KR100651252B1 - Method for copolymerizing cyclic olefins and vinyl olefins, copolymer produced by the method and optically anisotropic film compising the same - Google Patents

Abstract

Provided are a method for producing a copolymer of a cyclic olefin and a polar vinyl olefin type, a copolymer prepared by the method, and an optically anisotropic film containing the copolymer. According to the copolymer production method according to the present invention, it is possible to effectively copolymerize the cyclic olefin and the polar vinyl olefin using a catalyst system composed of a group 13 compound and a radical initiator, and the copolymer prepared by the production method of the present invention has high transparency, It has excellent adhesion, low dielectric constant, excellent thermal stability, optical anisotropy and strength, and the optical film including the polymer of the present invention has a polarizing plate protective film, an adhesive film, a compensation film, an optical lens and a liquid crystal display device due to the physical properties. Can be used.

Group 13 compounds, cyclic olefins, polar vinyl olefins, optical films

Description

Method for copolymerizing cyclic olefins and vinyl olefins, copolymer produced by the method and optically anisotropic film compising the same}

1 is a diagram showing a ¹ H NMR spectrum of a norbornene-methyl acrylate copolymer.

2 is a diagram showing a ¹ H NMR spectrum of a butyl norbornene-methyl acrylate copolymer.

3 is a diagram showing a ¹ H NMR spectrum of a norbornene-methyl methacrylate copolymer.

4 is a diagram showing a ¹ H NMR spectrum of a norbornene-methyl acrylate-styrene terpolymer.

FIG. 5 is a diagram showing differential scanning calorimetry (DSC) thermodiagram for norbornene-methyl acrylate copolymer. FIG.

FIG. 6 is a diagram showing differential scanning calorimetry (DSC) thermodiagram for norbornene-methyl methacrylate copolymer. FIG.

FIG. 7 is a diagram showing differential scanning calorimetry (DSC) thermodiagram for norbornene-methyl acrylate-styrene terpolymer.

The present invention relates to a method for preparing a copolymer of a cyclic olefin and a polar vinyl olefin-based copolymer, a copolymer prepared by the method and an optically anisotropic film comprising the copolymer, and more particularly, to a high yield of cyclic olefin and vinyl. The present invention relates to a production method capable of producing a copolymer of olefins, a high heat resistant copolymer prepared by the above method, and an optical film having anisotropy comprising the copolymer.

Until now, the inorganic materials such as silicon oxide and silicon nitride have been mainly used in the information electronics industry. As the demand for small size and high efficiency devices increases, the need for high functional new materials increases. Due to these high functional properties, there is a growing interest in polymers having low dielectric constant and hygroscopicity, excellent metal adhesion, strength, thermal stability and transparency, and high glass transition temperature (Tg > 250 ° C).

The resins for optical materials currently used in general use may include methacrylic resins, polycarbonates, polyimides, etc., which are not suitable for use in high-performance optical materials because of problems such as low thermal stability, high birefringence, and coloring.

Recently, it is a polymer that replaces it, and has properties such as Tg of 100 ° C or higher, transmittance of 90% or higher, low birefringence, and low water absorption. As a resin, polyacrylate, polyethersulfone (PES), polynorbornene (PNB), and cycloolefin Copolymer (COC) appeared. These polymers are mainly composed of a carbonyl group which is a polar group and an aromatic or cyclic olefin moiety which is a nonpolar group. In addition, fluorine (F) may be introduced to improve physical properties such as high heat resistance, low refractive index and low water absorption.

PES is an amorphous heat-resistant engineering plastic consisting of a diaryl sulfone backbone, which has a high Tg of about 225 ° C and a very strong resistance to thermal aging. PNB is a polymer composed of a norbornene derivative which is a cyclic olefin, and has a very high Tg of about 330 ° C., a transparency of 92% or more, and low birefringence.

COC (or COP) is a polymer consisting of a cyclic olefin and an ethylene main chain, having a Tg of 100 to 200 ° C., and having high transparency, low birefringence, and injection molding. Excellent transparency, heat resistance, chemical resistance and very low birefringence and water absorption rate, mobile phone camera lens, CD / DVD pickup lens, optical materials such as LCD LGP, capacitor film, information electronic materials such as low dielectric, low absorption syringe, Various applications include medical materials such as blister packaging.

On the other hand, polyacrylate is very excellent in hardness (hardness) and adhesiveness, high transparency is widely used in addition to applications such as glass.

Therefore, when copolymerizing norbornene and acrylate, a new polymer having all of these advantages and applicable to a wider range is possible. Generally, however, polar vinyl olefin monomers are polymerized via radical or anionic initiators, while norbornene monomers are addition polymerized by post-transition metal catalysts such as Ni and Pd. Direct copolymerization of both monomers was difficult because of the opposing polymerization properties of these two monomers.

Initially, the production of norbornene and polar vinyl olefin-based copolymers was accomplished by a radical polymerization method, but the content of norbornene in the polymer was very low, below 5.5% by weight (Morris et al., US Pat. No. 3,536,681; Starmer et al. , US Pat. No. 3,679,490). Since then, norbornene and acrylate copolymerizations using palladium metal catalysts have been reported but have low polymerization yields or difficult to obtain reproducible polymerization results (Goodall et al., US Pat. No. 6,303,724; Sen al., US Pat. No. 6,111,041). , US Pat. No. 6,593,440).

Therefore, there is a need for a new method that can produce copolymers of norbornene and vinyl olefins in high molecular weight and high yields.

The first technical problem to be achieved by the present invention is to provide a copolymer production method capable of copolymerizing cyclic olefin and polar vinyl olefin monomers in high molecular weight and high yield.

The second technical problem of the present invention is to have excellent properties such as low dielectric constant, high glass transition temperature, excellent thermal stability, excellent oxidative stability, toughness, good chemical resistance and good metal adhesion. It is to provide a copolymer that can be used for materials.

The third technical problem to be achieved by the present invention is to provide an optical film that can be used in a polarizing plate protective film, an adhesive film, an optically anisotropic compensation film, and a liquid crystal display device because the transparency and the refractive index can be adjusted.

