WO2007010830A1 - Cyclic olefin ring-opening copolymer, use thereof, and process for production of retarder comprising the copolymer - Google Patents

Abstract

A cyclic olefin ring-opening copolymer comprising a constituent unit which is derived from a cyclic olefin having a polar group and a hydrocarbon group, a constituent unit which is derived from tricyclo[4.3.0.12,5]deca-3-ene which may have a substituent or the like and a constituent unit which is derived from a cyclic olefin having no polar group. There are provided: a cyclic olefin copolymer which is excellent in heat resistance and optical properties, can be suitably formed into a film or sheet, and can be stretched even at a relatively low temperature around Tg without causing disadvantages such as whitish turbidity; a film or sheet comprising the cyclic olefin copolymer which is excellent in optical properties and heat resistance and is suitable for stretching at a relatively low temperature; a retarder which is excellent in optical properties and heat resistance, shows a steady phase difference, and shows no fluctuation of an optical axis; and a process for producing the retarder.

Description

 Specification

 Cyclic olefin-based ring-opening copolymer, its use, and method for producing a retardation plate containing the copolymer

 Technical field

 The present invention relates to a cyclic polyolefin ring-opening copolymer that can be stretched at a relatively low temperature without causing problems such as cloudiness. The present invention also relates to a film, a sheet and a retardation plate containing such a cyclic olefin-based ring-opening copolymer, and a method for producing the retardation plate.

 Background art

 [0002] Cyclic olefin-based ring-opening (co) polymers are amorphous and transmit light due to the presence of bulky groups in the main chain structure with high glass transition temperature due to the rigidity of the main chain structure. It has features such as a high refractive index and low birefringence due to low refraction anisotropy, and has attracted attention as a transparent thermoplastic resin with excellent heat resistance, transparency and optical properties. Yes. Examples of such cyclic olefin-based ring-opening (co) polymers include those described in Patent Documents 1 to 6.

 [0003] In recent years, using the above characteristics, in the fields of optical materials such as optical discs, optical lenses, optical fibers, and sealing materials such as optical semiconductor sealing, cyclic olefin-based ring-opening (co) recovery Application of coalescence is being studied. In addition, attempts have been made to improve the problems of conventional optical films by applying them to films or sheets (hereinafter referred to as films including sheets).

[0004] That is, films such as polycarbonate, polyester, or triacetyl acetate, which have been used as optical films in the past, have a large photoelastic coefficient, so that a phase difference is caused by a slight change in stress. As a solution to these problems, films that have cyclic olefin-based ring-opening (co) polymer strength have been proposed as various optical films. ing. For example, in Patent Documents 7 to 10, there is a phase difference plate (an optical film having a function of imparting a phase difference to transmitted light, also referred to as a phase difference film) that also has a film strength of a cyclic olefin-based ring-opening (co) polymer. Record It is listed. Patent Documents 11 to 13 describe the use of a cyclic olefin-based ring-opening (co) polymer film as a protective film for a polarizing plate. Furthermore, Patent Document 14 describes a liquid crystal display element substrate having a film strength of a cyclic olefin-based ring-opening (co) polymer.

 [0005] By the way, with the recent increase in size and functionality of liquid crystal display elements (LCDs), the required characteristics for retardation plates used in LCDs have become more sophisticated. For example, LCDs have larger screens and are lighter. On the other hand, higher levels of uniformity of phase difference and optical axis fluctuation are required, and control of phase difference in the thickness direction is required to improve the viewing angle of LCD. Yes. In order to meet these requirements, ring-opening homopolymers (homopolymers) and ring-opening copolymers of various cyclic olefin-based monomers have been proposed as materials for retardation plates.

 [0006] However, in the case of a homopolymer, the characteristics of the polymer obtained are uniquely determined by the characteristics of the cyclic olefin-based monomer used, and all of the various required characteristics are supported. There are limits to doing it.

 On the other hand, in the case of a copolymer, stretching near the glass transition temperature (hereinafter also referred to as Tg) of the copolymer may cause the film after stretching to become cloudy or reduce the uniformity of retardation. Serious problems may occur. Of course, these problems can be avoided by increasing the film stretching temperature and then stretching, but the stretching ratio decreases to obtain the desired retardation value because the development of the retardation decreases when stretching at a high temperature. There is a problem in controlling the retardation value, such as increasing the film thickness, or increasing the film thickness.

 [0007] For this reason, it has excellent properties of cyclic olefin-based resin such as heat resistance and transparency, and even when film forming or film stretching is performed at a relatively low temperature such as near Tg, Thus, there has been a strong demand for a resin suitable for applications such as a phase difference plate.

As a result of diligent research in view of such a situation, the present inventors have found that cyclic olefins having a polar group and a hydrocarbon group and tricyclo [4.3.0.I ² ' ⁵ ] deca which may have a substituent. Even if a cyclic olefin-based ring-opening copolymer obtained from 1-3ene and a cyclic olefin having no polar group such as bicyclo [2.2.1] hept-2-ene is stretched under a temperature condition near Tg, White The present invention has been completed by finding that it does not cause problems such as turbidity and is suitable for use as a film or sheet and a retardation plate.

 Patent Document 1: JP-A-1 132625

 Patent Document 2: JP-A-1 132626

 Patent Document 3: Japanese Patent Laid-Open No. 63-218726

 Patent Document 4: JP-A-2-133413

 Patent Document 5: Japanese Patent Laid-Open No. 61-120816

 Patent Document 6: Japanese Patent Laid-Open No. 61-115912

 Patent Document 7: Japanese Patent Laid-Open No. 4-245202

 Patent Document 8: JP-A-4-36120

 Patent Document 9: JP-A-5-2108

 Patent Document 10: JP-A-5-64865

 Patent Document 11: JP-A-5-212828

 Patent Document 12: JP-A-6-51117

 Patent Document 13: JP-A-7-77608

 Patent Document 14: JP-A-5-61026

 Disclosure of the invention

 Problems to be solved by the invention

[0008] The present invention is capable of meeting high-level characteristic requirements as a retardation plate, and does not cause problems such as white turbidity even when stretched under temperature conditions close to the glass transition temperature (Tg). A cyclic olefin-based ring-opening copolymer that is suitable for film or sheet use, has a uniform desired retardation, and can easily obtain a retardation plate without optical axis fluctuation is provided. The subject is to provide. Another object of the present invention is to provide a film or sheet containing the cyclic olefin-based ring-opening copolymer, a phase difference plate comprising the film or sheet, and a method for producing the phase difference plate.

 Means for solving the problem

The cyclic olefin-based ring-opening copolymer of the present invention has a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a formula represented by the following formula (3). Having a structural unit Is characterized by;

 [0010] [Chemical 1]

(In the formula (1), m is 0, 1 or 2; X is independently a group represented by the formula: CH = CH 2 or a group represented by the formula: CH 2 CH—; Ri each to R ⁴ independently represent a hydrogen atom; Nono Rogge

 twenty two

A substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, which may have a linking group containing oxygen, nitrogen, iodo or kei; or a polar group. However, at least one of Ri to R ⁴ is a polar group, and at least one of the other Ri to R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms. ),

[0012] [Chemical 2]

 (In the formula (2), X is independently a group represented by the formula: CH = CH 2 or a formula: CH 2 CH 1

R ^{5 to} R ^1Q are each independently a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom that may have a linking group containing oxygen, nitrogen, iodo or silicon. Represents a hydrocarbon group of the number 1 to 10; or a polar group. ),

[0014] [Chemical 3]

R ^{12 13} … ( ₃₎

(In the formula (3), n is 0, 1 or 2, X is independently a group represented by the formula: CH = CH 2 or a group represented by the formula: —CH 2 CH 1, R ^{U to} R "each independently represents a hydrogen atom;

 twenty two

 Or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, which may have a linking group containing oxygen, nitrogen, iodo or keen. ).

 The cyclic olefin-based ring-opening copolymer of the present invention preferably has a DSC differential differential scanning calorimetry curve with a single peak and a glass transition temperature (Tg) of 110 ° C. or higher! /.

[0016] The cyclic olefin-based ring-opening copolymer of the present invention preferably has no structural unit other than the structural units represented by the formulas (1) to (3).

 In the cyclic olefin-based ring-opening copolymer of the present invention, the polar group in the structural unit represented by the formula (1) is preferably a group represented by the following formula (4);

 -(CH) COOR '--(4)

 2 p

 (In formula (4), p is 0 or an integer of 1 to 5, and R ′ is a hydrocarbon group having 1 to 15 carbon atoms).

 [0017] The film or sheet of the present invention is characterized by including the cyclic olefin-based ring-opening copolymer of the present invention.

 The retardation plate of the present invention is characterized in that the film or sheet of the present invention is stretched and oriented.

 Further, in the method for producing a retardation plate of the present invention, the film or sheet of the present invention is stretched under a temperature condition of Tg to (Tg + 10) ° C. of the cyclic olefin-based copolymer contained in the film or sheet. It is characterized by being oriented.

The invention's effect [0018] According to the present invention, the film and sheet are excellent in heat resistance and optical properties, and can be formed without causing problems such as cloudiness even at a relatively low temperature near Tg. A cyclic olefin-based copolymer that can be provided can be provided. Further, according to the present invention, it is possible to provide a film or sheet containing such a cyclic olefin-based copolymer, which has excellent optical characteristics and heat resistance and is suitable for stretching at a relatively low temperature. Furthermore, according to the present invention, it is possible to provide a retardation plate excellent in optical characteristics and heat resistance, exhibiting a uniform retardation, and free from optical axis fluctuation, and a method for producing the same.

