KR101206721B1 - Retardation films and liquid crystal display comprising the sames - Google Patents

Abstract

The present invention provides a composition comprising: 1) at least one monomer selected from (a1) alkyl methacrylate monomers, (a2) (meth) acrylic monomers containing aliphatic rings or aromatic rings, and alphamethyl styrene, and (a3) aromatic vinyl monomers. And (a4) an acrylic copolymer resin comprising an acid anhydride monomer, and 2) a blend resin of a resin containing an aromatic ring or an aliphatic ring in a polymer main chain, a method for preparing the same, and the phase difference film. It relates to a liquid crystal display device. Retardation film according to the present invention is excellent in heat resistance, optical transparency, mechanical strength, durability, adhesion.

Retardation film, liquid crystal display

Description

Retardation film and liquid crystal display including the same {RETARDATION FILMS AND LIQUID CRYSTAL DISPLAY COMPRISING THE SAMES}

SUMMARY OF THE INVENTION The present invention provides a retardation film having excellent heat resistance and optical transparency, low haze, poor breakage, excellent mechanical strength, and excellent adhesion, a method for manufacturing the same, and a liquid crystal display device including the retardation film. This application claims the benefit of the application date of Korean Patent Application No. 10-2009-0000886 filed to the Korea Intellectual Property Office on January 6, 2009, the entire contents of which are incorporated herein.

Recently, display technologies using various methods such as plasma display panels (PDPs) and liquid crystal displays (LCDs), which replace conventional CRTs, have been proposed and marketed based on the development of optical technologies. Polymer materials for such displays are becoming more sophisticated. For example, in the case of liquid crystal displays, as thin film thickness, light weight, and large screen area are promoted, wide viewing angles, high contrast, suppression of image color tone change according to viewing angle, and uniformity of screen display have become particularly important problems.

Accordingly, various polymer films are used for polarizing films, polarizer protective films, retardation films, plastic substrates, light guide plates, and the like. Twisted nematic (TN) and super twisted nematic (STN) liquid crystals are used. Various types of liquid crystal display devices using vertical alignment (VA), in-plane switching (IPS) liquid crystal cells, and the like have been developed. All of these liquid crystal cells have an inherent liquid crystal array, have inherent optical anisotropy, and in order to compensate for this optical anisotropy, films have been proposed in which various kinds of polymers are drawn to give a retardation function.

Specifically, since the liquid crystal display uses high birefringence characteristics and orientations of the liquid crystal molecules, the refractive index varies according to the viewing angle, and thus the color and brightness of the screen change. For example, since most liquid crystal molecules used in the vertical alignment method have a positive phase difference in the thickness direction of the liquid crystal display surface, a compensation film having a negative phase difference in the thickness direction is required to compensate for this. In addition, the front of the two polarizers orthogonal to each other do not pass light, but when the angle is inclined, the optical axis of the two polarizers are not orthogonal to cause light leakage. In addition, the display device using the liquid crystal requires both phase difference compensation in the thickness direction and plane direction difference compensation in order to widen the viewing angle.

A requirement for retardation compensation films is that birefringence must be easily controlled. By the way, the birefringence of the film is made not only by the fundamental birefringence of the material but also by the orientation of the polymer chain in the film. Orientation of the polymer chain is mostly caused by the force applied from the outside or due to the inherent properties of the material, the method of aligning the molecule by the external force is to stretch the polymer film uniaxially or biaxially.

There is a need in the art for the development of polymer materials that meet the aforementioned requirements for use in displays.

The present invention can adjust the in-plane retardation, thickness direction retardation, etc. of the film through the stretching method, and can produce a film having excellent optical properties and excellent optical transparency, the drawback of the acrylic film brittle through the stretching orientation It is an object of the present invention to provide a retardation film that can be eliminated, is excellent in workability and adhesiveness, and also has excellent durability such as heat resistance.

Moreover, an object of this invention is to provide the manufacturing method of the said retardation film, and the liquid crystal display device containing the said retardation film.

The present invention provides a composition comprising: 1) at least one monomer selected from (a1) alkyl methacrylate monomers, (a2) (meth) acrylic monomers containing aliphatic rings or aromatic rings, and alphamethyl styrene, and (a3) aromatic vinyl monomers. And (a4) an acrylic copolymer resin containing an acid anhydride monomer, and 2) a blend resin of a resin containing an aromatic ring or an aliphatic ring in a polymer main chain.

