WO2019221573A1

WO2019221573A1 - Anti-reflective film, polarizing plate, and display apparatus

Info

Publication number: WO2019221573A1
Application number: PCT/KR2019/006006
Authority: WO
Inventors: 변진석; 고경문; 이상헌; 서광석; 장영래
Original assignee: 주식회사 엘지화학
Priority date: 2018-05-18
Filing date: 2019-05-14
Publication date: 2019-11-21

Abstract

The present invention relates to an anti-reflective film having mechanical properties, such as high wear resistance and scratch resistance, and excellent optical properties; a polarizing plate comprising same; and a display device comprising same.

Description

2019/221573 1 »（： 1 ^ 1 {2019/006006

[Name of invention]

Antireflection Films, Polarizers and Display Devices

Technical Field

Cross Citation with Related Application (s)

This application is filed with Korean Patent Application No. 10-2018-0057299 dated May 18, 2018, and

Claiming the benefit of priority based on Korean Patent Application No. 10-2019-0055866 dated May 13, 2019, all the contents disclosed in the literature of those Korean patent applications are incorporated as part of this specification.

The present invention relates to an antireflection film, a polarizing plate and a display device. [Technique to become background of invention]

In general, a flat panel display device such as a PDP or LCD is equipped with an anti-reflection film for minimizing reflection of light incident from the outside. As a method for minimizing the reflection of light, a method of dispersing a filler such as inorganic fine particles in a resin and coating on a base film to give irregularities (ant i-glare: AG coating); And a method of forming a plurality of layers having different refractive indices on a base film to use interference of light (ant i-reflect ion: AR coating) or a method of mixing them.

Among them, in the case of the AG coating, the absolute amount of reflected light is on the same level as a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by scattering light through irregularities. However, since the AG coating has poor screen clarity due to surface irregularities, much research has recently been conducted on AR coatings.

As the film using the AR coating, a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film is commercialized. However, the film using the conventional AR coating has a disadvantage in that visibility is lowered due to an increase in reflectance at a portion damaged or deformed by an external rub or friction. Accordingly, many studies have been made to obtain an antireflection film in which the reflectance does not increase even when some surfaces are damaged or deformed due to external influences.

[Content of invention]

【Problem to solve】 2019/221573 1 »（： 1 ^ 1 {2019/006006

The present invention is to provide an anti-reflection film that has high mechanical properties such as high wear resistance and scratch resistance and excellent suppression of the increase in reflectance of a part damaged or deformed by external rubbing or friction.

Moreover, this invention is providing the polarizing plate containing the said antireflection film.

In addition, the present invention is to provide a display device including the anti-reflection film and provides a high screen sharpness.

[Measures of problem]

In the present specification, the hard coating layer; And it may be provided an anti-reflection film comprising a low refractive index layer satisfying the following formula (1).

[Formula 1]

0.2% p ³ AR = | ¾ -Ro l

In Equation 1,

¾ is the average reflectance in the wavelength range of 380 to 780 nm of the low refractive layer,

¾ was measured in the same manner as the method of measuring ¾ for the low refractive layer after performing a rubbing test for rubbing the surface of the low refractive layer by applying a steel load of 500 g and reciprocating 10 times at a speed of 33 rpm. Average reflectance in the wavelength range from 780 nm to 780 nm.

Moreover, in this specification, the polarizing plate containing the said antireflection film is provided.

In addition, in the present specification, a display device including the anti-reflection film may be provided.

Hereinafter, an anti-reflection film and a display device including the same according to a specific embodiment of the present invention will be described in detail. In the present specification, the low refractive index layer may mean a layer having a low refractive index, for example, a layer exhibiting a refractive index of about 1.2 to 1.6 in a wavelength region of 380 to 780 nm or a wavelength of 550 nm.

In addition, (meth) acrylate [(Meth) acrylate] is an acrylate (acrylate) and 2019/221573 1 »（： 1 ^ 1 {2019/006006

Methacrylate means both.

In addition, the photocurable resin generally refers to the polymer resin superposed | polymerized by irradiation of light, for example, irradiation of visible light or an ultraviolet-ray.

In addition, a fluorine-type compound means the compound in which at least 1 or more fluorine elements are contained among the compounds. According to one embodiment of the invention, the hard coating layer; And it is provided with an antireflection film comprising a low refractive index layer satisfying the following formula (1).

[Equation 1]

0.2% p> AR = | Rx -R ₀ |

In Equation 1,

¾ was measured in the same manner as the method of measuring ¾ for the low refractive layer after performing a rubbing test that rubs the surface of the low refractive layer by applying a steel load of 500 g and reciprocating 10 times at a speed of 33 rpm. Average reflectance in the wavelength range from 780 nm to 780 nm.

Anti-reflection film according to the embodiment can effectively suppress the increase in reflectance of the damaged or deformed portion due to external rubbing or friction. In addition, the anti-reflection film has mechanical properties such as high wear resistance and scratch resistance and excellent optical properties. Accordingly, when it is used in a display device, it is possible to remarkably improve the glare caused by light incident from the outside of the device without degrading the image quality, and effectively protect the surface of the device from external impact or stimulus.

More specifically, the low refractive index layer may satisfy the above formula (1). In Equation 1, ¾ is the average reflectance in the wavelength range of 380 to 780 nm of the low refractive index layer, Ri is the average reflectance in the wavelength range of 380 to 780 nm of the low refractive layer after the friction test.

The friction test is a test that rubs the surface of the low refractive layer by applying 500g load to the steel wool and reciprocating 10 times at a speed of 33 rpm, and when the loaded steel wool is rubbed on the surface of the low refractive layer, the low refractive layer is cut off. Damage or low refractive index 2019/221573 1 »（： 1 ^ 1 {2019/006006

Compression may occur such that the thickness itself becomes thinner. Therefore, through the degree of average reflectance change before and after the friction test of Equation 1, the effect of suppressing the increase in reflectance of the part damaged or deformed by external rubbing, friction, or the like can be evaluated. Since the low refractive index layer is excellent in suppressing the increase in reflectivity, the degree of change of the average reflectance before and after the friction test of Equation 1 may be less than 0.2¾), less than 0.018¾), or less than 0.115¾). Since the low refractive index layer may have no change in the average reflectance even after the friction test is performed, the average reflectance change degree (switch may be 0).

