KR102363875B1 - 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 and increasing screen clarity of a display device, a polarizing plate including the same, and a display device.

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 polarizer and a display device.

In general, flat panel display devices such as PDPs and LCDs are equipped with an anti-reflection film to minimize 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 screen clarity due to surface irregularities, a lot of research on AR coating has been recently made.

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, this method of forming a plurality of layers 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 antireflection 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 reflectivity 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 have been made to improve the anti-soiling properties as well as scratch resistance of the surface while reducing the absolute reflection amount of light incident from the outside, but the degree of improvement in physical properties is insufficient.

An object of the present invention is to provide an anti-reflection film capable of simultaneously implementing high scratch resistance and antifouling properties and increasing 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 this specification, hard coating layer; and a (co)polymer of a photopolymerizable compound, a hollow inorganic particle, and a low refractive layer comprising a fluorine-containing compound including a photoreactive functional group, wherein the content of the hollow inorganic particles relative to the total weight of the low refractive layer is 29 to 60% by weight, the content of the fluorine-containing compound including the photoreactive functional group with respect to the total weight of the low refractive layer is 1 to 9% by weight, the content (F) of the fluorine-containing compound including the photoreactive functional group and the hollow type There is provided an antireflection film in which the content (V) of inorganic particles satisfies Equation 1 below.

[Equation 1]

F ≥ 0.26V-6.11

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

In the present specification, the low-refractive layer may mean a layer having a low refractive index, for example, may mean a layer having a refractive index of about 1.2 to 1.6 at a wavelength of 550 nm.

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

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

According to one embodiment of the invention, a hard coating layer; and a (co)polymer of a photopolymerizable compound, a hollow inorganic particle, and a low refractive layer comprising a fluorine-containing compound including a photoreactive functional group, wherein the content of the hollow inorganic particles relative to the total weight of the low refractive layer is 29 to 60% by weight, the content of the fluorine-containing compound including the photoreactive functional group with respect to the total weight of the low refractive layer is 1 to 9% by weight, the content of the fluorine-containing compound including the photoreactive functional group (F) and the hollow type An antireflection film having an inorganic particle content (V) satisfying Equation 1 below may be provided.

[Equation 1]

F ≥ 0.26V-6.11

Accordingly, the present inventors conducted research on the anti-reflection film, and the anti-reflection film containing the fluorine-containing compound including the hollow inorganic particles and the photoreactive functional group in a specific content can simultaneously implement high scratch resistance and antifouling properties, The point of having the clarity of the screen of the display device was confirmed through an experiment and the invention was completed.

In addition, the anti-reflection film 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 limitation to a display device or a polarizing plate manufacturing process.

Specifically, the antireflection film according to the exemplary embodiment includes a hard coating layer and a low refractive index layer, and the low refractive index layer includes a (co)polymer of a photopolymerizable compound, a hollow inorganic particle, and a photoreactive functional group. It may contain a fluorine compound.

The content of the hollow inorganic particles with respect to the total weight of the low refractive layer may be 29 to 60% by weight, 30 to 55% by weight, or 35 to 50% by weight. If the content of the hollow inorganic particles is less than 29% by weight, it may be difficult to obtain a low-reflection effect, and if it exceeds 60% by weight, too many irregularities are formed on the surface of the low refractive index layer, and the surface area increases, so it may be difficult to have excellent antifouling properties.

The content of the fluorine-containing compound including the photoreactive functional group with respect to the total weight of the low refractive layer may be 1 to 9 wt%, 2 to 8 wt%, or 3 to 7 wt%. The fluorine-containing compound including the photoreactive functional group serves to improve the antifouling property by imparting slip property to the surface of the low refractive index layer. The effect of cannot be obtained, and when it exceeds 9% by weight, the fluorine-containing compound content is relatively high on the surface of the low-refractive layer, and the conversion rate of the photopolymerizable compound into the (co)polymer on the surface of the low-refractive layer is lowered. can occur

In addition, the content (F) of the fluorine-containing compound including the photoreactive functional group and the content (V) of the hollow inorganic particles may satisfy Equation 1 below.

[Equation 1]

F ≥ 0.26V-6.11

The content of the fluorine-containing compound including the photoreactive functional group is 29 to 60% by weight based on the total weight of the low refractive layer, and the content of the fluorine-containing compound including the photoreactive functional group is 1 to 9 based on the total weight of the low refractive layer At the same time, since the content of the fluorine-containing compound including the photoreactive functional group and the hollow inorganic particles satisfies Equation 1, excellent antifouling and scratch resistance can be implemented, and the visible light wavelength range of 380 nm to 780 nm An average reflectance of 2% or less in the area may be exhibited to increase the sharpness of the screen of the display device.

