KR101234781B1 - Optical anisotropic film, preparation method thereof, and liquid crystal display comprising optical anisotropic film - Google Patents

Abstract

The present invention relates to an optically anisotropic film, and more particularly, to an optically anisotropic film comprising a cyclic olefin polymer and a styrene-maleic anhydride copolymer, a manufacturing method thereof, and a liquid crystal display device including the same. The optically anisotropic film according to the present invention can be manufactured at low cost, and the refractive index in the thickness direction can be adjusted, so that the phase difference control range is large by the optical design, and thus it can be used as various types of optical compensation films for liquid crystal display devices.

Cyclic olefin type, styrene maleic anhydride, negative C-plate, optically anisotropic film, liquid crystal display device

Description

Optically anisotropic film, a method of manufacturing the same, and a liquid crystal display including the same {OPTICAL ANISOTROPIC FILM, PREPARATION METHOD THEREOF, AND LIQUID CRYSTAL DISPLAY COMPRISING OPTICAL ANISOTROPIC FILM}

The present invention relates to an optically anisotropic film, and more particularly, to an optically anisotropic film comprising a cyclic olefin polymer and a styrene-maleic anhydride copolymer, a manufacturing method thereof, and a liquid crystal display device including the same.

The liquid crystal display has been used for various purposes due to low power consumption, which can be driven by a battery for several hours, a small space, a small space, and a light weight, making it easy to carry. In addition, the size of the product also varies from small to medium to large size, and as a display device is being used as a small mobile phone large large TV as a display device. In particular, in the case of a medium-large size liquid crystal display device, it is important to secure display quality at the wide viewing angle of a wide angle and to improve the brightness contrast when the driving cell is turned on or off.

The liquid crystal display includes various liquid crystals such as dual domain TN, axially symmetric aligned microcell (ASM), vertical alignment (VA), surrounding electrode (SE), patterned VA (PVA), and in-plane switching (IPS) mode. It is being used or developed in mode. Each of these modes has a unique liquid crystal array and has inherent optical anisotropy. Therefore, in order to compensate for the change in the optical axis of linearly polarized light due to the optical anisotropy of these liquid crystal modes, various optical anisotropy compensation films are required.

The compensation film is important not only for optical compensation due to liquid crystal which is an optical anisotropic body, but also for improving light outflow occurring at an optical viewing angle of about 45 ° from an optical axis of an orthogonal polarizing element, a compensation film having optical anisotropy is important. Therefore, in order to compensate optically for liquid crystal displays in various modes, it is important to develop an optical film capable of precisely and effectively controlling optical anisotropy.

Optical anisotropy may be divided into R _e , which is an in-plane retardation value, and R _th , which is a phase difference value in the fast axis (y-axis) and the thickness direction (z-axis) in the plane, as shown in Equations 1 and 2 below.

In Equations 1 and 2, n _x is the refractive index of the in-plane slow axis (x-axis), n _y is the refractive index of the fast axis in the plane (y-axis), n _z Is the refractive index in the thickness direction (z-axis), and d is the thickness of the film.

When one component of R _e or R _th obtained from Equation 1 and Equation 2 is much larger than the other value, it can be used as a compensation film having uniaxial optical anisotropy. It can be used as a compensation film having biaxial optical anisotropy.

Compensation films having uniaxial optical anisotropy include A-plate (n _x ≠ n _y ≒ n _z ) and C-plate (n _x ≒ n _y ≠ n _z ). The phase difference in the plane direction can be controlled through secondary film processing such as precision stretching, and an optically isotropic material can be produced by uniaxial stretching. However, the control of the optical anisotropy in the thickness direction is limited to control through the secondary processing, it is preferable to use a transparent material having a characteristic different from the molecular arrangement in the thickness direction and the molecular arrangement in the plane direction of the polymer. In particular, when only the compensation of the polarized optical axis due to the liquid crystal is considered, the ideal compensation film should have an optical optical axis on the optical axis of the liquid crystal layer, so that the refractive index in the thickness direction is larger than the refractive index in the plane direction. In the case of an alignment mode liquid crystal display, a negative C-plate having negative birefringence in the thickness direction is required.

Such polymeric materials that can be applied as negative C-plates are discotic liquid crystals (e.g. U.S. Patent No. 5,583,679), polyimides having planar phenyl groups in the main chain (e.g. U.S. Patent No. 5,344,916) And cellulose ester films (eg, International Patent Publication No. WO 2000/55657) comprising a low molecular weight aromatic compound which is a phase retarder in the thickness direction.

Among these materials, the discotic liquid crystal cannot be used by itself and must be used by precisely coating the transparent support with a thickness of several μm, so that not only the cost incurred in the coating process but also the micro birefringence of the discotic liquid crystal can cause a small coating thickness. One difference also causes a relatively large phase difference, and there are problems such as optical defects due to foreign matter such as dust remaining on the surface of the coating substrate film or present in the discotic liquid crystal solution.

In addition, polyimide has defects such as light loss due to light absorption in the visible light band, and lacks adhesion and has a high water absorption rate so that peeling occurs easily at an adhesive interface.