In addition, the present invention is 1) at least one monomer selected from (a1) alkyl methacrylate monomers, (a2) (meth) acrylic monomers including aliphatic rings or aromatic rings and alphamethyl styrene, (a3) aromatic vinyl (B) preparing a blend resin composition of an acrylic copolymer resin comprising a monomer and an acid anhydride monomer, and (b) a resin including an aromatic ring or an aliphatic ring in a polymer main chain; And 2) provides a method for producing a retardation film comprising the step of molding a film using the resin composition. This manufacturing method may further comprise the step of uniaxially or biaxially stretching the film.

In addition, the present invention provides a liquid crystal display including at least one phase difference film.

The retardation film according to the present invention is excellent in optical characteristics and also excellent in optical transparency, and is excellent in workability, heat resistance, retardation characteristics and durability.

The retardation film according to the present invention comprises: 1) at least one monomer selected from (a1) alkyl methacrylate monomers, (a2) (meth) acrylic monomers including aliphatic rings or aromatic rings, and alphamethyl styrene, (a3) It is characterized by including an acrylic copolymer resin comprising an aromatic vinyl monomer and an (a4) acid anhydride monomer, and 2) a blend resin of a resin containing an aromatic ring or an aliphatic ring in the polymer main chain.

In the retardation film according to the present invention, the alkyl group of the alkyl methacrylate monomer of 1) preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably a methyl group or an ethyl group. Specific examples of the alkyl methacrylate monomers include methyl methacrylate, ethyl methacrylate, and the like, and more preferably methyl methacrylate, but are not limited thereto.

The optical film according to the present invention comprises heat resistance of the acrylic copolymer resin by including at least one monomer selected from (meth) acrylic monomer and alphamethyl styrene containing an aliphatic ring or an aromatic ring in the 1) acrylic copolymer resin. Can be improved.

In the retardation film according to the present invention, specific examples of the (meth) acrylic monomer containing the aliphatic ring or the aromatic ring of 1) include cyclohexyl methacrylate, benzyl methacrylate, cyclohexyl acrylate and 2-phenoxy. Ethyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, phenyl methacrylate, naphthyl methacrylate, and the like, and more preferably cyclohexyl methacrylate, but not limited thereto. no.

In the retardation film according to the present invention, as the aromatic vinyl monomer of 1), it is preferable to use a monomer having a structure in which a benzene nucleus is substituted or unsubstituted with at least one C ₁ to C ₅ alkyl group or halogen group. For example, one or more styrene monomers selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and the like are preferable.

In the retardation film according to the present invention, the acid anhydride-based monomer of 1) may be used a carboxylic acid anhydride having heat resistance properties, monovalent or divalent or higher polyhydric carboxylic acid anhydride. Preferably, maleic anhydride or a derivative thereof can be used.

In the retardation film according to the present invention, 1) the content of the alkyl methacrylate monomer in the acrylic copolymer resin is 70% or more and less than 100% by weight, the content of the acrylic comonomer containing an aliphatic ring or an aromatic ring is 0 More than 30% by weight or less, the content of the aromatic vinyl monomer is more than 0 to 10% by weight, and the content of the acid anhydride monomer is preferably more than 0 to 15% by weight.

The retardation film according to the present invention can further improve the adhesiveness and heat resistance of the retardation film by including the aromatic vinyl monomer and the acid anhydride monomer in the 1) acrylic copolymer.

In the retardation film according to the present invention, the 1) acrylic copolymer resin is more preferably a copolymer resin of methyl methacrylate-cyclohexyl methacrylate-styrene-maleic anhydride, but is not limited thereto.

In the retardation film according to the present invention, the polycarbonate resin, polyarylate resin, polynaphthalene resin, polynorbornene resin, etc. may be used as the resin containing an aromatic ring or an aliphatic ring in the polymer main chain. Although it is more preferable that it is polycarbonate resin, it is not limited only to this.

In the retardation film according to the present invention, 1) the content of the acrylic copolymer resin in the blend resin is 60 to 99% by weight, and 2) the content of the resin containing an aromatic ring or aliphatic ring in the polymer backbone is 1 to 40% by weight. It is preferable that the content of 1) the acrylic copolymer resin in the blend resin is 70 to 99% by weight, and 2) the content of the resin containing an aromatic ring or aliphatic ring in the polymer backbone is 1 to 30% by weight. More preferred.

In the retardation film which concerns on this invention, it is preferable that the glass transition temperature of the said blend resin is 100 degreeC or more, and it is preferable that it is 120 degreeC or more. In addition, the weight average molecular weight of the blend resin is preferably 50,000 to 200,000 in terms of heat resistance, sufficient processability, productivity and the like.