 Brief Description of Drawings

FIG. 1 shows a ¹ H—NMR measurement chart of copolymer (1 ′), which is the copolymer before hydrogenation obtained in Example 1.

FIG. 2 shows a ¹ H-NMR measurement chart of copolymer (1), which is the copolymer after hydrogenation obtained in Example 1.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0020] The present invention will be specifically described below.

 <Cyclic olefin copolymer>

 The cyclic olefin-based ring-opening copolymer of the present invention includes a structural unit represented by the above formula (1), a structural unit represented by the above formula (2), and a structure represented by the above formula (3). Has units. The structural unit represented by the formula (1) is derived from a cyclic olefin monomer (1) represented by the following formula (1 ′) by ring-opening copolymerization.

[0021] [Chemical 4]

 R3 (1)

(In the formula (1 ′), m and Ri to R ⁴ are the same as in the above formula (1), m is 0, 1 or 2, and RR ⁴ is independently a hydrogen atom; a halogen atom; an oxygen , Nitrogen, yeow or kay A substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a linking group containing silicon; or a polar group. However, at least one of polar groups R -R ^4, at least one 1 to carbon atoms other Ri～R ⁴ of Katsuso: a hydrocarbon group LO. )

 In the formula (1) or formula (1 ′), examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carboxy group, an alkoxy carbo group, an aryloxy carbo group, and a cyan group. Amide group, imide group, triorganosiloxy group, triorganosilyl group, amino group, acyl group, alkoxysilyl group, sulfol group, carboxyl group and the like. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the carbo-oxy group include an alkyl carbo-oxy group such as an acetooxy group and a propio-oxy group, and a benzoyl group. Examples of the alkoxy carbyl group include a methoxy carbo yl group and an ethoxy carbonyl group, and examples of the aryl carboxy group include a phenoxy carbo ol group and a naphthyl group. An oxycarbonyl group, a fluoro-carboxyl group, a bi-phenyloxycarbol group, etc .; examples of the triorganosiloxy group include a trimethylsiloxy group, a triethylsiloxy group, etc .; a triorganosilyl group As trimethylsilyl group, triethylsilyl group Do etc. can be mentioned are; the amino group include primary Amino group, the alkoxysilyl group, for example trimethoxysilyl groups, such as triethoxysilyl group.

 Examples of the hydrogen atom and the rogen atom include a fluorine atom, a chlorine atom and a bromine atom.

 Examples of the hydrocarbon group having 1 to 10 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; a bur group, an aryl group, and a propenyl group. Alkenyl groups such as groups.

 In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linkage. As the linking group, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, one (CH 3) (wherein m is an integer of 1 to 10)

 2 m

Represented by an alkylene group); a linking group containing oxygen, nitrogen, iodo or silicon (for example, a carbo group (—CO—), an oxy group (—O (CO) —), a sulfone group (— SO-)

2 One-tel bond (one O—), thioether bond (one S—), imino group (—NH—), amide bond (one NHCO-, — CONH—), siloxane bond (— OSi (R)-(where R is methyl, ethyl

 2

 And a linking group containing a plurality of them may be used.

 As the cyclic olefin-based monomer (1), specifically, for example,

 5-Methyl-5-methoxycarbo-rubicyclo [2.2.1] hepto 2

 5-methyl-5-phenoxycarbo-rubicyclo [2.2.1] hept-2-ene,

5-Methyl-6-methoxycarbo-rubicyclo [2.2.1] hepto 2

 5-methyl-6-phenoxycarbo-rubicyclo [2.2.1] hept-2-ene,

8-methyl-8-methoxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹ ' ³ ] — 3 -dodecene,

8-Methyl-8-ethoxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. I ¹ ' ¹ . ] — 3—Dodecene

-. 2,5 7,10 _τ τ_

8-Methyl-8-n-propoxycarbonyltetracyclo [4. 4. 0. 1 .1]

3—Yen,

-. 2,5 7,10 _τ τ_

8-methyl-8-isopropoxycarbonyltetracyclo [4. 4. 0. 1 .1]

3—Yen,

8-methyl-8-n-butoxycarbo-rutetracyclo [4. 4. 0. I ² ' ^5. l ⁷ ' ¹⁰ ]

8-Methyl-8-phenoxycarbo-rutetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] dodeca 3

 The force S that can be cited is not limited to these examples.

In the present invention, the polar group in the structural unit represented by the formula (1) is preferably a group represented by the following formula (4). That is, in the structural unit represented by the above formula (1) or the cyclic olefin-based monomer (1) represented by the above formula (1 ′), at least one of Ri R ⁴ is represented by the following formula (4): U, which is preferably a group represented by

 -(CH) COOR '--(4)

 2 p

 (In the formula (4), p is an integer of 0 or 15 and R ′ is a hydrocarbon group having 1 to 15 carbon atoms o)

In the above formula (4), the smaller the value of n and the smaller R ′ is, the higher the glass transition temperature of the copolymer obtained and the better the heat resistance. Snow That is, n is usually a force that is an integer of 0 or 15 and is preferably 0 or 1, and R ′ is usually a hydrocarbon group having 115 carbon atoms, preferably an alkyl group having 13 carbon atoms. It is desirable that

 [0026] Furthermore, in the above formula (1), when an alkyl group is further bonded to the carbon atom to which the polar group represented by the general formula (4) is bonded, the heat resistance of the resulting copolymer is reduced. This is preferable in order to balance the properties and water absorption (wet) properties. The alkyl group preferably has 15 carbon atoms, more preferably 12 and particularly preferably 1.

 The structural unit represented by the formula (2) is derived from a cyclic olefin monomer (2) represented by the following formula (2 ′) by ring-opening copolymerization.

 [0027] [Chemical 5]

[0028] (In the formula (2 '), R ⁵ R ^1Q is the same as in the formula (2), and each independently has a hydrogen atom; a halogen atom; a linking group containing oxygen, nitrogen, iodo or keine. An optionally substituted substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms; or a polar group.)

 In the above formula (2) or (2 ′), the halogen atom, hydrocarbon group and polar group are the same as those described for the above formula (1) or ().

[0029] As such a cyclic olefin-based monomer (2), specifically, for example,

Tricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3-Yen,

7- -Methyl- 卜 licyclo [4. 3. 0. I ² ' ⁵ ] De-force--3-

8-Methyl- 卜 licyclo [4. 3. 0. I ² ' ⁵ ] De-force--3-

7- -Ethyl- 卜 Licyclo [4. 3. 0. I ² ' ⁵ ] De-force--3-

7-Isopropyl monotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3- 7 cyclohexyl monotricyclo [4. 3. 0. I ² ' ⁵ ]

7 fertricyclo [4. 3. 0. I ² ' ⁵ ]

7, 7 Dimethyl monotricyclo [4. 3. 0. I ² ' ⁵ ] Deca-3

7, 8 Dimethyl monotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3,

7-methyl 8-ethyltricyclo [4. 3. 0. I ² ' ⁵ ]

7-methoxycarbonyl monotricyclo [4. 3. 0. I ² ' ⁵ ]

8-methoxycarbonyl monotricyclo [4. 3. 0. I ² ' ⁵ ]

7 Phenoxycarbon tricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3

7-methyl 7-methoxycarbocycle tricyclo [4. 3. 0. I ² ' ⁵ ]

8-methyl 8-methoxycarbotritricyclo [4. 3. 0. I ² ' ⁵ ]

7 Fluorotricyclo [4. 3. 0. I ² ' ⁵ ]

8 Fluorotricyclo [4. 3. 0. I ² ' ⁵ ]

7 Chlorotricyclo [4. 3. 0. I ² ' ⁵ ]

8 Chlorotricyclo [4. 3. 0. I ² ' ⁵ ]

7, 7 Difluoro-tricyclo [4. 3. 0. I ² ' ⁵ ] Deca- 3,

7, 8 Difluoro-tricyclo [4. 3. 0. I ² ' ⁵ ] Deca- 3,

7, 8 Dichlorotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3

 The force S that can be cited is not limited to these examples.

[0030] The structural unit represented by the formula (2) is a cyclic olefin-based monomer represented by the following formula (2-2) (where R ^{5 to} R ⁷ and R ⁹ are represented by the formula (2) ) Can be obtained by ring-opening copolymerization and then hydrogenating the five-membered ring.

 [0031] [Chemical 6]

[0032] このような環状ォレフィン系単量体（2— 2)としては、具体的には、たとえば、 トリシクロ [4. 3. 0. I²'⁵]デカ一 3, 7 ジェン（DCP)、

[0032] Specific examples of such cyclic olefin-based monomers (2-2) include tricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen (DCP),

7-methyl monotricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen,

8-methyl monotricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen,

9-methyl monotricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen,

7, 8 Dimethyl monotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7 Gen,

7 ethyl tricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen,

7 cyclohexyl monotricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen,

7 Fertricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7 Gen,

7— (4 biphenyl) monotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7 Gen

7-methoxycarbon monotricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen,

7 Phenoxycarbole tricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7 Gen,

7-methyl 7-methoxycarbocycle tricyclo [4. 3. 0. I ² ' ⁵ ] deca 3, 7 gen,

7 Fluorotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7 Gen,

7, 8 Difluorotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7 Gen,

7 Chlorotricyclo [4. 3. 0. I ² ' ⁵ ] Deca 3, 7 Gen

However, it is not limited to these examples. Of these, tricyclo [4.3.0.I ² ' ⁵ ] deca-1,7-gen is particularly preferably used in the present invention.