Cellulose ester-based films have problems such as dimensional stability and peeling on the adhesive surface due to high water absorption rate, and are disadvantageous to cyclic olefin polymers in durability due to the relatively high content of low molecular weight phase retardant compounds. .

For these reasons, stretched films of cyclic olefin polymers have recently been used for negative C-plate applications rather than the polymer films. Since the cyclic olefin polymer has no light absorbing means in the visible region, the wavelength dispersion characteristic is flat, so that the phase difference value with respect to the wavelength is small, the hydrocarbon content is high, and the dielectric constant is low and the hygroscopicity is low. Has an advantage.

Polymers or copolymers of cyclic olefins are well known from the literature and the like. The cyclic olefin polymer obtained by addition polymerization using a homogeneous catalyst has a rigid and three-dimensional bulky ring structure in all the main chain monomer units, and thus has a very high glass transition temperature (Tg). As it is an amorphous polymer, there is no light loss due to scattering as in the crystalline polymer, and there is no light absorption in the visible light region due to π-conjugation. In particular, the cyclic olefin polymer having a relatively high molecular weight composed of addition polymerization using an organometallic compound as a catalyst has a low dielectric constant and has excellent electrical isotropy.

Due to such high permeability, low birefringence, and high glass transition temperature (Tg), polymers polymerized using norbornene monomers can be used in optical applications such as light guide plates or optical discs, as well as in low dielectric constants, good adhesion, electrical isotropy, and high glass transition temperatures. Tg) can also be used as an insulating material.

However, since the optical film prepared by using the cyclic olefin polymer has no light absorbing means in the visible region, there is no change in wavelength dispersion characteristics, so the phase difference value with respect to the wavelength is small, and also the polymer having different moisture absorption rate is used. On the other hand, there are a lot of very low advantages, but it takes a high manufacturing cost to produce a compensation film having a uniform retardation using this polymer, and only two or more types of compensation films can be used to exhibit the effect of having a uniform retardation. This likewise requires high manufacturing costs. In addition, there is a disadvantage that the retardation value of the compensation film thus prepared is larger than that of the compensation film prepared using another polymer.

In order to solve the problems of the prior art, it is necessary to develop an optically anisotropic film having not only a low-cost resin composition but also freely control negative birefringence in the thickness direction.

In order to achieve the above object,

1) cyclic olefin polymer and

2) Styrene-maleic anhydride copolymer having a weight average molecular weight of 1,000 to 50,000

It provides an optically anisotropic film comprising a.

The present invention also provides a method for producing the optically anisotropic film.

Moreover, this invention provides the liquid crystal display device containing the said optically anisotropic film.

The optically anisotropic film according to the present invention can freely control the negative birefringence in the thickness direction by using a low molecular weight styrene-maleic anhydride copolymer together with the cyclic olefin polymer, and in this way the cyclic olefin system It is possible to solve the problem that the negative birefringence in the thickness direction is a problem that occurs when only the polymer is used.

Hereinafter, the present invention will be described in detail.

The inventors believe that the conformational unit of a common cyclic olefin has one or two stable rotational states, thus extending it like a polyimide backed by a rigid phenyl ring. It has an extended conformation and thus may have anisotropy in monomolecules, and a film containing a norbornene-based polymer and an styrene-maleic anhydride copolymer having an extended conformation has good transparency and a styrene- According to the content of the maleic anhydride copolymer it was found that the negative birefringence, that is, the optical anisotropy can be adjusted as necessary to complete the present invention.

The optically anisotropic film according to the present invention comprises 1) a cyclic olefin polymer and 2) a styrene-maleic anhydride copolymer having a weight average molecular weight of 1,000 to 50,000.

In the optically anisotropic film according to the present invention, the 1) cyclic olefin-based polymer is preferably an addition polymer of norbornene-based monomer represented by Formula 1 or a copolymer of different norbornene-based monomers represented by Formula 1 below.

In Formula 1,

m is an integer from 0 to 4;

R ₁ , R ₂ , R ₃ and R ₄ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or a polar group comprising at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron;

When R ₁ , R ₂ , R ₃ and R ₄ are not hydrogen, halogen, or a polar functional group, R ₁ And saturation of R _2, or R ₃ and R ₄ is connected is formed in the alkylidene group having 1 to 10 carbon atoms, or R ₁ or R ₂ is connected with any one of R ₃ and R ₄ each having 4 to 12 carbon atoms, Or an unsaturated aliphatic ring or an aromatic ring having 6 to 24 carbon atoms.

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Specifically, in Chemical Formula 1, the polar functional group is -R ₅ OR ₆ , -OR ₆ , -OC (O) OR ₆ , -R ₅ OC (O) OR ₆ , -C (O) OR ₆ , -R ₅ C (O) OR _6, -C (O) R ₆ , -R ₅ C (O) R ₆ , -OC (O) R ₆ , -R ₅ OC (O) R ₆ ,-(R ₅ O) _n -OR ₆ ,-(OR ₅ ) _n -OR ₆ , -C (O) -OC (O) R ₆ , -R ₅ C (O) -OC (O) R ₆ , -SR ₆ , -R ₅ SR ₆ , -SSR ₆ , -R ₅ SSR ₆ , -S (= O) R ₆ , -R ₅ S (= O) R ₆ , -R ₅ C (= S) R _6- , -R ₅ C (= S) SR ₆ , -R ₅ SO ₃ R ₆ , -SO ₃ R ₆ , -R ₅ N = C = S, -N = C = S, -NCO, -R ₅ -NCO, -CN, -R ₅ CN, -NNC (= S) R ₆ , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

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In the polar functional group,

R ₅ is the same as or different from each other, and each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxyylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy,

R ₆ , R ₇ and R ₈ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxy of 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy,

n is each independently an integer of 1 to 10.

