KR20210092185A - Anti-reflective film, polarizing plate, and display apparatus - Google Patents

Abstract

The present invention relates to an anti-reflection film capable of simultaneously implementing 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, and a polarizing plate and display device including the same. The anti-reflection film is a low moisture permeable polymer film; hard coating layer; and a low refractive layer, wherein average reflectance deviation is 0.2%p or less, transmittance deviation is 0.2%p or less, and average reflectance is 2.0% or less in a wavelength range of 380 nm to 780 nm.

Description

Anti-reflection film, polarizer 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 for minimizing reflection of light incident from the outside. As a method for minimizing light reflection, a method of dispersing a filler such as inorganic fine particles in a resin, coating it on a base film, and imparting irregularities (anti-glare: AG coating); There is a method of using light interference by forming a plurality of layers having different refractive indices on a 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 using light scattering through irregularities. However, since the AG coating lowers the clarity of the screen due to surface irregularities, a lot of research has been done on the AR coating in recent years.

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, etc. are laminated on a light-transmitting base film is commercially available. However, the conventional anti-reflection film using the AR coating has a problem in that the reflectance and transmittance deviation for each part of the film is large. In addition, the method of forming a plurality of layers as described above has a disadvantage in that the interlayer adhesion (interfacial adhesion) is weak as the process of forming each layer is separately performed, and thus scratch resistance is poor.

In addition, in the past, in order to improve the scratch resistance of the low refractive index layer included in the anti-reflection film, a method of adding various particles of nanometer size (eg, particles such as silica, alumina, zeolite, etc.) was mainly tried. However, when nanometer-sized particles are used 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 property of the low-refractive layer surface due to the nanometer-sized particles is large. was lowered

Accordingly, many studies are being made to reduce the absolute reflection amount of light incident from the outside, to reduce the variation in reflectance and transmittance for each film part, and to improve the scratch resistance and antifouling properties of the surface. It is insufficient.

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

Another object of the present invention is to provide a polarizing plate including the anti-reflection film.

Another object of the present invention is to provide a display device including the anti-reflection film and providing high screen clarity.

In the present specification, a low moisture permeability polymer film; hard coating layer; and a low refractive layer, wherein in an X-ray diffraction (XRD) pattern of reflection mode, a first peak appears at a 2θ value of 22 to 24°, and a second peak at a 2θ value of 24 to 27° An antireflection film that appears is provided.

In addition, in the present specification, a polarizing plate including the anti-reflection film is provided.

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

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

In this specification, the terms first and second are used to describe various elements, and the terms are used only for the purpose of distinguishing one element from another element.

In addition, the low-refractive layer may mean a layer having a low refractive index, 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, for specific measurands x and y, when the value of x is changed and the value of y is recorded for the specific measurand, the peak means the portion where the maximum value (or extreme value) of y appears. In this case, the maximum value means the largest value in the periphery, and the extreme value means a value having an instantaneous rate of change of zero.

In addition, the hollow inorganic particle refers to a particle having an empty space on the surface and/or inside of the inorganic particle.

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

In addition, the (co)polymer is meant to include both a copolymer (co-polymer) and a homo-polymer (homo-polymer).

In addition, the fluorine-containing compound refers to a compound containing at least one element of fluorine among the compounds.

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

According to an embodiment of the invention, a low moisture permeability polymer film; hard coating layer; and a low refractive layer, wherein in an X-ray diffraction (XRD) pattern of reflection mode, a first peak appears at a 2θ value of 22 to 24°, and a second peak at a 2θ value of 24 to 27° An antireflection film that appears may be provided.

Accordingly, the present inventors conducted research on the anti-reflection film, In the X-ray diffraction pattern of the reflection mode, the antireflection film having a first peak at a 2θ value of 22 to 24° and a second peak at a 2θ value of 24 to 27° has a similar reflectance throughout the antireflection film and light transmittance, so that the deviation of reflectance and transmittance is small, high scratch resistance and antifouling properties can be simultaneously implemented, and the fact that the screen of the display device has sharpness was confirmed through experiments and the invention was completed.

The anti-reflection film has a small variation in reflectance and transmittance throughout the film, so it can increase the clarity of the screen of the display device, and has excellent scratch resistance and high antifouling properties, so that it can be easily applied without major limitations in the display device or the polarizing plate manufacturing process.