 [0033] The structural unit represented by the formula (3) is derived from a cyclic olefin monomer (3) represented by the following formula (3 ') by ring-opening copolymerization.

 [0034] [Chemical 7]

… ，) [0035] (式（3' )中、 nは 0、 1または 2であり、 R^U〜R"はそれぞれ独立に水素原子;ノヽロゲン 原子;または、酸素、窒素、ィォゥもしくはケィ素を含む連結基を有していてもよい置 換又は非置換の炭素原子数 1〜10の炭化水素基を表す。 )

…,) [0035] (In the formula (3 '), n is 0, 1 or 2, and R ^{U to} R "each independently represents a hydrogen atom; a norogen atom; or a linkage containing oxygen, nitrogen, iow or keine. And represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms which may have a group.

 Specific examples of such cyclic olefin-based monomers (3) include, for example, bicyclo [2.2.1] hept-2-ene,

Tetracyclo [4. 4. 0. I ² ' ^5. 1 ⁷ . ]

To Kisashikuro ^{[6. 6. 1. I 3 '6} . I 10' 13. O 2 '7. 0 9' 14] Heputo 4 En

 5 ethyl bicyclo [2.2.1] heptoe 2

 5-methylbicyclo [2. 2. 1] hepto-2

 However, it is not limited to these examples. Of these, bicyclo [2.2.1] hept-2-ene is particularly preferably used.

[0036] The cyclic olefin-based ring-opening copolymer of the present invention comprises one or more cyclic olefin-based monomers (1), cyclic olefin-based monomers (2) (or (2-2)), and It can be produced by ring-opening copolymerization of the cyclic olefin-based monomer (3). Cyclic Orefi emissions based ring-opening copolymer of the present invention, 8-methyl 8-methoxycarbonyl - Rutetorashikuro ^{[4. 4. 0. I 2 '5} I 7.' 10] - 3 -dodecene and tricyclo [4.3. Particularly preferred is a copolymer comprising 0.I ² ' ⁵ ] deca-1,7-gen and bicyclo [2.2.1] hept-2-enca.

In the present invention, the copolymerization ratio of the cyclic olefin monomer (1), the cyclic olefin monomer (2) (or (2-2)) and the cyclic olefin monomer (3) is When the total of these is 100 parts by weight, the cyclic olefin-based monomer (1) is usually 50 to 90 parts by weight, and the cyclic olefin-based monomer (2) (or (2-2)) is 10-40 parts by weight, cyclic olefin-based monomer (3) is in the range of 0.5-20 parts by weight, preferably 50-80 parts by weight of cyclic olefin-based monomer (1), cyclic olefin-based monomer It is desirable that the monomer (2) (or (2-2)) is in the range of 10 to 30 parts by weight and the cyclic olefin monomer (3) is in the range of 1 to 10 parts by weight. If the amount of the cyclic olefin-based monomer (1) exceeds 90 parts by weight, the glass transition temperature of the resulting polymer may become too high, making extrusion molding difficult. The glass transition temperature can be adjusted by copolymerizing the cyclic olefin-based monomer (2) (or (2-2)). However, if the amount exceeds 40 parts by weight, the resulting polymer solution can be used in the solution. The filtration performance may be poor. For this reason, By using a small amount of a cyclic olefin-based monomer (3) as a copolymerizable monomer together with the olefin-based monomer (2), it has an objective glass transition temperature without reducing the filtration performance. Can be obtained.

 [0038] In the present invention, in addition to these cyclic olefin monomers (1), (2) (or (2-2)) and (3), others are within the range not impairing the object of the present invention. A small amount of the cyclic olefin-based monomer or other copolymerizable monomer can be used as a copolymerization raw material monomer, and the cyclic olefin-based ring-opening copolymer according to the present invention has the above formulas (1), (2) And a structural unit other than the structural unit represented by (3). Such structural units include, for example, cycloolefin monomers such as cyclobutene, cyclopentene, cycloheptene, and cyclootaten, and the above cyclic olefin monomers (1), (2) (or (2-2)) and ( It can be formed by ring-opening copolymerization with 3). In addition, in the presence of unsaturated hydrocarbon polymers having an olefinic unsaturated bond in the main chain such as polybutadiene, polyisoprene, styrene butadiene copolymer, ethylene non-conjugated gen copolymer, polynorbornene, etc. Monomers (1), (2) (or (2-2)) and (3) can also be formed by ring-opening copolymerization and have such structural units However, the impact resistance of the copolymer of the present invention tends to be improved.

 However, in the present invention, it is preferable to carry out copolymerization using only the cyclic olefin-based monomers (1), (2) (or (2-2)) and (3). That is, the cyclic olefin-based ring-opening copolymer according to the present invention has other structures in addition to the structural units represented by the above formulas (1), (2) and (3) as long as the object of the present invention is not impaired. Although it may have a unit, it is preferred not to have a structural unit other than the structural units represented by the formulas (1), (2) and (3).

[0040] Copolymerization of each cyclic olefin monomer can be carried out by appropriately selecting the polymerization conditions in consideration of the reactivity of each monomer used. When copolymerization, it is preferable that the monomer composition ratio in the polymerization system does not change significantly between the early and late stages of polymerization. It is preferable to keep the monomer composition ratio constant by supplying the monomer having a reduced concentration in the polymerization system continuously or intermittently into the polymerization system. When copolymerization is performed while controlling the monomer composition ratio in this way, A copolymer capable of forming an optical film having excellent transparency can be obtained.

 [0041] A ring-opening copolymer obtained by ring-opening copolymerization of each cyclic olefin-based monomer has an olefinic unsaturated bond in the molecule and has problems such as heat-resistant coloring. Therefore, it is preferable that the olefinic unsaturated bond is hydrogenated, but a known method can be applied to the hydrogenation reaction.

 For example, the catalyst, solvent and temperature conditions described in JP-A-63-218726, JP-A-1-132626, JP-A-1-240517, JP-A-2-10221, etc. are applied. Thus, ring-opening polymerization reaction and hydrogenation reaction can be carried out.

 [0042] The hydrogenation rate of the olefinic unsaturated bond is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. As described above, the hydrogenation reaction in the present invention refers to an intraolefin olefinic unsaturated bond, and when the cyclic olefin-based ring-opening copolymer of the present invention has an aromatic group, such an aromatic Group groups do not necessarily have to be hydrogenated because they may have an advantageous effect on optical properties such as refractive index and heat resistance.

 [0043] As the molecular weight of the cyclic olefin-based ring-opening copolymer of the present invention, the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 8000 to 1,000,000. 000, preferably <10,000 to 500,000, more preferably <10,000 to 100,000, and the weight average molecular weight (Mw) in terms of polystyrene is usually from 10,000 to 3,000, 000, 000, preferred <is 20,000-1,000,000, more preferred <is in the range of 30,000-500, 000!

 [0044] If the molecular weight is too small, the strength of the resulting film may be low. On the other hand, if the molecular weight is excessive, the solution viscosity becomes too high, and the productivity and processability of the copolymer of the present invention may deteriorate.

 The molecular weight distribution (MwZMn) of the copolymer of the present invention is usually 1.5 to 10, preferably 2 to 8, and more preferably 2.2 to 5.

[0045] cyclic Orefin based ring-opening copolymer of the present invention, the saturated water absorption force normally 0 in 23 ° C. 01~1 weight _^0/0, preferably from 0.05 to 0.7 wt _^0/0, further Preferably 0.1 to 0.5 weight % Is desirable. When the saturated water absorption rate of the copolymer of the present invention is within the above range, various optical properties, transparency, retardation and retardation uniformity, or dimensional accuracy of the obtained film are high temperature and high humidity. In addition to being stable even under such conditions, it has excellent adhesion and adhesiveness to other materials, so that peeling does not occur during use, and it is compatible with additives such as antioxidants. Since the solubility is also good, the degree of freedom in selecting the type and amount of additive is increased.

 [0046] When the saturated water absorption is less than 0.01% by weight, the resulting film has low adhesion and adhesiveness to other materials, and tends to be peeled off during use. The addition amount of additives such as an acid inhibitor may be limited. On the other hand, when the saturated water absorption exceeds 1% by weight, water absorption tends to cause changes in optical characteristics and dimensional changes. Here, the saturated water absorption is a value obtained by immersing in 23 ° C water for 1 week and measuring the increased weight according to ASTM D570.

 [0047] The glass transition temperature (Tg) of the cyclic olefin-based ring-opening copolymer of the present invention is usually 110 to 250 ° C, preferably 115 to 220 ° C, more preferably 120 to 200 ° C. is there. A Tg of 110 ° C. or higher is preferable because of excellent heat resistance. If Tg is less than 110 ° C, the heat distortion temperature becomes low, which may cause a problem in heat resistance, and the problem that the change in optical properties due to temperature in the resulting film becomes large may occur. There is. On the other hand, when Tg exceeds 250 ° C, the processing temperature becomes too high during the drawing process, and the copolymer of the present invention may be thermally deteriorated.