It is preferable that the retardation film which concerns on this invention is 30-80 nm of surface direction retardation values represented by following formula (1), and it is preferable that the thickness direction retardation value represented by following formula (2) is -50--100 nm.

R _in = (n _x -n _y ) × d

R _th = (n _z -n _y ) × d

In Equations 1 and 2,

n _x is a refractive index of the direction of the largest refractive index in the plane direction of the film,

n _y is a refractive index in the vertical direction in the n _x direction in the plane direction of the film,

n _z is the refractive index in the thickness direction,

d is the thickness of the film.

In addition, the method for producing a retardation film according to the present invention is 1) at least one selected from (a1) alkyl methacrylate monomers, (a2) (meth) acrylic monomers containing aliphatic rings or aromatic rings, and alphamethyl styrene. Preparing a blend resin composition of an acrylic copolymer resin comprising a monomer, (a3) an aromatic vinyl monomer and (a4) an acid anhydride monomer, and (b) a resin containing an aromatic ring or an aliphatic ring in a polymer backbone; And 2) molding the film using the resin composition. The method of manufacturing the retardation film may further include uniaxially or biaxially stretching the film.

Specific details of the acrylic copolymer resin, a resin including an aromatic ring or an aliphatic ring in the polymer backbone are the same as described above, and thus the description thereof will be omitted.

In the retardation film production method according to the invention, the resin composition of step 1) may be prepared by melt-blending and blending the above-described components. Melt mixing of the components can be carried out using a solution cast method, extrusion method and the like.

In the method for producing a retardation film according to the present invention, it is more preferable to prepare a film by using a solution casting method and to perform a stretching step.

In addition, in some cases, it is also possible to proceed with the extrusion method by adding a modifier.

The resin composition may further include antioxidants, UV stabilizers, heat stabilizers and the like commonly used in the art.

The method of manufacturing a retardation film according to the present invention may further include the step of uniaxially or biaxially stretching the film. The stretching step may be performed in the longitudinal direction (MD) stretching or in the transverse direction (TD) stretching, or both. When extending | stretching both a longitudinal direction and a lateral direction, after extending | stretching either one, you can extend in another direction and you may extend | stretch both directions simultaneously. Stretching can be done in one step or stretched in multiple steps. When extending | stretching in a longitudinal direction, extending | stretching by the speed difference between rolls can be performed, and when extending | stretching in a lateral direction, a tenter can be used. The starting angle of the tenter is 10 degrees or less in total, suppressing the bowing phenomenon which arises at the time of a lateral stretch, and controls the angle of an optical axis regularly. The same boeing suppression effect can also be obtained by making transverse stretching into multiple stages.

The stretching may be performed at a temperature of (Tg-20 ° C) to (Tg + 30 ° C) when the glass transition temperature of the resin composition is Tg. The glass transition temperature refers to a region from the temperature at which the storage modulus of the resin composition begins to decrease, and thus the loss modulus becomes larger than the storage modulus, at which the orientation of the polymer chain is relaxed and lost. Glass transition temperatures can be measured by differential scanning calorimetry (DSC). The temperature at the time of the stretching step is more preferably the glass transition temperature of the film.

The drawing speed is preferably in the range of 1 to 100 mm / min in the case of a universal drawing machine (Zwick Z010) and in the range of 0.1 to 2 m / min in the case of a pilot drawing machine. It is preferable to stretch the film by applying an elongation of 5 to 300%.

The retardation film according to the present invention can be uniaxially or biaxially stretched by the above-described method, thereby adjusting the retardation characteristics.

In addition, the present invention provides a liquid crystal display device comprising one or two or more retardation films.

Preferably, the liquid crystal display is a VA (vertical alignment) mode liquid crystal display.

In the VA mode liquid crystal display, a retardation film can be used for viewing angle compensation, which has two elements to be compensated for. The first is compensation for light leakage of the polarizing plate when the absorption axis of the two polarizing plates is not orthogonal in appearance when the liquid crystal display is tilted, and the second is birefringence of the liquid crystal molecules when the VA cell is observed from the oblique direction. This is necessary compensation because light leakage due to cell generation occurs during black display, whereby a decrease in contrast is observed.

Since the polarizer combined with the retardation film is made of a uniaxially stretched polyvinyl alcohol film containing a dichroic dye, the polarizer is very fragile and is laminated with a protective film because of its poor resistance to temperature and moisture. If the retardation film can be directly adhered to the polarizer instead of the protective film, the thinned retardation film integrated polarizing film for one layer of the protective film can be obtained.