Specifically, the X-ray diffraction pattern may be calculated using a reflection mode among X-ray irradiation modes.

Two or more peaks may appear in the X-ray diffraction (XRD) pattern of the reflection mode obtained from the anti-reflection film according to the exemplary embodiment. Specifically, two peaks may appear at 2θ values of 22 to 27°. Among the two peaks in the 2θ values of 22 to 27°, a peak appearing at a relatively small 2θ value is defined as a first peak, and a peak appearing at a relatively large 2θ value is defined as a second peak. More specifically, the first peak and the second peak may be divided based on 24°.

As a specific example, a peak appearing at a 2θ value of 22 to 24° is a first peak, and a peak appearing at a 2θ value of 24 to 27° is a second peak.

The antireflection film has a peak at a 2θ value of 22 to 24° and a 2θ value of 24 to 27°, respectively, and the ratio of the intensity of the first peak (P1) to the intensity (P2) of the second peak is 0.4 It may be more than, 0.45 to 2.5, 0.5 to 2. Accordingly, similar reflectance and transmittance are shown throughout the antireflection film, thereby implementing an antireflection film having low reflectance and light transmittance deviation, and improvement in scratch or stain resistance can also be implemented.

On the other hand, the angle of incidence (θ) means an angle between the crystal plane and the X-ray when the X-ray is irradiated to a specific crystal plane, and the diffraction peak is the angle of incidence of the X-ray at which the horizontal axis (x-axis) in the xy plane is incident. On the graph where it is a double (2θ) value and the vertical axis (y axis) in the xy plane is the diffraction intensity, as the horizontal axis (x axis) doubles (2θ) value of the incident angle of the incident X-ray increases in the positive direction , the first derivative (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) with respect to the diffraction intensity, which is the vertical axis (y-axis), from a positive value to a negative value It means a point where the first derivative (slope of the tangent line, dy/dx) is 0, which is changing.

The 2θ value of the first peak and the second peak may be due to the crystalline state of the polymer in the low moisture permeability polymer film, and the intensity of the first peak relative to the intensity of the second peak (P2) (P1) The ratio may be due to the degree of alignment of the polymer crystals in the low moisture permeability polymer film.

Specifically, the polymer crystal state in the low moisture permeability polymer film may be indicated by whether a peak occurs in a reflection mode X-ray diffraction (XRD) pattern. More specifically, the (100) crystal plane in the low moisture permeability polymer film appears as a second peak at a 2θ value of 24 to 27°, and the (-110) crystal plane in the low moisture permeability polymer film has a 2θ value of 22 to 24°. 1 may appear as a peak.

In addition, the degree of alignment of the polymer crystals in the low moisture permeability polymer film may be expressed as a ratio of the intensity of the first peak (P1) to the intensity (P2) of the second peak, and the higher the value of the ratio, the higher the value of the polymer crystal The degree of alignment is high, so that the polymer crystals can be evenly arranged in the low moisture permeability polymer film.

The low refractive index 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 (meth)acrylate or a monomer or oligomer including a vinyl group. Specifically, the photopolymerizable compound may include a monomer or oligomer containing 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, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) acrylate, tripentaerythritol hepta (meth) acrylate, torylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylic Late, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate, or a mixture of two or more thereof, or urethane-modified acrylate oligomer, epoxy side acrylate oligomer, ether acrylate oligomer, dendritic acrylate oligomer, or a mixture of two or more thereof. In this case, the molecular weight of the oligomer may be 1,000 to 10,000.

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

Although the content of the portion derived from the photopolymerizable compound in the binder resin is not particularly limited, the content of the photopolymerizable compound is 10% by weight to 80% by weight in consideration of the mechanical properties of the finally manufactured low-refractive layer or anti-reflection film. weight percent, 15 to 70 weight percent, 20 to 60 weight percent, or 30 to 50 weight percent. If the content of the photopolymerizable compound is less than 10% by weight, scratch resistance and antifouling properties of the low-refractive layer may be greatly reduced, and if it exceeds 80% by weight, a problem of increasing reflectance may occur.

Meanwhile, the binder resin may further include a crosslinked polymer between a photopolymerizable compound, a fluorine-containing compound including a photoreactive functional group, and polysilsesquioxane in which one or more reactive functional groups are substituted.

