KR102235481B1 - Anti-reflective film, polarizing plate, and display apparatus - Google Patents

Abstract

The present invention relates to an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having low reflectance and light transmittance deviation, and improving the clarity of a screen of a display device, and a polarizing plate and a display device including the same.

Description

Anti-reflection film, polarizing plate, and display device {ANTI-REFLECTIVE FILM, POLARIZING PLATE, AND DISPLAY APPARATUS}

The present invention relates to an antireflection film, a polarizing plate, and a display device.

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

Among them, in the case of the AG coating, the absolute amount of reflected light is equivalent to that of a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by using scattering of light through irregularities. However, since the AG coating deteriorates the sharpness of the screen due to surface irregularities, many studies on AR coating have recently been conducted.

As a 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 light-transmitting base film is commercially available. However, the conventional anti-reflection film using AR coating has a problem in that the reflectance and transmittance of each film portion have large variations. In addition, the method of forming a plurality of layers as described above has a disadvantage in that scratch resistance is inferior due to weak interlayer adhesion (interface adhesion) as the process of forming each layer is separately performed.

In addition, previously, in order to improve the scratch resistance of the low refractive index layer included in the antireflection film, a method of adding various nanometer-sized particles (eg, particles such as silica, alumina, zeolite, etc.) has been mainly attempted. However, in the case of using nanometer-sized particles as described above, there is a limitation in that it is difficult to simultaneously increase scratch resistance while lowering the reflectance of the low refractive layer, and the antifouling properties of the surface of the low refractive layer are large due to nanometer-sized particles. Fell down.

Accordingly, many studies have been conducted to reduce the variation in reflectance and transmittance of each film part while reducing the absolute reflection amount of light incident from the outside, and to improve the scratch resistance and antifouling properties of the surface. It is inadequate.

An object of the present invention is to provide an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having low reflectance and light transmittance deviation, and improving the clarity of a screen of a display device.

In addition, the present invention is to provide a polarizing plate including the anti-reflection film.

In addition, the present invention is to provide a display device that includes the anti-reflection film and provides high clarity of the screen.

In this specification, Low moisture permeable polymer film; Hard coating layer; And an azimuth distribution curve calculated by performing an azimuthal scan at a 2θ value of 17 to 18°, including a low refractive layer, and obtained by X-ray diffraction (XRD) in a transmission mode. Distribution Curve), an anti-reflective film is provided with an average of 160-200° between peaks.

In addition, in the present specification, a polarizing plate including the antireflection film is provided.

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

Hereinafter, an antireflection film according to a specific embodiment of the present invention, a polarizing plate including the same, and a display device will be described in more detail.

In the present specification, the low refractive index layer may mean a layer having a low refractive index, and for example, may mean a layer exhibiting a refractive index of about 1.2 to 1.8 at a wavelength of 550 nm.

In addition, the peak refers to a portion when the maximum value (or extreme value) of y appears when the value of x is changed and the value of y is recorded for the specific measured quantities x and y. In this case, the maximum value means the largest value at the periphery, and the extreme value means a value whose instantaneous rate of change is 0.

In addition, hollow inorganic particles refer to particles in the form of an empty space present on the surface and/or inside of the inorganic particles.

In addition, (meth)acrylate [(Meth)acrylate] is meant to include both acrylate and methacrylate.

In addition, (co)polymer means including both a copolymer (co-polymer) and a homo-polymer (homo-polymer).

In addition, the fluorine-containing compound means a compound containing at least one or more fluorine elements among the compounds.

In addition, the photopolymerizable compound refers to a polymer compound polymerized by irradiation with light, for example, by irradiation with visible light or ultraviolet light.

According to one embodiment of the invention, a low moisture permeable polymer film; Hard coating layer; And a low-refractive-index layer, and an azimuthal angle distribution curve calculated by performing an azimuthal scan at a 2θ value of 17 to 18° on a diffraction image obtained by X-ray diffraction (XRD) in a transmission mode. Distribution Curve), an antireflective film having an average of 160 to 200° between peaks can be provided. The average of the intervals between the peaks means the arithmetic average of the intervals between the peaks in the azimuth distribution curve in the range of 0 to 360°.

Accordingly, the present inventors proceeded with a study on an antireflection film, and in an azimuth distribution curve calculated by performing an azimuthal scan at a 2θ value of 17 to 18°, the diffraction image obtained by X-ray diffraction in the transmission mode, The antireflection film having an average of the intervals between peaks of 160 to 200° shows similar reflectance and light transmittance throughout the antireflection film, resulting in less variation in reflectance and transmittance, as well as high scratch resistance and antifouling properties. Through an experiment, it was confirmed that it has the sharpness of the screen of the device, and the invention was completed.

The anti-reflective film has little variation in reflectance and light transmittance throughout the film, so that the clarity of the screen of the display device can be increased, but has excellent scratch resistance and high antifouling properties, so that it can be easily applied without great limitation to a display device or a polarizing plate manufacturing process.

The X-ray diffraction image can be obtained by using a transmission mode among the X-ray irradiation modes. Specifically, after the X-ray is incident on the measurement object, it is scattered by the atomic layer in the crystal of the measurement object to form an X-ray diffraction image. You can get it. Through this X-ray diffraction image, the crystal structure of the material can be confirmed and qualitative analysis can be performed.

In addition, from the X-ray diffraction image obtained from the antireflection film according to the embodiment, an azimuth distribution curve may be calculated by performing an azimuthal scan at a 2θ value of 17 to 18°.

In the azimuth distribution curve calculated from the hard coating film according to the embodiment, the average of the intervals between peaks may be 160 to 200°, 165 to 195°, 170 to 190°, or 175 to 185°.

In addition, three or more peaks may appear in the azimuth distribution curve, and the average of the intervals between the three or more peaks may be 160 to 200°, 165 to 195°, 170 to 190°, or 175 to 185°. In this case, the average of the intervals between the peaks is an arithmetic average of the intervals between the peaks in the azimuth distribution curve in the range of 0 to 360°.

As the average of the intervals between the peaks satisfies the above-described range, a similar reflectance and light transmittance may appear in all portions of the antireflection film, thereby implementing an antireflection film having a low reflectance and light transmittance deviation, and improving scratch or antifouling properties. have.