The present invention to achieve the first technical problem,

A method for producing a copolymer comprising a cyclic olefin and a polar vinyl olefin, the cyclic olefin monomer and the polar vinyl olefin monomer

Iii) a Group 13 compound represented by Formula 1 below; And

Ii) a method of preparing a copolymer which is polymerized by contacting a catalyst system comprising a radical initiator comprising an azo compound represented by the following formula (2) or a peroxide compound represented by the following formula (3):

<Formula 1>

M (R ⁰ ) _n1 (OR ¹ ) _n2 (X) _n3

In the formula of Formula 1,

M is a group 13 element,

n1, n2, n3 are integers from 0 to 3, and n1 + n2 + n3 = 3;

O is an oxygen atom,

R ⁰ and R ¹ are each independently hydrogen; Linear or branched alkyl, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Or linear or branched C1-C20 alkyl, or aryl, containing one to ten hetero atoms, such as N, O, a halogen element;

X is halogen,

<Formula 2>

A ₁ -N = NA ₂

In the formula (2),

N is a nitrogen element,

A ₁ and A ₂ are each independently hydrogen; Linear or branched alkyl, alkoxy, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Linear or branched alkyl, alkoxy, alkenyl, aryl or cycloalkylheterocarbons having 1 to 20 carbon atoms, including cyan, carbonyl, carboxyl, ether and amide groups,

<Formula 3>

B ₁ -OOB ₂

In the formula (3),

O is an oxygen element,

B ₁ and B ₂ are each independently hydrogen; Linear or branched alkyl, alkoxy, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Linear or branched alkyl, alkoxy, alkenyl, aryl or cycloalkylheterocarbons having 1 to 20 carbon atoms, including cyan, carbonyl, carboxyl, ether and amide groups.

The present invention provides a copolymer excellent in various physical properties produced by the production method in order to achieve the second technical problem.

In order to achieve the third technical problem of the present invention, there is provided a polarizing plate protective film, an adhesive film, an optically anisotropic film, an optical compensation film and a liquid crystal display module and the like comprising a copolymer produced by the manufacturing method.

According to the method for preparing a copolymer according to the present invention, a cyclic olefin and a polar vinyl olefin can be copolymerized in high yield using a catalyst system composed of a Group 13 compound and a radical initiator, and the cyclic olefin produced by the production method of the present invention and Polar vinyl olefin polymers are excellent in physical properties such as transparency, adhesion to metals or other polymers, low dielectric constant, excellent thermal stability and strength. Therefore, the optical film containing the polymer of this invention provides an optical film which can be used for a polarizing plate protective film, an adhesive film, an anisotropic compensation film, a liquid crystal display module, etc.

The inventors have found that when the cyclic olefin monomer and the polar vinyl olefin monomer are contacted with a catalyst system consisting of a Group 13 compound and an azo compound (or peroxide compound), a copolymer of the monomers is obtained in high yield and the copolymer is transparent. And it discovered that it has optical anisotropy, and completed this invention.

Hereinafter, the present invention will be described in more detail.

The polymerization of the present invention is polymerized by dissolving and mixing a cyclic olefin monomer, a polar vinyl olefin monomer and a catalyst in a solvent as in a conventional polymerization method. The catalyst system used for contacting the monomers in the present invention is a Group 13 compound represented by Chemical Formula 1 and an azo compound represented by Chemical Formula 2 (or a peroxide compound represented by Chemical Formula 3). Radical initiators).

The cyclic olefin monomer used in the polymerization method is represented by the following formula (4).

<Formula 4>

In the formula (4),

m is an integer from 0 to 4,

R ² , R ³ , R ⁴ , and R ⁵ Is hydrogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or a nonpolar functional group selected from alkynyl having 3 to 20 carbon atoms; -(CH ₂ ) _n C (O) OR ⁶ ,-(CH ₂ ) _n OC (O) R ⁶ ,-(CH ₂ ) _n OC (O) OR ⁶ ,-(CH ₂ ) _n C (O) R ⁶ ,-(CH ₂ ) _n OR ⁶ ,-(CH ₂ O) _n -OR ⁶ ,-(CH ₂ ) _n C (O) -OC (O) R ⁶ ,-(CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR ⁶ ,-(CH ₂ ) _n C (O) N (R ⁶ ) ₂ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR ⁶ ,-(CH ₂ ) _n N (R ⁶ ) ₂ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR ⁶ ,-(CH ₂ ) _n OC (O) N (R ⁶ ) ₂ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ⁶ ,-(CH ₂ ) _n SSR ⁶ ,-(CH ₂ ) _n SO ₂ R ⁶ ,-( CH ₂ ) _n SO ₂ R ⁶ ,-(CH ₂ ) _n OSO ₂ R ⁶ ,-(CH ₂ ) _n SO ₃ R ⁶ ,-(CH ₂ ) _n OSO ₃ R ⁶ ,-(CH ₂ ) _n B ( R ⁶ ) ₂ ,-(CH ₂ ) _n B (OR ⁶ ) ₂ ,-(CH ₂ ) _n B (R ⁶ ) (OR ⁶ ),-(CH ₂ ) _n N = C = S,-(CH ₂ ) _n NCO,-(CH ₂ ) _n N (R ⁶ ) C (= 0) R ⁶ ,-(CH ₂ ) _n N (R ⁶ ) C (= 0) (OR ⁶ ),-(CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ ,,-(CH ₂ ) _n P (R ⁶ ) ₂ ,-(CH ₂ ) _n P (OR ⁶ ) ₂ ,-(CH ₂ ) _n P (R ⁶ ) ( OR ⁶ ),-(CH ₂ ) _n P (= 0) (R ⁶ ) ₂ ,-(CH ₂ ) _n P (= 0) (OR ⁶ ) ₂ , and-(CH ₂ ) _n P (= 0) It may be a polar functional group selected from the group consisting of (R ⁶ ) (OR ⁶ ),

R ⁶ included in the polar functional group may be each hydrogen, linear or branched alkyl having 1 to 20 carbon atoms, alkenyl or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms,

N is an integer from 0 to 10 and R ² , R ³ , R ⁴ , and R ⁵ are R ² and R ³ or R ⁴ and R ⁵ if they are not polar functional groups, hydrogen, or halogen. May be linked to each other to form an alkylidene group having 1 to 10 carbon atoms, or R ² or R ³ may be connected to any one of R ⁴ and R ⁵ to be a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or It is possible to form 6 to 17 aromatic cyclic compounds.