Since the cellulose derivative has excellent water permeability, the cellulose derivative has an advantage in that the water contained in the polarizer can be volatilized through the film in the manufacturing process of the polarizing plate. However, on the other hand, in the high temperature and high humidity atmosphere, the dimensional change and optical property change due to moisture absorption are relatively large, and the phase difference value when the humidity is changed near room temperature is large, so that there is a limit in improving the stable viewing angle. There is a problem that the durability is lowered.

In addition, in the polycarbonate system, the glass transition temperature is high, so that not only the stretching at high temperature is required but also the photoelastic coefficient of the film is large, thereby causing optical deformation due to stress. When extending | stretching a norbornene-type film, there exists a problem of the stress at the time of extending | stretching or the stress nonuniformity at the time of extending | stretching generate | occur | producing. The solution of this problem can be solved by adopting an acryl-based retardation film having a good viewing angle compensation effect and a small change in retardation value even with environmental changes.

A liquid crystal display including one or two or more retardation films will be described in more detail as follows.

In 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, a retardation film may be provided between the liquid crystal cell and the first polarizing plate and / or the second polarizing plate. have. That is, a retardation film may be provided between the first polarizing plate and the liquid crystal cell, and one retardation film is 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. 2 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 film, 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 the retardation film according to the present invention on one or both surfaces of the polarizing film as a protective film.

When the retardation film according to the present invention 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, vinyl chloride / vinyl acetate copolymer, polyvinyl alkyl ether, polyacrylate or modified polyolefin-based pressure-sensitive adhesive and the like, and a curing agent such as isocyanate is added thereto. Curable adhesives are 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 retardation films according to the present invention may be further included between the polarizing plate and the liquid crystal cell.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention by the following examples.

< Example >

< Example  1>

Copolymers were prepared from methyl methacrylate (82 parts by weight), cyclohexyl methacrylate (10 parts by weight), styrene (3 parts by weight) and maleic anhydride (5 parts by weight). The weight average molecular weight of the prepared copolymer was 125,000. Resin was prepared from 90 parts by weight of the copolymer prepared above and 10 parts by weight of polycarbonate. As a result of measuring the glass transition temperature of manufactured resin, the resin of glass transition temperature of 124 degreeC was obtained. After this resin was produced the film using the solution casting method, it extended | stretched at the glass transition temperature, and measured the phase difference value of the film. As a result, surface direction retardation value / thickness direction retardation value obtained 33 nm / -66 nm.

< Example  2>

Copolymers were prepared from methyl methacrylate (75 parts by weight), cyclohexyl methacrylate (10 parts by weight), styrene (5 parts by weight) and maleic anhydride (10 parts by weight). The weight average molecular weight of the produced copolymer was 120,000. Resin was prepared from 90 parts by weight of the copolymer prepared above and 10 parts by weight of polycarbonate. As a result of measuring the glass transition temperature of manufactured resin, resin which is 130 degreeC of glass transition temperature was obtained. After this resin was produced the film using the solution casting method, it extended | stretched at the glass transition temperature, and measured the phase difference value of the film. As a result, the plane retardation value / thickness retardation value was 33 nm / -67 nm.

< Comparative example  1>

Copolymers were prepared from methyl methacrylate (90 parts by weight) and cyclohexyl methacrylate (10 parts by weight). The weight average molecular weight of the produced copolymer was 130,000. Resin was prepared from 90 parts by weight of the copolymer prepared above and 10 parts by weight of polycarbonate. As a result of measuring the glass transition temperature of manufactured resin, the resin of glass transition temperature of 121 degreeC was obtained. After this resin was produced the film using the solution casting method, it extended | stretched at the glass transition temperature, and measured the phase difference value of the film. As a result, surface direction retardation value / thickness direction retardation value obtained 32 nm / -64 nm.

< Comparative example  2>

Copolymers were prepared from methyl methacrylate (87 parts by weight), cyclohexyl methacrylate (10 parts by weight) and styrene (3 parts by weight). The weight average molecular weight of the prepared copolymer was 105,000. Resin was prepared from 90 parts by weight of the copolymer prepared above and 10 parts by weight of polycarbonate. As a result of measuring the glass transition temperature of manufactured resin, the resin of glass transition temperature 119 degreeC was obtained. After this resin was produced the film using the solution casting method, it extended | stretched at the glass transition temperature, and measured the phase difference value of the film. As a result, the surface direction retardation value / thickness direction retardation value obtained 30 nm / -60 nm.

< Comparative example  3>

Copolymers were prepared from methyl methacrylate (85.5 parts by weight), cyclohexyl methacrylate (9.5 parts by weight) and maleic anhydride (5 parts by weight). The weight average molecular weight of the prepared copolymer was 122,000. Resin was prepared from 90 parts by weight of the copolymer prepared above and 10 parts by weight of polycarbonate. However, the blend resin was not obtained due to the lack of compatibility between the two resins.