Due to the characteristics of the element fluorine included in the fluorine-containing compound including the photoreactive functional group, the interaction energy of the anti-reflection film may be lowered with respect to liquids or organic materials, and thus the contaminants transferred to the anti-reflection film may be reduced. In addition to greatly reducing the amount, it is possible to prevent the transferred contaminant from remaining on the surface, and has the property that the contaminant itself can be easily removed.

In addition, in the process of forming the low refractive index layer and the antireflection film, the reactive functional group included in the fluorine-containing compound including the photoreactive functional group performs a crosslinking action, and thus the low refractive index layer and the antireflection film have physical durability, resistance It is possible to increase scratch resistance and thermal stability.

One or more photoreactive functional groups may be included or substituted in the fluorine-containing compound including the photoreactive functional group, and the photoreactive functional group may participate in a polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light. means a functional group. The photoreactive functional group may include various functional groups known 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) can be mentioned.

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

When the weight average molecular weight of the fluorine-containing compound including the photoreactive functional group is too small, the fluorine-containing compounds are not uniformly and effectively arranged on the surface of the low-refractive layer and are located therein. Accordingly, the low-refractive layer and anti-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 mechanical properties such as overall strength and scratch resistance may be lowered. In addition, when the weight average molecular weight of the fluorine-containing compound including the photoreactive functional group is too high, the haze of the low refractive layer and the antireflection film may be increased or the light transmittance may be lowered, and the strength of the low refractive layer and the antireflection film is also may be lowered.

Specifically, the fluorine-containing compound including the photoreactive functional group includes: i) an aliphatic compound or an aliphatic ring compound in which one or more photoreactive functional groups are substituted and one or more fluorine is substituted on at least one carbon; ii) a heteroaliphatic compound or a heteroaliphatic ring compound substituted with one or more photoreactive functional groups, wherein at least one hydrogen is substituted with fluorine and one or more carbons are substituted with silicon; iii) a polydialkylsiloxane-based polymer (eg, polydimethylsiloxane-based polymer) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicone; iv) may include one or more selected from the group consisting of polyether compounds substituted with one or more photoreactive functional groups and wherein at least one hydrogen is substituted with fluorine.

The binder resin included in the low refractive index layer may include a crosslinked polymer between a photopolymerizable compound and a fluorine-containing compound including a photoreactive functional group.

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

The fluorine-containing compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorine-containing compound including the photoreactive functional group may optionally contain silicon or a silicon compound therein, and specifically, the content of silicon in the fluorine-containing compound including the photoreactive functional group is 0.1 wt% to 20 wt% can

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

Silicon included 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 thus haze occurs in the finally manufactured low refractive layer. It can serve to increase the transparency by preventing it, and in addition, it is possible to improve the scratch resistance by improving the slip property of the surface of the finally manufactured low-refractive layer or anti-reflection film.

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 index layer or the antireflection film may not have sufficient light transmittance or antireflection performance, and the antifouling property of the surface may also be reduced.

On the other hand, the polysilsesquioxane in which one or more reactive functional groups are substituted has a reactive functional group on the surface, so that 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 , the alkali resistance of the low refractive layer can be improved, and appearance characteristics such as average reflectance and color can be improved.

The polysilsesquioxane (RSiO _1.5 ) _{may be represented by n} (in this case, n is 4 to 30 or 8 to 20), and may have various structures such as random, ladder type, cage and partial cage. Preferably, in order to increase the physical properties and quality of the low refractive index layer and the antireflection film, polysilsesquioxane in which one or more reactive functional groups are substituted with one or more reactive functional groups is substituted with polyhedral oligomer having a cage structure Silsesquioxane (Polyhedral Oligomeric Silsesquioxane) can be used.

Also, more preferably, the polyhedral oligomeric silsesquioxane having one or more functional groups substituted and having a cage structure may include 8 to 20 silicon atoms in a molecule.