The polar vinyl olefin monomer used in the polymerization method is represented by the following formula (5).

<Formula 5>

In the formula (5),

m is an integer from 0 to 4,

At least one of R ⁷ and R ⁸ is-(CH ₂ ) _n C (O) OR ^9- (CH ₂ ) _n OC (O) R ⁹ ,-(CH ₂ ) _n OC (O) OR ⁹ ,-( CH ₂ ) _n C (O) R ⁹ ,-(CH ₂ ) _n OR ⁹ ,-(CH ₂ O) _n -OR ⁹ ,-(CH ₂ ) _n C (O) -OC (O) R ⁹ ,- (CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR ⁹ ,-(CH ₂ ) _n C (O) N (R ⁹ ) ₂ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR ⁹ ,-(CH ₂ ) _n N (R ⁹ ) ₂ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR ⁹ ,- (CH ₂ ) _n OC (O) N (R ⁹ ) ₂ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ⁹ ,-(CH ₂ ) _n SSR ⁹ ,-(CH ₂ ) _n SO ₂ R ⁹ ,-(CH ₂ ) _n SO ₂ R ⁹ ,-(CH ₂ ) _n OSO ₂ R ⁹ ,-(CH ₂ ) _n SO ₃ R ⁹ ,-(CH ₂ ) _n OSO ₃ R ⁹ ,-(CH ₂ ) _n B (R ⁹ ) ₂ ,-(CH ₂ ) _n B (OR ⁹ ) ₂ ,-(CH ₂ ) _n B (R ⁹ ) (OR ⁹ ),-(CH ₂ ) _n N = C = S,-(CH ₂ ) _n NCO,-(CH ₂ ) _n N (R ⁹ ) C (= O) R ⁹ ,-(CH ₂ ) _n N (R ⁹ ) C (= O) (OR ⁹ ),-(CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ ,-(CH ₂ ) _n P (R ⁹ ) ₂ ,-(CH ₂ ) _n P (OR ⁹ ) ₂ ,-(CH ₂ ) _n P (R ⁹ ) (OR ⁹ ),-(CH ₂ ) _n P (= O) (R ⁹ ) ₂ ,-(CH ₂ ) _n P (= O) (OR ⁹ ) ₂ , and-(CH _{2) n P (= O)} (R 9) (OR 9) polarity is selected from the group consisting of jakyonggiyi ,

The rest are hydrogen; halogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms,

N is an integer of 0 to 10,

R ⁹ contained in the polar functional group is hydrogen, linear or branched alkyl having 1 to 20 carbon atoms, alkenyl or vinyl, respectively; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms.

On the other hand, the cyclic olefin monomer may be composed of a nonpolar cyclic olefin monomer or a mixture of a polar cyclic olefin monomer and a nonpolar cyclic olefin monomer.

The solvent used in the polymerization method is an organic solvent using dichloromethane (CH ₂ Cl ₂ ), dichloroethane (CH ₂ ClCH ₂ Cl), chloroform, benzene, toluene, chlorobenzene (C ₆ H ₅ Cl). It is preferable. The amount of the solvent used is preferably 0.5 to 10 times, more preferably 1 to 8 times, and most preferably 2 to 4 times the volume of the monomer to be additionally polymerized. If less than 0.5 times the gel is formed and there is a post-treatment problem, if more than 10 times there is a problem that the polymerization yield is low. On the other hand, bulk polymerization may be performed without using such a solvent. In this case, the reaction solution may form a gel or harden during the polymerization reaction, thereby causing post-treatment problems.

The temperature range during the polymerization reaction is preferably 20 to 150 ° C, and the polymerization temperature can be changed during the reaction to change the polymerization conditions. If the polymerization temperature is less than 20 ℃ there is a problem that the catalyst is not activated due to low polymerization yield, if the polymerization temperature exceeds 150 ℃ there is a problem that the catalyst is thermally unstable and decomposes.

On the other hand, in the polymerization method, the cyclic olefin monomer and the polar vinyl olefin monomer are not limited to only two monomers, but two cyclic olefin monomers and polar vinyl olefin monomers containing different functional groups; Or it is also possible to include 3 types of monomers, such as a combination of 2 types of polar vinyl olefin monomers and cyclic olefin monomers containing different functional groups.

It is also possible to further include a nonpolar vinyl olefin monomer in addition to the cyclic olefin monomer and the polar vinyl monomer. The non-polar vinyl olefin monomer that is additionally included may be represented by the following formula (6).

<Formula 6>

In the formula (6),

m is an integer from 0 to 4,

R ¹⁰ and R ¹¹ are hydrogen; halogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms.

In the copolymer production method, the Group 13 compound is an organoaluminum compound represented by the following formula (7), the radical initiator is preferably an azo (azo) compound represented by the formula (2).

<Formula 7>

Al (R ⁰ ) _n1 (OR ¹ ) _n2 (X) _n3

In the formula of Formula 1,

n1, n2, n3 are integers from 0 to 3, and n1 + n2 + n3 = 3;

O is an oxygen atom,

R ⁰ and R ¹ are each independently hydrogen; Linear or branched alkyl, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Or linear or branched C1-C20 alkyl, or aryl, containing one to ten hetero atoms, such as N, O, a halogen element; X is halogen;

<Formula 2>

A ₁ -N = NA ₂

In the formula (2), N is a nitrogen element,

A ₁ and A ₂ are each independently hydrogen; Linear or branched alkyl, alkoxy, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Linear or branched alkyl, alkoxy, alkenyl, aryl or cycloalkylheterocarbons having 1 to 20 carbon atoms, including cyan, carbonyl, carboxyl, ether and amide groups.

The cyclic olefin and vinyl olefin copolymers prepared by the method of the present invention contain 0.1 to 99.9 mol% of polar vinyl olefin monomers, and the weight average molecular weight (Mw) of the copolymer is preferably 10,000 or more. If the molecular weight is less than 10,000 there is a problem difficult to manufacture a film. It is preferable that the glass transition temperature (Tg) of the said copolymer manufactured by the method of this invention is 100 degreeC or more. When it is less than 100 degreeC, there exists a problem in the thermal stability of a film.