[0048] Further, the cyclic olefin-based ring-opening copolymer of the present invention has a differential differential scanning calorimetric curve of DSC showing a single peak, and a Tg distribution force of 0 ° C or less, which is a rising temperature width of the peak. Preferably, it has a narrow distribution of 35 ° C or less. The differential differential scanning calorimetry curve of DSC used in the present invention is obtained when measured in a nitrogen atmosphere at a rate of temperature increase of 20 ° CZ. The peak rising temperature width is the width between the inflection points where the base line force rises. In addition, the Tg of the cyclic olefin-based ring-opening copolymer is plotted on the differential scanning calorimetry curve with the maximum peak temperature (point A) of differential differential scanning calorific value and the temperature (point B) at 20 ° C from the maximum peak temperature. It is obtained as the intersection of the tangent on the base line starting from point B and the tangent starting from point A. <Additives>

 In the cyclic olefin-based ring-opening copolymer of the present invention, addition of known antioxidants and ultraviolet absorbers for the purpose of improving the heat resistance and the light resistance, as long as the effects of the present invention are not impaired. An agent can be added. For example, at least one compound selected from the group consisting of the following phenol compounds, thiol compounds, sulfide compounds, disulfide compounds, and phosphorus compounds may be added to 0.01 parts by weight of the copolymer of the present invention. Addition of ˜10 parts by weight can improve heat deterioration resistance.

 'Phenol compounds

 Examples of phenolic compounds include triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenol) proonate], 1,6-hexanediol monobis [3— (3,5 di-tert-butyl 4-hydroxyphenol) propionate], 2, 4 bis (n-octylthio) 6- (4-hydroxy-3,5-di-tert-butylamino) -3,5-triazine, pentaerythrityl-tetrakis [ 3— (3,5-Di-tert-butyl-4-hydroxyphenol) propionate], 2, 2 Diethylenebis [3 -— (3,5-di-tert-butyl—4-hydroxyphenol) propionate], Octadecyl-3 — (3,5-di-tert-butyl 4-hydroxyphenol) propionate], N, N-hexamethylenebis (3,5-di-tert-butyl 4-hydroxy monohydrocinnamamide), 1, 3 , 5 Trimethyl 2, 4, 6 Tris 3, 5-di-tert-butyl 4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) monoisocyanurate, 3, 9 bis [2- [3- (3-t-butyl 4-hydroxy-5-methylphenol) propio-loxy] 1,1 dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane. Preferably, octadecyl 3- (3,5-di-tert-butyl 4-hydroxyphenol) propionate], 1, 3, 5 trimethyl 2, 4, 6 tris (3,5 di-tert-butyl 4-hydroxy Benzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate], particularly preferably otadecyl-3- (3,5-di-tert-butyl) 4-hydroxyphenyl) propionate].

'Thiol compounds Examples of thiol compounds include alkyl mercaptans such as t-decyl mercaptan and hexyl mercaptan, 2 mercaptobenzimidazole, 2 mercapto 6 methyl benzimidazole, 1-methyl-2- (methyl mercapto) benzimidazole, 2-mercapto 1 methylbenz. Imidazole, 2 Mercapto 4 Methylbenzimidazole, 2 Mercapto 5 Methylbenzimidazole, 2 Mercapto 5, 6 Dimethylbenzimidazole, 2- (Methylmercapto) benzimidazole, 1-Methyl-2- (methylmercapto) benzimidazole, 2 Mercapto Examples thereof include 1,3 dimethylbenzimidazole and mercaptoacetic acid.

• Sulfide compounds

 Sulfide compounds include 2,2 thiodiethylenebis [3- (3,5 di-tert-butyl 4-hydroxyphenol) propionate], 2,2 thiobis (4-methyl-6-tert-butylphenol), 2, 4 Bis (n-octylthiomethyl) 6 methylphenol, dilauryl 3, 3'-thiodipropionate, dimyristyl 3, 3'-thiodipropionate, distearyl 3, 3'-thiodipropionate, pentaerythrityl Examples include tetrakis (3-lauryl thiopropionate) and ditridecyl 3, 3'-thiodipropionate.

 • Disulfide compounds

 Disulfide compounds include bis (4 black mouth file) disulfide, bis (2 black mouth file) disulfide, bis (2,5 dichrome mouth file) disulfide, and bis (2, 4, 6-trichrome). Mouth-Fuel) Disulfide, Bis (2—-Trophele) disulfide, 2, 2'-Dithiodiethyl benzoate, Bis (4-acetyl-di) disulfide, Bis (4) 1, 1'-dinaphthyl disulfide, 2, 2'-dinaphthyl disulfide, 1, 2'-dinaphthyl disulfide, 2, 2'-bis (1 chlorodinaphthyl) disulfide, 1, 1 ' —Bis (2-chloronaphthalyl) disulfide, 2, 2′-bis (1 cyanonaphthyl) disulfide, 2,2′-bis (1-acetylacetylnaphthyl) disulfide, dilauryl 3,3′—thiodipropionic acid ester, etc. Raised Rukoto can.

 'Phosphorus compounds

Phosphorus compounds include tris (4-methoxy-1,3,5-diphenyl) phosphite, tris (no -Rufyl) phosphite, tris (2,4 di-tert-butylphenol) phosphite, bis (2,6 di-tert-butyl-4-methylphenol) pentaerythritol diphosphite, bis (2,4 (Dibutylbutyl) pentaerythritol diphosphite.

 [0049] Further, a benzophenone compound such as 2,4-dihydroxybenzophenone, 2hydroxy-4-methoxybenzophenone, a benzotriazole compound such as N- (benzyloxycarbo-loxy) benzotriazole, or An oxa-lide type compound such as 2-ethyloxy uride, 2-ethyl yl 2′-ethoxy oxalide, etc. is preferably 0.01-3 parts by weight, preferably 100 parts by weight of the copolymer of the present invention. By adding 0.05 to 2 parts by weight, light resistance can be improved.

[0050] Further, when the cyclic olefin-based ring-opening copolymer according to the present invention is formed into a film or the like by melt extrusion, the ring-opening copolymer is prevented from being thermally deteriorated due to a heat history at the time of melt extrusion. Therefore, it is an important technical element to select an anti-oxidation agent to be added. That is, when a film obtained by melt extrusion is stretch-processed, the glass of a cyclic olefin-based ring-opening copolymer that is melt-extruded so as not to decrease the expression of the retardation or to minimize the degree of decrease. A hindered phenolic compound having a melting point in the temperature range from + 20 ° C to Tg + 130 ° C, preferably from ₈ + 30 to ₈ + 130, than the transition temperature (Tg) is used as an antioxidant. I prefer to use it.

 [0051] If the melting point is less than + 20 ° C than the Tg of the cyclic olefin-based ring-opening copolymer to be melt-extruded, even if a hindered phenol compound is used, the phase difference will Expression may be greatly reduced. On the other hand, if the melting point exceeds + 130 ° C above the Tg of the cyclic olefin-based ring-opening copolymer that is melt-extruded, the antioxidant will not dissolve during processing, which may cause fish defects and other film defects and foreign matter. There is. Even if the melting point is Tg + 20 ° C to Tg + 130 ° C of the cyclic olefin-based ring-opening copolymer, if a compound other than the hindered phenolic compound is used as the acid-detergent, There may be a decrease in the development of phase differences.

[0052] Specific examples of the anti-oxidation agent preferably used when the cyclic olefin-based ring-opening copolymer of the present invention is formed by melt extrusion include, for example, 1,3,5 trimethyl 2,4, 6-tris (3,5-di-tert-butyl 4-hydroxybenzyl) benzene, Ν, Ν 'hexamethylene bis (3,5-di-tert-butyl 4-hydroxy monohydrocinnamide), tris (3,5 —Di-t-butyl-4 hydroxybenzyl) -isocyanate, tris (2,4 di-t-butylphenyl) phosphite, and the like. The present invention is not limited to these. Depending on the Tg of the cyclic olefin-based ring-opening copolymer to be melt-extruded, it may be unsuitable. In addition, as long as the effect of this invention is not impaired, these may be used in combination and may be used independently.

 [0053] The amount of these antioxidants to be added is usually 0.01-5 parts by weight, preferably 0.05-4 parts by weight, more preferably 100 parts by weight of the cyclic olefin-based ring-opening copolymer. Preferably, it is 0.1 to 1.5 parts by weight. If the addition amount of the anti-oxidation agent is less than 0.01 parts by weight, gel is likely to occur in the resin during the extrusion process, and as a result, it is recognized as a defect on the obtained film. This is not preferable. On the other hand, when the amount of the additive exceeds 5 parts by weight, it may cause generation of eyes or the like during processing, which is preferable because it causes die lines, fish eyes on the film, and burns.

 [0054] Such an acid-fouling inhibitor may be added when producing the cyclic olefin-based ring-opening copolymer, or may be blended together with the pellets of the cyclic olefin-based ring-opening copolymer when melt-extruding. Also good.

 Further, in the case where the cyclic olefin-based ring-opening copolymer of the present invention is formed by melt extrusion, the above acid such as a lubricant, an ultraviolet absorber, a dye, or a pigment is used as long as the effects of the present invention are not impaired. Additives other than anti-wrinkle agents can be used. Of course, even in this case, in the case of an additive having a melting point, the melting point is preferably in the range of the melting point of the essential antioxidation agent of the present invention.

 [0055] The cyclic olefin-based ring-opening copolymer according to the present invention enables the amount of foreign matter gel contained in the copolymer, particularly when used for the production of films and sheets, the production of retardation plates, and the like. As few as possible are preferred. When there are many foreign objects and gels, fish-eye defects and die lines occur in the extruded film obtained by melt molding, resulting in a film with insufficient surface accuracy, especially for use in optical applications. Sometimes.

[0056] In the present invention, in order to obtain a film having good surface properties, it is contained in the copolymer lg used. The gel content is preferably 30 or less, more preferably 20 or less, and particularly preferably 10 or less.

