount of the solvent used for the ring-opening polymerization reaction is such that the weight ratio of “solvent: total monomer” is usually 1: 1 to: LO: 1, preferably 1: 1 to 5: 1. It is desirable that the amount be

[0204], Ring-opening polymerization reaction temperature

The ring-opening copolymerization reaction is usually an exothermic reaction, and it is not always necessary to keep the reaction temperature constant during the polymerization reaction, but the temperature at the start of the polymerization, that is, the temperature of the monomer solution when the catalyst is added is controlled. It is preferable. The temperature of the monomer solution when the catalyst is added is preferably 30 to 200, more preferably 50 to 180 ° C. If the temperature is lower than 30 ° C, the polymer yield may decrease. If the temperature exceeds 200 ° C, it may be difficult to control the molecular weight.

[0205] Hydrogenation

The cyclic olefin-based ring-opening copolymer obtained by the ring-opening copolymer has a structure of an olefinic unsaturated group in which X in the structural units (1) to (3) is represented by the formula: CH = CH Is. This ring-opened polymer can be used as it is, but in order to further improve the heat resistance stability, the above olefinic unsaturated group is hydrogenated to form the formula: CH 2 -CH

It is preferable to obtain a hydrogenated ring-opened polymer (hydrogenated product) by converting it to a group represented by 2 2. However, the hydrogenated product referred to in the present invention is a product obtained by hydrogenating the olefinic unsaturated group generated by ring-opening copolymerization, and an aromatic ring such as a benzene ring derived from a monomer structure. The intracyclic conjugated double bond in the skeleton is preferably one that is not substantially hydrogenated.

[0206] Hydrogenation rate of the cyclic olefin-based ring-opening copolymer of the present invention, that is, the structural unit (1) to

There are a plurality of ratios in which X in (3) is converted into a group represented by the formula: —CH 2 —CH 1

twenty two

The total amount of X is 80 mol% or more, preferably 85 mol% or more, more preferably 90 mol% or more. The higher the hydrogenation rate, the more preferable the occurrence of coloring and deterioration of the cyclic olefin-based copolymer under high temperature conditions.

[0207] The hydrogenation reaction is desirably performed 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 ring-opening polymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is usually added thereto. And usually at 0 to 200 ° C, preferably 50 to 200 ° C.

[0208] As the hydrogenation reaction catalyst, those used in 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 catalytic material such as radium, platinum, nickel, rhodium, or ruthenium is supported on a carrier such as carbon, silica, alumina, or titanium. . Examples of homogeneous catalysts include nickel naphthenate Z-triethyl chloride, nickel acetyl acetate toner z-triethyl aluminum, oxalate cobalt butyl lithium, titanocene dichloride Z jetyl aluminum monochloride, rhodium acetate, Examples thereof include chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbotris (triphenylphosphine) ruthenium, and the like. The form of these catalysts may be powdery or granular. Further, the hydrogenation reaction catalyst can be used alone or in combination of two or more.

[0209] 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. polymer weight ratio of hydrogenation catalyst "is ^{generally, 1: 1 X 10- 6 ~1} : is used in a ratio of two.

[0210] <Molding of cyclic olefin-based copolymer>

The cyclic olefin-based ring-opening copolymer of the present invention has excellent moldability and is suitably formed 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). Can be molded.

[0211] The physical property value of the cyclic olefin-based ring-opening copolymer of the present invention can be controlled by the copolymer composition ratio and the amount of use of the molecular weight regulator of the cyclic olefin copolymer of the present invention. Various additives may be added as long as the characteristics are not lost. In addition, various known additives can be added to the cyclic polyolefin-based ring-opening polymer of the present invention for other purposes.

[0212] Examples of additives include 2, 6-dibutyl-4 methylphenol, 2, 2'-medium. Tylene bis (4-ethyl-6-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythritol 'tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4, 4'-thiobis (6-t-butyl-3 methylphenol), 1,1-bis (4 hydroxyphenol) cyclohexane, octadecyl 3- (3,5 di-tert-butyl-4-hydroxyphenol) propionate, 3, 3 ', 3 ", 5, 5', 5" —Hexanes t-Butyl-a, a ', a ,,-(mesitylene-2,4,6 tolyl) tri-p-taresol and other phenolic systems, hydroquinone Antioxidants such as tris (4-methoxy 3,5-diphenyl) phosphite, tris (noulefel) phosphite, tris (2,4 di-t-butylphenol) phosphite Agents. Addition of one or more of these acid / antioxidants can improve the acid / acid deterioration resistance of the ring-opening copolymer. Also, for example, 2,4-dihydroxybenzophenone, 2hydroxy-4-methoxybenzophenone, 2,2, -methylenebis [4- (1, 1, 3, 3-tetramethylbutyl) 1-6- [(2H Light resistance can also be improved by adding an ultraviolet absorber such as benzotriazole 2-yl) phenol]]. Furthermore, additives such as lubricants can be added for the purpose of improving processability. These additives can be used singly or in combination of two or more.