The low refractive index layer, together with excellent optical and mechanical properties, has a low average reflectance in the visible light region, thereby effectively preventing glare of the display device. Specifically, before the friction test is performed on the low refractive index layer, the average reflectance (¾ value of Equation 1) in the wavelength region of 380 to 780 ä may be 0.1 to 2.0%, 0.2 to 1.9%, or 0.3 to 1.8%. have.

In addition, the low refractive index layer can effectively suppress the increase in reflectance of the portion damaged or deformed by external rubbing or friction. Specifically, after the friction test, the average reflectance (¾ value of Equation 1) in the wavelength range of 380 to 7800111 may be 0.3 to 2.2%, 0.4 to 2. 1%, or 0.5 to 2.0%.

The low refractive index layer according to the embodiment may satisfy the following Equation 2.

[Formula 到

1 ³ ᅀ 1 / = "、-1） ^* ₀ 1

In Equation 2,

0 The International Lighting Commission

Value,

1) 'Rubber test for rubbing the surface of the low refractive index layer by reciprocating 10 times at a speed of 33 with a load of 500 _§ on a silver steel wool 0¾13 뱌 1¾ 1 ₆ ) It can be the value of the measured ^ (1 ^* 3V) color coordinate system. Therefore, through the degree of color change of the low refractive layer before and after the friction test of Equation 2, it is possible to evaluate the effect of suppressing the color change in the damaged or deformed portion by the external rub or friction.

Since the low refractive index layer has an excellent effect of suppressing color change, the degree of color change (s ^* ) before and after the friction test of Equation 2 is 1 or less, 0.8 or less, or 0.5 2019/221573 1 »（： 1 ^ 1 {2019/006006

It may be: Since the low refractive index layer may have no color change even after the friction test, the color change degree (s1) may be zero.

! 8) value of said Formula 2 is a thing of the low refractive layer

It may be a value of a coordinate system, and specifically, may be 2 to -10. In the 01 ^ (1 ^* 3 V) color coordinate system, a positive value represents a color biased to yellow, and a negative value represents a color biased to blue. Therefore, the low refractive layer exhibits the color coordinate values as described above, thereby effectively preventing the glare while transmitting the image as it is without changing the quality of the display device image.

In addition, the low refractive layer can effectively suppress the color change of the part damaged or deformed by external rubbing or friction. For example, after the friction test is performed on the low refractive layer, the value of the 01 ^ 0/310 color coordinate system (^ ₁ value in Equation 2) may be specifically 3 to -9.

On the other hand, the low refractive index layer may include a binder resin. The binder resin may include a copolymer of a polyfunctional (meth) acrylate monomer containing a 2 to 4 functional (meth) acrylate monomer and a 5 to 6 functional (meth) acrylate monomer.

The 2 to 4 functional (meth) acrylate-based monomer may have a pentaerythritol structure in the center, and the kind thereof is not limited thereto. For example, pentaerythritol di (meth) acrylate and pentaerythrate. It may be lititol tri (meth) acrylate or a mixture thereof.

Specifically, the 2 to 4 functional (meth) acrylate monomer having a pentaerythritol structure in the center may be represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

¾ to ¾ are hydroxyl groups; (Meth) acrylate groups; Or a substituted or unsubstituted 0 _1-40 alkoxy group, provided that at least one of them is 2019/221573 1 »（： 1 ^ 1 {2019/006006

It is a (meth) acrylate group.

On the other hand, the 5 to 6 functional (meth) acrylate monomers may have a dipentaerythritol structure in the center, the kind is not limited thereto, for example, dipentaerythritol penta (meth) acrylic Latent, dipentaerythritol nucleated (meth) acrylate or mixtures thereof.

Specifically, the 5- to 6-functional (meth) acrylate monomer having a dipentaerythritol structure in the center may be represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

Rn to R e are hydroxy groups; (Meth) acrylate groups; Or a substituted or unsubstituted Ci-40 alkoxy group, provided that at least one of them is a (meth) acrylate group.

According to the formulas (1) and (2), the 2-4 functional (meth) acrylate monomer having a pentaerythritol structure is about 5-6 functional (meth) acrylate monomers having a dipentaerythritol structure. Since it has twice the molecular weight and volume, the packing density of the (meth) acrylate and the relatively small molecular weight and (meth) acrylate in the copolymer are packed dens i in the unit volume. ty) can be maximized, so that the degree of crosslinking can be increased and the free volume can be minimized.

Further, the 2 to 4 functional (meth) acrylate monomers and the 5 to 6 functional (meth) acrylate monomers are 9: 1 to 6: 4, 8.5: 1.5 to 6.5: 3.5, or 8: 2 to Due to the crosslinking polymerization at a weight ratio of 7: 3, the degree of crosslinking of the copolymer is maximized and the free volume of the low refractive layer including the same can be minimized. As a result, it is possible to prevent the increase in the reflectance of the portion where external rubbing or friction is applied to the low refractive layer. 2019/221573 1 »（： 1 ^ 1 {2019/006006

The copolymer in which the 2 to 4 functional (meth) acrylate and the 5 to 6 functional (meth) acrylate are cross-polymerized at a weight ratio of 9: 1 to 6: 4 has a free volume of 420 or less in ³ volumes of 12511111. Can be. When the free volume in the 125 ä ³ volume of the copolymer is more than 420, the increase in reflectance of the part damaged or deformed by external rubbing or friction cannot be prevented.

In addition, the degree of crosslinking of the low refractive layer including the copolymer may be 85% or more, 85 to 99%, 90 to 99%, or 95 to 99%. If the crosslinking density is less than 85%, the reflectance of the portion where the low refractive index layer is damaged or deformed due to external rubbing or friction may increase.