The low-refractive layer of the anti-reflection film according to the embodiment is a binder resin including a (co)polymer of the photopolymerizable compound and a fluorine-containing compound including the photoreactive functional group, and a hollow type dispersed in the binder resin. It may contain inorganic particles.

The photopolymerizable compound forming the (co)polymer of the photopolymerizable compound may include (meth)acrylate or a monomer or oligomer including a 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 containing 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 oligomers, ether acrylate oligomers, dendritic acrylate oligomers, or mixtures 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.

The content of the (co)polymer of the photopolymerizable compound derived from the photopolymerizable compound with respect to the total weight of the low refractive layer is not particularly limited, but considers the mechanical properties of the finally manufactured low refractive layer or antireflection film. Thus, the content of the (co)polymer of the photopolymerizable compound may be 10 to 80% by weight, 15 to 70% by weight, 20 to 60% by weight, or 30 to 50% by weight. When the content of the (co)polymer of the photopolymerizable compound is less than 10% by weight, an empty space between inorganic particles is formed, and the periodicity of the arrangement between particles is lost, thereby inducing a decrease in the packing density of the particles, which causes stress (stress) Scratch resistance may decrease because dispersion does not occur smoothly. When the content of the (co)polymer of the photopolymerizable compound exceeds 80% by weight, the conversion ratio of the photopolymerizable compound to the (co)polymer may be low.

On the other hand, the hollow inorganic particle means a particle having an empty space on its surface and/or inside.

The hollow inorganic particles may have an average diameter of 10 to 200 nm, 15 to 150 nm, 20 to 130 nm, 30 to 110 nm, or 40 to 100 nm. If the average diameter of the hollow inorganic particles is less than 10 nm, the amount of air contained in the hollow inorganic particles itself may decrease, making it difficult to implement a low refractive index, and if it exceeds 200 nm, excessively large irregularities are formed on the surface of the low refractive index layer It is difficult to implement antifouling and scratch resistance, and a problem in that the thickness of the low refractive index layer is inevitably increased may occur.

As the hollow inorganic particles, those coated with a fluorine-containing compound including the photoreactive functional group on the surface may be used alone. Alternatively, a mixture of the hollow inorganic particles coated with the fluorine-containing compound including the photoreactive functional group and the hollow inorganic particles having an uncoated surface may be used. If the surface of the hollow inorganic particles is coated with a fluorine-containing compound including the photoreactive functional group, the surface energy can be lowered, thereby improving the antifouling property of the low refractive layer, and also, the durability or The scratch resistance can be further improved.

As a method of coating a fluorine-containing compound containing a photoreactive functional group on the surface of the hollow inorganic particles, a particle coating method or a polymerization method, which is commonly known, can be used without major limitation, for example, the hollow inorganic particles and the photoreactivity A fluorine-containing compound including a functional group may be subjected to a sol-gel reaction in the presence of water and a catalyst to bind the fluorine-containing compound including a photoreactive functional group to the surface of the hollow inorganic particle through hydrolysis and condensation reaction.

Specific examples of the hollow inorganic particles may include hollow silica particles. The hollow silica particles 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.

As described above, the content of the hollow inorganic particles relative to the total weight of the low refractive layer may be 29 to 60% by weight, 30 to 55% by weight, or 35 to 50% by weight. If the content of the hollow inorganic particles is less than 29% by weight, it may be difficult to obtain a low-reflection effect, and if it exceeds 60% by weight, too many irregularities are formed on the surface of the low refractive index layer, and the surface area increases, so it may be difficult to have excellent antifouling properties.

In addition, since the hollow inorganic particles satisfy the content relationship satisfying Formula 1 with the fluorine-containing compound including the photoreactive functional group, excellent antifouling properties and excellent scratch resistance can be realized at the same time, 380 An average reflectance of 2% or less in a visible light wavelength range of nm to 780 nm may be exhibited, thereby increasing the clarity of the screen of the display device.

The low refractive index layer may include solid inorganic particles. The solid inorganic particles refer to particles having no empty space therein. By including the solid inorganic particles in the low refractive layer, even if a smaller amount of the hollow inorganic particles are used, the reflectance of the antireflection film may be lowered, and scratch resistance and antifouling properties may be improved. The solid inorganic particles may have an average diameter of 0.5 to 100 nm, 1 to 50 nm, 2 to 30 nm, or 5 to 20 nm.