Meanwhile, θ is an incident angle, and the incident angle refers to the angle formed by the crystal plane and the X-ray when X-rays are irradiated on a specific crystal plane, and the diffraction peak refers to the horizontal axis (x-axis) of the incident X-ray in the xy plane. On a graph where the angle of incidence is twice (2θ) and the vertical axis (y-axis) in the xy plane is the diffraction intensity, the horizontal axis (x-axis) is twice the incident angle (2θ) of the incident X-ray increases in the positive direction. As a result, the first derivative value (the slope of the tangent line, dy/dx) of the double (2θ) value of the incident angle of the X-ray, which is the horizontal axis (x-axis) to the diffraction intensity, which is the vertical axis (y-axis), is negative from the positive value. It refers to the point where the first derivative value (the slope of the tangent line, dy/dx) is 0, which changes to a value.

Meanwhile, the diffraction peak means that the full width at half maximum is 5° or more in the azimuth distribution curve. Peaks with a full width of less than 5° correspond to noise.

The average of the intervals between the peaks in the azimuth distribution curve may be due to the uniformity of the crystal state of the polymer and the crystal direction of the polymer in the low moisture permeable polymer film.

Specifically, the polymer crystals in the low moisture permeable polymer film are observed in a transmission mode X-ray diffraction (XRD) pattern, and more specifically, the (010) crystal plane in the low moisture permeable polymer film is 2θ of 17 to 18°. It can appear as a peak in the value.

In addition, the uniformity of the crystal direction of the polymer in the low moisture permeability polymer film may appear as an interval between peaks in an azimuth distribution curve calculated by an azimuthal scan at a 2θ value of 17 to 18°, for example, the The interval between the peaks may be 160° to 200°.

The low refractive layer may include a binder resin and inorganic nanoparticles dispersed in the binder resin.

Meanwhile, the binder resin may include a (co)polymer of a photopolymerizable compound. The photopolymerizable compound forming the binder resin may include a monomer or oligomer including a (meth)acrylate or vinyl group. Specifically, the photopolymerizable compound may include a monomer or oligomer including one or more, or two or more, or three or more (meth)acrylate or vinyl groups.

Specific examples of the monomer or oligomer including the (meth)acrylate include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate. )Acrylate, tripentaerythritol hepta(meth)acrylate, triethylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylic Rate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate, or a mixture of two or more thereof, or urethane-modified acrylate oligomer, epoxide Side acrylate oligomers, ether acrylate oligomers, dendritic acrylate oligomers, or mixtures of two or more thereof. At this time, the molecular weight of the oligomer may be 1,000 to 10,000.

Specific examples of the monomer or oligomer including the vinyl group may include divinylbenzene, styrene, or paramethylstyrene.

Although the content of the portion derived from the photopolymerizable compound in the binder resin is not largely limited, the content of the photopolymerizable compound is 10% by weight to 80% by weight in consideration of the mechanical properties of the finally produced low refractive layer or antireflection film. It may be weight %, 15 to 70 weight %, 20 to 60 weight %, or 30 to 50 weight %. If the content of the photopolymerizable compound is less than 10% by weight, scratch resistance and stain resistance of the low refractive layer may be greatly reduced, and if it exceeds 80% by weight, the reflectance may increase.

Meanwhile, the binder resin may further include a crosslinked polymer between a photopolymerizable compound, a fluorinated compound including a photoreactive functional group, and a polysilsesquioxane substituted with one or more reactive functional groups.

Due to the characteristics of the fluorine element included in the fluorine-containing compound including the photoreactive functional group, the antireflection film may have low interaction energy with respect to liquids or organic substances, and thus, the contaminants transferred to the antireflection film Not only can the amount be greatly reduced, it is possible to prevent a phenomenon in which the transferred contaminants remain on the surface, and the contaminants themselves can be easily removed.

In addition, in the process of forming the low refractive layer and the antireflection film, the reactive functional groups included in the fluorine-containing compound including the photoreactive functional group undergo a crosslinking action. Accordingly, the physical durability and resistance of the low refractive layer and the antireflection film Scratch properties and thermal stability can be improved.

The fluorine-containing compound including the photoreactive functional group may contain or be substituted with one or more photoreactive functional groups, and the photoreactive functional group may participate in the polymerization reaction by irradiation of light, for example, irradiation with visible or ultraviolet rays. Refers to a functional group that is present. The photoreactive functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl), or a thiol group ( Thiol).

The fluorinated compound including the photoreactive functional group may have a weight average molecular weight of 2,000 to 200,000 or 5,000 to 100,000 (weight average molecular weight in terms of polystyrene measured by the GPC method).

If the weight average molecular weight of the fluorinated compound including the photoreactive functional group is too small, the fluorine-containing compounds cannot be uniformly and effectively arranged on the surface of the low refractive layer and are located inside, thereby preventing the low refractive layer and reflection. The antifouling property of the surface of the film is lowered, and the crosslinking density inside the low refractive layer and the antireflection film is lowered, so that the overall strength and mechanical properties such as scratch resistance may be deteriorated. In addition, if the weight average molecular weight of the fluorinated compound including the photoreactive functional group is too high, the haze of the low refractive layer and the antireflection film may increase or the light transmittance may decrease, and the strength of the low refractive layer and the antireflection film may also be It can be degraded.

Specifically, the fluorinated compound including a photoreactive functional group is i) an aliphatic compound or an alicyclic compound in which at least one photoreactive functional group is substituted and at least one carbon is substituted with at least one fluorine; ii) a hetero aliphatic compound or a heteroaliphatic ring compound in which at least one photoreactive functional group is substituted, at least one hydrogen is substituted with fluorine, and at least one carbon is substituted with silicon; iii) a polydialkylsiloxane polymer (eg, polydimethylsiloxane polymer) in which at least one photoreactive functional group is substituted and at least one silicone is substituted with at least one fluorine; iv) It may contain at least one selected from the group consisting of polyether compounds substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine.

The crosslinked polymer is 1 to 300 parts by weight, 2 to 250 parts by weight, 3 to 200 parts by weight, 5 parts derived from the fluorine-containing compound containing the photoreactive functional group based on 100 parts by weight of the part derived from the photopolymerizable compound. To 190 parts by weight or 10 to 180 parts by weight. When the fluorine-containing compound including the photoreactive functional group is added in an excessive amount compared to the photopolymerizable compound, the low refractive layer may not have sufficient durability or scratch resistance. In addition, when the amount of the fluorine-containing compound including the photoreactive functional group is too small compared to the photopolymerizable compound, the low refractive layer may not have sufficient antifouling properties or mechanical properties such as scratch resistance.