[0213] The cyclic olefin-based ring-opening polymer 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. Of these, formation into a film or sheet (in the present invention, these are collectively referred to as a film) is preferable, and can be suitably used for various optical films.

[0214] · Optical film

The cyclic olefin-based ring-opening polymer of the present invention is composed of the substituents Ri to R ⁷ of the monomer (lm), the monomer (2m), the substituent R ^ R ⁴ of the monomer (3m). By setting the copolymer composition ratio, etc., the absolute value of the birefringence and the wavelength dispersion of the retardation of a molded product such as a film can be prepared. Further, by appropriately blending the cyclic olefin-based ring-opening polymer of the present invention with a known cyclic olefin-based rosin or the like, a polymer film or the like formed from the rosin composition obtained can also be obtained. The absolute value of birefringence and the wavelength dispersion of the phase difference can be adjusted. [0215] When the cyclic olefin-based ring-opening polymer of the present invention is selected and used, the absolute value of birefringence and the wavelength dispersion of retardation can be easily controlled. The film obtained by the coalescence can be suitably used as an optical compensation film. For this reason, the cyclic olefin-based ring-opening copolymer of the present invention or a composition containing the same is preferably formed into an optical film by casting or extrusion. Furthermore, since the above optical film exhibits its performance sufficiently by stretching, it is free width uniaxial stretching (longitudinal stretching), width constrained uniaxial stretching (lateral stretching), sequential biaxial stretching, simultaneous biaxial stretching or optical It is preferable to apply a shrinkable film to the film during stretching or after stretching to adjust the refractive index in the film thickness direction, and to make a stretched film by performing so-called Z-axis orientation (Z-axis stretching).

[0216] The optical film of the present invention can be suitably used as various protective films because it exhibits excellent transparency in a film formed by extrusion molding or cast molding. In addition, a stretched film obtained by further stretching a film obtained by forming a film can be suitably used as a film constituting a retardation plate or a liquid crystal display device because it has a unique wavelength dispersibility.

[0217] A film obtained by stretching a film obtained from the cyclic olefin-based ring-opening copolymer of the present invention or a resin composition containing the same, obtained by stretching a film, particularly a free-width uniaxial stretching. By selecting the type of copolymer and the resin composition, the film can be made into a film having positive wavelength dispersibility in which the phase difference Re decreases as the transmitted wavelength increases in the visible light region. . Such a film can be suitably used as a retardation film, and is suitable as a film constituting a polarizing plate and a liquid crystal display device such as a large liquid crystal television and a monitor.

[0218] The stretched film of the present invention can preferably satisfy the optical properties of the following formulas (a), (b) and (c) at the same time.

[0219] Re550> 0---(a)

Re450 / Re550> 1. 022 ••• (b)

Re650 / Re550 <0. 990---(c)

(In the above formulas (a) to (c), Re450, Re550, and Re650 represent in-plane retardation (nm) at wavelengths of 450 nm, 550 ηm, and 650 nm, respectively.) In particular, the free-width uniaxially stretched film obtained by thermally stretching the optical film having the cyclic olefin-based ring-opening copolymer force of the present invention with a stress of 1 to 150 kg fZcm ² is preferably the following optical characteristics (a ′), (B ′), (c ′) and (d) can be satisfied simultaneously.

(a ') Onm≤Re550≤1000nm

(b ') l. 022 <Re450 / Re550≤ 1. 200

(c ') 0. 900≤Re650 / Re550 <0. 990

(d) 1 OOOOnm≤ d≤ 300000nm

(In the above formula, Re450, Re550, and Re650 represent the in-plane retardation Re at wavelengths of 450 nm, 550 nm, and 650 nm, respectively, and are represented by Re = (ηχ−ny) X d, where n X and ny represents the refractive index in the X-axis direction and the y-axis direction when the stretching direction is the X-axis and the vertical direction in the film plane is the y-axis, and d represents the thickness (nm) of the film.