On the other hand, each of the solid inorganic particles and the hollow inorganic particles has at least one reactive functional group selected from the group consisting of a (meth)acrylate group, an epoxide group, a vinyl group and a thiol group. may contain. As each of the solid inorganic particles and the hollow inorganic particles contains the above-described reactive functional group on the surface, the low refractive layer may have a higher degree of crosslinking, thereby securing improved scratch resistance and antifouling properties. have.

Based on 100 parts by weight of the hollow inorganic particles, the content of the solid inorganic particles may be 1 to 50 parts by weight, 2 to 40 parts by weight, 3 to 35 parts by weight, or 5 to 30 parts by weight. When the hollow inorganic particles are added in excess, the scratch resistance or abrasion resistance of the coating film may be deteriorated due to a decrease in the binder content.

The low refractive layer includes a fluorine-containing compound including a photoreactive functional group, and due to the characteristics of elemental fluorine included in the fluorine-containing compound including a photoreactive functional group, the antireflection film has an interaction energy with respect to liquids or organic materials can be lowered, thereby greatly reducing the amount of contaminants transferred to the anti-reflection film, as well as preventing the transferred contaminants from remaining on the surface, and the contaminants themselves can be easily removed have the characteristics

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 or ultraviolet rays. It means that there is 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.

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.

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 or 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, if 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 anti-reflection film may be increased or the light transmittance may be lowered, and the strength of the low refractive layer and the anti-reflection film is also can be lowered

Specifically, 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 (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 in which at least one hydrogen is substituted with fluorine.

As described above, the content of the fluorine-containing compound including the photoreactive functional group with respect to the total weight of the low refractive layer may be 1 to 9% by weight, 2 to 8% by weight, or 3 to 7% by weight. If the content of the fluorine-containing compound including the photoreactive functional group is less than 1% by weight, the antifouling effect cannot be obtained, and when it exceeds 9% by weight, the fluorine-containing compound content is relatively high on the surface of the low-refractive layer, and the surface of the low-refractive layer There may be a problem in that the conversion rate at which the photopolymerizable compound is converted into a (co)polymer is lowered.

In addition, since the fluorine-containing compound including the photoreactive functional group satisfies the content relationship satisfying Formula 1 with the hollow inorganic particles, excellent antifouling properties and excellent scratch resistance can be realized at the same time, 380 nm An average reflectance of 2% or less in a visible ray wavelength range of from to 780 nm may be exhibited, thereby increasing the clarity of the screen of the display device.

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, thereby preventing haze from occurring 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 low refractive index layer or the anti-reflection film finally manufactured.

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.

The low refractive index layer may include polysilsesquioxane in which one or more reactive functional groups are substituted. 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 fine particles of silica, alumina, zeolite, etc. known before Unlike the case of using particles, it is possible to improve alkali resistance of the low-refractive layer, and to improve appearance characteristics such as average reflectance and color.

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. For example, in order to improve the physical properties and quality of the low refractive index layer and the anti-reflection film, polysilsesquioxane in which one or more reactive functional groups are substituted with one or more reactive functional groups is substituted with polyhedral oligomers having a cage structure Silsesquioxane (Polyhedral Oligomeric Silsesquioxane) can be used.

In addition, for example, the polyhedral oligomeric 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 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, for example, may be 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 the 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 substituted with one or more reactive functional groups 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 other than 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 such, 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 being 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 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. substituted with 1 or more amines; 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)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 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 content of polysilsesquioxane in which one or more reactive functional groups are substituted with respect to the total weight of the low refractive layer may be 1 to 20 wt%, 3 to 15 wt%, or 5 to 10 wt%. When the content of the moiety derived from polysilsesquioxane substituted with one or more reactive functional groups is too small, it may be difficult to sufficiently secure scratch resistance of the low refractive index layer. 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 transparency of the low refractive index layer or the antireflection film is may be lowered, and scratch resistance may be rather deteriorated.

On the other hand, the low refractive layer is a photopolymerizable compound, a fluorine-containing compound including a photoreactive functional group, a photocurable coating composition comprising polysilsesquioxane substituted with one or more reactive functional groups and hollow inorganic particles on a substrate, and It can be obtained by photocuring the applied result. For this reason, the low refractive index layer may include a cross-linked 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.