The fluorinated compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorinated compound including the photoreactive functional group may optionally contain silicon or a silicon compound therein, and specifically, the content of silicon in the fluorinated compound including the photoreactive functional group is 0.1% to 20% by weight. I can.

The content of silicon or silicon compound contained in each of the fluorinated compounds including the photoreactive functional group can also be confirmed through a commonly known analysis method, for example, an Inductively Coupled Plasma [ICP] analysis method.

The silicon contained in the fluorine-containing compound including the photoreactive functional group can increase compatibility with other components included in the low refractive layer of the embodiment, and accordingly, haze occurs in the low refractive layer finally prepared. It can play a role of increasing transparency by preventing it, and also improves the scratch resistance by improving the slip property of the surface of the low-refractive-index layer or the anti-reflection film to be finally produced.

On the other hand, when the content of silicon in the fluorine-containing compound including the photoreactive functional group is too large, the low refractive layer or the antireflection film may not have sufficient light transmittance or antireflection performance, and the antifouling property of the surface may also decrease.

On the other hand, polysilsesquioxane in which one or more reactive functional groups are substituted has a reactive functional group on the surface, so that the mechanical properties of the low refractive layer, for example, scratch resistance, can be improved, and previously known silica, alumina, zeolite, etc. Unlike the case of using fine particles of, it is possible to improve the alkali resistance of the low refractive layer and improve appearance characteristics such as average reflectance and color.

The polysilsesquioxane _{may be represented by (RSiO 1.5} ) _n (where n is 4 to 30 or 8 to 20), and may have various structures such as random, ladder-shaped, cage, and partial cage. For example, in order to improve the physical properties and quality of the low refractive layer and the anti-reflection film, polysilsesquioxane having one or more reactive functional groups substituted with one or more reactive functional groups and a polyhedral oligomer having a cage structure Silsesquioxane (Polyhedral Oligomeric Silsesquioxane) can be used.

In addition, for example, the polyhedral oligomer silsesquioxane having one or more functional groups substituted and having a cage structure may include 8 to 20 silicones in a molecule.

In addition, at least one of the silicones of the polyhedral oligomer silsesquioxane having a cage structure may be substituted with a reactive functional group, and silicones in which the reactive functional group is not substituted may be substituted with the above-described non-reactive functional group. I can.

As a reactive functional group is substituted in at least one of the silicones of the polyhedral oligomer silsesquioxane having the cage structure, it is possible to improve the mechanical properties of the low refractive layer and the binder resin. As the non-reactive functional group is substituted, a steric hinderance appears in the molecular structure, and the frequency or probability of exposing the siloxane bond (-Si-O-) to the outside is greatly reduced, thereby preventing the alkali resistance of the low refractive layer and the binder resin. Can be improved.

The reactive functional groups substituted for the polysilsesquioxane are alcohols, amines, carboxylic acids, epoxides, imides, (meth)acrylates, nitriles, norbornene, olefins (ally, cycloalkenyl) Or vinyldimethylsilyl, etc.], polyethylene glycol, thiol, and may include one or more functional groups selected from the group consisting of vinyl groups, and may be, for example, epoxide or (meth)acrylate.

More specific examples of the reactive functional group include (meth)acrylate, an alkyl (meth)acrylate having 1 to 20 carbon atoms, a cycloalkyl epoxide having 3 to 20 carbon atoms, and an alkyl cycloalkane having 1 to 10 carbon atoms. ) Epoxide is mentioned. The alkyl (meth)acrylate means that the other part of'alkyl' not bonded to (meth)acrylate is a bonding position, and the cycloalkyl epoxide is another part of'cycloalkyl' not bonded to the epoxide This refers to the bonding position, and the alkyl cycloalkane epoxide means that the other part of the'alkyl' that is not bonded to the cycloalkane epoxide is the bonding site.

On the other hand, the polysilsesquioxane in which one or more reactive functional groups are substituted is a straight or branched alkyl group having 1 to 20 carbon atoms, a cyclohexyl group having 6 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms other than the above-described reactive functional group. One or more unreactive functional groups selected from the group consisting of may further include one or more. As described above, as the reactive functional group and the unreactive functional group are substituted on the surface of the polysilsesquioxane, a siloxane bond (-Si-O-) is located inside the molecule in the polysilsesquioxane in which one or more reactive functional groups are substituted. While not exposed to the outside, the alkali resistance and scratch resistance of the low refractive layer and the antireflection film can be further improved.

Examples of polyhedral oligomeric silsesquioxane (POSS) having a one or more phase substitution of such a reactive functional group and having a cage structure include TMP DiolIsobutyl POSS, Cyclohexanediol Isobutyl POSS, 1,2-PropanediolIsobutyl POSS, Octa( POSS in which one or more alcohols are substituted, such as 3-hydroxy-3 methylbutyldimethylsiloxy) POSS; AminopropylIsobutyl POSS, AminopropylIsooctyl POSS, Aminoethylaminopropyl Isobutyl POSS, N-Phenylaminopropyl POSS, N-Methylaminopropyl Isobutyl POSS, OctaAmmonium POSS, AminophenylCyclohexyl POSS, AminophenylIsobutyl POSS, and other amine-substituted POSS; POSS in which one or more carboxylic acids are substituted, such as Maleamic Acid-Cyclohexyl POSS, Maleamic Acid-Isobutyl POSS, and Octa Maleamic Acid POSS; POSS in which one or more epoxides are substituted, such as EpoxyCyclohexylIsobutyl POSS, Epoxycyclohexyl POSS, Glycidyl POSS, GlycidylEthyl POSS, GlycidylIsobutyl POSS, and GlycidylIsooctyl POSS; POSS in which one or more imides are substituted, such as POSS Maleimide Cyclohexyl and POSS Maleimide Isobutyl; AcryloIsobutyl POSS, (Meth)acrylIsobutyl POSS, (Meth)acrylate Cyclohexyl POSS, (Meth)acrylate Isobutyl POSS, (Meth)acrylate Ethyl POSS, (Meth)acrylEthyl POSS, (Meth)acrylate Isooctyl POSS, (Meth)acrylIsooctyl POSS, ( POSS in which one or more (meth)acrylates are substituted, such as Meth)acrylPhenyl POSS, (Meth)acryl POSS, and Acrylo POSS; POSS in which one or more nitrile groups, such as CyanopropylIsobutyl POSS, are substituted; POSS in which a norbornene group is substituted with 1 or more, such as NorbornenylethylEthyl POSS, NorbornenylethylIsobutyl POSS, Norbornenylethyl DiSilanoIsobutyl POSS, and Trisnorbornenyl Isobutyl POSS; POSS substituted with one or more vinyl groups such as AllylIsobutyl POSS, MonoVinylIsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, and OctaVinyl POSS; POSS in which one or more olefins are substituted, such as AllylIsobutyl POSS, MonoVinylIsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, and OctaVinyl POSS; POSS substituted with PEG having 5 to 30 carbon atoms; Or POSS in which one or more thiol groups such as MercaptopropylIsobutyl POSS or MercaptopropylIsooctyl POSS are substituted; Etc. are mentioned.