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

As a reactive functional group is substituted in at least one of the silicones of the polyhedral oligomeric silsesquioxane having the cage structure, the mechanical properties of the low refractive layer and the binder resin can be improved, and the remaining silicones As the non-reactive functional group is substituted, a molecular structural steric hindrance appears, greatly reducing the frequency or probability of exposing the siloxane bond (-Si-O-) to the outside, thereby improving the alkali resistance of the low refractive index layer and the binder resin. can be improved

The reactive functional group substituted for the polysilsesquioxane is alcohol, amine, carboxylic acid, epoxide, imide, (meth)acrylate, nitrile, norbornene, olefin [ally, cycloalkenyl) or vinyldimethylsilyl, etc.], polyethylene glycol, thiol, and at least one functional group selected from the group consisting of a vinyl group, and preferably an epoxide or (meth)acrylate.

More specific examples of the reactive functional group include (meth)acrylate, alkyl (meth)acrylate having 1 to 20 carbon atoms, cycloalkyl epoxide having 3 to 20 carbon atoms, and alkyl cycloalkane having 1 to 10 carbon atoms. ) epoxides. The alkyl (meth)acrylate means that the other part of the 'alkyl' not bonded to the (meth)acrylate is a bonding position, and the cycloalkyl epoxide is another part of the 'cycloalkyl' not bonded to the epoxide. It means this bonding site, and in the case of an alkyl cycloalkane epoxide, it 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 linear 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 in addition to the reactive functional group described above. One or more non-reactive functional groups selected from the group consisting of may further include one or more. As described above, as the reactive functional group and 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 anti-reflection film can be further improved.

Examples of the polyhedral oligomeric silsesquioxane (POSS) in which one or more reactive functional groups are substituted and having a cage structure include TMP DiolIsobutyl POSS, Cyclohexanediol Isobutyl POSS, 1,2-PropanediolIsobutyl POSS, Octa (3 -hydroxy-3 methylbutyldimethylsiloxy) POSS in which one or more alcohols such as POSS are substituted; AminopropylIsobutyl POSS, AminopropylIsooctyl POSS, Aminoethylaminopropyl Isobutyl POSS, N-Phenylaminopropyl POSS, N-Methylaminopropyl Isobutyl POSS, OctaAmmonium POSS, AminophenylCyclohexyl POSS, AminophenylIsobutyl POSS, etc.; 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; EpoxyCyclohexylIsobutyl POSS, Epoxycyclohexyl POSS, Glycidyl POSS, GlycidylEthyl POSS, GlycidylIsobutyl POSS, GlycidylIsooctyl POSS, etc. POSS substituted with one or more epoxides; POSS Maleimide Cyclohexyl, POSS Maleimide Isobutyl, etc. POSS in which one or more imides are substituted; 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)acrylIs 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 one or more norbornene groups are substituted, such as NorbornenylethylEthyl POSS, NorbornenylethylIsobutyl POSS, Norbornenylethyl DiSilanoIsobutyl POSS, Trisnorbornenyl Isobutyl POSS; AllylIsobutyl POSS, MonoVinylIsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethylsilyl POSS, OctaVinyl POSS, etc. POSS substituted with one or more vinyl groups; 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; and the like.

The cross-linked 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 polysilsesquioxane substituted with one or more reactive functional groups relative to 100 parts by weight of the photopolymerizable compound. It may include 0.5 to 60 parts by weight of silsesquioxane, 1.5 to 45 parts by weight, 3 to 40 parts by weight, or 5 to 30 parts by weight.

When the content of the portion derived from polysilsesquioxane substituted with one or more reactive functional groups compared to the portion derived from the photopolymerizable compound in the binder resin is too small, the scratch resistance of the low refractive index layer is sufficiently secured It can be difficult to do. In addition, even when the content of the portion derived from polysilsesquioxane substituted with one or more reactive functional groups compared to the portion derived from the photopolymerizable compound in the binder resin is too large, the low refractive index layer or the anti-reflection film The transparency may be lowered, and the scratchability may be rather lowered.

Meanwhile, the inorganic fine particles refer to inorganic particles having a diameter of nanometers or micrometers.

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

The solid inorganic nanoparticles mean particles having an average diameter of 100 nm or less and 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 thereof.

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.

On the other hand, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles has at least one reactivity 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 layer may have a higher degree of crosslinking, thereby securing improved scratch resistance and antifouling properties. can do.

As the hollow inorganic nanoparticles, those having a surface coated with a fluorine-based compound may be used alone or mixed with hollow inorganic nanoparticles whose surface is not coated with a fluorine-based compound may be used. 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 index layer may be further improved.