In addition, the copolymer may be in the form of a copolymer blend further comprising one or more cyclic olefin monomers, polar vinyl olefin monomers, nonpolar vinyl olefin monomers or copolymers of cyclic olefin and polar vinyl olefins. have.

The cyclic olefin and polar vinyl olefin copolymers prepared by the present invention are transparent, have excellent adhesion to metals and polymers having other polar functional groups, and have a low dielectric constant such that they can be used as insulating electronic materials, It is an olefin copolymer having excellent thermal stability and strength. Accordingly, the polymer can be attached to a substrate of an electronic material without a coupling agent, can be attached to a metal substrate such as copper, silver, or gold, and has excellent optical properties, integrated circuits, It can be used in electronic materials such as printed circuit boards or multichip modules.

Therefore, the cyclic olefin and the polar olefin copolymer produced according to the present invention are transparent thermoplastic resins having a Tg of 100 to 200 ° C., which enables extrusion / injection molding for optical elements. The molding method is not particularly limited, and ordinary plastic extrusion and injection molding methods can be applied. This molding method can be applied to optical devices such as mobile phone lenses or aspherical lenses.

In addition, the optical film produced by the present invention has a strong heat resistance and can be used as a polarizing plate protective film by using its strength, and excellent adhesion to a material such as polyvinyl alcohol (PVA) and the like attached to a polyvinyl alcohol polarizing plate, etc. Can be used. In addition, if necessary, a method selected from corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, ultraviolet irradiation treatment or coating treatment may be used without degrading the transparency.

The copolymer of the cyclic olefin and vinyl olefin system according to the present invention can be produced as an optically anisotropic film which can control the birefringence which could not be conventionally produced. In other words, the conformational unit of a general cyclic olefin has one or two stable rotational states, so it is extended like a polyimide having a rigid phenyl ring as a main chain. Extended conformation can be achieved. When the monomer having a polar group is introduced into the norbornene-based polymer having an extended conformation, the intermolecular interaction (intermolecular interaction) is introduced through the introduction of the polar monomer than the polymer having the compact conformation. It has been found that the interaction is increased, and therefore, the directional order in packing between molecules can be optically and electrically anisotropic.

The birefringence may be adjusted according to the type and content of the polar functional groups introduced into the cyclic olefin and the polar vinyl olefin-based polymer, and in particular, the refractive index of the thickness direction to be manufactured is easily controlled, thereby allowing various modes of liquid crystal display (LCD). It can be prepared as an optical compensation film.

In the method for producing an optically anisotropic film, copolymers of cyclic olefins and polar vinyl olefins are dissolved in a solvent to prepare a film or sheet by a solvent casting method or a melting method. It is also possible to produce films from blends of one or more of these cyclic olefins and polar vinyl olefin copolymers.

The method for preparing a film by dissolving the cyclic olefin and the polar vinyl olefin polymer in a solvent is carried out using a polymer content of 5 to 95% by weight, more preferably 10 to 60% by weight of the cyclic olefin and the polar vinyl olefin polymer. It is preferably prepared by adding to a solvent and stirring at room temperature. In this case, the viscosity of the prepared solution is preferably 100 to 10000 cps, more preferably 300 to 8000 cps for solvent casting, and in order to improve the mechanical strength, heat resistance, light resistance, and handleability of the film, a plasticizer, a deterioration inhibitor, and an ultraviolet stabilizer. Or an additive such as an antistatic agent may be added.

The film thus prepared is an optically anisotropic film whose retardation value R _th represented by the following formula 1 satisfies 70 to 1000 nm:

<Equation 1>

R _th = Δ (n _y -n _z ) × d

Where n _y is the refractive index of the in-plane fast axis measured at wavelength 550 nm; n _z is the refractive index in the thickness direction measured at a wavelength of 550 nm;

d is the thickness of the film.

The optically anisotropic film is included in the liquid crystal display device to have a clear image quality at a wide viewing angle of a wide angle and to improve the brightness contrast of the on / off of the driving cell can be used as an optical compensation film.

n_y 〉n_z 관계(n_x는 면내의 저속 축(slow axis)의 굴절률이고; n_y는 면내의 고속 축(fast axis)의 굴절률이며; n_z는 두께 방향의 굴절률)를 만족하는 네가티브 C-플레이트(negative C-plate)형 광학 보상 필름이므로 전압이 on 또는 off 상태일때 액정층의 굴절률이 n_x

n_y＜n_z 인 관계(n_x 는 면내의 저속 축(slow axis)의 굴절률이고; n_y는 고속 축(fast axis)의 굴절률이며; n_z는 두께 방향의 굴절률임)를 만족하는 일반적인 액정 모드의 액정 디스플레이 장치를 구현할 수 있다. In particular, the film has a refractive index of n _x while the optical axis is perpendicular to the plate.

n _y 〉 N _z Negative C-plate satisfying the relationship (n _x is the refractive index of the in-plane slow axis; n _y is the refractive index of the in-plane fast axis; n _z is the refractive index of the thickness direction) Since the plate type optical compensation film, the refractive index of the liquid crystal layer is n _x when the voltage is on or off.

n _y <n _z Liquid crystal display device of general liquid crystal mode satisfying the phosphorus relationship (n _x is the refractive index of the in-plane slow axis; n _y is the refractive index of the fast axis; n _z is the refractive index of the thickness direction) Can be implemented.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

Example

All operations dealing with air or water sensitive compounds were carried out using standard Schlenk techniques or dry box techniques. Nuclear magnetic resonance spectra were obtained using a Bruker 300 spectrometer, ¹ H NMR at 300 MHz and ¹³ C NMR at 75 MHz. The molecular weight and molecular weight distribution of the polymer were measured using gel permeation chromatography (GPC), in which polystyrene samples were used as the standard. Thermal analyzes such as TGA and DSC were performed using a TA Instrument (TGA 2050; heating rate 10 K / min). Toluene was purified by distillation in potassium / benzophenone.