In the present invention, the norbornene-based monomer is at least one norbornene (bicyclo [2,2,1] hept-2-ene), such as the formula (2) It means the monomer containing a unit.

In the optically anisotropic film according to the present invention, the 1) cyclic olefin-based polymer can be prepared by addition polymerization or copolymerization of norbornene-based monomer represented by the formula (1), and various rings depending on the catalyst system selected during addition polymerization A type olefin type addition polymer or copolymer can be manufactured and used.

The type of the cyclic olefin-based polymer prepared may be a homopolymer of norbornene-based monomers, or may be a copolymer of norbornene-based monomers containing at least one polar or nonpolar functional group different from each other.

In general, in order to obtain a high R _th value, the cyclic olefin having a high m value of Formula 1 is introduced, the content of the polar functional group is increased, or the R ₁ to R ₄ present in determining the length of the substituent of the norbornene-based monomer. Cyclic olefins having reduced carbon number to reduce the length of substituents, introducing functional groups with high polarity, or R ₁ or R ₂ linked to any one of R ₃ and R ₄ to form an aromatic ring compound having 6 to 24 carbon atoms It can be achieved by introducing.

In the optically anisotropic film according to the present invention, it is preferable that the 1) cyclic olefin polymer has a weight average molecular weight of 10,000 to 1,000,000. When the weight average molecular weight of the cyclic olefin-based polymer is less than 10,000, there is a problem that the film is brittle when manufacturing the film. When the molecular weight exceeds 1,000,000, the workability as a sheet is lowered, and in the case of solution casting, the organic solvent It is difficult to melt | dissolve and there exists a problem of inferior workability.

The addition copolymerization method of these norbornene-based monomers may be prepared by mixing a monomer and a catalyst to be polymerized in a solvent as in a conventional polymerization method.

These cyclic olefin polymers are not limited in the polar groups that can be introduced depending on the specific catalyst system, and by changing the type and amount of these polar functional groups or nonpolar functional groups, a series of polymer polymerizations capable of controlling optical anisotropy are possible. The same polymer can be applied to compensation films for liquid crystal displays.

In the optically anisotropic film according to the present invention, the 2) styrene-maleic anhydride copolymer has a weight average molecular weight of 1,000 to 50,000. When the molecular weight exceeds 50,000, compatibility with the cyclic olefin polymer may be reduced.

The optically anisotropic film according to the present invention has a relatively high cost by including a low molecular weight styrene-maleic anhydride copolymer having excellent compatibility with a cyclic olefin polymer compared to a high molecular weight styrene-maleic anhydride copolymer. Since the content of the cyclic olefin polymer can be reduced, it is possible to reduce the manufacturing cost of the optically anisotropic film.

In the optically anisotropic film according to the present invention, the weight ratio of the 1) cyclic olefin polymer and 2) the styrene-maleic anhydride copolymer is preferably 99: 1 to 30:70, and 95: 5 to 60:40 More preferably.

In the optically anisotropic film according to the present invention, the retardation value (R _th ) represented by the formula (2) is preferably 30 to 1,000 nm.

In addition, the method for producing an optically anisotropic film according to the present invention comprises a) a cyclic olefin polymer and a weight average molecular weight of 1,000 to 50,000 Dissolving the phosphorus styrene-maleic anhydride copolymer in a solvent to prepare a resin composition solution; And b) coating or casting and drying the resin composition solution on a substrate.

In the method for producing an optically anisotropic film according to the present invention, the cyclic olefin-based polymer of step a) is an addition polymer of norbornene-based monomer represented by Formula 1 as described above or different Novo represented by Formula 1 It is preferable that it is a copolymer of a nene type monomer.

Step a) is a step of dissolving the cyclic olefin polymer and the styrene-maleic anhydride copolymer in a solvent to prepare a resin composition solution.

The content of the cyclic olefin polymer in the resin composition solution is preferably contained in 1 to 70% by weight.

In addition, the content of the styrene-maleic anhydride copolymer in the resin composition solution is preferably included in 1 to 70% by weight, more preferably in 5 to 40% by weight. If the content is less than 1% by weight, there is a disadvantage that the optical birefringence is not freely controlled. If the content exceeds 70% by weight, the impact strength of the blend is lowered.