As a method for coating the fluorine-based compound on the surface of the hollow inorganic nanoparticles, a particle coating method or a polymerization method known in general can be used without great limitation, for example, the hollow inorganic nanoparticles and the fluorine-based compound are mixed with water and a catalyst. A fluorine-based compound can be bound to the surface of the hollow inorganic nanoparticles through hydrolysis and condensation reaction by sol-gel reaction in the presence of .

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

The binder resin of the low refractive layer includes 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 excess, scratch resistance or abrasion resistance of the coating film may be deteriorated due to a decrease in the binder content.

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

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

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

Based on 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, an uncured material remaining 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 may remain as an impurity or the crosslinking density may be lowered, so that mechanical properties of the produced film may be reduced or 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 ethyl kenone, 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, and polyethylene glycol monomethyl ether acetate; ethers such as tetrahydrofuran or propylene glycol monomethyl ether; or a mixture of two or more thereof.

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 the 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, and defects such as streaks may occur in the finally manufactured film. In addition, when an excessive amount of the organic solvent is added, the solid content is lowered, and 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 solid content of the components included is 1% to 50% by weight, or 2 to 20% by weight.

On the other hand, the method and apparatus commonly used for applying the photocurable coating composition may 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 A die coating method, a 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 the exposure amount during irradiation is preferably 100 to 4,000 mJ/cm 2 . The exposure time is not particularly limited, either, and can be appropriately changed depending on the exposure apparatus used, the wavelength of the irradiation light, or the exposure amount.

In addition, in the step of photocuring the photocurable coating composition, nitrogen purging may be performed in order to apply nitrogen atmospheric conditions.

On the other hand, as the hard coating layer, a commonly known hard coating layer may be used without significant limitation.

As an example of the hard coating layer, a binder resin comprising 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 that can cause a polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art. Specifically, the photocurable resin may include a reactive acrylate oligomer group consisting of a urethane acrylate oligomer, an epoxide acrylate oligomer, a polyester acrylate, and a 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 consisting of polyfunctional acrylate monomers consisting of acrylate, 1,6-hexanediol diacrylate, propoxylated glycero triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate. may include.

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

In addition, specific examples of the organic or inorganic fine particles included in the hard coating layer are not limited, but for example, the organic or inorganic fine particles are organic fine particles made of an acrylic resin, a styrene-based resin, an epoxide resin, and a nylon resin, or silicon oxide, It may be inorganic fine particles made 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-based polymer, an acrylic polymer, a styrene-based polymer, an epoxide-based polymer, a nylon-based polymer, a urethane-based polymer, and a polyolefin-based 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 salts; cationic compounds having 1 to 3 amino groups; anionic compounds such as sulfonic acid bases, sulfuric acid ester bases, phosphoric acid ester bases and phosphonic acid bases; an amphoteric compound such as an amino acid-based compound or an amino sulfate ester-based compound; nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; organometallic compounds such as metal alkoxide compounds containing tin or titanium; metal chelate compounds such as acetylacetonate salts of the above organometallic compounds; two or more reactants or polymers 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 salt groups in the molecule, and a low molecular type or a high molecular type may be used without limitation.

Moreover, as said antistatic agent, a conductive polymer and metal oxide microparticles|fine-particles can also be used. Examples of the conductive polymer include aromatic conjugated poly(paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing conjugated polyaniline, mixed type conjugated poly( phenylene vinylene), a double-chain conjugated compound having a plurality of conjugated chains in the molecule, and a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain to a saturated polymer. In addition, examples of 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, and aluminum-doped zinc oxide.

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

The alkoxysilane-based compound may be conventional in the art, but for example, 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 including a metal alkoxide-based compound and water. The sol-gel reaction may be performed by a method similar to the above-described method for preparing an alkoxysilane-based oligomer. 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. In this case, in consideration of reaction efficiency, etc., the molar ratio of the metal alkoxide compound to water (based on metal ions) may be adjusted within the 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 made, in which moisture moves from a high place to a low water vapor pressure through the film, for example, the low moisture permeability polymer film is 30 to At a temperature of 40° C. and 90 to 100% relative humidity, the moisture permeability is 50 g/m ² ·day or less, 30 g/m ² ·day or less, 20 g/m ² ·day or less, or 15 g/m ² · It can be less than one day. When the moisture permeability of the low moisture-permeable polymer film ^{exceeds 10 g/m 2} ·day, moisture permeates into the anti-reflection film, which may cause deterioration of the display to which the anti-reflection film is applied in a high-temperature environment.