The low refractive index layer may further include a portion derived from a fluorine-based compound including a photoreactive functional group. The binder resin of the low refractive index layer may have a lower reflectance and an improved light transmittance as the fluorine-based compound including a photoreactive functional group is included, and may effectively suppress an increase in reflectance of a part damaged or deformed by external rubbing or friction. . Accordingly, the low refractive layer of the antireflection film according to an embodiment may further include a copolymer of the multifunctional (meth) acrylate monomer and a fluorine compound including a photoreactive functional group.

The fluorine-based compound may include or substitute one or more photoreactive functional groups, and the photoreactive functional group refers to a functional group capable of participating in a polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light. The photoreactive functional group may include various functional groups known to be able to participate in a polymerization reaction by irradiation of light, and specific examples thereof may be a (meth) acrylate group, an epoxide group, a vinyl group (1 1) or a thiol group. 0¾ 比 1）.

The fluorine-based compound including the photoreactive functional group may include 1 to 60% by weight, 2 to 50% by weight, or 3 to 40% by weight of fluorine. If the content of the fluorine is less than 1% by weight, the surface of the low refractive index layer may not be sufficiently arranged to reduce the surface slip properties. If the content exceeds 60% by weight, the scratch resistance of the low refractive layer may be deteriorated. Reflectance increase may occur due to friction. The fluorine-based compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorine-based containing the photoreactive functional group 2019/221573 1 »（： 1 ^ 1 {2019/006006

The compound may optionally contain a silicon or silicon compound therein, specifically, the content of silicon in the fluorine-based compound including the photoreactive functional group may be 0.1 to 20% by weight, 0.5 to 18% by weight, or 1 to 15% by weight. Can be. Silicon contained in the fluorine-based compound including the photoreactive functional group may serve to prevent transparency of the haze 11326 from occurring in the low refractive layer. On the other hand, when the content of silicon in the fluorine-based compound including the photoreactive functional group is too large, the alkali resistance of the low refractive index layer may be lowered.

The fluorine-based compound including the photoreactive functional group may have a weight average molecular weight in terms of polystyrene measured by a weight average molecular weight ½ ᄄ method of 2,000 to 200,000, 3,000 to 180,000, or 4,000 to 170,000. When the weight average molecular weight of the fluorine-based compound including the photoreactive functional group is less than 2,000, the surface slidability may be lowered because the fluorine component may not be sufficiently arranged on the surface of the low refractive index layer. The reflectance of the deteriorated or damaged or deformed portion may be increased due to external rubbing or friction, and also the compatibility between the fluorine-based compound including the photoreactive functional group and other components may be lowered, resulting in uniform dispersion in the low refractive index layer. As a result, the internal structure or surface properties of the final product may be degraded.

Specifically, the fluorine-based compound including the photoreactive functional group may be an aliphatic compound or an aliphatic ring compound in which at least one photoreactive functional group is substituted and at least one fluorine is substituted for at least one carbon; A) heteroaromatic) substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon)) an aliphatic compound or a heteronight muscle) aliphatic ring compound; 111) polydialkylsiloxane polymers (eg, polydimethylsiloxane polymers) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; IV) polyether compounds substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine, or mixtures of two or more of 0 to IV) or copolymers thereof.

The low refractive layer may include 0.1 to 50 parts by weight, 0.3 to 40 parts by weight, or 0.5 to 30 parts by weight of the fluorine compound including the photoreactive functional group based on 100 parts by weight of the copolymer. The photoreactivity compared to the copolymer 2019/221573 1 »（： 1 ^ 1 {2019/006006

If the content of the fluorine-based compound including the functional group is less than 0.1 part by weight, the surface slip resistance of the low refractive index layer may be lowered. If the content of the fluorine-based compound is greater than 50 parts by weight, the scratch resistance may be deteriorated or damaged or deformed by external rubbing or friction. The reflectance of the part may rise.

On the other hand, the low refractive layer is a binder resin; And two or more hollow inorganic particles dispersed in the binder resin and having different particle diameters.

The two or more hollow inorganic particles having different particle diameters include hollow inorganic particles having a particle diameter of 40 nm to 60 nm and hollow inorganic particles having a particle size of 65 nm to 100 nm, as measured by dynamic light scattering (DLS). can do. When the two or more kinds of hollow inorganic particles having different particle diameters are included in the low refractive layer, hollow inorganic particles having a relatively small particle diameter are disposed between the hollow inorganic particles having a relatively large particle diameter, thereby The ideal arrangement makes it possible to prevent an increase in reflectance due to rubbing or friction from the outside, and to secure physical properties such as wear resistance and scratch resistance, and furthermore, the anti-reflection film improves the sharpness of the screen of the display device. High mechanical properties can be exhibited at the same time.

The hollow inorganic particles included in the low refractive index layer are fine particles having a hollow portion therein, and may have a low refractive index of about 1.20 to 1.40 because the hollow portion contains air having a refractive index of 1.0. In the case where such particles are included in the low refractive layer, even if the hollow inorganic particles themselves have a high density, the refractive index of the low refractive layer can be controlled to be low, thereby achieving low reflectance.

The weight ratio between the hollow inorganic particles having a particle size of 40 nm to 60 nm and the hollow inorganic particles having a particle size of 65 nm to 100 nm is 7: 3 to 3: 7, 6: 4 to 4: 6, or 6.5: 4.5 to 5: 5 may be. If the weight ratio range is not satisfied, the arrangement of the hollow inorganic particles may be disturbed, thereby increasing the average reflectance of the low refractive layer due to external rubbing or friction.

The two or more types of hollow inorganic particles having different particle diameters may be at least 40 nm to 60 nm, 42 to 60 nm, or 45 to 60 nm hollow inorganic particles having a particle size of 65 nm to 100 nm, 65 nm to 95 nm, or 65 nm to 90 nm. One type of hollow inorganic particles may be included. The particle size of the hollow inorganic particles is 40nm 2019/221573 1 »（： 1 ^ 1 {2019/006006

If it is less than the refractive index of the low refractive index layer may be increased to increase the reflectance, and if it exceeds 100ä, the strength of the low refractive layer is weakened, scratch resistance may be lowered.