The crosslinked polymer between the photopolymerizable compound, the fluorine-containing compound including a photoreactive functional group, and polysilsesquioxane substituted with one or more reactive functional groups is a poly(polysilsesquioxane) substituted with one or more reactive functional groups relative to 100 parts by weight of the photopolymerizable compound. Silsesquioxane may contain 0.5 to 60 parts by weight, 1.5 to 45 parts by weight, 3 to 40 parts by weight, or 5 to 30 parts by weight.

If the content of the portion derived from polysilsesquioxane having one or more substituted reactive functional groups in the binder resin compared to the portion derived from the photopolymerizable compound is too small, it may be difficult to sufficiently secure the scratch resistance of the low refractive layer. have. In addition, even when the content of the portion derived from polysilsesquioxane in which one or more reactive functional groups are substituted relative to the portion derived from the photopolymerizable compound in the binder resin is too large, the transparency of the low refractive layer or the antireflection film is It may be deteriorated, and the scratch property may be rather deteriorated.

On the other hand, the inorganic fine particles mean inorganic particles having a diameter in the unit of nanometers or micrometers.

Specifically, the inorganic fine particles may include solid inorganic nanoparticles and/or hollow inorganic nanoparticles.

The solid inorganic nanoparticles have an average diameter of 100 nm or less and refer to particles having no empty space therein.

In addition, the hollow inorganic nanoparticles mean particles having an average diameter of 200 nm or less and having an empty space on the surface and/or inside.

The solid inorganic nanoparticles are 0.5 to 100 nm, It may have an average diameter of 1 to 80 nm, 2 to 70 nm or 5 to 60 nm.

The hollow inorganic nanoparticles are 1 to 200 nm, It may have an average diameter of 10 to 150 nm, 20 to 130 nm, 30 to 110 nm or 40 to 100 nm.

Meanwhile, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles has at least one reactive group selected from the group consisting of a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl) and a thiol group (Thiol) on the surface. It may contain functional groups. As each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles contains the above-described reactive functional groups on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby securing more improved scratch resistance and antifouling properties. can do.

As the hollow inorganic nanoparticles, those coated with a fluorine-based compound may be used alone, or may be mixed with hollow inorganic nanoparticles whose surface is not coated with a fluorine-based compound. When the surface of the hollow inorganic nanoparticles is coated with a fluorine-based compound, the surface energy may be lowered, and thus the durability or scratch resistance of the low refractive layer may be further improved.

As a method of coating a fluorine-based compound on the surface of the hollow inorganic nanoparticles, a commonly known particle coating method or a polymerization method may be used without great limitation. For example, the hollow inorganic nanoparticles and the fluorine-based compound are mixed with water and a catalyst. In the presence of a sol-gel reaction, the fluorine-based compound may be bonded to the surface of the hollow inorganic nanoparticles through hydrolysis and condensation reactions.

A specific example of the hollow inorganic nanoparticles may be hollow silica particles. The hollow silica may include a predetermined functional group substituted on the surface to be more easily dispersed in an organic solvent. Examples of the organic functional groups that can be substituted on the surface of the hollow silica particles are not largely limited, for example, (meth)acrylate group, vinyl group, hydroxy group, amine group, allyl group, epoxy group, isocyanate group, amine group, Alternatively, fluorine or the like may be substituted on the hollow silica surface.

The binder resin of the low refractive layer contains 10 to 600 parts by weight, 20 to 550 parts by weight, 50 to 500 parts by weight, 100 to 400 parts by weight, or 150 to 350 parts by weight of the inorganic fine particles based on 100 parts by weight of the photopolymerizable compound can do. When the inorganic fine particles are added in an excessive amount, scratch resistance or abrasion resistance of the coating film may decrease due to a decrease in the content of the binder.

On the other hand, the low refractive layer is a photopolymerizable compound, a fluorine-containing compound containing a reactive functional group, polysilsesquioxane having one or more reactive functional groups substituted, and a photocurable coating composition containing the inorganic fine particles on the low moisture permeable polymer film. It can be obtained by applying and photocuring the applied result.

In addition, the photocurable coating composition may further include a photoinitiator. Accordingly, the photopolymerization initiator may remain in the low refractive layer prepared from the photocurable coating composition described above.

As the photoinitiator, any compound known to be used in a photocurable resin composition may be used without limitation, and specifically, a benzophenone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or A mixture of two or more of these may be used.

With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight, 5 to 90 parts by weight, 10 to 80 parts by weight, 20 to 70 parts by weight, or 30 to 60 parts by weight. If the amount of the photopolymerization initiator is too small, a material that remains uncured in the photocuring step of the photocurable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the unreacted initiator remains as an impurity or the crosslinking density is low, so that the mechanical properties of the produced film may be deteriorated or the reflectance may be greatly increased.

In addition, the photocurable coating composition may further include an organic solvent. Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or a mixture of two or more thereof.

Specific examples of such an organic solvent include ketones such as methyl ethylkenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more of these may be mentioned.

The organic solvent may be added at the time of mixing each component included in the photocurable coating composition, or may be included in the photocurable coating composition while each component is added in a dispersed or mixed state in an organic solvent. If the content of the organic solvent in the photocurable coating composition is too small, the flowability of the photocurable coating composition may be lowered, resulting in defects such as streaks in the finally produced film. In addition, when an excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation are not sufficiently performed, so that physical properties or surface properties of the film may be deteriorated, and defects may occur during drying and curing. Accordingly, the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1% by weight to 50% by weight, or 2 to 20% by weight.