When the stretched film according to the present invention satisfies the optical characteristics (a ′), (b ′), () and (d) at the same time, optical compensation for monitors of various specifications, televisions, mopile equipment, etc. It can be particularly suitably used as a material.

[Example]

Hereinafter, the power for further specifically explaining the present invention based on examples The present invention is not limited to these examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. The room temperature is about 25 ° C.

[0220] Methods for measuring various physical property values in the present invention are described below.

[0221] 'Glass transition temperature (Tg)

Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., trade name: DSC6200), an extrapolated glass transition start temperature was determined according to Japanese Industrial Standard K7121. Hereinafter, it is simply referred to as the glass transition temperature (Tg).

[0222] · Weight average molecular weight and molecular weight distribution

Weight average molecular weight (Mw) and molecular weight distribution (MwZMn) in terms of polystyrene using gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020), using tetrahydrofuran (THF) as a solvent. Was measured. The Mn is Number average molecular weight.

[0223], Polymer molecular structure

Using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, product name: AVANCE500), ¹ H-NMR was measured in deuterated black mouth form to calculate the copolymer composition ratio and hydrogenated calorie rate. did.

[0224] Evaluation of phase difference and birefringence

A ring-opened polymer of toluene and methylene chloride solution (concentration: 25%) was cast on a smooth glass plate, dried, and then 94-140 111 thick with a residual solvent of 0.5-0.8% colorless. A transparent film was obtained. The film was uniaxially stretched 2.0 times at temperatures of 5, 10, and 15 ° C. higher than the extrapolated glass transition temperature (Tg). The retardation and birefringence values of the stretched film were measured using a letter measurement instrument (trade name: KOBRA21DH, manufactured by Oji Scientific Instruments).

'Logarithmic viscosity

Using a Ubbelohde viscometer, the sample concentration was measured at 0.5 g / dL and a temperature of 30 ° C. in the black mouth form.

[0225] [Example 1]

As a cyclic olefin-based monomer (lm), 1, 2 -— (2H, 3H— [1,3] epicyclopenta) -1,2-dihydroacenaphthylene represented by the following formula (A) 2. OOg, cyclic Orefin based single-mer (2m) as a 8-methoxy-carbonitrile represented by the following formula (B) - Lou 8-methyl-tetra consequent opening ^{^{[4. 4. 0. I 2 '5}} 1 "°.] - 3- dodecene 16. Bisquish represented by OOg and the following formula (C) [2. 2. 1] hept-2-ene 2. Charge OOg and 40 g of toluene as a polymerization solvent into a nitrogen-substituted reaction vessel, and further adjust the molecular weight. 2.09 g of 1-hexene was added as an agent and heated to 80 ° C.

[0226] [Chemical 75]

… (B),… (C)

[0227] In this reaction system, 0.13 mL of toluene solution of triethylaluminum (concentration 0.6 mol Z L) and methanol-modified WC1 toluene solution (concentration 0.025 mol) were used as catalysts.

6 ZU 0.40 mL was added and reacted for 3 hours, and then the polymerization was stopped with methanol water. Subsequently, the entire amount of the polymerization solution was transferred to a 2 L autoclave, and further, 40 g of toluene, and RuHCl (CO) [P (CH) as a hydrogenation catalyst in an amount of 500 ppm with respect to the charged amount of all monomers. ], Hydrogen gas pressure is 9 ~: L0MPa, temperature is 160 ~ 165 ° C, 3

6 5 3 3

An hour hydrogenation reaction was performed. After completion of the reaction, the reaction solution was added to a large amount of methanol solution to cause precipitation, and dried in a vacuum dryer at 100 ° C for 12 hours to obtain a hydrogenated cyclic olefin-based ring-opening copolymer (hereinafter referred to as this product). The cyclic olefin-based ring-opening copolymer hydrogenated product is referred to as “ring-opening copolymer hydrogenated product (D).) ₀ ) The obtained hydrogenated product (D) has a weight average molecular weight (Mw) = 73600, The molecular weight distribution (MwZMn) was 6.00, the logarithmic viscosity (7? Inh) was 0.54, and the extrapolated glass transition start temperature (Tg) was 139.0 ° C. The hydrogenation rate of this hydrogenated product (D) determined by NMR measurement was 99.7% or more, and the aromatic ring residual rate was 100%. Figures 1 and 2 show the IR spectrum and ¹ H-NMR ^ vector of the resulting hydrogenated ring-opening copolymer (D).