The average particle diameter difference between the average particle diameter of one hollow inorganic particle having a particle diameter of 40ä to 60ä and the average particle diameter of one hollow inorganic particle having a particle size of 6511111 to 10011111 is

60 ä, 7 ^ ₁ to 4011111, or 8! ^ To 30 ^ 1. If the difference in particle size is too small or large, the reflectance of the portion where the low refractive index layer is damaged or deformed by external rubbing or friction may increase. With respect to 100 parts by weight of the binder resin, the content of the two or more hollow inorganic particles may be 30 to 500 parts by weight, 50 to 450 parts by weight, or 60 to 400 parts by weight. If the content of the at least two hollow inorganic particles is less than 30 parts by weight, the reflectance of the low refractive index layer may be increased. As a result, the reflectance of the damaged or deformed portion may increase.

On the other hand, each of the hollow inorganic particles may contain at least one reactive functional group selected from the group consisting of (meth) acrylate group, epoxide group, vinyl group (1 1) and thiol group 0¾ 比 1) on the surface. . As each of the hollow inorganic particles contains the above-described reactive functional group on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby effectively suppressing the increase in reflectance of the part damaged or deformed by external rubbing or friction. It is possible to further improve the scratch resistance and antifouling.

The hollow inorganic particles may be coated on a surface thereof with a fluorine compound. When the surface of the hollow inorganic particles is coated with a fluorine-based compound, it is possible to lower the surface energy, thereby increasing the durability and scratch resistance of the low refractive layer. Particle coating methods or polymerization methods commonly known as coating the fluorine-based compound on the surface of the hollow inorganic particle may be used without any significant limitation. For example, the hollow inorganic particles and the fluorine-based compound may be formed of water and a catalyst. In the presence of the sol-gel reaction can be bonded to the fluorine-based compound on the surface of the hollow inorganic particles through the hydrolysis and condensation reaction.

Specific examples of the hollow inorganic particles include hollow silica particles. The hollow silica is deposited on the surface in order to be more easily dispersed in an organic solvent. 2019/221573 1 »（： 1 ^ 1 {2019/006006

It may include certain functional groups substituted. Examples of organic functional groups that can be substituted on the surface of the hollow silica particles are not particularly limited, and examples thereof include (meth) acrylate groups, vinyl groups, hydroxy groups, amine groups, allyl groups (1), epoxy groups, hydroxy groups, isocyanate groups, and amines. A group or fluorine may be substituted on the hollow silica surface.

The low refractive index layer may have a refractive index of 1.2 to 1.55, 1.25 to 1.45, or 1.3 to 1.43.

On the other hand, as a specific example of the low refractive layer, 2 to 4 functional

Binder resin containing the copolymer of the (meth) acrylate type monomer and the polyfunctional (meth) acrylate type monomer containing a 5-6 functional (meth) acrylate type monomer; And two or more hollow inorganic particles dispersed in the binder resin and having different particle diameters.

Further, the 2 to 4 functional (meth) acrylate monomers and the 5 to 6 functional (meth) acrylate monomers are 9: 1 to 6: 4, 8.5: 1.5 to 6.5: 3.5, or 8: 2 to Due to the crosslinking polymerization at a weight ratio of 7: 3, the degree of crosslinking of the copolymer is maximized and the free volume of the low refractive index layer containing the same (root ratio \ 1111116) can be minimized. As a result, it is possible to prevent the increase in the reflectance of the part where external rubbing or friction is applied to the low refractive layer.

The weight ratio between the hollow inorganic particles having a particle size of 40ä to 60ä and the hollow ^' inorganic particles having a particle size of 6511111 to 100ä is 7: 3 to 3: 7, 6: 4 to 4: 6, or 6.5 : 4.5 to 5: 5. If the weight ratio range is not satisfied, the arrangement of the hollow inorganic particles may be disturbed, and the average reflectance of the low refractive layer may increase due to external rubbing or friction.

The low refractive index layer may be obtained by applying a photopolymerizable coating composition comprising the copolymer and the hollow inorganic particles on a predetermined substrate and photopolymerizing the applied resultant. The specific kind or thickness of the substrate is not particularly limited, and a substrate known to be used in the manufacture of a hard coating layer or an antireflection film may be used without any significant limitation.

On the other hand, methods and apparatus conventionally used to apply the photopolymerizable coating composition can be used without particular limitation, for example, 2019/221573 1 »（： 1 ^ 1 {2019/006006

Bar coating methods such as Meyer bar, gravure coating, 2 reverse reverse coating, vacuum s lot die coating and the like can be used.

In the step of photopolymerizing the photopolymerizable coating composition may be irradiated with ultraviolet rays or visible light having a wavelength of 200 to 400m, the exposure dose is preferably 100 to 4,000 mJ / cin ² when irradiated. Exposure time is not specifically limited, either, The exposure apparatus used can be suitably changed according to the wavelength or exposure amount of irradiation light. In addition, in the step of photopolymerizing the photopolymerizable coating composition, nitrogen purging may be performed to apply nitrogen atmospheric conditions.

The antireflection film may have an average reflectance in a wavelength range of 380 nm to 780 nm of less than 3%, 2.5% or less, or 2% or less.

On the other hand, the hard coating layer can be used without a large limitation to the conventional known hard coating layer. As an example of the hard coating layer, Binder resin containing a photocurable resin; And it may be a hard coating layer comprising organic or inorganic fine particles dispersed in the binder resin.

The low refractive index layer may be formed on one surface of the hard coating layer, and an additional functional layer may be further included between the low refractive layer and the hard coating layer. As mentioned above, the photocurable resin is a polymer resin polymerized by irradiation of light, for example, by irradiation of visible light or ultraviolet light, for example, a urethane acrylate oligomer, an epoxide acrylate oligomer, Reactive acrylate oligomer group consisting of polyester acrylate, and polyether acrylate; And dipentaerythritol nuxaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy tri At least one member selected from the group of polyfunctional acrylate monomers consisting of acrylate, 1,6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate and ethylene glycol diacrylate can do.

The organic or inorganic fine particles are not specifically limited in particle size, for example, the organic fine particles may have a particle size of 1 to 10 / rni, the inorganic 2019/221573 1 »（： 1 ^ 1 {2019/006006

Particles

500 1 ^ or 1ä to 300ä.