On the other hand, the method and apparatus commonly used to apply the photocurable coating composition can be used without any other limitation. For example, a bar coating method such as Meyer bar, a gravure coating method, a 2 roll reverse coating method, a vacuum slot Die coating method, 2 roll coating method, etc. can be used.

In the step of photocuring the photocurable coating composition, ultraviolet or visible light having a wavelength of 200 to 400 nm may be irradiated, and an exposure amount during irradiation may be 100 to 4,000 mJ/cm 2. The exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiated light, or the amount of exposure.

In addition, in the step of photocuring the photocurable coating composition, nitrogen purging may be performed to apply a nitrogen atmosphere.

Meanwhile, as the hard coating layer, a conventionally known hard coating layer may be used without great limitation.

As an example of the hard coating layer, a binder resin including a photocurable resin; And a hard coating layer including organic or inorganic fine particles dispersed in the binder resin.

The photocurable resin included in the hard coating layer is a polymer of a photocurable compound capable of causing a polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art. Specifically, the photocurable resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylpropane ethoxy tri At least one selected from the group of polyfunctional acrylate monomers consisting of acrylate, 1,6-hexanediol diacrylate, propoxylated glycero triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may include.

The organic or inorganic fine particles are not specifically limited in particle diameter, for example, the organic fine particles may have a particle diameter of 1 to 10 μm, and the inorganic particles may have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm. Can have. The particle size of the organic or inorganic fine particles may be defined as a volume average particle size.

In addition, a specific example of the organic or inorganic fine particles included in the hard coating layer is not limited, for example, the organic or inorganic fine particles are organic fine particles composed of acrylic resin, styrene resin, epoxide resin, and nylon resin, or silicon oxide, It may be inorganic fine particles composed of titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide.

The binder resin of the hard coating layer has a number average molecular weight It may further include a high molecular weight (co)polymer of 10,000 or more, 13,000 or more, 15,000 to 100,000, or 20,000 to 80,000. The high molecular weight (co)polymer may be at least one selected from the group consisting of a cellulose polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer.

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

The antistatic agent is a quaternary ammonium salt compound; Pyridinium salt; Cationic compounds having 1 to 3 amino groups; Anionic compounds such as a sulfonic acid base, a sulfuric acid ester base, a phosphoric acid ester base, and a phosphonic acid base; Amphoteric compounds such as amino acid or amino sulfuric acid ester compounds; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Reactants or polymers of two or more of these compounds; It may be a mixture of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium base groups in the molecule, and a low molecular or high molecular type may be used without limitation.

In addition, a conductive polymer and metal oxide fine particles may be used as the antistatic agent. Examples of the conductive polymer include aromatic conjugated poly(paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, hetero atom-containing conjugated polyaniline, mixed conjugated poly( Phenylene vinylene), a conjugated multi-chain conjugated compound having a plurality of conjugated chains in a molecule, and a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain onto a saturated polymer. Further, the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminum oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, and the like.

An organic polymer resin of the photopolymerizable resin; And the hard coating layer including the antistatic agent dispersed in the organic polymer resin may further include one or more compounds selected from the group consisting of alkoxy silane-based oligomers and metal alkoxide-based oligomers.

The alkoxy silane-based compound may be conventional in the art, but, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be one or more compounds 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 may be performed in a manner similar to the method for preparing the alkoxysilane-based oligomer described above. However, since the metal alkoxide-based compound may react rapidly with water, the sol-gel reaction may be performed by slowly dropping water after diluting the metal alkoxide-based compound in an organic solvent. At this time, in consideration of reaction efficiency, etc., the molar ratio of the metal alkoxide compound to water (based on metal ions) may be adjusted within a range of 3 to 170.

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

Meanwhile, the low moisture permeability polymer film may be a transparent film having a light transmittance of 90% or more and a haze of 1% or less.

The low moisture permeability polymer film is a polymer film having a low moisture permeability characteristic in which moisture permeation is hardly achieved in which moisture moves from a high moisture vapor pressure to a low moisture through the film.For example, the low moisture permeability polymer film is 30 to moisture permeation rate in temperature and 90 to conditions of 100% relative humidity for 40 ℃ is 50 g / m ² · day or less, 30 g / m ² · day or less, 20 g / m ² · day or less, or 15g / m ² · day It can be below. When the moisture permeability of the low moisture permeability polymer film ^{exceeds 10 g/m 2} ·day, moisture permeates into the anti-reflective film, and the display to which the anti-reflective film is applied may be deteriorated in a high temperature environment.

As described above, the average of the intervals between peaks in the azimuth distribution curve may be due to the uniformity of the crystal state of the polymer and the crystal direction of the polymer in the low moisture permeable polymer film.

In addition, the degree of alignment of the polymer crystals in the low moisture permeable polymer film is related to the stretching ratio, stretching temperature, cooling rate after stretching, and process temperature in the manufacturing process of the low moisture permeable polymer film. Since the degree of alignment of the polymer crystals in the film may be disturbed, the process temperature may be controlled to 100°C or less to prevent this.

In addition, the degree of alignment of the polymer crystals in the low moisture permeable polymer film may be related to a ratio of tensile strength between one direction of the low moisture permeable polymer film and a direction perpendicular to the one direction.

Specifically, the low moisture permeable polymer film has different values of tensile strength in one direction and in a direction perpendicular to the one direction, for example, tensile strength in one direction and a tensile strength in a direction perpendicular to the one direction. The ratio of strength may be 2 or more, 2.1 to 20, 2.2 to 10, or 2.3 to 5. In this case, the tensile strength in one direction has a value smaller than the tensile strength in a direction perpendicular to the one direction. When the tensile strength ratio is less than 2, a variation in reflectance and transmittance of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.

The tensile strength in one direction may be the tensile strength in the MD (Machine Direction) or TD (Transverse Direction) direction of the low moisture permeable polymer film, specifically 30Mpa to 1Gpa, 40Mpa to 900Mpa, or 50Mpa to 800Mpa. .

The tensile strength perpendicular to the one direction may be the tensile strength in the MD or TD direction of the low moisture permeable polymer film, and specifically 30Mpa to 1Gpa, 40Mpa to 900Mpa, or 50Mpa to 800Mpa.