Contents of the blend resins of Examples 1 to 2 and Comparative Examples 1 to 3, characteristics of the retardation film, and the like are shown in Tables 1 and 2 below.

MMA: methyl methacrylate

CHMA: cyclohexyl methacrylate

SM: Styrene

MAH: Maleic anhydride

PC: Polycarbonate

(1) Weight average molecular weight (Mw): The prepared resin was dissolved in tetrahydrofuran and measured by gel osmosis chromatography (GPC).

(2) Glass transition temperature (Tg): Measured using a DSC (Differential Scanning Calorimeter) from TA Instrument.

(3) Retardation value (R _in / R _th ): After stretching at the glass transition temperature of the film was measured using AxoScan from Axometrics.

From the results of Examples 1 to 2 and Comparative Examples 1 to 3, the retardation film according to the present invention is excellent in optical properties and also excellent in optical transparency, excellent mechanical properties, workability, heat resistance, adhesion, retardation characteristics and It can be seen that the durability is excellent.

Claims (17)

1) (a1) methyl methacrylate or ethyl methacrylate monomer 75 wt% or more and 82 wt% or less, (a2) cyclohexyl methacrylate or phenyl methacrylate monomer 10 wt%, (a3) styrene, α-methyl At least 3% by weight and at least 5% by weight of at least one aromatic vinyl monomer selected from the group consisting of styrene, p-methylstyrene and vinyltoluene, and (a4) at least one acid anhydride monomer selected from maleic anhydride or derivatives thereof. 60 to 99% by weight of an acrylic copolymer resin containing 5% by weight to 10% by weight, and 2) a blend resin containing 1 to 40% by weight of a polycarbonate resin, The retardation film whose surface direction retardation value represented by following formula (1) is 30-80 nm, and the thickness direction retardation value represented by following formula (2) is -50--100 nm. [Equation 1] R _in = (n _x -n _y ) × d &Quot; (2) &quot; R _th = (n _z -n _y ) × d In Equations 1 and 2, n _x is a refractive index of the direction of the largest refractive index in the plane direction of the film, n _y is a refractive index in the vertical direction in the n _x direction in the plane direction of the film, n _z is the refractive index in the thickness direction, d is the thickness of the film. delete delete delete delete delete The retardation film according to claim 1, wherein the 1) acrylic copolymer resin is a copolymer resin of methyl methacrylate-cyclohexyl methacrylate-styrene-maleic anhydride. delete delete The retardation film of claim 1, wherein the blend resin has a glass transition temperature of 100 ° C. or higher and a weight average molecular weight of 50,000 to 200,000. delete 1) (a1) methyl methacrylate or ethyl methacrylate monomer 75 wt% or more and 82 wt% or less, (a2) cyclohexyl methacrylate or phenyl methacrylate monomer 10 wt%, (a3) styrene, α-methyl At least 3% by weight and at least 5% by weight of at least one aromatic vinyl monomer selected from the group consisting of styrene, p-methylstyrene and vinyltoluene, and (a4) at least one acid anhydride monomer selected from maleic anhydride or derivatives thereof. Preparing a blend resin composition comprising 60 to 99 wt% of an acrylic copolymer resin including 5 wt% or more and 10 wt% or less, and (b) 1 to 40 wt% of a polycarbonate resin; And 2) forming a film using the resin composition, The surface direction retardation value represented by following formula (1) is 30-80 nm, The thickness direction retardation value represented by following formula (2) is -50--100nm The manufacturing method of the retardation film. [Equation 1] R _in = (n _x -n _y ) × d &Quot; (2) &quot; R _th = (n _z -n _y ) × d In Equations 1 and 2, n _x is a refractive index of the direction of the largest refractive index in the plane direction of the film, n _y is a refractive index in the vertical direction in the n _x direction in the plane direction of the film, n _z is the refractive index in the thickness direction, d is the thickness of the film. The method of claim 12, further comprising, after the step 2), uniaxially or biaxially stretching the film. The liquid crystal display device containing the retardation film of any one of Claims 1, 7, and 10. The liquid crystal display of claim 14, wherein the liquid crystal display is a vertical alignment (VA) mode liquid crystal display. An integrated polarizing plate comprising a polarizing film and comprising the retardation film of any one of claims 1, 7 and 10 as a protective film on one or both surfaces of the polarizing film. A liquid crystal display device comprising the integrated polarizer of claim 16.