In addition, specific examples of the organic or inorganic fine particles included in the hard coating layer are not limited. For example, the organic or inorganic fine particles may be organic fine particles made of acrylic resin, styrene resin, epoxide resin and nylon resin, or silicon oxide, It may be an inorganic fine particle consisting of titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide.

On the other hand, as another example of the hard coating layer, a binder resin of a photocurable resin; And an antistatic agent dispersed in the binder resin.

The antistatic agent may be a quaternary ammonium salt compound, a conductive polymer or a mixture thereof. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium salt groups in a molecule, and may use a low molecular type or a polymer type without limitation. In addition, the conductive polymer may be a low molecular type or a polymer type without limitation, the kind thereof may be conventional in the art to which the present invention pertains, and is not particularly limited.

Binder resin of the photopolymerizable resin; And the hard coating layer comprising an antistatic agent dispersed in the binder resin may further comprise at least one compound selected from the group consisting of alkoxy silane oligomer and metal alkoxide oligomer. The alkoxy silane compound may be conventional in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be at least one compound selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane and glycidoxypropyl triethoxysilane.

In addition, the metal alkoxide-based oligomer may be prepared through a sol-gel reaction of a composition comprising a metal alkoxide-based compound and water. The sol-gel reaction can be carried out by a method similar to the method for producing an alkoxy silane oligomer described above. However, since the metal alkoxide compound may react with water rapidly, the sol-gel reaction may be performed by diluting the metal alkoxide compound in an organic solvent and slowly dropping water. At this time, in consideration of the reaction efficiency, the molar ratio (metal ion basis) of the metal alkoxide compound to water is in the range of 3 to 170. 2019/221573 1 »（： 1 ^ 1 {2019/006006

It is desirable to adjust within.

Here, the metal alkoxide-based compound may be at least one compound selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide and aluminum isopropoxide.

On the other hand, the anti-reflection film may further include a substrate bonded to the other surface of the hard coating layer. The substrate may have a light transmittance of 90% or more and a haze of 1% or less. In addition, the material of the substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate and the like. In addition, the thickness of the base film may be 10 to 300_ in consideration of productivity, but is not limited thereto.

More specifically, the anti-reflection film has a thickness of retardation (inside the cemetery) measured at wavelengths 400) 1111 to 80011111 of 3, 000 1¾1 or more, or 5, 000 or more, or 5,000 11111 to 20,000 1 pad. It may further include a light transmissive substrate.

Specific examples of such a light transmissive substrate include a uniaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene terephthalate film.

The anti-reflection film includes a light transmissive substrate having a retardation in the thickness direction measured at the wavelengths 40011111 to 800 ™ of at least 3, 000 ■, or at least 5, 000 11111, or at 5, 000 1ä to 20, 000 1ä. In this case, the rainbow phenomenon due to the interference of visible rays may be alleviated as compared with the case of using a retardation of 3000 이하 or less. Retardation in the thickness direction can be confirmed through a commonly known measuring method and measuring apparatus. For example, as a measuring apparatus of retardation of the thickness direction, the brand name "Exo-Cans" by the Tombstone company, etc. are mentioned.

For example, as a measurement condition of the retardation of thickness direction, after inputting the refractive index (589ä) value to the said measuring apparatus about the said light-transmissive base film, under the conditions of temperature: 251 :, humidity: 40%, Using the light of wavelength 590ä, the retardation of the thickness direction of the transparent base film was measured, and based on the obtained retardation immediate value (immediate value by automatic instantaneous (automatic calculation) of the instantaneous device) of the obtained thickness direction, It can be obtained by converting the retardation value per 10 쌘! The size of the light transmissive substrate of the measurement sample is larger than that of the light metering portion (diameter: about 1011) of the stage of the measuring instrument. 2019/221573 1 »（： 1 ^ 1 {2019/006006

Since it is large, it does not restrict | limit especially, It can be set as the size of 76 mm in length, 52 mm in width, and 13 mm thick.

In addition, the value of the "refractive index (589 nm) of the said light-transmissive base material" used for the measurement of retardation of the thickness direction is unburned containing the resin film of the same kind as the light-transmissive base material which forms the film used as the measurement object of retardation. After forming a new film, such an unstretched film is used as a measurement sample (in addition, when the film used as a measurement object is an unstretched film, the film can be used as a measurement sample as it is), and a refractive index measurement as a measuring apparatus In-plane direction of the measurement sample (direction perpendicular to the thickness direction) using a device (trade name "NAR-1T SOLID" manufactured by Atago, Ltd.), using a light source of 589 nm, and a temperature condition of 23 ^° C. It can be obtained by measuring the refractive index of the light of 589nm. According to another embodiment of the invention, a polarizing plate including the anti-reflection film may be provided. The polarizing plate may include a polarizing film and an antireflection film formed on at least one surface of the polarizing film.

The material and manufacturing method of the polarizing film are not particularly limited, and conventional materials and manufacturing methods known in the art may be used. For example, the polarizing film may be a polyvinyl alcohol polarizing film.

A protective film may be provided between the polarizing film and the antireflection film. Examples of the protective film are not limited, and for example, C0P (cycloolef in polymer) film, acrylic film, TAC (tr i acetylcel lulose) film,

COC cycloolef in copolymer (PNB) films, polynorbornene (PNB) films, and

PEK polyethylene terephtalate) film may be any one or more.

The protective film may be used as it is a substrate for forming a single coating layer in the production of the anti-reflection film. The polarizing film and the anti-reflection film may be laminated by an adhesive such as an aqueous adhesive or a non-aqueous adhesive. According to another embodiment of the invention, a display device including the anti-reflection film may be provided. Specific examples of the display device are not limited, and for example, a liquid crystal display device, 2019/221573 1 »（： 1 ^ 1 {2019/006006

Or a device such as a plasma display device, an organic light emitting diode device, and the like.

As one example, the display device includes a pair of polarizing plates facing each other; A thin film transistor, a color filter, and a liquid crystal cell sequentially stacked between the pair of polarizing plates; And it may be a liquid crystal display device including a backlight unit.