The resin composition solution is prepared by adding the cyclic olefin-based polymer and styrene-maleic anhydride copolymer to the solvent at 5 to 95% by weight, more preferably 10 to 40% by weight in the total resin composition solution and stirring at room temperature. It is preferable. In this case, the viscosity of the prepared solution is preferably 100 to 30,000 cps, more preferably 500 to 10,000 cps. In addition, an additive such as a plasticizer, an antioxidant, an ultraviolet stabilizer, an antistatic agent, or the like may be added to the resin composition solution in order to improve mechanical strength, heat resistance, light resistance, handleability, and the like of the film.

In the method of manufacturing an optically anisotropic film according to the present invention, the step b) is a step of casting or coating the prepared resin composition solution on a polished band or drum or glass plate and drying the solvent to obtain an optical film or sheet to be. The solvent drying temperature can be selected according to the kind of solvent used. It is preferable that the surface temperature of a metal or glass base material polished in the mirror surface state is below normal temperature. After the solvent has been sufficiently dried, the formed film or sheet is peeled off from the metal or glass substrate.

The optically anisotropic film prepared as described above is an optically anisotropic transparent film having the characteristics of negative C-plate, and the retardation value R _th represented by Equation 2 satisfies 30 to 1,000 nm. :

In particular, the R _th value can have a range of 50 to 600㎚ when the R _th value hayeoteul when the film thickness to 30 to 200㎛ hayeoteul 30 to 1,000nm, more preferably a film thickness of 50 to 120㎛. This film is excellent in transparency and has a light transmittance of 90% or more at 400 to 800 nm.

The optically anisotropic film according to the present invention has excellent optical anisotropy and adhesiveness with a material such as polyvinyl alcohol (PVA), and can be attached to a polyvinyl alcohol (PVA) polarizing plate or the like.

In addition, transparency, anisotropy, and the like are reduced even when used with a surface treatment selected from the group consisting of corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, ultraviolet irradiation treatment, and coating treatment, if necessary. Can be used without

In addition, the present invention provides a liquid crystal display device including one or two or more optical anisotropic films.

The optically anisotropic film according to the present invention is included in the liquid crystal display device to have a clear image quality at a wide viewing angle, and to improve brightness contrast when the driving cell is turned on and off, in particular, when the voltage is turned on or off. When the refractive index of the liquid crystal layer is a C-plate (n _x ≒ n _y ≠ n _z ) relationship (n _x is the refractive index of the in-plane slow axis, n _y is the fast axis It is possible to implement a liquid crystal display of the liquid crystal mode satisfying the refractive index of, and n _z is the refractive index of the thickness direction).

The optically anisotropic film which concerns on this invention is used suitably as an optical compensation member for liquid crystal display devices. Examples include phase difference films such as Super Twist Nematic (STN) type LCD, Thin Film Transistor-Twisted Nematic (TFT-TN) type LCD, Vertical Alignment (VA) type LCD, and In-Plane Switching (IPS) type LCD; Half wave plate; Quarter wave plate; Reverse wavelength dispersion film; Optical compensation films; Color filters; Laminated film with a polarizing plate; Polarizing plate compensation film, etc. are mentioned. The use to which the present invention is applied is not limited to this, and the present invention can be widely used if the birefringence property of R _th > 0 is used.

In particular, the optically anisotropic film according to the present invention is advantageous to improve the viewing angle characteristics by applying to the liquid crystal display of the VA mode.

The liquid crystal display including one or two or more optically anisotropic films will be described in more detail as follows.

A liquid crystal display device comprising a liquid crystal cell and a first polarizing plate and a second polarizing plate respectively provided on both surfaces of the liquid crystal cell, wherein the optically anisotropic film is provided between the liquid crystal cell and the first polarizing plate and / or the second polarizing plate. Can be. That is, an optically anisotropic film may be provided between the first polarizing plate and the liquid crystal cell, and the optically anisotropic film may be provided between the second polarizing plate and the liquid crystal cell, or between the first polarizing plate and the liquid crystal cell and between the second polarizing plate and the liquid crystal cell. One or more It may be provided.

The first polarizing plate and the second polarizing plate may include a protective film on one or both surfaces. The inner protective film may include a triacetate cellulose (TAC) film, a polynorbornene-based film made of ring opening metathesis polymerization (ROMP), and a hydrogenated cyclic olefin-based polymer that is ring-opened polymerized. ring opening metathesis polymerization followed by hydrogenation) may be a polymer, a polyester film, or a polynorbornene-based film made by addition polymerization. In addition, a protective film or the like made of a transparent polymer material may be used, but is not limited thereto.

The present invention also provides an integrated polarizing plate including a polarizing film and including one or more optically anisotropic films according to the present invention on one or both surfaces of the polarizing film as a protective film.

When the retardation film is provided only on one surface of the polarizing film, the other surface may be provided with a protective film known in the art.

As the polarizing film, a film made of polyvinyl alcohol (PVA) containing iodine or dichroic dye may be used. The polarizing film may be prepared by dyeing iodine or dichroic dye on a PVA film, but a method of manufacturing the same is not particularly limited. In the present specification, the polarizing film means a state not including a protective film, and the polarizing plate means a state including a polarizing film and a protective film.

In the integrated polarizing plate of the present invention, the protective film and the polarizing film may be laminated by a method known in the art.