 Here, the gel content contained in the copolymer lg can be measured, for example, as follows. Ie;

 The precisely weighed copolymer is filtered through a 0.1 μm membrane filter and dissolved in tetrahydrofuran (THF) from which foreign substances have been completely removed, and this resin solution is dissolved in a 0.5 μm membrane filter. Suction filtration is performed.

 Heat the filtered membrane filter at 260 ° C for about 30 minutes in a pine furnace.

 Observe the gel on the membrane filter (observed as “buzz” discolored brown) with a 20x stereo microscope and count the number.

 In the present invention, in order to obtain a film having good surface properties, it is preferable that there is no foreign matter of 50 m or more contained in the cyclic olefin-based ring-opening copolymer to be used. In particular, it is preferable that there is no foreign matter of 10 μm or more. In addition, the foreign material in a copolymer can be measured as follows, for example. That is, 10 g of the copolymer was filtered through a 0.1 m membrane filter and dissolved in tetrahydrofuran (THF) from which foreign matter had been completely removed, and 10 m, 20 m, and 50 m were obtained using a particle counter (light scattering method). Count the number of foreign objects of μm. If not observed by this method, the corresponding size of foreign material is defined as not present in the copolymer. Film or sheet>

 The cyclic olefin-based ring-opening copolymer of the present invention can be formed into a film by a known solution casting method (solvent casting method or melt molding method). Thus, the film according to the present invention A sheet (hereinafter referred to as a film including a sheet) can be obtained.

As the solvent casting method, for example, a film-forming solution containing the copolymer of the present invention in an appropriate concentration is prepared by dissolving or dispersing the copolymer resin of the present invention in a solvent. The forming liquid is cast on an appropriate carrier or casted to form a liquid phase of the film forming liquid on the carrier, and then the solvent is removed from the liquid layer by drying or the like. And the resulting film is peeled off. Can be cited as a preferred method.

 [0058] In the preparation of the film-forming solution by the solvent casting method, the concentration of the copolymer of the present invention is usually 0.1 to 70% by weight, preferably 1 to 50% by weight, more preferably 10 to 35%. Weight%. If this concentration is too low, it will be difficult to obtain a film having the required thickness, and when removing the solvent by drying, foaming will occur as the solvent evaporates, and surface smoothness will soon occur. However, it may be difficult to obtain a good film. On the other hand, if this concentration is excessive, the viscosity of the film-forming solution becomes too high, and it may be difficult to obtain a film having a uniform thickness and surface condition.

 [0059] The viscosity of the film-forming solution is usually 1 to 1,000, OOO (mPa-s), preferably 10 to: LOO, OOO (mPa-s), more preferably 100 to 80, at room temperature. OOO (mPa-s), particularly preferably 1000 to 60, OOO (mPa's).

 Solvents used for the preparation of the film-forming solution include aromatic solvents such as benzene, toluene and xylene, cellosolve solvents such as methyl cetosolve, ethylcelesolve, 1-methoxy 2-propanol, diacetone alcohol, acetone , Cyclohexanone, methyl ethyl ketone, 4-methyl-2 pentanone, cyclohexanone, ethyl cyclohexanone, ketone solvents such as 1,2-dimethylcyclohexane, ester solvents such as methyl lactate and ethyl lactate, 2, 2 , 3,3-tetrafluoro-1-propanol, halogen-containing solvents such as methylene chloride and chloroform, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as 1 pentanol and 1-butanol.

In addition to the above solvents, SP value (solubility parameter) force is usually 10 to 30 (MPa ^{1 2} ), preferably 10 to 25 (MPa ^1/2 ), more preferably 15 to 25 (MPa ^{1 / 2} ) Particularly preferably, by using a solvent in the range of 15 to 20 (MPa ^1/2 ), a film having excellent surface state uniformity and optical properties can be obtained.

The above solvents can be used alone or in combination of two or more. When two or more solvents are used in combination, the resulting mixed solvent preferably has an SP value within the above range. Here, the SP value of the mixed solvent can also determine the SP value of each solvent and their weight specific force. For example, in a mixed solvent that also obtains two types of solvent power, the weight fraction of each solvent is set to W1 and When W2 and SP values are SP1 and SP2, mixed The SP value of the solvent can be calculated by the following formula: 3 value = ¹ \ ^ 1 '3? 1 + ¹ ^ 2'3? 2.

[0061] The temperature at which the copolymer of the present invention is dissolved or dispersed in a solvent may be a room temperature or a high temperature so that the film of the present invention is uniformly dissolved or dispersed by sufficiently stirring. A liquid is obtained.

 Moreover, coloring agents, such as dye and a pigment, can be suitably added to a film formation liquid as needed, and thereby a colored film can be obtained.

[0062] Further, for the purpose of improving the surface smoothness of the obtained film, a leveling agent may be added to the film-forming solution. As a powerful leveling agent, various kinds of general ones can be used. Specific examples thereof include a fluorine-based nonionic surfactant and a special acrylic resin-based leveling agent. And silicone leveling agents. As the carrier for forming the liquid layer of the film forming solution, a metal drum, steel benolet, a polyester film made of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a belt made of polytetrafluoroethylene, or the like is used. be able to.

 [0063] As a method for applying the film-forming solution, a method using a die coater, a spray method, a brush coating method, a roll coating method, a spin coating method, a dating method, or the like can be used.

 Moreover, the thickness and surface smoothness of the film obtained can be controlled by repeatedly applying the film-forming solution.

 [0064] When a polyester film is used as the carrier, a surface-treated film may be used. Here, as a surface treatment method, a commonly used lyophilic treatment method, for example, by coating or laminating acrylic resin containing sulfonic acid group-containing resin, from these resins. Or a method of improving the hydrophilicity of the film surface by corona discharge treatment or the like.

[0065] Further, as a carrier, for example, a surface of a metal drum, a steel belt, a polyester film, or the like that has been subjected to sand mat treatment or emboss treatment to form irregularities is used. The unevenness on the surface is transferred, whereby a film having a light diffusion function can be produced. Of course, directly on the film It is also possible to impart a light diffusing function to the film by applying a matte treatment.

 [0066] A specific method for removing the solvent in the liquid layer in the solvent casting method is not particularly limited, and a commonly used drying treatment method, for example, a large number of rollers in the drying furnace. Although it is possible to use a method of passing through, if bubbles are generated as the solvent evaporates in the drying process, the properties of the resulting film are significantly deteriorated. To avoid this, the drying process is performed in two or more stages. It is preferable to control the temperature or air volume in each process.

 [0067] The amount of residual solvent in the film thus obtained is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. Here, when the amount of residual solvent in the film exceeds 10% by weight, the dimensional change with time becomes large when the film is actually used, which is not preferable. Further, the residual solvent lowers the glass transition temperature and lowers the heat resistance, which is not preferable.

 [0068] In order to suitably perform the stretching step described later, it may be necessary to appropriately adjust the amount of residual solvent in the film within the above range. Specifically, the amount of residual solvent in the film is usually 10 to 0.1% by weight, preferably 5 to 0.1% by weight, in order to stably and uniformly develop the retardation in the film by the stretching and orientation treatment. More preferably, it may be 1 to 0.1% by weight. By leaving a trace amount of solvent in the film, the stretching and orientation treatment may be facilitated or the retardation may be easily controlled.

 [0069] The thickness of the film of the present invention obtained by the solvent casting method is usually 0.1 to 3,000 μm, preferably 0.1 to 1,000 μm, more preferably 1 to 500 / ζ. πι, most preferably 5 to 300 m. 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.

 [0070] Further, the thickness distribution of the film of the present invention obtained by the solvent casting method is usually compared to the average value.

Within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3%. Further, the variation rate of thickness per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less. By controlling the thickness distribution of the film within the above range, the film is stretched and oriented. When this is done, it is possible to prevent the occurrence of phase difference unevenness.

 • Extrusion molding method (melt extrusion method)

 The film of the present invention can also be obtained by subjecting the cyclic olefin-based ring-opening copolymer according to the present invention to melt extrusion molding.

 [0071] Hereinafter, facilities such as an extruder used in the present invention will be described with specific examples, but the present invention is not limited to these specific examples.

 In the melt extrusion method of the present invention, normally, before the cyclic olefin-based ring-opening copolymer is charged into the extruder, the moisture and gas contained in the cyclic olefin-based ring-opening copolymer (oxygen, etc.) Dry the resin at an appropriate temperature below Tg for the purpose of removing residual solvent in advance.

 [0072] The dryer used for drying is not particularly limited. Usually, a hot-air circulating dryer, a dehumidifying dryer, a vacuum dryer, an inert gas circulating dryer such as nitrogen is used, and thermoplasticity is used. In terms of efficient removal of volatile components or dissolved oxygen from norbornene

In particular, it is preferable to use an inert gas circulation dryer or a vacuum dryer. In order to suppress moisture absorption and oxygen absorption in the hopper, it is also preferable to seal the hopper with an inert gas such as nitrogen or argon, or to use a vacuum hopper that can be kept under reduced pressure. In addition, the extruder cylinder must be provided with a vent function to remove volatile components generated during melt extrusion and a function to seal with an inert gas such as nitrogen or argon in order to suppress polymer deterioration due to oxygen contamination. Is preferred.

[0073] As an extrusion molding method, the resin is melted by an extruder, supplied in a fixed amount by a gear pump, impurities are removed by filtration with a metal filter, and the film shape is formed with a die, and the take-out machine Generally, a method of cooling a film using a roll and winding it using a winder is generally used.