Preparation Example 1

(Production of norbornene-methyl acrylate copolymer)

In a 250 mL Schlenk flask, contains norbornene (15.8 g, 168 mmol), methylacrylate (10 mL, 112 mmol), AIBN (2,2'-azobisisobutyronitrile) (0.037 g, 0.22 mmol) . Put 30 mL toluene in this flask and dissolve it. In another 100 mL flask, add ethylaluminum sesquichloride (0.277 g, 1.12 mmol) and dissolve in 20 mL toluene. Ethyl aluminum sesquichloride toluene solution is slowly dropped into a 250 mL Schlenk flask at -70 ^° C. The reaction temperature was raised to room temperature with stirring for 2 hours and then reacted at 45 ^o C for 20 hours. At this time, as the reaction proceeds, the color changes to slightly green green color. After the reaction, the reaction solution was slowly dropped into 3000cc of 5% v / v HCl-MeOH to form a white polymer precipitate. The polymer precipitate was filtered through a glass filter and dried in a vacuum oven at 70 ^° C. for 12 hours to obtain 11.7 g of norbornene-methylacrylate copolymer (58.2% by weight, based on the total amount of monomers introduced). Tg was 140 ^° C., Molecular weight (Mw) was 46,600 and Mw / Mn was 1.99.

¹ H-NMR (300MHz in CDCl ₃ ): 3.55 (br s, 3H), 2.5 ~ 1.5 (br m, 13H)

Preparation Example 2

(Production of norbornene-methyl acrylate copolymer)

Diethylaluminium chloride (1.36 g, 1.12 mmol) was used in place of the ethyl aluminum sesquichloride used in Preparation Example 1, and norbornene and methyl acrylate were copolymerized in the same manner as in Preparation Example 1. The polymerization yield was 12.1 g (60.2% by weight based on the total amount of monomer introduced). The molecular weight (Mw) was 68,000 and Mw / Mn was 2.12.

Preparation Example 3

(Production of norbornene-methyl acrylate copolymer)

Diethylaluminum ethoxide (1.15 g, 1.12 mmol) was used in place of the ethyl aluminum sesquichloride used in Preparation Example 1, and norbornene and methyl acrylate were copolymerized in the same manner as in Preparation Example 1. The polymerization yield was 12.5 g (62.1% by weight based on the total amount of monomers injected). The molecular weight (Mw) was 54,000 and Mw / Mn was 2.10.

Preparation Example 4

(Production of norbornene-methyl acrylate copolymer)

Norbornene (15.8 g, 168 mmol), methylacrylate (10 mL, 112 mmol), di-t-butyl peroxide (0.32 g, 2.2 mmol) in a 250 mL Schlenk flask Put it. Put 30 mL toluene in this flask and dissolve it. In another 100 mL flask, add ethylaluminum sesquichloride (0.277 g, 1.12 mmol) and dissolve in 20 mL toluene. Ethyl aluminum sesquichloride toluene solution is slowly dropped into a 250 mL Schlenk flask at -70 ^° C. After stirring for 2 hours, the reaction temperature was raised to room temperature and reacted at 80 ^° C. for 18 hours. After the reaction, the reaction solution was slowly dropped into 3000cc of 5% v / v HCl-MeOH to form a white polymer precipitate. The polymer precipitate was filtered through a glass filter and dried in a vacuum oven at 70 ^° C. for 12 hours to obtain 10.5 g of norbornene-methyl acrylate copolymer (52.0% by weight based on the total amount of monomer introduced). The molecular weight (Mw) was 38,500 and Mw / Mn was 2.29.

Preparation Example 5

(Preparation of 2-butylnorbornene-methyl acrylate copolymer)

In a 250 mL Schlenk flask, 2-butylnorbornene (16.8 g, 112 mmol), methylacrylate (5 mL, 56 mmol), AIBN (0.28 g, 1.68 mmol). Put 30 mL toluene in this flask and dissolve it. In another 100 mL flask, add ethylaluminum sesquichloride (15.2 g, 61.6 mmol) and add 20 mL toluene to dissolve it. Ethyl aluminum sesquichloride toluene solution is slowly dropped into a 250 mL Schlenk flask at -70 ^° C. The reaction temperature was raised to room temperature with stirring for 2 hours and then reacted at 65 ^° C. for 12 hours. At this time, as the reaction proceeds, the color changes to slightly green green color. After the reaction, the reaction solution was slowly dropped into 3000cc of 5% v / v HCl-MeOH to form a white polymer precipitate. The polymer precipitate was filtered through a glass filter and dried in a vacuum oven at 70 ^° C. for 12 hours to obtain 5 g of 2-butylnorbornene-methylacrylate copolymer (38.0 wt% based on the total amount of monomer introduced). Tg was 100 ^° C., Mw was 8,180 and Mw / Mn was 3.2.

¹ H-NMR (300MHz in CDCl ₃ ): 3.64 (br s, 3H), 2.5 ~ 0.5 (br m, 21H)

Preparation Example 6

(Production of norbornene-methyl methacrylate copolymer)

In a 250 mL Schlenk flask, contains norbornene (8.8 g, 93 mmol), methylmethacrylate (5 mL, 47 mmol), AIBN (0.23 g, 1.40 mmol). Put 30 mL toluene in this flask and dissolve it. Ethyl aluminum sesquichloride (12.7 g, 51.4 mmol) is added to another 100 mL flask and 20 mL toluene is added to dissolve. Ethyl aluminum sesquichloride toluene solution is slowly dropped into a 250 mL Schlenk flask at -70 ^° C. The reaction temperature was raised to room temperature with stirring for 2 hours and then reacted at 65 ^o C for 12 hours. At this time, as the reaction proceeds, the color changes to slightly green green color. After the reaction, the reaction solution was slowly dropped into 3000cc of 5% v / v HCl-MeOH to form a white polymer precipitate. The polymer precipitate was filtered through a glass filter and dried in a vacuum oven at 70 ^° C. for 12 hours to obtain 0.3 g of norbornene-methyl methacrylate copolymer (3.0 wt% based on the total amount of monomer introduced). Tg was 167 ^° C, molecular weight (Mw) was 10,700 and Mw / Mn was 3.4.