For example, the lamination of the protective film and the polarizing film may be made by an adhesive method using an adhesive. That is, first, an adhesive is coated on the surface of the PVA film, which is a protective film of the polarizing film or a polarizing film, using a roll coater, a gravure coater, a bar coater, a knife coater or a capillary coater. Before the adhesive is completely dried, the protective film and the polarizing film are laminated by heat pressing at room temperature or pressing at room temperature. In the case of using a hot melt adhesive, a heat press roll should be used.

Adhesives that can be used when the protective film and the polarizing plate are laminated include one-component or two-component PVA adhesives, polyurethane adhesives, epoxy adhesives, styrene butadiene rubber (SBR) adhesives, or hot melt adhesives, but are not limited thereto. Do not. When using a polyurethane adhesive, it is preferable to use the polyurethane adhesive manufactured using the aliphatic isocyanate type compound which does not yellow by light. When using one-component or two-component dry laminate adhesives or adhesives with relatively low reactivity between isocyanates and hydroxyl groups, a solution-type adhesive diluted with an acetate solvent, a ketone solvent, an ether solvent, or an aromatic solvent may be used. Can also be used. At this time, it is preferable that adhesive viscosity is a low viscosity type of 5,000 cps or less. It is preferable that the adhesives have excellent storage stability and have a light transmittance of 90% or more at 400 to 800 nm.

A tackifier can also be used if it can exert sufficient adhesive force. It is preferable that the adhesive is sufficiently cured by heat or ultraviolet rays after lamination, and thus the mechanical strength is improved to the level of the adhesive. The adhesive strength is also large so that the adhesive does not peel off without breaking of either film to which the adhesive is attached. It is preferable.

Specific examples of the pressure-sensitive adhesive that can be used include natural rubber, synthetic rubber or elastomer having excellent optical transparency, a vinyl chloride / vinyl acetate copolymer, polyvinyl alkyl ether, polyacrylate or modified polyolefin-based pressure-sensitive adhesive, and a curing type in which a curing agent such as isocyanate is added thereto. An adhesive is mentioned.

In addition, the present invention provides a liquid crystal display including the integrated polarizer.

Even when the liquid crystal display device according to the present invention includes the aforementioned integrated polarizing plate, one or more optically anisotropic films according to the present invention may be further included between the polarizing plate and the liquid crystal cell.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

< Example  And Comparative example >

< Manufacturing example  1> 5- Nobonen -2- Methyl acetate  Polymer manufacture

5-norbornene-2-methyl acetate (3,324 g) was added to the reactor at room temperature, followed by toluene (9,972 g). The inside of the reactor was replaced with nitrogen, and the reactor was heated to 90 ° C. Subsequently, palladium diacetate (0.229 g) and tricyclohexylphosphonium tetrakis (pentafluorophenyl) borate (2.561 g) as catalysts were dissolved in dichloromethane and then charged into the reactor and reacted with stirring for 18 hours.

After 18 hours, the reaction product was prepared using acetone and ethanol to obtain a white polymer precipitate. The precipitate was collected by filtration with a glass funnel and dried in a vacuum oven at 60 ° C. for 24 hours to obtain 5-norbornene-2-methylacetate polymer having a weight average molecular weight of 301,000 and a PDI of 2.80.

< Manufacturing example  2> 5- Nobonen -2- Methyl acetate  And 2-butyl-5- Norbornene  80: 20 (molar ratio) copolymer preparation

5-norbornene-2-methylacetate (3,324 g) and 2-butyl-5-norbornene (745 g) were added to the reactor at room temperature, followed by toluene (18,310 g). The inside of the reactor was replaced with nitrogen, and the reactor was heated to 90 ° C. Subsequently, palladium diacetate (0.374 g) and tricyclohexylphosphonium tetrakis (pentafluorophenyl) borate (3.20 g) as catalysts were dissolved in dichloromethane, and then charged into the reactor and reacted with stirring for 18 hours.

After 18 hours, the reaction product was prepared using acetone and ethanol to obtain a white polymer precipitate. The precipitate was collected by filtration with a glass funnel, and the polymer was dried in a vacuum oven at 60 ° C. for 24 hours to give a weight average molecular weight of 463,400 and PDI of 3.61, 5-norbornene-2-methylacetate and 2-butyl-5-novo. The 80:20 copolymer of nene was obtained.

< Manufacturing example  3> 5- Nobonen -2- Methyl acetate  And 5- Nobonen -2- Butyl ester  Preparation of 70:30 (molar ratio) copolymer

5-norbornene-2-methyl acetate (2,326 g) and 5-norbornene-2-butyl ester (1,165 g) were added to the reactor at room temperature, followed by toluene (6,984 g). The inside of the reactor was replaced with nitrogen, and the reactor was heated to 90 ° C. Subsequently, palladium diacetate (0.449 g) and tricyclohexylphosphonium tetrakis (pentafluorophenyl) borate (3.84 g) as catalysts were dissolved in dichloromethane, and then charged into the reactor and reacted with stirring for 18 hours.