Specifically, the low moisture permeability polymer film has a retardation (Rth) in the thickness direction measured at a wavelength of 550 nm. It may be 5,000 nm or more, 7,000 to 50,000 nm, or 8,000 to 40,000 nm. Specific examples of such a low moisture permeable polymer film include a uniaxially oriented polyethylene terephthalate film or a biaxially oriented polyethylene terephthalate film.

If the retardation (Rth) in the thickness direction of the low moisture permeable polymer film is less than 10,000 nm, the reflectance and transmittance variation of each portion of the antireflection film may be large, and a rainbow phenomenon may occur due to interference of visible light.

The retardation in the thickness direction can be confirmed through a commonly known measuring method and measuring device. For example, as an apparatus for measuring retardation in the thickness direction, the brand name "AxoScan" manufactured by AXOMETRICS, etc. is mentioned.

For example, as a measurement condition for retardation in the thickness direction, after inputting a refractive index (589 nm) value into the measuring device with respect to the light-transmitting base film, under the conditions of temperature: 25°C and humidity: 40%, Using light having a wavelength of 550 nm, the retardation in the thickness direction of the light-transmitting base film is measured, and based on the obtained thickness direction retardation measurement (measured value by automatic measurement (automatic calculation) of the measuring device), the film It can be calculated|required by converting it to the retardation value per 10 micrometers of thickness of. In addition, the size of the light-transmitting substrate of the measurement sample is not particularly limited, since it is sufficient to be larger than the light metering portion (diameter: about 1 cm) of the stage of the measuring device, but it can be made into a size of 76 mm in length, 52 mm in width, and 13 μm in thickness. .

In addition, the value of the ``refractive index of the light-transmitting substrate (589 nm)'' used for the measurement of retardation in the thickness direction is unconventional including a resin film of the same type as the light-transmitting substrate forming a film to be measured for retardation. After forming a new film, such an unstretched film is used as a measurement sample (in addition, when the film to be measured is an unstretched film, the film can be used as a measurement sample as it is), and a refractive index measurement as a measuring device Using a device (trade name "NAR-1T SOLID" manufactured by Atago Co., Ltd.), using a light source of 589 nm, under a temperature condition of 23°C, in the in-plane direction (direction perpendicular to the thickness direction) of the measurement sample. It can be obtained by measuring the refractive index for light of 589 nm.

In addition, the material of the low moisture permeable polymer substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate, or the like. In addition, the thickness of the base film may be 10 to 300 μm in consideration of productivity, but is not limited thereto.

The antireflection film of the embodiment may exhibit a low reflectance, thereby implementing high light transmittance and excellent optical properties. Specifically, the antireflection film has an average reflectance of 2.0% or less, 1.6% or less, 1.2% or less, 0.05% to 0.9%, 0.10% to 0.70%, or 0.2% in the visible light wavelength range of 380 nm to 780 nm. It may have an average reflectivity of 0.5%.

In addition, the anti-reflection film of the embodiment may exhibit low reflectance deviation and light transmittance deviation, thereby implementing excellent optical properties. Specifically, the average reflectance deviation of the antireflection film may be 0.2%p or less, 0.01 to 0.15%p, or 0.01 to 0.1%p. In addition, the light transmittance deviation of the antireflection film may be 0.2%p or less, 0.01 to 0.15%p, or 0.01 to 0.1%p.

The average reflectance deviation refers to the difference (absolute value) between the average reflectance in the visible light wavelength range of 380 to 780 nm of two or more specific portions (points) selected in the antireflection film and the average value of the average reflectance. . As a method of calculating the average reflectance deviation, specifically, 1) selecting two or more points in the antireflection film, 2) measuring the average reflectance at each of the two or more points, and 3) the average measured in step 2) By calculating the arithmetic mean of the reflectance, and 4) calculating the difference (absolute value) between the average reflectance of each point and the arithmetic mean of step 3), finally, a deviation of two or more average reflectances can be calculated. In this case, the average reflectance deviation having the largest value among the deviations of the two or more average reflectances may be 0.2%p or less.

On the other hand, the light transmittance deviation refers to the difference (absolute value) between the transmittance of two or more specific portions (points) selected from the antireflection film and the average value of the transmittance. Instead of measuring the average reflectance, the transmittance is measured. Except for the point, the transmittance deviation may be calculated in the same manner as the method of calculating the average reflectance deviation. In this case, a light transmittance deviation having a largest value among the two or more light transmittance deviations may be 0.2%p or less.

According to another embodiment of the present invention, a polarizing plate including the anti-reflection film may be provided. The polarizing plate may include a polarizer and an antireflection film formed on at least one surface of the polarizer.

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

The polarizer and the antireflection film may be laminated by an adhesive such as a water-based adhesive or a non-aqueous adhesive.

According to another embodiment of the present invention, a display device including the above-described anti-reflection film may be provided. The specific example of the display device is not limited, and may be, for example, a liquid crystal display device, a plasma display device, or an organic light emitting diode device.

As an example, the display device may include 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 a backlight unit.

In the display device, the antireflection film may be provided on the outermost surface of the display panel on the viewer side or the backlight side.

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

In addition, the display device may include a display panel, a polarizer provided on at least one surface of the panel, and an antireflection film provided on an opposite surface in contact with the panel of the polarizer.

According to the present invention, an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having a low reflectance and light transmittance deviation and increasing the clarity of a screen of a display device, a polarizing plate including the antireflection film, and the antireflection A display device including a film may be provided.

1 and 2 are transmission mode diffraction images of the antireflection film of Example 1. FIG.
3 shows an azimuth distribution curve calculated from the antireflection film of Example 1. FIG.
4 shows an azimuth distribution curve calculated from the antireflection film of Comparative Example 1. FIG.

The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Manufacturing example One: Hard coating layer Preparation of forming coating solution

The components shown in Table 1 were mixed to prepare a coating solution (B1, B2, and B3) for forming a hard coating layer.