¹ H-NMR (300MHz in CDCl ₃ ): 3.60 (br s, 3H), 2.5 ~ 0.8 (br m, 15H)

Preparation Example 7

(Production of norbornene-styrene-methylacrylate polymer)

In a 250 mL Schlenk flask, contains norbornene (10.5 g, 112 mmol), styrene (0.6 g, 5.6 mmol), methylacrylate (5 mL, 56 mmol), AIBN (0.028 g, 0.17 mmol). Put 30 mL toluene in this flask and dissolve it. In another 100 mL flask, add ethylaluminum sesquichloride (1.38 g, 5.6 mmol) and add 20 mL toluene. Ethyl aluminum sesquichloride toluene solution is slowly dropped into a 250 mL Schlenk flask at -70 ^° C. The reaction temperature was raised to room temperature with stirring for 2 hours and then reacted at 65 ^° C. for 12 hours. At this time, as the reaction proceeds, the color changes to slightly green green color. After the reaction, the reaction solution was slowly dropped into 3000cc of 5% v / v HCl-MeOH to form a white polymer precipitate. The polymer precipitate was filtered through a glass filter and dried in a vacuum oven at 70 ^° C. for 12 hours to obtain 7.1 g of norbornene-styrene-methylacrylate polymer (66.7 wt% based on the total amount of monomer introduced). Tg was 120 ^° C, molecular weight (Mw) was 228,000, and Mw / Mn was 16.

¹ H-NMR (300MHz in CDCl ₃ ): 7.4 ~ 6.6 (br m, 5H), 3.8 ~ 3.1 (br m, 3H), 2.4 ~ 0.6 (br m, 16H)

Examples 1-4

(Manufacture of optically anisotropic film)

To prepare a coating solution by mixing the polymer obtained in Preparation Examples 1, 5 to 7, as shown in Table 1 below, the coating solution was cast on a glass substrate using a knife coater or a bar coater, and then 1 hour at room temperature It dried again and dried at 100 degreeC for 18 hours in nitrogen atmosphere. After drying for 10 seconds after drying, the film on the glass substrate was peeled off with a knife to obtain a transparent film having a uniform thickness with a thickness variation of less than 2%. The thickness and light transmittance at 400 to 700 nm for these films are shown together in Table 1 below.

division Film solution composition Film properties Polymer (parts by weight) Solvent (part by weight) Thickness (㎛) Light transmittance (%) Example 1 Polymer 100 prepared in Preparation Example 1 THF 560 114 92 Example 2 Polymer 100 prepared in Preparation Example 5 MC 360, and TOLUENE 200 120 92 Example 3 Polymer 100 prepared in Preparation Example 6 TOLUENE 550 118 90 Example 4 Polymer 100 prepared in Preparation Example 7 TOLUENE 400 103 91

In Table 1 above,

THF is tetrahydrofuran and MC is methylenechloride.

(Optical anisotropy measurement)

Each of the transparent films according to Examples 1 to 4 measures the refractive index n using an Abbe refractometer, and uses an automatic birefringence meter (manufactured by prince measuring instrument; KOBRA-21 ADH) to measure the in-plane retardation value ( R _e ) is measured, and the phase difference value (R _θ ) when the angle between the incident light and the film surface is 50 °, and the phase difference value (R _th) between the film thickness direction and the in-plane x-axis according to Equation 2 ) Was obtained.

<Equation 2>

Furthermore, the refractive index difference (n _x -n _y ) and the refractive index difference (n _y -n _z ) were obtained by dividing the thickness of the film by the values of R _e and R _th . In Table 2 below, (n _x -n _y ), R _θ of each transparent film, R _{th ,} (n _y -n _z ) Indicated.

Transparent film n (refractive index) (nx-ny) x103 Rth (nm / μm) (ny-nz) x103 Example 1 1.52 0.008 5.78 5.78 Example 2 1.50 0.009 2.13 2.13 Example 3 1.52 0.007 1.47 1.47 Example 4 1.51 0.013 3.59 3.59

In addition, when R _θ was measured by overlapping a triacetate cellulose film having n _y > n _z , the R _θ value of all the cyclic olefin films was increased, and R _th of the cyclic olefin film was negative in birefringence ( negative birefringence; n _y > n _z ).

Example 5

(Lamination test with surface treatment and PVA polarizing film)

The surface tension of the NB-MA copolymer film obtained in Example 1 was measured to determine the surface tension from the relationship represented by Equations 3 and 4 below (Wu, SJ Polym. Sci. C Vol 34, P19, 1971).

<Equation 3>

<Equation 4>

는 필름의 표면 장력,

는 액체의 표면 장력,

은 필름과 액체의 계면 장력,

는 접촉각,

는 표면장력의 분포(dispersion)항 및

는 표면장력의 극성(polar)항이다.In Equations 3 and 4,

Surface tension of the film,

The surface tension of the liquid,

Interfacial tension of silver film and liquid,

Is the contact angle,

Is the distribution term of surface tension and

Is the polar term of the surface tension.

The contact angle was 74.3 ° when water was used, and the contact angle was 33.5 ° when diode methane was used, and the surface tension calculated from this value was 49.5 mN / m.

The contact angle was measured after corona treatment of the NB-MA copolymer film three times at a line speed of 6 m / min with a current of 8 mA. As a result, the contact angle was 20.7 ° using water, the contact angle was 22 ° using diode methane, and the calculated surface tension was 76.9 mN / m.

Within 30 minutes after the corona treatment, the film was rolled onto a sufficiently dried polyvinylalcohol (PVA) polarizing film with an aqueous 10 wt% PVA solution and dried at 80 ° C. for 10 minutes. After drying, the PVA polarizing plate on which the NB-MA copolymer film was laminated was excellent in adhesiveness.

Example 6

(Manufacture of Plastic Lens)

The polymers obtained in Production Examples 1 to 4 were molded under a mold temperature of 110 ° C. and an injection temperature of 300 ° C. using an injection mold for lenses. The obtained transparent plastic lenses were observed through a monitor for 24 hours under high temperature, high humidity of 70 ° C. and 95%, and all of them were in good condition. The light transmittance was measured through a spectrophotometer, and showed a light transmittance of more than 90% in the 400 ~ 700nm region.

According to the copolymer production method of the present invention, it is possible to effectively copolymerize the cyclic olefin and the polar vinyl olefin using a catalyst system composed of a Group 13 compound and a radical initiator, and the cyclic olefin and vinyl olefin produced by the production method of the present invention. The polymer is transparent and has a low dielectric constant, good thermal stability and strength, which can be used as an excellent adhesion to metals or other polymers, insulating electronic materials, etc., and the optical film including the polymer of the present invention has a polarizing plate due to the above properties. Protective films, adhesive films, anisotropic films, compensation films, optical lenses and liquid crystal display devices.