As an extruder used for extrusion molding, any of a single screw, a twin screw, a planetary type, a kneader, a Banbury single mixer type, etc. may be used, but a single screw extruder is preferably used. In addition, the screw shape of the extruder includes a vent type, a tip dull mage type, a double freight type, and a full flight type, and the compression type includes a slow compression type and a quick compression type. The compression type is preferred. [0074] Regarding the gear pump used for measurement, there are an internal lubrication method in which the grease returned from the downstream side between the gears enters the system and an external lubrication method in which the grease is discharged to the outside, but the thermal stability is good. In the case of an unfavorable thermoplastic norbornene resin, an external lubrication system is preferred. As for the gear teeth of the gear pump, the helical type is preferred from the standpoint of weighing stability rather than the direction parallel to the shaft.

 [0075] Examples of filters used for filtering foreign substances include leaf disc type, candle filter type, leaf type, and screen mesh, but it is possible to increase the filtration area with relatively small residence time distribution. The leaf disc type is preferred. Examples of filter elements include metal fiber sintered type, metal powder sintered type, and metal fiber Z powder laminated type.

 [0076] Examples of the shape of the center pole of the filter include an external flow type, a hexagonal column internal flow type, and a circular column internal flow type, but any shape can be selected as long as the retention portion is small. Possible force Preferably, it is an external flow type.

 The molten cyclic olefin-based ring-opening copolymer is discharged from a die, and is tightly solidified on a cooling drum to be formed into a target film. Regarding the die shape, it is essential to make the resin flow uniform inside the die, and in order to keep the film thickness uniform, the pressure distribution inside the die near the die outlet is constant in the width direction. It is essential. In addition, the flow rate of the resin in the width direction is almost constant, and the fine adjustment of the flow rate at the die outlet is constant within the range that can be adjusted by the lip opening. It is matter. In order to satisfy the above conditions, the shape of the hold is preferably the coat nonger type, but the straight hold, fishtail type, etc. are preferred because flow distribution in the width direction is likely to occur. .

 [0077] Further, in order to make the thickness distribution of the film uniform, it is important to make the temperature distribution at the die exit constant in the width direction, and the temperature distribution is preferably ± 1 ° C or less. More preferably, it is ± 0.5 ° C or less. If temperature unevenness exceeds ± 1 ° C in the width direction, a difference in melt viscosity of the resin will occur, resulting in thickness unevenness, stress distribution unevenness, etc. Phase difference unevenness is likely to occur, which is preferable.

[0078] Further, the lip opening amount of the die outlet (hereinafter referred to as "lip gap") is usually 0.05 to lmm, preferably 0.3 to 0.8 mm, and more preferably 0.35 to 0.7 mm. When the lip gap is less than 0.05 mm, the grease pressure inside the die becomes excessively high, and the grease is liable to cause a location force other than the lip of the die and to cause grease leakage. On the other hand, if the lip gap exceeds 1 mm, it is difficult to increase the grease pressure of the die, so that the thickness uniformity in the width direction of the film is deteriorated.

 [0079] Die force Examples of methods for tightly solidifying the extruded film include a -roll method, an electrostatic application method, an air knife method, a vacuum chamber method, a calendar method, and the like. According to the film thickness and application, An appropriate method is selected.

 Die force As for the surface of the cooling roll for solidifying the extruded film, various surface treatments are preferably performed as in the case of the extruder cylinder and the inner surface of the die. These surface treatments prevent the extruding film from sticking to the roll surface, prevent film thickness unevenness, increase the accuracy of the surface of the cooling roll, and the surface hardness is high so that scratches and other defects can be continuously applied. It is preferable in that it can stably produce the film even if the film is manufactured, and the film surface accuracy can be stably maintained, and there is no thickness unevenness.

 [0080] The material of the extruder (cylinder 'screw, etc.) and the die includes forces such as SCM steel and stainless steel such as SUS. Also, the inner surface of the extruder cylinder, the die and the screw surface of the extruder are coated with chromium, nickel, titanium, etc., PVD (Physical Vapor Deposition) method, etc., TiN, TiAlN, TiCN, CrN It is preferable to use a film formed with a film such as DLC (diamond-like carbon), a tungsten-based material such as WC, a ceramic sprayed such as cermet, or a surface nitrided. Such a surface treatment is preferable in that a uniform molten state of the resin can be obtained because the coefficient of friction with the resin is small.

[0081] In the present invention, the resin temperature (extruder cylinder temperature) at the time of producing a melt-extruded film is usually 200 to 350 ° C, preferably 220 to 320 ° C. If the temperature of the resin is less than 200 ° C, the resin cannot be melted uniformly. On the other hand, if the temperature exceeds 350 ° C, the resin will be thermally deteriorated during melting to produce a high-quality film with excellent surface properties. Becomes difficult. Furthermore, Tg + 120 ° C within the above temperature range and relative to the glass transition temperature (Tg) of the resin. A temperature in the range of ~ Tg + 160 ° C is particularly preferred. For example, if the Tg of the resin is 130 ° C, it is particularly preferred for film production, and the temperature range is 250 ° C to 290 ° C.

 [0082] The shear rate during melt extrusion is usually 1 to 500 (lZsec), preferably 2 to

 350 (lZsec), more preferably 5 to 200 (lZsec). If the shear rate during extrusion is less than l (lZ sec), the resin cannot be uniformly melted, so an extruded film with small thickness unevenness cannot be obtained. If the force is too great, the resin and additives will decompose and deteriorate, and defects such as foaming, die lines and deposits may occur on the surface of the extruded film.

 [0083] In the present invention, the thickness of the melt-extruded film is usually 10 to 800 µm, preferably 20 to 500 µm, more preferably 40 to 500 µm. If the thickness is less than 10 μm, it may be difficult to perform post-processing such as stretching due to insufficient mechanical strength. On the other hand, if the thickness exceeds 800 m, the film has uniform thickness and surface properties. It may be difficult to manufacture the film, and it may be difficult to wind up the resulting film.

 [0084] The thickness distribution of the raw film of the present invention obtained by the melt extrusion method is usually within ± 5%, preferably within ± 3%, more preferably within ± 1% of the average value. . If the thickness distribution exceeds 5%, retardation unevenness may occur when the film is stretched to obtain a retardation film.

 <Phase difference plate and manufacturing method thereof>

 The film of the present invention has a function of regularly aligning the molecular chains of the copolymer of the present invention forming the film in a certain direction by performing a stretching process (stretching and orientation treatment), and giving a retardation to transmitted light. Thus, the retardation film according to the present invention can be obtained.

[0085] Here, "regularly oriented" means that when a normal polymer compound (polymer) is formed into a film shape by a melt extrusion method or a casting method, the distortion of the film generated during the process. Although the molecular chain of the polymer compound is in a random state without facing a specific direction, the molecular chain of the polymer compound is uniaxially or biaxially or thick in the plane of the film. It means that it is oriented regularly in the direction. The degree of regularity of the orientation of the polymer compound varies and can be controlled by the stretching conditions. [0086] Specific examples of the stretching method include known uniaxial stretching methods and biaxial stretching methods. That is, horizontal uniaxial stretching using the tenter method, compression stretching between rolls, vertical uniaxial stretching using two pairs of rolls with different circumferences, and certain ヽ is a biaxial stretching method combining horizontal uniaxial and vertical uniaxial, inflation A stretching method by the method can be used.

 When the uniaxial stretching method is used, the stretching speed is usually 1 to 5,000% Z, preferably 50 to: L, 000% Z, and more preferably 100 to 1,000% Z. Minutes, particularly preferably 100 to 500% Z minutes.

[0087] As the biaxial stretching method, a method of stretching in two directions intersecting each other at the same time or a method of stretching in a direction different from the 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 properties, but is usually in the range of 120 to 60 degrees. Also, the stretching speed is the same for each extension Shin direction, Yogu usually 1-5 be different, a 000% Z min, preferably rather ί or _{^{50~: L, 000 0/0}} / min , and the further [this preferably ί or 100 to 1, is 000 _^0/0 / min, Japanese [this good Mashiku is 100~500% Ζ minutes.

 [0088] The processing temperature in the stretching process is not particularly limited. When the glass transition temperature of the copolymer used is Tg, it is usually Tg—5 ° C to Tg + 20 ° C, preferably Tg It is desirable to be in the range of ~ 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 it is preferable because the control of the refractive index ellipsoid becomes easy.

 [0089] Even when the drawing is performed in such a temperature range, as long as the cyclic olefin-based ring-opening copolymer of the present invention is used, problems such as cloudiness do not occur in the obtained retardation plate. This is presumably because the copolymer of the present invention has a relatively small Tg distribution, and is plasticized substantially uniformly by heating in the vicinity of Tg. On the other hand, in the case of a cyclic olefin-based ring-opening copolymer having a large Tg distribution, it is not uniformly plasticized just by heating in the vicinity of Tg, and there is a part in an unplasticized state. It is thought to cause white turbidity.

[0090] Since the draw ratio is determined according to the desired properties such as phase difference, it is not particularly limited. Repulsive force Normally 1.01 to 10 times, preferably ί to 1. 03 to 5 times, more preferably to ί. 1. 03 to 3 times. In the case of the cyclic olefin-based ring-opening copolymer of the present invention, since the film can be stretched in the vicinity of Tg, it is possible to apply a high stress to the film even at a low magnification, so that a high phase difference can be obtained. In addition, when the draw ratio is relatively low as described above, it is possible to easily produce a retardation plate without transparency and optical axis deviation. When the draw ratio is excessive, it may be difficult to control the phase difference and the optical axis.