As described above, the 2θ value of the first peak and the second peak may be due to the crystal state of the polymer in the low moisture permeability polymer film, and the first for the intensity (P2) of the second peak The intensity (P1) ratio of the peak may be due to the degree of alignment of the polymer crystals in the low moisture permeability polymer film.

In addition, the degree of alignment of the polymer crystals in the low moisture permeability polymer film is related to the draw ratio, the stretching temperature and the cooling rate after stretching in the manufacturing process of the low moisture permeability polymer film, and also in one direction of the low moisture permeability polymer film and the It may be related to the ratio of tensile strength between one direction and the perpendicular direction.

Specifically, the low moisture permeability polymer film shows different values of tensile strength in one direction and in a direction perpendicular to the one direction, for example, with respect to the tensile strength in one direction, the tensile strength in the 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 the one direction has a smaller value than the tensile strength in the direction perpendicular to the one direction. When the tensile strength ratio is less than 2, the reflectance and transmittance for each part of the anti-reflection film may have large variations, 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 permeability polymer film, and 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 permeability polymer film, and specifically may be 30Mpa to 1Gpa, 40Mpa to 900Mpa, or 50Mpa to 800Mpa.

The low moisture permeability polymer film has a retardation (Rth) in the thickness direction measured at a wavelength of 400 nm to 800 nm. 5,000 nm or more, 7,000 to 50,000 nm, or 8,000 to 40,000 nm. Specific examples of the low moisture permeability polymer film include a uniaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene terephthalate film.

If the retardation (Rth) in the thickness direction of the low moisture permeability polymer film is less than 5,000 nm, the reflectance and transmittance deviation for each part 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 a measuring apparatus of retardation of thickness direction, the brand name "AxoScan (AxoScan) etc. by the AXOMETRICS company is mentioned.

For example, as the measurement conditions for retardation in the thickness direction, after inputting a refractive index (589 nm) value to the measurement device for the light transmissive base film, temperature: 25 ° C., humidity: 40% under conditions, The retardation in the thickness direction of the light-transmitting base film was measured using the light of wavelength 590nm, and based on the retardation measured value (measured value by automatic measurement (automatic calculation) of a measuring apparatus) in the thickness direction obtained, the film It can be obtained by converting it into a retardation value per 10 μm in thickness. In addition, the size of the light-transmitting substrate of the measurement sample is not particularly limited, since it may be larger than the light metering part (diameter: about 1 cm) of the stage of the measuring instrument, but it can be set to a size of 76 mm in length, 52 mm in width, and 13 μm in thickness. .

In addition, the value of "refractive index (589 nm) of the said light transmissive base material" used for the measurement of retardation in the thickness direction is the same as the light transmissive base material which forms the film used for retardation measurement. After forming the stretched film, this 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 the refractive index is measured as a measurement device. Using an apparatus (trade name "NAR-1T SOLID" manufactured by Atago Corporation), using a light source of 589 nm, and at a temperature of 23°C, 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 at 589 nm.

In addition, the material of the low moisture permeability polymer base 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 μm in consideration of productivity, but is not limited thereto.

The anti-reflection film of the embodiment may exhibit a low reflectance, thereby realizing high transmittance and excellent optical properties. Specifically, the anti-reflection 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% to It may have an average reflectance of 0.5%.

In addition, the anti-reflection film of the exemplary embodiment exhibits low reflectance deviation and transmittance deviation, thereby implementing excellent optical properties. Specifically, the average reflectance deviation of the anti-reflection 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 anti-reflection 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 means 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 anti-reflection film and the average value of the average reflectance . As a method of calculating the average reflectance deviation, specifically, 1) two or more points are selected in the anti-reflection film, 2) the average reflectance is measured at the two or more points, respectively, 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), it is possible to finally calculate the deviation of two or more average reflectances. In this case, the average reflectance deviation having the largest value among the deviations of the two or more average reflectance may be 0.2%p or less.