In the display device, the anti-reflection film may be provided on the outermost surface of the observer side or the backlight side of the display panel.

In the display device including the anti-reflection film, the anti-reflection film may be positioned on one surface of the polarizing plate relatively far from the backlight unit among the pair of polarizing plates.

In addition, the display apparatus may include a display panel, a polarizing film provided on at least one surface of the panel, and an antireflection film provided on an opposite side of the panel contacting the panel of the polarizing film.

【Effects of the Invention】

According to the present invention, an anti-reflection film having high mechanical properties such as high abrasion resistance and scratch resistance and an excellent anti-reflective property of a part damaged or deformed by an external rub or friction, and an anti-reflection film, And a display device including the polarizing plate and the anti-reflection film.

[Specific contents for carrying out invention]

The invention is explained in more detail in the following examples. However, the following examples are only for exemplifying the present invention, and the contents of the present invention are not limited to the following examples. <Production Examples 1 to 3: Production of Hard Coating Layer>

Preparation Example 1

30 g of pentaerythritol triacrylate, high molecular weight copolymer (BEAM 況 T 371, Arakawa, 2.5 g of epoxy acrylate (molecular weight 40,000), 20 g of methyl ethyl ketone and 0.5 g of leveling agent (Tego wet 270) are uniformly mixed After the mixing, acryl-styrene copolymer resin fine particles having a refractive index of 1.525 (volume average particle diameter: 2 pm 2019/221573 1 »（： 1 ^ 1 {2019/006006

2 g of Seki sui Plast i c) was added to prepare a hard coating composition.

The hard coating composition thus obtained was coated with a # 10 mayer bar on a triacetyl cellulose film and dried at 90 ^° C. for 1 minute. This dried material was irradiated with ultraviolet light of 150 mJ / cin ² to prepare a hard coating layer having a thickness of 4 ,. Preparation Example 2

The hard coating composition of Preparation Example 1 was coated with # 10 mayer bar on a PET film having a thickness of 80 iM and a retardation 10000 · and dried at 60 ^° C. for 1 minute. This dried material was irradiated with ultraviolet light of 150 mJ / oif to prepare a hard coating layer having a thickness of 4 쌘!. Preparation Example 3-

KY0EISHA salt type antistatic hard coating solution (50 wt% solids, product name: LJD-1000) was coated on a triacetyl cellulose film with # 10 mayer bar and dried at 90 ^° C for 1 minute, then UV light of 150 mJ / cm ² Irradiated to prepare a hard coating layer having a thickness of about 5.

Example 1

Hollow silica nanoparticles (diameter: about 50) with respect to 100 parts by weight of the mixed binder of pentaerythritol triacrylate (PETA) and dipentaerythritol nuxaacrylate (DPHA) (mixing ratio of PETA: DPHA is 7: 3). To 60 nm, manufactured by JGC Catalyst and Chemicals, 100 parts by weight, fluorine-based compound (RS-907, DIC) 12 parts by weight, and initiator (Irgacure 127, Ciba) 13.4 parts by weight, MIBK (methyl i sobutyl ketone) solvent The photocurable coating composition was prepared by diluting to 3 wt% solids concentration.

On the hard coat film of Preparation Example 1, the photocurable coating composition was coated with a # 4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at 60 ^° C. for 1 minute to prepare an antireflection film. At the time of curing, the dried coating was irradiated with ultraviolet rays of 252 mJ / cm ² under nitrogen purge. 2019/221573 1 »（： 1 ^ 1 {2019/006006

Example 2

Hollow silica nanoparticles (diameter: about 50) with respect to 100 parts by weight of the mixed binder of pentaerythritol triacrylate (PETA) and dipentaerythritol nuxaacrylate (DPHA) (mixing ratio of PETA: DPHA is 6: 4). To 60 ran, 150 parts by weight of JGC catalyst and chemicals), 100 parts by weight of solid silica nanoparticles (diameter: about 15 nm), 16 parts by weight of fluorine-based compound (RS-90, DIC), and an initiator (Irgacure 127, Ciba G) 8 parts by weight was diluted in a MIBK (methyl isobutyl ketone) solvent to have a solid content of 3.5% by weight to prepare a photocurable coating composition.

On the hard coat film of Preparation Example 1, the photocurable coating composition was coated with a # 4 mayer bar to a thickness of about 110 to 120 times, and dried and cured at 60 ^° C. for 1 minute to prepare an antireflection film. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge. Example 3

Hollow silica nanoparticles (diameter: about 50) with respect to 100 parts by weight of the mixed binder of pentaerythritol triacrylate (PETA) and dipentaerythritol nuxaacrylate (DPHA) (mixing ratio of PETA: DPHA is 7: 3). To 60 ran, 350 parts by weight of JGC catalyst and chemicals), 100 parts by weight of solid silica nanoparticles (diameter: about 13 nm), 30 parts by weight of fluorine-based compound (F477, DIC), and an initiator (Irgacure 127,

Ciba) 37 parts by weight was diluted in a MIBR (methyl isobutyl ketone) solvent to a solid content of 3.0% by weight to prepare a photocurable coating composition.

On the hard coating film of Preparation Example 2, the photocurable coating composition was coated with a # 4 mayer bar to have a thickness of about 110 to 120 ran, and dried and cured at 60 ^° C. for 1 minute to prepare an antireflection film. . At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge. Example 4

100 parts by weight of the mixed binder of pentaerythritol triacrylate (PETA) and dipentaerythritol nuxaacrylate (DPHA) (PETA: DPHA 2019/221573 1 »（： 1 ^ 1 {2019/006006

6: 4), 400 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, manufactured by JGC catalyst and chemicals), 120.1 parts by weight of solid silica nanoparticles (diameter: about 14 nm), fluorine-based compound ( 41 parts by weight of RS-537, DIC), and 22.2 parts by weight of an initiator (Irgacure 127, Ciba) were diluted to a solid content of 3.3% by weight in a methyl isobutyl ketone (MIBK) solvent to prepare a photocurable coating composition.