After 18 hours, the reaction product was prepared using acetone and ethanol to obtain a white polymer precipitate. The precipitate was collected by filtration with a glass funnel, and the polymer was dried in a vacuum oven at 60 ° C. for 24 hours to obtain a weight average molecular weight of 436,000 and a PNO of 2.33, 5-norbornene-2-methylacetate and 5-norbornene-2- A 70:30 copolymer of butyl ester was obtained.

< Manufacturing example  4> 5- Nobonen -2- Butyl ester  And 2- Phenyl -5- Norbornene  50: 50 (molar ratio) copolymer preparation

5-norbornene-2-butyl ester (7,772 g), 2-phenyl-5-norbornene (6,810 g) and 1-octene (268.8 g) were added to the reactor at room temperature, followed by toluene (72,912 g). The inside of the reactor was replaced with nitrogen, and the reactor was heated to 90 ° C. Subsequently, palladium diacetate (1.796 g) and tricyclohexylphosphonium tetrakis (pentafluorophenyl) borate (15.37 g), which are catalysts, were dissolved in dichloromethane, and then charged into the reactor and reacted with stirring for 18 hours. .

After 18 hours, the reaction product was prepared using acetone and ethanol to obtain a white polymer precipitate. The precipitate was collected by filtration with a glass funnel and the polymer was dried in a vacuum oven at 60 ° C. for 24 hours to give a weight average molecular weight of 302,400 and PDI of 2.74, 5-norbornene-2-butylester and 2-phenyl-5-novo. A 50:50 copolymer of nene could be obtained.

< Example  1>

In order to produce the negative C-plate type optically anisotropic film of the present invention, using the 5-norbornene-2-methyl acetate polymer obtained in Preparation Example 1 using 70% by weight, the weight average molecular weight of SARTOMER company This 7,500 SMA 2000 was dissolved in methylene chloride solvent using 30% by weight to 13% by weight. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  2>

In order to produce the negative C-plate type optically anisotropic film of the present invention, using the 5-norbornene-2-methyl acetate polymer obtained in Preparation Example 1 using 70% by weight, the weight average molecular weight of SARTOMER company This 11,500 SMA EF-60 was dissolved in methylene chloride solvent using 30% by weight to 13% by weight. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  3>

In order to produce the negative C-plate type optically anisotropic film of the present invention, using the 5-norbornene-2-methyl acetate polymer obtained in Preparation Example 1 70% by weight and weight average of SARTOMER company SMA EF-80 having a molecular weight of 14,400 was dissolved in methylene chloride solvent using 30% by weight to 13% by weight. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  4>

80: 20 of 5-norbornene-2-methylacetate and 2-butyl-5-norbornene obtained in Preparation Example 2 for producing an optically anisotropic film of the negative C-plate type of the present invention Using 80% by weight of copolymer and 20% by weight of SMA EF-60 having a weight average molecular weight of 11,500 of SARTOMER was dissolved in methylene chloride solvent to 10% by weight. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  5>

70 of 5-norbornene-2-methylacetate and 5-norbornene-2-butylester obtained in Preparation Example 3 to produce an optically anisotropic film of the negative C-plate type of the present invention: SMA EF-80 having 90 weight percent of 30 copolymer and SARTOMER weight average molecular weight of 14,400 was dissolved in methylene chloride solvent to 10 weight percent using 10 weight percent. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  6>

70 of 5-norbornene-2-methylacetate and 5-norbornene-2-butylester obtained in Preparation Example 3 to prepare a negative C-plate type optically anisotropic film of the present invention: The 30 copolymer was dissolved in methylene chloride solvent to 12% by weight using 80% by weight of SMA EF-80 having a weight average molecular weight of 14,400 by SARTOMER. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  7>

70 of 5-norbornene-2-methylacetate and 5-norbornene-2-butylester obtained in Preparation Example 3 to produce an optically anisotropic film of the negative C-plate type of the present invention: The 30 copolymer was dissolved in methylene chloride solvent to 14% by weight using SMA EF-80 having a weight average molecular weight of 14,400 using 70% by weight of SARTOMER. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  8>

50: 50 of 5-norbornene-2-butylester and 2-phenyl-5-norbornene obtained in Preparation Example 4 to produce a negative C-plate optical anisotropic film of the present invention Using 90% by weight of copolymer and 10% by weight of SMA EF-60 having a weight average molecular weight of 11,500 from SARTOMER, it was made to be 13% by weight in methylene chloride solvent. This solution was filtered neatly using a filter with 0.45 μm pores.