On the other hand, the transmittance deviation means the difference (absolute value) between the transmittance of two or more specific portions (points) selected in the anti-reflection film and the average value of the transmittance, and the transmittance is measured instead of measuring the average reflectance. 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, the transmittance deviation having the largest value among the two or more 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 anti-reflection 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. A 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 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 viewer 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 that is relatively far from the backlight unit among the 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 anti-reflection film provided on an opposite surface of the polarizer in contact with the panel.

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

1 is an X-ray diffraction (XRD) pattern for the anti-reflection film of Example 1. FIG.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

Preparation Example 1: Preparation of a coating solution for forming a hard coating layer

The components shown in Table 1 were mixed and mixed to prepare coating solutions (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

PETA: pentaerythritol triacrylate

UA-306T: Reaction product of toluene diisocyanate and pentaerythritol triacrylate as urethane acrylate (Kyoeisha)

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

IRG-184: Initiator (Irgacure 184, Ciba)

Tego-270: Tego leveling agent

BYK350: BYK company leveling agent

IPA isopropyl alcohol

XX-103BQ (2.0㎛ 1.515): Polystyrene and polymethyl methacrylate copolymer particles (Sekisui Plastics)

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

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 (Nissan Chemical)

Preparation Example 2-1: Preparation of a coating solution (C1) for forming a low refractive index layer

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

Preparation Example 2-2: Preparation of a coating solution (C2) for forming a low refractive index layer

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

<Examples and Comparative Examples: Preparation of anti-reflection film>

Each of the prepared coating solutions (B1, B2, B3) for forming a hard coating layer (B1, B2, B3) on each of the low moisture permeability polymer films (thickness 80 μm) described in Table 2 below were coated with #12 mayer bar and then 2 at a temperature of 60 ℃ Minute drying and UV curing to form a hard coating layer (coating thickness is 5㎛). The UV lamp used H bulb, and the curing reaction was carried out under a nitrogen atmosphere. The amount of UV light irradiated during curing is 100mJ/cm ² .

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

anti-reflection film Tensile strength ratio ^* hard coating layer low refractive index Example 1 4.1 Coating liquid (B1) Coating solution (C1) Example 2 3.7 Coating liquid (B2) Coating solution (C1) Example 3 3.1 Coating liquid (B2) Coating solution (C1) Example 4 2.7 Coating liquid (B3) Coating solution (C1) Example 5 2.3 Coating liquid (B1) Coating liquid (C2) Comparative Example 1 1.9 Coating liquid (B3) Coating solution (C1) Comparative Example 2 1.5 Coating liquid (B2) Coating solution (C1) Comparative Example 3 1.2 Coating liquid (B2) Coating solution (C1) Comparative Example 4 1.7 Coating liquid (B1) Coating liquid (C2)

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

evaluation

1. X-ray diffraction (XRD) evaluation of reflection mode

After preparing a sample with a size of 2 cm * 2 cm (horizontal * vertical) with respect to the anti-reflection film obtained in Examples and Comparative Examples, Cu-Kα rays with a wavelength of 1.54 Å were irradiated to form an X-ray diffraction (XRD) pattern in reflection mode. was measured.

Specifically, the sample was prepared by fixing it so that it would not float on a low background Si holder (Bruker, Inc.), and the measuring equipment was a Bruker AXS D4 Endeavor XRD. The voltage and current used are 40 kV and 40 mA, respectively, and the optics and detector used are as follows.

-Primary (incident beam) optics: motorized divergence slit, soller slit 2.3°

-Secondary (diffracted beam) optics: soller slit 2.3°

-LynxEye detector (1D detector)

The measurement mode is a coupled 2θ/θ mode, and using FDS (Fixed Divergence Slit) 0.3°, a region having a 2θ value from 6° to 70° was measured every 0.04° for 175 seconds.

Then, when a peak appears between 2θ values of 22 to 27°, the 2θ values are shown in Table 3 below. In addition, when two peaks appear between 2θ values of 22 to 27°, the ratio of the intensity of the peak with a relatively large 2θ value to the intensity of the peak with a relatively large 2θ value is calculated, and the results are shown in Table 3 described in.

Meanwhile, FIG. 1 is an X-ray diffraction (XRD) pattern of the antireflection film of Example 1. As shown in FIG.

2. Average reflectance evaluation

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

3. Evaluation of deviations in average reflectance

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

4. Evaluation of Transmittance Deviation

For the antireflection films obtained in Examples and Comparative Examples, 20 arbitrary points were selected, and transmittance was measured for each point.