 [0091] The stretched film may be cooled as it is at room temperature, but Tg—at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute in a temperature atmosphere of about 100 ° C. to Tg. It is also preferable to hold for 60 minutes, heat set, and then cool to room temperature, so that a phase difference plate having stable phase difference characteristics with little change over time in the phase difference of transmitted light can be obtained.

 The retardation plate obtained as described above gives a phase difference to transmitted light due to the orientation of the molecules by stretching. This phase difference depends on the stretching ratio or the pre-stretching phase. It can be controlled by adjusting the thickness of the film. For example, with regard to the draw ratio, even if the film has the same thickness before being stretched, the absolute value of the retardation of transmitted light tends to increase as the stretch ratio increases. It is possible to obtain a film that provides the transmitted light with a phase difference of. 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 larger the absolute value of the retardation given to transmitted light tends to increase. By changing the thickness of the retardation plate, it is possible to obtain a retardation plate that imparts a desired retardation to transmitted light.

 [0093] In the retardation plate obtained as described above, the value of the phase difference given to the transmitted light is determined according to its use and is not uniquely determined. When it is used for a wave plate of an oral luminescence display element or a laser optical system, it is usually desired to be 1 to: LO, OOOnm, preferably 10 to 2, OOOnm, more preferably 15 to 1, OOOnm! / ヽ.

[0094] 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%. In the following, it is more desirable that it is ± 5% or less. Phase difference variation is ± 20 If the% range is exceeded, color unevenness or the like may occur when used in a liquid crystal display element or the like, resulting in a problem that the performance of the display main body deteriorates. Similarly, it is desirable that the optical axis variation is usually ± 2.0 degrees or less, preferably ± 1.0 degrees or less, and more preferably ± 0.5 degrees or less.

[0095] The retardation plate of the present invention can be used singly or in a laminate of two or more or bonded to a transparent substrate or the like. It can also be used by stacking it on other films, sheets, and substrates.

 When laminating a film or the like, a pressure-sensitive adhesive or an adhesive can be used. As such adhesives and adhesives, it is preferable to use those having excellent transparency. Specific examples thereof include natural rubber, synthetic rubber, butyl acetate, butyl chloride copolymer, polybutyl ether, acrylic resin. Curing adhesives such as fats, modified polyolefin-based resin, etc., curing resins such as isocyanate-containing compounds added to the resin having functional groups such as hydroxyl and amino groups, and polyurethane-based dry laminates Adhesives, synthetic rubber adhesives, and epoxy adhesives.

[0096] In addition, a pressure-sensitive 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. In the case of laminating the pressure-sensitive adhesive layer or the adhesive layer, the pressure-sensitive adhesive or adhesive as described above can be used as the pressure-sensitive adhesive or adhesive.

 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 or% are based on weight unless otherwise specified.

[0097] Various physical properties were measured or evaluated as follows.

Glass transition temperature (T _g )

Using a DSC6200 manufactured by Seiko Instruments Inc., the rate of temperature increase was measured at 20 ° C. per minute under nitrogen flow. Tg is the differential peak scanning calorie maximum peak temperature (point A) and the temperature 20 ° C from the maximum peak temperature (point B) plotted on the differential scanning calorimetry curve. And the intersection of the tangent starting from point A. The nuclear magnetic resonance spectrometer (NMR) was Bruker AVANCE500, and the measurement solvent was ¹ H-NMR with d-chloroform. 5. After calculating the monomer composition from the integral value of 1 to 5.8 ppm beylene group, 3.7 ppm methoxy group, and 0.6 to 2.8 ppm aliphatic proton, calculate the hydrogenation rate. did. Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene were measured with tetrahydrofuran (THF) solvent using HLC-8020 gel permeation chromatography (GPC) manufactured by Tosoh Corporation. Mn represents a number average molecular weight. The sample was dissolved in toluene and measured using GC-14B gas chromatography manufactured by Shimadzu Corporation.

ADVANTEC compact cartridge filter: MCP—HX—E10S (average pore diameter 2.0 _i um, filtration area 2000 cm ² ), MCP—JX—E10S (average pore diameter l., Filtration surface ¾2000 cm ² ), MCS— 020-E10SR (^ ¾ ^ 0.2 m, filtration area 1800 cm ² ) Each one is connected in series in this order, and the polymer solution after hydrogenation is continuously filtered at room temperature and nitrogen pressure 3. Okgf / cm ² , The change over time in the filtration rate was measured. These filters were used with a compact cartridge housing: MTA-2000T.

 Mokume Mura, Mura

A film 20cm long, 20cm wide and 130 μm thick is stretched at a stretch ratio of Tg + 5 ° C of the copolymer and stretched 1.5 times under the condition of 300% Z in the longitudinal direction using the free end uniaxial stretching method. It was. Vertical than the film center portion of the stretched 26cm, cut into 312Cm ² lateral 12cm, vertical 2cm intervals, horizontal 2c phase difference m intervals, the optical axis Oji Keiki Co., OPTICAL Birefringence

Measured using ANALYZER KOBRA-21ADH.

 [Example 1]

Represented by the following formula 8-methyl-8-methoxycarbonyl - Rutetorashikuro ^{[4. 4. 0. I 2 '5} 1 7.' 10] - 3- dodecene (DNM) 71 parts of dicyclopentadiene (DCP) 15 Department and Bish Chromium [2. 2. 1] Hepto-2-ene (NB) 1 part as a monomer, together with 18 parts of molecular weight regulator 1-hexene and 200 parts of toluene were charged into a nitrogen-substituted reaction vessel. Heated to 100 ° C.

[0099] [Chemical 8]

 [0100] Triethyl aluminum 0.005 part, methanol-modified WC1 (anhydrous methanol: Ph

 6

 POC1: WC1 = 103: 630: 427 weight ratio) Add 0.005 parts and react for 1 minute, then

2 6

 10 parts of DCP and 3 parts of NB were additionally added in 5 minutes, and the mixture was further reacted for 45 minutes to obtain a copolymer (1 ′).

FIG. 1 shows a ¹ H-NMR measurement chart of the obtained copolymer (1 ′). 5. DCP-derived berylene proton (He) at 8 ppm, methoxy proton (He) from DNM at 65 ppm, double bond of copolymer main chain was observed at 5.2 to 5.6 ppm . The NB content in the copolymer is calculated by subtracting the DCP structural unit (protons 3 times that of Hb) and DNM structural units (protons 2 times 3 times that of He). As a result, DNMZDCP / NB = 69.77 / 26.01 / 4.23 (wt%).

[0101] Next, the solution of the obtained copolymer (1 ') was put in an autoclave, and 200 parts of toluene was further added. Next, 1 part octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate as a reaction modifier and RuHCl (CO) [P (C

 6

H)] is added to 0.06 parts, and after heating to 155 ° C, hydrogen gas is charged into the reactor and the pressure is reduced.

5 3

lOMPa. Thereafter, the reaction was carried out at 165 ° C for 3 hours while maintaining the pressure at lOMPa. After completion of the reaction, 100 parts by weight of toluene, 3 parts by weight of distilled water, 0.72 parts by weight of lactic acid and 0.00194 parts by weight of hydrogen peroxide were added and heated at 60 ° C. for 30 minutes. Thereafter, 200 parts by weight of methanol was added and heated at 60 ° C for 30 minutes, and when cooled to 25 ° C, it was separated into two layers. Remove 500 parts by weight of the supernatant, add 350 parts by weight of toluene and 3 parts by weight of water again, heat at 60 ° C for 30 minutes, and then heat 240 parts by weight of methanol at 60 ° C for 30 minutes. Cooled to ° C and separated into two layers. Remove 500 parts by weight of the supernatant, then add 350 parts by weight of toluene and 3 parts by weight of water. The mixture was heated at 60 ° C for 30 minutes, and then 240 parts by weight of methanol was heated at 60 ° C for 30 minutes, cooled to 25 ° C, and separated into two layers. Finally, after removing 500 parts by weight of the supernatant, the remaining polymer solution was filtered at a temperature of 50 ° C. with 2.0 m, 1.0 m, and 0.2 m filters connected in series. The polymer solution is then concentrated to a solids concentration of 55% and 250. Solvent removal treatment was carried out at C, 4 torr and residence time of 1 hour, and a 10 m polymer filter was passed through to obtain a copolymer (1). In addition, when the polymer solution before the solvent removal treatment was continuously filtered and the change in filtration rate with time was traced, the filtration rate without clogging the filter did not decrease even after 1000 hours.

[0102] The obtained copolymer (1) has a weight average molecular weight (Mw) = 6.10 X 10 ⁴ , a molecular weight distribution (Mw / Mn) = 3.8, and an intrinsic viscosity (7?) = 0. 52, glass transition temperature (Tg) = 131 ° C

 uih

. The Tg distribution was 25 ° C. FIG. 2 shows a ¹ H-NMR chart of copolymer (1), which is a hydrogenated copolymer. From this, the hydrogenation rate of the copolymer (1) was determined, and the olefinic unsaturated bond was hydrogenated by 99.9% or more.

[0103] The copolymer (1) was formed by melt extrusion to obtain a cast film (1) having a thickness of 130 m. After that, the copolymer (1) was Tg + 5 ° C, 136 ° C, free end uniaxial stretching method, stretching speed = 300% Zmin, 1.5 times stretching, and stretched film (1) Got.