Claims (20)

A method for producing a copolymer comprising a cyclic olefin and a polar vinyl olefin, Cyclic olefin monomers and polar vinyl olefin monomers Iii) a Group 13 compound represented by Formula 1 below; And Ii) a radical initiator comprising an azo compound represented by the following formula (2) or a peroxide compound represented by the following formula (3) Method for producing a copolymer to polymerize in contact with the catalyst system comprising a. <Formula 1> M (R ⁰ ) _n1 (OR ¹ ) _n2 (X) _n3 In the formula of Formula 1, M is a group 13 element, n1, n2, n3 are integers from 0 to 3, and n1 + n2 + n3 = 3; O is an oxygen atom, R ⁰ and R ¹ are each independently hydrogen; Linear or branched alkyl, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Or linear or branched C1-C20 alkyl, or aryl, containing one to ten hetero atoms, such as N, O, a halogen element; X is halogen. <Formula 2> A ₁ -N = NA ₂ In the formula (2), N is a nitrogen element, A ₁ and A ₂ are each independently hydrogen; Linear or branched alkyl, alkoxy, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Linear or branched alkyl, alkoxy, alkenyl, aryl or cycloalkylheterocarbons having 1 to 20 carbon atoms, including cyan, carbonyl, carboxyl, ether and amide groups, <Formula 3> B ₁ -OOB ₂ In the formula (3), O is an oxygen element, B ₁ and B ₂ are each independently hydrogen; Linear or branched alkyl, alkoxy, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Linear or branched alkyl, alkoxy, alkenyl, aryl or cycloalkylheterocarbons having 1 to 20 carbon atoms, including cyan, carbonyl, carboxyl, ether and amide groups. The method of claim 1, wherein the cyclic olefin monomer is represented by the following formula (4). <Formula 4>

In the formula (4), m is an integer from 0 to 4, R ² , R ³ , R ⁴ , and R ⁵ Is hydrogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or a nonpolar functional group selected from alkynyl having 3 to 20 carbon atoms; -(CH ₂ ) _n C (O) OR ⁶ ,-(CH ₂ ) _n OC (O) R ⁶ ,-(CH ₂ ) _n OC (O) OR ⁶ ,-(CH ₂ ) _n C (O) R ⁶ ,-(CH ₂ ) _n OR ⁶ ,-(CH ₂ O) _n -OR ⁶ ,-(CH ₂ ) _n C (O) -OC (O) R ⁶ ,-(CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR ⁶ ,-(CH ₂ ) _n C (O) N (R ⁶ ) ₂ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR ⁶ ,-(CH ₂ ) _n N (R ⁶ ) ₂ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR ⁶ ,-(CH ₂ ) _n OC (O) N (R ⁶ ) ₂ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ⁶ ,-(CH ₂ ) _n SSR ⁶ ,-(CH ₂ ) _n SO ₂ R ⁶ ,-( CH ₂ ) _n SO ₂ R ⁶ ,-(CH ₂ ) _n OSO ₂ R ⁶ ,-(CH ₂ ) _n SO ₃ R ⁶ ,-(CH ₂ ) _n OSO ₃ R ⁶ ,-(CH ₂ ) _n B ( R ⁶ ) ₂ ,-(CH ₂ ) _n B (OR ⁶ ) ₂ ,-(CH ₂ ) _n B (R ⁶ ) (OR ⁶ ),-(CH ₂ ) _n N = C = S,-(CH ₂ ) _n NCO,-(CH ₂ ) _n N (R ⁶ ) C (= 0) R ⁶ ,-(CH ₂ ) _n N (R ⁶ ) C (= 0) (OR ⁶ ),-(CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ ,,-(CH ₂ ) _n P (R ⁶ ) ₂ ,-(CH ₂ ) _n P (OR ⁶ ) ₂ ,-(CH ₂ ) _n P (R ⁶ ) ( OR ⁶ ),-(CH ₂ ) _n P (= 0) (R ⁶ ) ₂ ,-(CH ₂ ) _n P (= 0) (OR ⁶ ) ₂ , and-(CH ₂ ) _n P (= 0) It may be a polar functional group selected from the group consisting of (R ⁶ ) (OR ⁶ ), R ⁶ included in the polar functional group may be each hydrogen, linear or branched alkyl having 1 to 20 carbon atoms, alkenyl or vinyl; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms, N is an integer from 0 to 10 and R ² , R ³ , R ⁴ , and R ⁵ are R ² and R ³ or R ⁴ and R ⁵ if they are not polar functional groups, hydrogen, or halogen. May be linked to each other to form an alkylidene group having 1 to 10 carbon atoms, or R ² or R ³ may be connected to any one of R ⁴ and R ⁵ to a saturated or unsaturated cyclic group having 4 to 12 carbon atoms, or Aromatic cyclic compounds having 6 to 17 carbon atoms can be formed. The method according to claim 1, wherein the polar vinyl olefin monomer is a polar vinyl olefin monomer represented by the following formula (5). <Formula 5>