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

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

5. Water vapor permeability evaluation

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

Peak (°) Peak Intensity Ratio ^* Average Reflectance (%) Average reflectance deviation (%p) Transmittance deviation (%p) Water vapor permeability (g/m ² day) Example 1 22.9 / 25.6 0.66 1.1 0.05 0.03 10.75 Example 2 22.8 /26.0 0.71 1.3 0.13 0.08 11.78 Example 3 22.9 /25.6 0.63 1.15 0.08 0.02 11.98 Example 4 22.8 /25.8 0.59 1.05 0.15 0.1 12.24 Example 5 23.1 / 25.7 0.91 1.6 0.03 0.15 11.81 Comparative Example 1 25.7 - 1.11 0.3 0.28 10.49 Comparative Example 2 - - 1.04 0.26 0.23 10.54 Comparative Example 3 - - 0.99 0.28 0.3 11.38 Comparative Example 4 25.8 - 1.51 0.33 0.25 12.01

* Peak intensity ratio: when two peaks appear between 2θ values of 22 to 27°, the ratio of the intensity of the peak with a relatively small 2θ value to the intensity of the peak with a relatively large 2θ value

According to Table 3, in Examples 1 to 5, peaks appear at 2θ values of 22 to 24° and 2θ values of 24 to 27°, respectively, and the peak intensity ratio is 0.4 or more, and, in addition, compared to Comparative Examples 1 to 4 It was confirmed that the average reflectance deviation and transmittance deviation were significantly low.

Claims (15)

low moisture permeability polymer film; hard coating layer; and a low refractive layer,
The average reflectance deviation is 0.2%p or less,
The light transmittance deviation is 0.2%p or less,
An average reflectance of 2.0% or less in a wavelength range of 380 nm to 780 nm,
anti-reflection film.
According to claim 1,
The anti-reflection film has a first peak at a 2θ value of 22 to 24° in an X-ray diffraction (XRD) pattern of a reflection mode, and a second peak appears at a 2θ value of 24 to 27°. anti-film.
3. The method of claim 2,
The ratio of the intensity (P1) of the first peak to the intensity (P2) of the second peak is 0.4 or more.
According to claim 1,
The low-refractive layer includes a binder resin, and inorganic fine particles dispersed in the binder resin, anti-reflection film.
5. The method of claim 4,
The binder resin is an antireflection film comprising a (co)polymer of a photopolymerizable compound.
6. The method of claim 5,
The binder resin further comprises a crosslinked polymer between a photopolymerizable compound, a fluorine-containing compound including a photoreactive functional group, and polysilsesquioxane substituted with one or more reactive functional groups.
7. The method of claim 6,
The fluorine-containing compound including the photoreactive functional group includes: i) an aliphatic compound or an aliphatic ring 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 heteroaliphatic compound or a heteroaliphatic ring compound substituted with one or more photoreactive functional groups, wherein at least one hydrogen is substituted with fluorine and one or more carbons are substituted with silicon; iii) a polydialkylsiloxane-based polymer in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicone; and iv) a polyether compound substituted with one or more photoreactive functional groups and wherein at least one hydrogen is substituted with fluorine.
7. The method of claim 6,
The reactive functional group substituted for the polysilsesquioxane is from the group consisting of alcohol, amine, carboxylic acid, epoxide, imide, (meth)acrylate, nitrile, norbornene, olefin, polyethylene glycol, thiol and vinyl group. An antireflection film comprising at least one selected functional group.
5. The method of claim 4,
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, anti-reflection film.
According to claim 1,
The hard coating layer is a binder resin comprising a photocurable resin, and organic or inorganic fine particles dispersed in the binder resin; Containing, an anti-reflection film.
11. The method of claim 10,
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, antireflection film.
According to claim 1,
The low moisture permeability 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 the direction perpendicular to the one direction to the tensile strength in one direction is 2 or more,
The tensile strength in the one direction has a value smaller than the tensile strength in the direction perpendicular to the one direction, the anti-reflection film.
According to claim 1,
The low moisture permeability polymer film is a polyethylene terephthalate film, an antireflection film.
A polarizing plate comprising the antireflection film according to claim 1 and a polarizer.
A display device comprising the anti-reflection film according to claim 1 .

Images