< Example  9>

50: 50 of 5-norbornene-2-butylester and 2-phenyl-5-norbornene obtained in Preparation Example 4 to produce a negative C-plate optical anisotropic film of the present invention Using 90% by weight of copolymer and 10% by weight of SMA EF-80 having a weight average molecular weight of 14,400 by SARTOMER was dissolved in methylene chloride solvent to 13% by weight. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  1>

To prepare a negative C-plate type optically anisotropic film of the present invention using the 5-norbornene-2-methyl acetate polymer obtained in Preparation Example 1 using a weight average of 70% by weight of NOVA Chemicals DYLARK 332 having a molecular weight of 167,800 was dissolved in methylene chloride solvent using 30% by weight to 13% by weight. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  2>

To prepare a negative C-plate type optically anisotropic film of the present invention using the 5-norbornene-2-methyl acetate polymer obtained in Preparation Example 1 using a weight average of 70% by weight of NOVA Chemicals DYLARK 232 having a molecular weight of 232,000 was dissolved in methylene chloride solvent using 30% by weight to 13% by weight. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  3>

80: 20 of 5-norbornene-2-methylacetate and 2-butyl-5-norbornene obtained in Preparation Example 2 to produce an optically anisotropic film of the negative C-plate type of the present invention. Using 80 wt% of the copolymer and 20 wt% of DYLARK 332 with a weight average molecular weight of 167,800 from NOVA Chemicals was dissolved in methylene chloride solvent to 10 wt%. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  4>

80: 20 of 5-norbornene-2-methylacetate and 2-butyl-5-norbornene obtained in Preparation Example 2 for producing an optically anisotropic film of the negative C-plate type of the present invention The copolymer was dissolved in methylene chloride solvent to 10% by weight using 80% by weight of DYLARK 232 having a weight average molecular weight of 232,000 by NOVA Chemicals. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  5>

70 of 5-norbornene-2-methylacetate and 5-norbornene-2-butylester obtained in Preparation Example 3 to produce an optically anisotropic film of the negative C-plate type of the present invention: 30 copolymers were dissolved in methylene chloride solvent using 10 wt% of DYLARK 332 with 80 wt% of NOVA Chemicals and a weight average molecular weight of 167,800. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  6>

70 of 5-norbornene-2-methylacetate and 5-norbornene-2-butylester obtained in Preparation Example 3 to produce an optically anisotropic film of the negative C-plate type of the present invention: 30 copolymers were dissolved in methylene chloride solvent using 80 wt% and DYLARK 232 having a weight average molecular weight of 232,000 by NOVA Chemicals using 20 wt% to 10 wt%. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  7>

50: 50 of 5-norbornene-2-butylester and 2-phenyl-5-norbornene obtained in Preparation Example 4 to produce a negative C-plate optical anisotropic film of the present invention Using 90 wt% of the copolymer and 10 wt% of DYLARK 332 with a weight average molecular weight of 167,800 from NOVA Chemicals was made to dissolve in methylene chloride solvent to 10 wt%. This solution was filtered neatly using a filter with 0.45 μm pores.

< Comparative example  8>

50: 50 of 5-norbornene-2-butylester and 2-phenyl-5-norbornene obtained in Preparation Example 4 to produce a negative C-plate optical anisotropic film of the present invention The copolymer was dissolved in a methylene chloride solvent to 10% by weight using DYLARK 232 having a weight average molecular weight of 232,000 by 90% by weight of the copolymer and NOVA Chemicals. This solution was filtered neatly using a filter with 0.45 μm pores.

< Experimental Example > Optics Anisotropy  Film manufacturing

The norbornene-based copolymers or homopolymers obtained in Preparation Examples and Comparative Examples and a styrene polymer composition solution were mixed as in the composition of each Example in Table 1 to prepare a casting solution, and this solution was prepared using a knife coater or a bar coater. After casting on a glass substrate, it was dried for 1 hour at room temperature, and again for 1 hour at 100 ℃ under a 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 of less than 2%. The transparency of these films is shown together in Table 1 below.

MC: methylene chloride

<Optical Anisotropy  Measurement>

Each of the transparent films of Examples and Comparative Examples measured the refractive index n using an Abbe refractometer, and used an automatic birefringence meter (manufactured by prince measuring instrument; KOBRA-21 ADH) to obtain an 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 plane is 50 °, and the phase difference value R between the film thickness direction and the in-plane y-axis according to Equation 3 below. _th ) was obtained.

Table 2 summarizes the refractive index, R _e , R _th of each transparent film. In addition, the film described in the comparative example was opaque and the measurement was unnecessary.

From the results of Tables 1 and 2 above, the optically anisotropic film according to the present invention includes a cyclic olefin-based polymer and a styrene-maleic anhydride copolymer, thereby providing excellent optical transparency and freely controlling the negative birefringence in the thickness direction. It can be seen that.

Claims (17)

1) cyclic olefin polymer and 2) Styrene-maleic anhydride copolymer having a weight average molecular weight of 1,000 to 50,000 To include, the retardation value (Rth) represented by the following formula (2) is an optically anisotropic film, characterized in that 30 to 1,000nm: &Quot; (2) &quot;

In Equation (2) ny is the index of refraction of the fast axis in plane measured at wavelength 550 nm, nz 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 of claim 1, wherein the 1) cyclic olefin polymer is an addition polymer of a norbornene monomer represented by Formula 1 or a copolymer of different norbornene monomers represented by Formula 1 below: [Formula 1]