The stretched film (1) has a thickness = 85 / ζ πι, a phase difference = 343 nm, a birefringence index = 0.00404, a haze value = 0.1, and is a transparent film having no appearance defect. It could be confirmed. The area satisfying the phase difference after stretching of ± 3 nm and the optical axis of ± 0.5 degrees or less was 64 cm ² .

[Comparative Example 1]

 A copolymer (2) was obtained in the same manner as in Example 1 except that 50 parts of DCP and 50 parts of DNM were used as monomers in Example 1.

Copolymer (2) has a weight average molecular weight (Mw) = 13.3 X 10 ⁴ , molecular weight distribution (MwZMn) = 4.0, intrinsic viscosity) = 0.74, glass transition temperature (Tg) = 130 ° C Met. T

 uih

The g distribution was 42 ° C. When the hydrogenation rate of copolymer (2) was determined by NMR measurement, the olefinic unsaturated bond was hydrogenated by 99.9% or more. Further, when the polymer solution before the solvent removal treatment was continuously filtered in the same manner as in Example 1 and the change in the filtration rate with time was followed, a decrease in the filtration rate was observed after 300 hours. Later, the filter was clogged, and it was found that the solution contained gel.

 [0105] Next, a film (2) having a thickness of 130 m was produced in the same manner as in Example 1. Thereafter, the copolymer (2) was stretched 1.5 times at 135 ° C. which is Tg + 5 ° C. to obtain a stretched film (2-1).

The stretched film (2-1) had a thickness of 85 μm, a retardation of 343 nm, a birefringence of 0.00401, and a haze value of 1.8, and was a film with poor transparency. The area satisfying the phase difference of ± 3 nm after stretching and the optical axis of ± 0.5 degrees or less was 32 cm ² , and the area without uniform phase difference and optical axis unevenness was very small.

[0106] Using the film (2), the copolymer (2) was stretched 1.5 times at 155 ° C, which is Tg + 25 ° C, to obtain a stretched film (2-2). It was. The stretched film (2-2) had a thickness = 85 / ζ πι, a phase difference = 163 nm, a birefringence index = 0.00192, and a haze value = 0.4. Further, the area satisfying the phase difference after stretching of ± 3 nm and the optical axis of ± 0.5 degrees or less was 64 cm ² . Although the area was improved without transparency, uniform phase difference and optical axis unevenness, the birefringence decreased and the phase difference was greatly reduced.

[Comparative Example 2]

 In Example 1, a copolymer (3) was obtained in the same manner as in Example 1 except that 86 parts of DNM and 14 parts of norbornene (NB) were used as monomers.

Copolymer (3) has a weight average molecular weight (Mw) = 10. 3 X 10 ⁴ , molecular weight distribution (Mw / Mn) = 3.5, intrinsic viscosity (r?) = 0.64, glass transition temperature (Tg ) = 121 ° C. T

 uih

 The g distribution was 45 ° C. When the hydrogenation rate of copolymer (3) was determined by NMR measurement, the olefinic unsaturated bond was hydrogenated by 99.9% or more. In addition, when the polymer solution before the solvent removal treatment was continuously filtered in the same manner as in Example 1 and the change in filtration rate with time was followed, the filtration rate at which the filter did not clog after 1000 hours was The power declined.

In the same manner as in Example 1, a film (3) having a thickness of 130 m was produced. Thereafter, the copolymer (3) was stretched 1.5 times at 126 ° C. which is Tg + 5 ° C. to obtain a stretched film (3-1). The stretched film (3-1) had a thickness of 85 μm, a retardation of 325 nm, a birefringence of 0.0032, and a haze value of 4.3, and was a film with poor transparency. Phase difference after stretching ± 3 The area satisfying nm and optical axis ± 0.5 ° or less was 24 cm ² , and the area without uniform phase difference and optical axis unevenness was very small.

 [0109] Using the cast film (3), the copolymer (3) was stretched 1.5 times at 146 ° C, which is Tg + 25 ° C, to obtain a stretched film (3-2) .

The stretched film (3-2) has a thickness = 85 μm, a retardation = 102 nm, a birefringence index = 0.00109, and a haze value = 0.8. The area satisfying the phase difference after stretching of ± 3 nm and the optical axis of ± 0.5 degrees or less was 56 cm ² . Transparency, uniform phase difference, and an area free from optical axis unevenness were improved as compared with Comparative Example 1, but the birefringence decreased and the phase difference was greatly reduced.

 [0110] [Example 2]

 The catalyst type, amount and hydrogenation start temperature of the hydrogenation reaction were changed, and the reaction modifier octadecyl-3- (3,5-di-tert-butyl 4-hydroxyphenol) propionate was used. A copolymer (1 ') was obtained in the same manner as in Example 1 except that. In the hydrogenation reaction, the obtained copolymer solution was placed in an autoclave, and 200 parts of toluene was further added. Next, p-n-C H-Ph-COO-RuH (CO) [P (C

 5 13 6

H)] is added to 0.0251 parts, heated to 85 ° C, hydrogen gas is charged into the reactor, and the pressure is increased.

5 2

 Was lOMPa. After that, the reaction was carried out at 165 ° C for 3 hours while maintaining the pressure at lOMPa o

[0111] The obtained copolymer (4) has a weight average molecular weight (Mw) = 6.08 X 10 ⁴ , a molecular weight distribution (M w / Mn) = 3.8, and an intrinsic viscosity (7?) = 0. 52, glass transition temperature (Tg) = 131 ° C uih

 . The Tg distribution was 25 ° C. Further, when the hydrogenation rate of the copolymer (4) was determined in the same manner as in Example 1, the olefinic unsaturated bond was hydrogenated by 99.9% or more.

[0112] Next, a film (4) having a thickness of 130 m was produced in the same manner as in Example 1. After that, at 136 ° C, which is Tg + 5 ° C of the copolymer (4), the free uniaxial stretching method was used in the same manner as in Example 1, and the stretching speed was 300% Zmin and the stretching was 1.5 times. And a stretched film (4) was obtained.

The stretched film (4) had a thickness of 85 μm, a retardation of 345 nm, a birefringence of 0.0000, and a haze value of 0.1, and was confirmed to be transparent and free from appearance defects. . The area satisfying the phase difference after stretching of ± 3 nm and the optical axis of ± 0.5 degrees or less was 64 cm ² . Industrial applicability

 The cyclic olefin-based ring-opening copolymer of the present invention has excellent heat resistance and can be suitably used by processing it into a film or sheet that can be suitably used for general optical applications. However, since it can be processed stably without problems such as cloudiness, it is optimal for applications that require stretching, for example, optical films such as retardation plates. More specifically, the film or sheet according to the present invention, and in particular the phase difference plate, is a mobile phone, a digital information terminal, a pager, a navigation, an in-vehicle liquid crystal display, a liquid crystal monitor, a light control panel, an OA device. It can be used for various liquid crystal display elements such as displays for TVs and displays for AV equipment, electoluminescence display elements or touch panels. It is also useful as a wave plate for use in recording / reproducing apparatuses for optical discs such as CD, CD-R, MD, MO, and DVD.

Claims

A cyclic olefin system comprising a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3): Ring-opening copolymer; (In the formula (1), m is 0, 1 or 2, X is independently a group represented by the formula: CH = CH 2 or a group represented by the formula: —CH 2 CH 1, Ri to R ⁴ are independently hydrogen atoms;  twenty two A substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, which may have a linking group containing oxygen, nitrogen, iodo or kei; or a polar group. However, at least one of Ri to R ⁴ is a polar group, and at least one of the other Ri to R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms. ), [Chemical 2]

 (In the formula (2), X is independently a group represented by the formula: CH 2 CH 2 or a formula: CH 2 CH 1. R ^{5 to} R ^1Q are each independently a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom that may have a linking group containing oxygen, nitrogen, iodo or silicon. Represents a hydrocarbon group of the number 1 to 10; or a polar group. ), [Chemical 3] R ¹² R ¹³ (3) (In the formula (3), n is 0, 1 or 2, X is independently a group represented by the formula: CH = CH or a group represented by the formula: —CH 2 CH 1, R ^{U to} R Are each independently a hydrogen atom;  twenty two  Or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, which may have a linking group containing oxygen, nitrogen, iodo or keen. ). [2] The cyclic olefin-based ring-opening copolymer according to claim 1, wherein the differential differential scanning calorimetry curve of DSC shows a single peak and the glass transition temperature (Tg) is 110 ° C. or higher. [3] The cyclic olefin-based ring-opening copolymer according to claim 1 or 2, wherein the cyclic olefin-based ring-opening copolymer has no structural unit other than the structural units represented by the formulas (1) to (3). [4] The cyclic olefins according to any one of claims 1 to 3, wherein the polar group in the structural unit represented by the formula (1) is a group represented by the following formula (4): Ring-opening copolymer;-(CH) COOR '--(4)  2 p  (In formula (4), p is 0 or an integer of 1 to 5, and R ′ is a hydrocarbon group having 1 to 15 carbon atoms).  [5] A film or sheet comprising the cyclic olefin-based ring-opening copolymer according to any one of claims 1 to 4. [6] A phase difference plate, wherein the film or sheet according to claim 5 is stretched and oriented.  [7] The retardation according to claim 5, wherein the film or sheet according to claim 5 is stretch-oriented under a temperature condition of Tg to (Tg + 10) ° C. of the cyclic olefin-based copolymer contained in the film or sheet. A manufacturing method of a board.