On the hard coat film of Preparation Example 3, the photocurable coating composition was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at 60 ^° C. for 1 minute to prepare an antireflection film. . At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge. Example 5

Hollow silica nanoparticles (diameter: about 60 to 70) with respect to 100 parts by weight of the mixed binder of pentaerythritol triacrylate and dipentaerythritol nuxaacrylate (DPHA) (mixing ratio of PETA: DPHA is 7: 3) nm, manufactured by JGC catalyst and chemicals) 323.5 parts by weight, solid zirconia nanoparticles (diameter: about 15 nm) 125 parts by weight, fluorine-based compound (RS-90, DIC) 29.4 parts by weight, initiator (Irgacure 127, Ciba) 17.6 The weight part was diluted in a MIBK (methyl isobutyl ketone) solvent so as to have a solid concentration of 3.2% by weight to prepare a photocurable coating composition.

On the hard coating film of Preparation Example 3, the photocurable coating composition was coated with a # 4 mayer bar to have a thickness of about 110 to 120, and dried and cured at 60 ^° C. for 1 minute to prepare an antireflection film. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge. Example 6

Trimethylolpropane triacrylate 01) Based on 100 parts by weight of the first hollow silica nanoparticles 0) 1 Measurement diameter: 58.2ä) 45 parts by weight of the second hollow silica nanoparticles (1) 1 Measurement diameter: 66.7 ^) 78 parts by weight, solid silica nanoparticles (diameter: about 1511111) 71 parts by weight, fluorine compound 犯 90, 1) 10 23 parts by weight, and initiator (1 301 127, (33 companies) 25 parts by weight,

0131 比 1 Urine 01½) Solids concentration in solvent 3. Dilute to 1% by weight of photocurable coating 2019/221573 1 »（： 1 ^ 1 {2019/006006

The composition was prepared.

On the hard coat film of Preparation Example 1, a photocurable coating

The furnace was coated to a thickness of about 110 to 120, dried and cured at 601: for 1 minute. In the dried coating under a nitrogen purge at the time of the curing it was irradiated with ultraviolet rays of ^252/2. Example 7

The mixing ratio of 100 parts by weight of the mixed binder of pentaerythritol triacrylate) and dipentaerythritol nuxaacrylate (8) is 8: 2). 58.211 parts) 55 parts by weight, second hollow silica nanoparticles (1) 1 measurement diameter: 66.7ä) 90 parts by weight, solid silica nanoparticles (diameter: about 15: 1111) 71 parts by weight (diameter: about 1511111) 150 parts by weight, fluorine-based compound 0¾-90, 1) 10 25 parts by weight, initiator (1 to 301 127, (3)) 15 parts by weight, solid concentration in solvent (11161 上 71 ᅵ 30131 ^ 71 Urine 61; 0116) 3. Dilution to 1% by weight to prepare a photocurable coating composition.

On the hard coat film of Preparation Example 3, a photocurable coating

The furnace was coated to a thickness of about 110 to 120 ä, dried and cured at 60 ^° (for 1 minute) to prepare an antireflection film. At the time of curing, the dried coating was irradiated with ultraviolet rays of 252 八 under nitrogen purge.

Comparative Example 1

An antireflective film was prepared in the same manner as in Example 1 except that only a pentaerythritol triacrylate was used without using a mixed binder. Comparative Example 2

Pentaerythritol

An antireflective film was prepared in the same manner as in Example 2 except that dipentaerythritol nuxaacrylate (X) was used at a mixing ratio of 5: 5. 2019/221573 1 »（： 1 ^ 1 {2019/006006

Comparative Example 3

An antireflective film was prepared in the same manner as in Example 3, except that pentaerythritol triacrylate 肝 and dipentaerythritol nuxaacrylate (¾h was used in a mixing ratio of 4: 6).

An antireflective film was prepared in the same manner as in Example 4 except that pentaerythritol triacrylate-myoxi and dipentaerythritol nuxaacrylate (^ ¾ hours were used in a mixing ratio of 2: 8). 5

An antireflective film was prepared in the same manner as in Example 5 except that only dipentaerythritol nuxaacrylate (IX) was used without using a mixed binder. Comparative Example 6

1st hollow silica nanoparticle (measured diameter: 58.2ä) 45 weight part, 2nd hollow silica nanoparticle (1) Instantaneous diameter: 66.7ä) Instead of 78 weight part, measured hollow silica nanoparticle diameter: 58.2 ^) An antireflection film was prepared in the same manner as in Example 6 except that only 123 parts by weight was used. evaluation

1. Reflectance measurement before and after friction test

With 500g load on steel wool of # 0000 grade, reciprocating 10 times at the speed of 33rpm, the darkening treatment was performed to prevent light from passing through the surface where the hard coating layer and the low refractive layer of the antireflection film obtained in Examples and Comparative Examples were not formed. The rubbing test was carried out to rub the surface of the low refractive layer, and the average reflectance of the low refractive layer of the antireflection film was measured at the time points before and after the friction test.

Specifically, before the friction test is carried out, the hard coating layer and the low refractive layer 2019/221573 1 »（： 1 ^ 1 {2019/006006

Darkness treatment is performed to prevent light from passing through the unformed surface, and the average reflectance in the wavelength range of 380 to 780 nm is measured using the reflectance mode of the Solidspec 3700 (UV-Vis spectrophotometer, Shimadzu Corporation). Is shown in Table 1 below. Then, after performing the friction test, the average reflectance was measured in the same manner as the method for measuring ¾ for the low refractive index layer, the results are shown in Table 1 below. In addition, by calculating the difference between the R _O and ¾, the degree of change in reflectance before and after the friction test is shown in "AR" of Table 1 below.

2. Color coordinate value (I) measurement

With 500g load on steel wool of # 0000 grade, reciprocating 10 times at the speed of 33rpm, the darkening treatment is performed to prevent light from penetrating the surface where the hard coating layer and the low refractive layer of the antireflection film obtained in Examples and Comparative Examples are not formed. After rubbing test to rub the surface of low refractive index layer, the reflectance was measured by using reflectance mode of Solidspec 3700 (UV-Vis spectrophotometer, Shimadzu) before and after friction test The color coordinate value () of the low refractive layer was measured using a -2401PC Color Analysis program.