[0228] 2.8 g of the resulting ring-opened polymer hydrogenated product (D) dissolved in 28 g of methylene chloride and filtered under reduced pressure (filter: GA200 manufactured by ADVANTEC) was used to prepare a smooth glass petri dish (size: inner diameter 146mm X depth 30mm). The film was peeled from the bath and then dried for 12 hours with a 100 ° C vacuum dryer to obtain a film having a thickness of 96 m. Residue in the obtained film The amount of residual solvent was 500 ppm.

[0229] This film was cut into a width of 10 mm and a length of 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. The film was stretched twice at 154, 149, and 144 ° C at a speed of 220% Z. The film thicknesses of the obtained films were 85, 72, and 67 m, respectively, and the phase difference was measured to be R550 = 393, 464, 666. Here, R550 represents a phase difference at a wavelength of 550 nm. Detailed results are shown in Table 1.

[0230] [Comparative Example 1]

Ring-opening polymerization in the same manner as in Example 1 except that monomers (A) and (C) were not used, and monomer (B) lOOg and 4.6 g of 1-hexene were used as molecular weight regulators. Reaction, hydrogenation reaction, hydrogenated substance recovery and drying, weight average molecular weight (Mw) = 135, 000, molecular weight distribution (MwZMn) = 3.06, logarithmic viscosity (r? Inh) = 0.78, complement An outer glass transition initiation temperature (Tg) = 167.degree. C. was obtained. The hydrogenation rate of this hydrogenated product obtained by NMR measurement was 99.8% or more. The obtained ring-opening polymerization hydrogenated product was formed into a film of 140 m in the same manner as in Example 1. The amount of residual solvent in the obtained film was 530 ppm.

[0231] This film was cut into a width of 10 mm and a length of 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. The film was stretched twice at a speed of 220% Z at 177 ° C. The film thickness of the obtained film was 100 m, and the phase difference was measured to be R450 = 396, R550 = 388, and R650 = 384 nm, respectively.

[0232] [Comparative Example 2]

A ring-opening polymerization reaction, hydrogen as in Example 1 except that 2.00 g of monomer (A) and 10.00 g of (B) were used, and 1.09 g of 1.-hexene was used as a molecular weight regulator. Addition reaction, hydrogenated substance recovery and drying, weight average molecular weight (Mw) = 115600, molecular weight distribution (MwZMn) = 3.52, logarithmic viscosity (η inh) = 0.70, extrapolated glass transition temperature (Tg ) = 1 A ring-opening polymerization hydrogenated product of 75.0 ° C was obtained. The hydrogenation rate of this hydrogenated product obtained by NMR measurement was 99.8% or more. The obtained ring-opening polymerization hydrogenated product was formed in the same manner as in Example 1 to obtain a 140 μm film. The amount of residual solvent in the obtained film is 530 ppm. [0233] This film was cut into a width of 10 mm and a length of 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. The film was stretched twice at 185 ° C at a speed of 220% Z. The film thickness of the obtained film was 100 m, and the phase difference was measured to be R45 0 = 510, R550 = 490, R650 = 480 nm.

[0234] The results are summarized in Table 1.

[0235] [Table 1]

【table 1】

As shown in Table 1, the stretched film of Example 1 obtained from a hydrogenated ring-opening copolymer containing monomer A as a copolymerization component has not been achieved with conventional norbornene-based resin. As the wavelength increases, the phase difference increases remarkably, and as the wavelength increases, the phase difference decreases remarkably.Positive wavelength dispersion is exhibited. Even if the stretching temperature (processing temperature) is lowered, the stretching process can be performed with the same stress as in Comparative Examples 1 and 2, and the same optical characteristics can be exhibited.

. In addition, since the stretching temperature is low, it is possible to reduce thermal deterioration and discoloration during processing. In addition, since the extrapolated glass transition start temperature is low, unlike the polymers of Comparative Examples 1 and 2, it can be molded by the melt extrusion method. Thus, the cyclic olefin-based ring-opening copolymer of the present invention is excellent in processability and strength, and a stretched film obtained therefrom is apparent. It has been shown to have “positive wavelength dispersion”. Such compatibility of wavelength dispersion and additiveness can be adjusted by changing the type of monomer used and its yarn composition ratio.