(Unit: g) B1 B2 B3 DPHA 6.237 PETA 16.421 10.728 13.413 UA-306T 3.079 2.069 6.114 8BR-500 6.158 6.537 6.114 IRG-184 1.026 1.023 1.026 Tego-270 0.051 0.051 0.051 BYK350 0.051 0.051 0.051 2-butanol 25.92 32.80 36.10 IPA 45.92 38.80 35.70 XX-103BQ(2.0㎛ 1.515) 0.318 0.460 0.600 XX-113BQ(2.0㎛ 1.555) 0.708 0.563 0.300 MA-ST (30% in MeOH) 0.342 0.682 0.542

DPHA: dipentaerythritol hexaacrylate PET: pentaerythritol triacrylate UA-306T: a reaction product of toluene diisocyanate and pentaerythritol triacrylate as urethane acrylate (Kyoeisha product)

8BR-500: Photo-curable urethane acrylate polymer (Mw 200,000, manufactured by Taisei Fine Chemical)

IRG-184: initiator (Irgacure 184, Ciba company)

Tego-270: Tego's leveling agent

BYK350: BYK leveling agent

IPA isopropyl alcohol

XX-103BQ (2.0㎛ 1.515): Copolymer particles of polystyrene and polymethyl methacrylate (Sekisui Plastic product)

XX-113BQ (2.0㎛ 1.555): Copolymer particles of polystyrene and polymethyl methacrylate (Sekisui Plastic product)

MA-ST (30% in MeOH): A dispersion in which nano silica particles with a size of 10 to 15 nm are dispersed in methyl alcohol (product of Nissan Chemical)

Manufacturing example 2-1: Low refractive layer Preparation of forming coating solution (C1)

Trimethylolpropane triacrylate (TMPTA) 100g, hollow silica nanoparticles (diameter range: about 42nm to 66nm, manufactured by JSC catalyst and chemicals) 283g, solid silica nanoparticles (diameter range: about 12nm to 19 nm) 59 g, the first fluorine-containing compound (X-71-1203M, ShinEtsu) 115 g, the second fluorine-containing compound (RS-537, DIC) 15.5 g and an initiator (Irgacure 127, Ciba) 10 g, MIBK A coating solution for forming a low refractive layer (photocurable coating composition) was prepared by diluting it in a (methyl isobutyl ketone) solvent to a solid content concentration of 3% by weight.

Manufacturing example 2-2: Low refractive layer Preparation of forming coating solution (C2)

Dipentaerythritol hexaacrylate (DPHA) 100g, hollow silica nanoparticles (diameter range: about 51nm to 72nm, manufactured by JSC catalyst and chemicals) 143g, solid silica nanoparticles (diameter range: about 12nm to 19) ㎚) 29g, fluorinated compound (RS-537, DIC) 56g and initiator (Irgacure 127, Ciba) 3.1g, diluted in MIBK (methyl isobutyl ketone) solvent to a solid content of 3.5% by weight to form a low refractive layer A coating solution (photocurable coating composition) was prepared.

< Example And Comparative example : Manufacturing of anti-reflective film>

After coating each of the hard coating layer forming coating solutions (B1, B2, B3) prepared above on each of the low moisture permeable polymer films (thickness 80 μm) described in Table 2 with #12 mayer bar, 2 at a temperature of 60°C. After drying for minutes, UV curing was performed to form a hard coating layer (coating thickness of 5 μm). The UV lamp used an H bulb, and the curing reaction was carried out in a nitrogen atmosphere. The amount of UV light irradiated during curing is 100mJ/cm ² .

On the hard coating layer, the low refractive layer forming coating solution (C1, C2) was coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at a temperature of 40° C. for 1 minute. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating solution under nitrogen purging.

Anti-reflective film Tensile strength ratio Hard coating layer Low refractive layer Example 1 3.9 Coating liquid (B1) Coating liquid (C1) Example 2 3.6 Coating liquid (B2) Coating liquid (C1) Example 3 4.2 Coating liquid (B2) Coating liquid (C1) Example 4 2.5 Coating liquid (B3) Coating liquid (C1) Example 5 2.3 Coating liquid (B1) Coating liquid (C2) Comparative Example 1 1.0 Coating liquid (B3) Coating liquid (C1) Comparative Example 2 1.5 Coating liquid (B2) Coating liquid (C1) Comparative Example 3 1.2 Coating liquid (B2) Coating liquid (C1) Comparative Example 4 1.9 Coating liquid (B1) Coating liquid (C2) Comparative Example 5 1.7 Coating liquid (B1) Coating liquid (C2)

*Tensile strength ratio: In a low moisture permeable polymer film, the ratio of the tensile strength in a direction perpendicular to the one direction having a larger value to the tensile strength in one direction having a smaller value

evaluation

1. Transmission Mode of X-ray diffraction ( XRD ) evaluation

For the antireflection films obtained in Examples and Comparative Examples, samples were prepared in a size of 2cm*2cm (horizontal*vertical), and then measured by irradiating Cu-K α-rays with a wavelength of 1.54 Å.

Specifically, the 10 samples were stacked and fixed to the support, and then placed so as to be in a goniometer center. In this case, the samples were stacked so that the one direction having a lower tensile strength and a vertical direction in the one direction having a higher tensile strength coincided with each other in the highly moisture-permeable polymer film of each sample.

The measuring equipment is Bruker AXS D8 Discover XRD, the voltage and current used are 50Kv and 1000μA, respectively, and the optics and detector used are as follows.

-Primary (incident beam) optics: beam collimator (0.3mm)

-Secondary (diffracted beam) optics: none

-VANTEC-500 (2D detector)

2 Fix the θ at 0° and the detector at 24° so that the (010) crystal plane in the low moisture permeable polymer film is measured near θ = 17.6°, and then set the psi from 0° to 90° at 30° intervals of 2400 seconds in 4 frames (frame ), and the beam collimator used a size of 0.3 mm. The conversion and analysis of the X-ray diffraction image by the Cu-Kα ray was performed using Bruker's DIFFRAC.EVA program, and 2 θ -integration was performed in the range of 17.25° to 18.25° using a wedge cursor. Converted to 1D-pattern.

The measured and converted patterns for each psi position are shifted by 30°, 60°, and 90° each according to the actual measured chi value, then merged, and the extreme value in the data obtained at Chi 0° is gamma 0 The azimuth distribution curve was obtained by shifting the pattern so as to be located at °.

In this azimuth distribution curve, the X axis is gamma (degree) and 0° is the position when the stretching axis is perpendicular to the sample stage, and the Y axis is the integrated intensity of the (010) plane. The interval between the displayed peaks was measured, the value of the arithmetic mean was calculated, and the results are shown in Table 3 below.

Meanwhile, FIGS. 1 and 2 are transmission mode diffraction images of the antireflection film of Example 1. In FIG. In particular, FIGS. 1 and 2 show a scratch by rotating the antireflection film of Example 1 by 90°. 3 shows the azimuth distribution curve calculated from the antireflection film of Example 1, and FIG. 4 shows the azimuth distribution curve calculated from the antireflection film of Comparative Example 1.