In the formula (5), m is an integer from 0 to 4, At least one of R ⁷ and R ⁸ is-(CH ₂ ) _n C (O) OR ^9- (CH ₂ ) _n OC (O) R ⁹ ,-(CH ₂ ) _n OC (O) OR ⁹ ,-( CH ₂ ) _n C (O) R ⁹ ,-(CH ₂ ) _n OR ⁹ ,-(CH ₂ O) _n -OR ⁹ ,-(CH ₂ ) _n C (O) -OC (O) R ⁹ ,- (CH ₂ ) _n C (O) NH ₂ ,-(CH ₂ ) _n C (O) NHR ⁹ ,-(CH ₂ ) _n C (O) N (R ⁹ ) ₂ ,-(CH ₂ ) _n NH ₂ ,-(CH ₂ ) _n NHR ⁹ ,-(CH ₂ ) _n N (R ⁹ ) ₂ ,-(CH ₂ ) _n OC (O) NH ₂ ,-(CH ₂ ) _n OC (O) NHR ⁹ ,- (CH ₂ ) _n OC (O) N (R ⁹ ) ₂ ,-(CH ₂ ) _n C (O) Cl,-(CH ₂ ) _n SR ⁹ ,-(CH ₂ ) _n SSR ⁹ ,-(CH ₂ ) _n SO ₂ R ⁹ ,-(CH ₂ ) _n SO ₂ R ⁹ ,-(CH ₂ ) _n OSO ₂ R ⁹ ,-(CH ₂ ) _n SO ₃ R ⁹ ,-(CH ₂ ) _n OSO ₃ R ⁹ ,-(CH ₂ ) _n B (R ⁹ ) ₂ ,-(CH ₂ ) _n B (OR ⁹ ) ₂ ,-(CH ₂ ) _n B (R ⁹ ) (OR ⁹ ),-(CH ₂ ) _n N = C = S,-(CH ₂ ) _n NCO,-(CH ₂ ) _n N (R ⁹ ) C (= O) R ⁹ ,-(CH ₂ ) _n N (R ⁹ ) C (= O) (OR ⁹ ),-(CH ₂ ) _n CN,-(CH ₂ ) _n NO ₂ ,,,-(CH ₂ ) _n P (R ⁹ ) ₂ ,-(CH ₂ ) _n P (OR ⁹ ) ₂ ,-( CH ₂ ) _n P (R ⁹ ) (OR ⁹ ),-(CH ₂ ) _n P (= 0) (R ⁹ ) ₂ ,-(CH ₂ ) _n P (= 0) (OR ⁹ ) ₂ , and- (CH ₂ ) _n P (= 0) (R ⁹ ) (OR ⁹ ) a polar functional group selected from the group consisting of ego, The rest are hydrogen; halogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms, N is an integer of 0 to 10, R ⁹ contained in the polar functional group is hydrogen, linear or branched alkyl having 1 to 20 carbon atoms, alkenyl or vinyl, respectively; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms. The method for producing a copolymer according to claim 1, wherein the cyclic olefin monomer is a nonpolar cyclic olefin monomer or a mixture of a polar cyclic olefin monomer and a nonpolar cyclic olefin monomer. The method for producing a copolymer according to claim 1, wherein the polymerization temperature is in the range of 20 to 150 ^° C. The cyclic olefin monomer and the polar vinyl olefin monomer according to claim 1, wherein the cyclic olefin monomer and the polar vinyl olefin monomer comprise two kinds of cyclic olefin monomers having different functional groups; Or three monomers such as a combination of two kinds of polar vinyl olefin monomers and cyclic olefin monomers containing different functional groups. The method according to claim 1, further comprising a nonpolar vinyl olefin monomer represented by the following Chemical Formula 6 in addition to the cyclic olefin monomer and the polar vinyl monomer. <Formula 6>

In the formula (6), m is an integer from 0 to 4, R ¹⁰ and R ¹¹ are hydrogen; halogen; Linear or branched alkyl, alkenyl or vinyl of 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl having 6 to 40 carbon atoms, optionally substituted with hydrocarbons; Aralkyl having 7 to 15 carbon atoms, substituted or unsubstituted with hydrocarbon; Or alkynyl having 3 to 20 carbon atoms. The method according to claim 1, wherein the Group 13 compound is an organoaluminum compound represented by the following Chemical Formula 7, and the radical initiator is an azo compound represented by the following Chemical Formula 2. <Formula 7> Al (R ⁰ ) _n1 (OR ¹ ) _n2 (X) _n3 In the formula of Formula 1, n1, n2, n3 are integers from 0 to 3, and n1 + n2 + n3 = 3; O is an oxygen atom, R ⁰ and R ¹ are each independently hydrogen; Linear or branched alkyl, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon having 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Or linear or branched C1-C20 alkyl, or aryl, containing one to ten hetero atoms, such as N, O, a halogen element; X is halogen; <Formula 2> A ₁ -N = NA ₂ In the formula (2), N is a nitrogen element, A ₁ and A ₂ are each independently hydrogen; Linear or branched alkyl, alkoxy, alkenyl, or vinyl having 1 to 20 carbon atoms; Cycloalkyl substituted or unsubstituted by hydrocarbon with 5 to 12 carbon atoms; Aryl of 6 to 40 carbon atoms, substituted or unsubstituted with hydrocarbon; Linear or branched alkyl, alkoxy, alkenyl, aryl or cycloalkylheterocarbons having 1 to 20 carbon atoms, including cyan, carbonyl, carboxyl, ether and amide groups. A copolymer prepared by the method of any one of claims 1 to 8. 10. The copolymer according to claim 9, wherein the copolymer comprises 0.1 to 99.9 mol% of a polar vinyl olefin monomer. The copolymer according to claim 9, wherein the copolymer has a weight average molecular weight (Mw) of 10,000 or more. The copolymer according to claim 9, wherein the copolymer has a glass transition temperature (Tg) of 100 ° C or higher. 10. The copolymer blend of claim 9, wherein the copolymer further comprises at least one cyclic olefinic monomer, a polar vinyl olefinic monomer, a nonpolar vinyl olefinic monomer or a copolymer of cyclic olefinic and polar vinyl olefinic. It is a copolymer characterized by the above-mentioned. 9. A polarizing plate protective film comprising a copolymer prepared by the method of any one of claims 1 to 8. An adhesive film comprising a copolymer prepared by the method of any one of claims 1 to 8. An optically anisotropic film comprising a copolymer prepared by the method of any one of claims 1 to 8. The optically anisotropic film according to claim 16, wherein the optically anisotropic film has a retardation value (R _th ) represented by the following formula (1): 70 to 1000 nm. (Equation 1) R _th = Δ (n _y -n _z ) × d Where n _y is the refractive index of the in-plane fast axis measured at wavelength 550 nm; n _z is the refractive index of the thickness direction measured at wavelength 550 nm; d is the thickness of the film. The method of claim 16, wherein the refractive index of the optical film is

Negative C- for liquid crystal displays satisfying the phosphorus relationship (n _x is the refractive index of the in-plane slow axis; n _y is the refractive index of the in-plane fast axis; n _z is the refractive index of the thickness direction). An optically anisotropic film, characterized in that the plate (negative C-plate) optical compensation film. The liquid crystal display device provided with the film containing the copolymer manufactured by the method of any one of Claims 1-8. An injection molded optical lens comprising a copolymer prepared by the method of any one of claims 1 to 8.

Images