Specifically, the color coordinate values of the low refractive layer were measured before the friction test was carried out, and the results are shown in “bV ′ of Table 1 below. Then, after performing the friction test, the color coordinate values were measured in the same manner as the method of measuring b ^* ₀ for the low refractive layer, and the results are shown in "b '" in Table 1 below. In addition, the difference between the b ^* ₀ and b ^* i was calculated, and the degree of change of the color coordinate values before and after the friction test is shown in "Ab ^* " in Table 1 below.

3. Scratch resistance measurement

The steel wool of grade # 0000 was hung and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in Examples and Comparative Examples. Thereafter, the maximum load at which one scratch or less of lcm or less observed with the naked eye was measured was measured, and the results are shown in Table 1 below.

4. Antifouling measurement 2019/221573 1 »(： 1 ^ 1 {2019/006006

Draw five straight lines with a black oil pen on the surface of the anti-reflective layer of the antireflection film obtained in the Examples and Comparative Examples, and measure the antifouling properties by checking the number of times erased when rubbed using a dust-free cloth. It is shown in Table 1 below.

<Measurement standard ñ

◦: 10 times to be erased

SE: 11-20 times

X: Cleared more than 20 times [Table 1]

As shown in Table 1, Examples 1 to 7 show the degree of change of the average reflectance before and after the friction test (swimming ratio of 0.02%? Since the degree of change in color before and after the friction test is 0.3 or less, compared with Comparative Examples 1 to 6, it is possible to effectively increase the reflectance and change in color at the damaged / deformed portion due to the friction test. 2019/221573 1 »（： 1/10 公 019/006006

It confirmed that it was suppressed and was excellent in visibility.

Claims

2019/221573 1 "(： 1 ^ 1 {2019/006006 [claim]] [claim 11] Hard coating layer; And an anti-reflection film comprising a low refractive index layer satisfying the following formula 1:

[Equation 1]

0.2¾） ³ required = 此-¾ |

In Equation 1,

¾ is the average reflectance in the wavelength range of 380 to 780: ä of the low refractive layer, ¾ is a friction rubbing the surface of the low refractive layer by reciprocating 10 times at a speed of 33 impression with a load of 500 _§ on steel wool. Exam 0? After the implementation, the average reflectance is measured in the wavelength range of 380 to 78011111 measured in the same manner as the method for measuring ¾ for the low refractive layer.

[Claim 2]

The method of claim 1,

The anti-reflection film of Formula 1 is 0.1 to 2.0%.

[Claim 3]

The method of claim 1,

The anti-reflection film of the formula 1 is 0.3 to 0.2%.

[Claim 4]

The method of claim 1,

The low refractive index layer is an antireflection film satisfying the following formula 2:

[Equation 2]

1 ³ four ^* = | ₁ - ₀ |

In Equation 2,

0 is the International Lighting Commission

The value in the color coordinate system

13 'is performed after the friction test under the load of 50½ rubbing the surface of the low refractive index increases by reciprocating 10 times with 33印01 speed to steel wool, a 1) ^* ₀ with respect to the low refractive index increases 2019/221573 1 »（： 1 ^ 1 {2019/006006

Measured with the same method

Value.

[Claim 5]

The method of claim 4,

The value of Equation 2 is 2 to -10 antireflection film.

[Claim 6]

The method of claim 4,

Equation 2 above! ^ Antireflective film with a value of 3 to 9.

[Claim 7]

The method of claim 1,

The low refractive index layer comprises a binder resin,

The binder resin is a polyfunctional containing 2 to 4 functional (meth) acrylate monomers and 5 to 6 functional (meth) acrylate monomers.

An antireflection film containing a copolymer of a (meth) acrylate monomer.

[Claim 8]

The method of claim 7,

Said 2-4 functional (meth) acrylate type monomer and 5-6 functional

The (meth) acrylate monomer is an antireflection film having a weight ratio of 9: 1 to 6: 4.

[Claim 91]

The method of claim 1,

The low refractive layer is a binder resin; And at least two hollow inorganic particles dispersed in the binder resin and having different particle diameters.

[Claim 10]

The method of claim 9,

Two or more types of hollow inorganic particles having different particle diameters, 2019/221573 1 »（： 1 ^ 1 {2019/006006

1 type of hollow inorganic particles having a particle diameter of 40 nm to 60 nm immediately determined by dynamic light scattering (DLS),

An antireflection film comprising one hollow inorganic particle having a particle diameter of 65 nm to 100 nm measured by dynamic light scattering.

[Claim 11]

The method of claim 10,

The hollow inorganic particles having a particle diameter of 40 nm to 60 nm and the hollow inorganic particles having a particle size of 65 nm to 100 nm have a weight ratio of 7: 3 to 3: 7.

[Claim 12]

The method of claim 1,

The low refractive layer is a polyfunctional containing 2 to 4 functional (meth) acrylate monomers and 5 to 6 functional (meth) acrylate monomers.

Binder resin containing a copolymer of a (meth) acrylate monomer; And

And at least two hollow inorganic particles dispersed in the binder resin and having different particle diameters.

[Claim 13]

The method of claim 12,

The 2 to 4 functional (meth) acrylate monomers and 5 to 6 functional (meth) acrylate monomers have a weight ratio of 9: 1 to 6: 4,

The two or more types of hollow inorganic particles having different particle diameters include anti-reflection including hollow inorganic particles having a particle diameter of 40 nm to 60 nm and hollow inorganic particles having a particle size of 65 nm to 100 nm in a weight ratio of 7: 3 to 3: 7. film.

[Claim 14]

The method of claim 1,

Retardation (Rth) in the thickness direction measured at a wavelength of 400 nm to 800 2019/221573 1 »(： 1 ^ 1 {2019/006006, 000) An antireflection film further comprising a light-transmissive base material of 1 1 or more.

[Claim 15]

Polarizing plate comprising the anti-reflection film according to claim 1.

[Claim 16]

Display device comprising an antireflective film according to claim 11.