2. Average reflectance evaluation

After dark color treatment of the back side of the antireflection film obtained in Examples and Comparative Examples (one side of the low moisture permeable polymer film on which the hard coating layer was not formed), 380 to 380 using the Reflectance mode of the Solidspec 3700 (SHIMADZU) equipment. The average reflectance was measured in the 780 nm wavelength region, and the results are shown in Table 3 below.

3. Evaluation of deviation of average reflectance

Twenty arbitrary points were selected for the antireflection films obtained in Examples and Comparative Examples, and the average reflectance was measured for each point by the above 2. average reflectance evaluation method. Then, the arithmetic mean value of the average reflectance of the measured 20 points was calculated. Thereafter, the difference (absolute value) between the average reflectance at each point and the arithmetic mean value was defined as the average reflectance deviation, and the average reflectance deviation was calculated at each of the 20 points. The average reflectance deviation having the largest value among the 20 average reflectance deviations is shown in Table 3 below.

4. Transmittance Deviation evaluation

Twenty arbitrary points were selected for the antireflection film obtained in Examples and Comparative Examples, and the transmittance was measured for each point.

Specifically, the anti-reflection film was measured for average transmittance in a wavelength range of 380 to 780 nm using the Transmittance mode of the Solidspec 3700 (SHIMADZU) equipment.

Thereafter, the arithmetic average value of the measured transmittance of the 20 points was calculated. Thereafter, the difference (absolute value) between the transmittance and the arithmetic mean value at each point was defined as the transmittance deviation, and the transmittance deviation was calculated at each of the 20 points. The light transmittance deviation, which has the largest value among the twenty light transmittance deviations, is shown in Table 3 below.

5. Evaluation of moisture permeability

The moisture permeability of the antireflection film obtained in Examples and Comparative Examples was measured using a MOCON test equipment (PERMATRAN-W, MODEL 3/61) under a temperature of 38°C and 100% relative humidity.

Average of intervals between peaks (°) Average reflectance (%) Average reflectance deviation (%p) Transmittance deviation (%p) Moisture permeability (g/m ² ·day) Example 1 173 1.05 0.04 0.02 10.61 Example 2 181 1.13 0.11 0.09 11.18 Example 3 195 1.12 0.07 0.08 10.44 Example 4 169 1.07 0.16 0.11 12.21 Example 5 177 1.6 0.03 0.15 11.81 Comparative Example 1 103.3 1.13 0.35 0.22 12.35 Comparative Example 2 79.8 1.04 0.26 0.23 10.54 Comparative Example 3 46.5 0.99 0.28 0.3 11.38 Comparative Example 4 50.6 1.55 0.25 0.28 11.25 Remarks Example 5 52.1 1.5 0.35 0.32 10.91

According to Table 3, in Examples 1 to 4, it was confirmed that the average of the intervals between the peaks satisfies 160 to 200°, and the average reflectance deviation and light transmittance deviation were significantly lower compared to Comparative Examples 1 to 4.

Claims (16)

Low moisture permeable polymer film; Hard coating layer; And a low refractive index layer,
Intervals between peaks in the azimuthal angle distribution curve calculated by performing an azimuthal scan at a 2θ value of 17 to 18° on the diffraction image obtained by X-ray diffraction (XRD) in the transmission mode The average of 160 to 200 °, the anti-reflection film.
The method of claim 1,
In the azimuth distribution curve, the average of the intervals between three or more peaks is 160 to 200°, an antireflection film.
The method of claim 1,
The low-refractive-index layer includes a binder resin and inorganic fine particles dispersed in the binder resin.
The method of claim 3,
The binder resin comprises a (co)polymer of a photopolymerizable compound, antireflection film.
The method of claim 3,
The binder resin further comprises a crosslinked polymer between a photopolymerizable compound, a fluorinated compound including a photoreactive functional group, and a polysilsesquioxane substituted with one or more reactive functional groups.
The method of claim 5,
The fluorinated compound including the photoreactive functional group is i) an aliphatic compound or an alicyclic compound in which at least one photoreactive functional group is substituted and at least one carbon is substituted with at least one fluorine; ii) a hetero aliphatic compound or a heteroaliphatic ring compound in which at least one photoreactive functional group is substituted, at least one hydrogen is substituted with fluorine, and at least one carbon is substituted with silicon; iii) a polydialkylsiloxane-based polymer in which at least one photoreactive functional group is substituted and at least one silicon is substituted with at least one fluorine; And iv) a polyether compound in which at least one photoreactive functional group is substituted and at least one hydrogen is substituted with fluorine; an antireflection film comprising at least one selected from the group consisting of.
The method of claim 5,
The reactive functional group substituted for the polysilsesquioxane is in the group consisting of alcohol, amine, carboxylic acid, epoxide, imide, (meth)acrylate, nitrile, norbornene, olefin, polyethylene glycol, thiol, and vinyl group. An anti-reflective film comprising at least one selected functional group.
The method of claim 3,
The inorganic fine particles include at least one selected from the group consisting of solid inorganic nanoparticles having an average diameter of 0.5 to 100 nm and hollow inorganic nanoparticles having an average diameter of 1 to 200 nm.
The method of claim 1,
The hard coating layer is a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin; containing, anti-reflection film.
The method of claim 9,
The binder resin of the hard coating layer further comprises a high molecular weight (co)polymer having a number average molecular weight of 10,000 or more, an antireflection film.
The method of claim 1,
The low moisture permeable polymer film,
The retardation (Rth) in the thickness direction measured at a wavelength of 550 nm is 5,000 nm or more,
The ratio of the tensile strength in a direction perpendicular to the one direction to the tensile strength in one direction is 2 or more,
The tensile strength in one direction has a value smaller than the tensile strength in a direction perpendicular to the one direction, the antireflection film.
The method of claim 1,
The low moisture permeable polymer film is a polyethylene terephthalate film, an antireflection film.
The method of claim 1,
The antireflection film has an average reflectance of 2.0% or less in a wavelength range of 380nm to 780nm.
The method of claim 1,
The anti-reflection film,
Average reflectance deviation is 0.2%p or less,
An antireflection film having a light transmittance deviation of 0.2%p or less.
A polarizing plate comprising the anti-reflection film and the polarizer according to claim 1.
A display device comprising the anti-reflection film according to claim 1.

Images