In Formula 1, m is an integer from 0 to 4; R ₁ , R ₂ , R ₃ and R ₄ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or a polar group comprising at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron; When R ₁ , R ₂ , R ₃ and R ₄ are not hydrogen, halogen, or a polar functional group, R ₁ And for R _2, or R ₃ and R ₄ is connected is 1 to 10 carbon atoms in the alkylidene group forming hageo or, or R ₁ or R ₂ is connected with any one of R ₃ and R ₄ each having 4 to 12 carbon atoms, It may form a saturated or unsaturated aliphatic ring or an aromatic ring having 6 to 24 carbon atoms. The optically anisotropic film of claim 2, wherein the polar functional group is selected from the group consisting of the following structural formulas: -R ₅ OR ₆ , -OR ₆ , -OC (O) OR ₆ , -R ₅ OC (O) OR ₆ , -C (O) OR ₆ , -R ₅ C (O) OR _6, -C (O ) R ₆ , -R ₅ C (O) R ₆ , -OC (O) R ₆ , -R ₅ OC (O) R ₆ ,-(R ₅ O) _n -OR ₆ ,-(OR ₅ ) _n- OR ₆ , -C (O) -OC (O) R ₆ , -R ₅ C (O) -OC (O) R ₆ , -SR ₆ , -R ₅ SR ₆ , -SSR ₆ , -R ₅ SSR ₆ , -S (= O) R ₆ , -R ₅ S (= O) R ₆ , -R ₅ C (= S) R _6- , -R ₅ C (= S) SR ₆ , -R ₅ SO ₃ R ₆ , -SO ₃ R ₆ , -R ₅ N = C = S, -N = C = S, -NCO, -R ₅ -NCO, -CN, -R ₅ CN, -NNC (= S) R ₆ , -R ₅ NNC (= S) R ₆ , -NO ₂ , -R ₅ NO ₂ ,

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In the above formula, R ₅ is the same as or different from each other, and each independently halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, Linear or branched alkylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from carbonyloxy, halocarbonyloxy, aryloxy, haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynylene having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, halo aralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkylene having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Arylene having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxyylene having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy, R ₆ , R ₇ and R ₈ are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Linear or branched alkenyl having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Alkoxy having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy , Carbonyloxy of 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy, n is each independently an integer of 1 to 10. The optically anisotropic film of claim 1, wherein the weight average molecular weight of the 1) cyclic olefin polymer is 10,000 to 1,000,000. The optically anisotropic film of claim 1, wherein the weight ratio of the 1) cyclic olefin polymer and 2) the styrene-maleic anhydride copolymer is 99: 1 to 30:70. delete a) preparing a resin composition solution by dissolving a cyclic olefin polymer and a styrene-maleic anhydride copolymer having a weight average molecular weight of 1,000 to 50,000 in a solvent; And b) coating or casting the resin composition solution on a substrate and drying Wherein, the cyclic olefin-based polymer of step a) is an addition polymer of norbornene-based monomer represented by Formula 1 or a copolymer of different norbornene-based monomers represented by Formula 1 below. Manufacturing Method: [Formula 1]

In Formula 1, m is an integer from 0 to 4; R1, R2, R3 and R4 are the same as or different from each other, and each independently hydrogen; halogen; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkyl having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkenyl of 2 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Linear or branched alkynyl having 3 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy, Cycloalkyl having 3 to 12 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, aryl, haloaryl, aralkyl, haloaralkyl, alkoxy, haloalkoxy, carbonyloxy, halocarbonyloxy, aryloxy Aryl having 6 to 40 carbon atoms unsubstituted or substituted with one or more substituents selected from haloaryloxy, silyl, and siloxy; Or a polar group comprising at least one of oxygen, nitrogen, phosphorus, sulfur, silicon, and boron; When R1, R2, R3 and R4 are not hydrogen, halogen, or polar functional groups, R1 and R2, or R3 and R4 are connected to each other to form an alkylidene group having 1 to 10 carbon atoms, or R1 or R2 is R3 And it may be connected to any one of R4 to form a saturated or unsaturated aliphatic ring having 4 to 12 carbon atoms, or an aromatic ring having 6 to 24 carbon atoms. Method for producing an optically anisotropic film. delete The method of claim 7, wherein the content of the cyclic olefin polymer in the resin composition solution of step a) is 1 to 70% by weight. The method of claim 7, wherein the content of the styrene-maleic anhydride copolymer in the resin composition solution of step a) is 1 to 70% by weight. The method of claim 7, wherein the resin composition solution of step a) comprises 5 to 95 wt% of the cyclic olefin polymer and the styrene-maleic anhydride copolymer in the total resin composition solution. . The method of claim 7, wherein the viscosity of the resin composition solution of step a) is 100 to 30,000 cps. The method of manufacturing an optically anisotropic film according to claim 7, wherein an additive selected from the group consisting of a plasticizer, an antioxidant, an ultraviolet stabilizer, and an antistatic agent is added to the resin composition solution of step a). The surface of claim 7, wherein the optically anisotropic film produced after step b) is selected from the group consisting of corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, ultraviolet irradiation treatment, and coating treatment. Method for producing an optically anisotropic film, characterized in that the addition of the step of treating. A liquid crystal display device comprising one or two or more of the optically anisotropic film of claim 1. A polarizing film, comprising one or two or more optical anisotropic films of any one of claims 1 to 5 as a protective film on one surface or both surfaces of the polarizing film. A liquid crystal display device comprising the integrated polarizer of claim 16.