Industrial applicability

The cyclic olefin-based ring-opening copolymer according to the present invention is very useful as an optical material, and includes an optical disk, a magneto-optical disk, an optical lens (FΘ lens, pickup lens, laser printer lens, camera, etc. Lenses, etc.), eyeglass lenses, optical film Z 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, optical fiber, light guide plate, optical card, optical mirror, IC, LSI, LED encapsulant, etc. Very high precision optical design is required Application to optical materials is possible.

[0237] The film of the present invention is useful as an optical film, and an unstretched film formed by extrusion molding or cast forming exhibits excellent transparency, and therefore can be suitably used as various protective films. Moreover, since the stretched film exhibits unique wavelength dispersion, it can be suitably used as a film constituting a retardation plate or a liquid crystal display device.

Claims

Claims Consists of a structural unit (1) represented by the following formula (1), a structural unit (2) represented by the following formula (2), and a structural unit (3) represented by the following formula (3) Cyclic olefin-based ring-opening copolymer having at least two kinds of structural units selected from:

(In the formula (1), a and b represent 0 or 1, and! ^-And a plurality of R ⁷ are independently hydrogen atom; halogen atom; oxygen atom, sulfur atom, nitrogen atom or key atom. A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, which may have a linking group, or a polar group, X represents —CH═CH— or —CH 2 CH—.

twenty two

X may be the same or different. )

[Chemical 2]

(In formula (2), a represents 0 or 1, and R to R ⁴ each independently have a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a key atom. May Represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group. X represents CH = CH or — CH CH—, and multiple Xs may be the same or different.

twenty two

May be. )

[Chemical 3]

(In formula (3), a represents 0 or 1, and R ¹ and R ² each independently represent a linking group containing a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a key 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—, and a plurality of X may be the same or different.

twenty two

You may go on. Y is one CH = CH, one CH CH—, or

twenty two

[Chemical 4]

Represents. ).

[2] In the above formulas (1), (2) and (3), the total of a plurality of Xs is 100 mol%, and 80 mol% or more of X is a group represented by CH 2 CH. The ring of claim 1

twenty two

Olefin-based ring-opening copolymer.

[3] The structural unit (1) according to claim 1 or 2, wherein 5 to 50 mol% of the structural unit (1) is contained in 100 mol% of the total amount of the structural units (1), (2) and (3). Cyclic olefin-based ring-opening copolymer.

[4] A structural unit in which R ¹ and R ² in the formula (2) are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom, an alkoxycarbonyl group or a phenyl group ( 2) The cyclic olefin-based ring-opening co-polymer according to any one of claims 1 to 3, Coalescence.

The structural unit force represented by the following formulas (2-1) to (2-5) has at least one structural unit (2) selected from the following formulas. The cyclic olefin-based ring-opening copolymer according to the description;

[Chemical 5]

[Chemical 6]

In 5), X is as defined in general formula (2). ) ₍ The structural unit force represented by the following formulas (3-1) to (3-3) has at least one structural unit (3) selected from any one of claims 1 to 5. Cyclic olefin-based ring-opening copolymer;

[Chemical 7]

(In the formulas (3-1) to (3-3), X is as defined in the general formula (3).) ₀

[7] The cyclic olefin-based ring-opening copolymer according to any one of [1] to [6], wherein an extrapolated glass transition start temperature measured according to Japanese Industrial Standard K7121 is 110 to 170 ° C.

[8] Using a Ubbelohde viscometer, the logarithmic viscosity measured at a sample concentration of 0.5 g / dL at a temperature of 30 ° C in a black mouth form is 0.4 to 0.8 dLZg. The cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 7.

[9] An optical component obtained by molding the cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 8.

[10] The cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 8 is cast or Is a film obtained by forming a film by an extrusion method.

[11] A stretched film obtained by forming and stretching the cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 8 by a casting method or an extrusion method.

[12] A stretched film force according to claim 11, wherein the stretched film satisfies the optical properties of the following formulas (a), (b) and (c):

Re550> 0---(a)

Re450 / Re550> 1. 022 ••• (b)

Re650 / Re550 <0. 990---(c)

[13] A polarizing plate comprising the stretched film according to claim 11 or 12.

[14] A liquid crystal display device comprising the stretched film according to [11] or [12].