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 major 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 is 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 in drying and curing processes. 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 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 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 may be 100 to 4,000 mJ/cm 2 . Exposure time is not specifically limited, either, It can change suitably according to the exposure apparatus used, the wavelength of irradiation light, or 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 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 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

Although the organic or inorganic fine particles are not specifically limited in particle size, for example, the organic fine particles may have a particle size of 1 to 10 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 may further include a high molecular weight (co)polymer having a weight average molecular weight 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 sulfuric acid 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.

In addition, as the antistatic agent, a conductive polymer and metal oxide 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, aluminum-doped zinc oxide, and the like.

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 at least one compound selected from the group consisting of alkoxysilane-based oligomers and metal alkoxide-based oligomers.

The alkoxysilane-based compound may be conventional in the art, 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 method for preparing an 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 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 antireflection film according to the exemplary embodiment may further include a light-transmitting substrate positioned on one surface of the hard coating layer to face the low refractive index layer.

The light-transmitting substrate may be a transparent film having a light transmittance of 90% or more and a haze of 1% or less. In addition, the light-transmitting substrate may include a cycloolefin polymer film, a poly(meth)acrylate-based film, a polycarbonate film, a triacetyl cellulose (TAC) film, a polynorbornene film, a polyester film, and At least one selected from the group consisting of a polyethylene terephthalate (PET) film may be included. In addition, the thickness of the light-transmitting substrate may be 10 to 300 μm in consideration of productivity and the like, but is not limited thereto.

Specifically, the light-transmitting substrate may have a retardation (Rth) in the thickness direction measured at a wavelength of 400 nm to 800 nm of 3,000 nm or more, 4,000 to 50,000 nm, or 5,000 to 40,000 nm. Specific examples of the light-transmitting substrate include a uniaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene terephthalate film. When the retardation (Rth) in the thickness direction of the light-transmitting substrate is less than 3,000 nm, 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 the 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 substrate, temperature: 25°C, humidity: 40%, wavelength The retardation in the thickness direction of the light-transmitting base film was measured using 590 nm light, and based on the obtained retardation measurement value in the thickness direction (measured value by automatic measurement (automatic calculation) of the measuring device), the film It can be calculated|required by converting into the retardation value per 10 micrometers 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 that of 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 measuring device Using an apparatus (trade name "NAR-1T SOLID" manufactured by Atago Corporation), using a 589 nm light source, and under a temperature condition 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.

The antireflection film of the exemplary embodiment may exhibit a relatively low reflectance and an overall haze value to realize high light transmittance and excellent optical properties. Specifically, the total haze of the antireflection film may be 0.45% or less, 0.05 to 0.45%, or 0.10% to 0.25% or less. In addition, the anti-reflection film has an average reflectance of 2.0% or less, 1.5% or less, 1.0% or less, or 0.1% to 0.10%, 0.40% to 0.80%, or 0.54% or less in a visible light wavelength band of 380 nm to 780 nm. It may have an average reflectance of 0.69%.

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, there is provided an anti-reflection film capable of simultaneously implementing high scratch resistance and anti-fouling properties and increasing the screen clarity of the display device, a polarizing plate including the anti-reflection film, and a display device including the anti-reflection film can do.

1 is a photograph of the antifouling property evaluation result of Example 2 taken with an optical microscope.
2 is a photograph taken with an optical microscope of the antifouling property evaluation result of Comparative Example 1.
3 is a photograph taken with an optical microscope of the antifouling property evaluation result of Comparative Example 4.

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.

production example 1: Preparation of a coating solution for forming a hard coating layer

Pentaerythritol triacrylate 16.421 g, UA-306T (urethane acrylate, a reaction product of toluene diisocyanate and pentaerythritol triacrylate, manufactured by Kyoeisha) 3.079 g, 8BR-500 (photocurable urethane acrylate polymer, Mw 200,000, Taisei) Fine Chemicals) 6.158 g, IRG-184 (initiator, Ciba) 1.026 g, Tego-270 (leveling agent, Tego) 0.051 g, BYK350 (leveling agent, BYK) 0.051 g, 2-butanol 25.92 g, iso Propyl alcohol 45.92g, XX-103BQ (copolymerized particles of polystyrene and polymethylmethacrylate, Sekisui Plastics, particle size 2.0㎛, refractive index 1.515) 0.318g, XX-113BQ (copolymerized particles of polystyrene and polymethylmethacrylate, Sekisui Plastic product, particle size 2.0㎛, refractive index 1.555) 0.708g, and MA-ST (dispersion solution in which nano silica particles with a size of 10-15 nm are dispersed in methyl alcohol, Nissan Chemical product, 30% in MeOH) 0.342g were mixed and mixed. A coating solution for forming a hard coat layer was prepared.

production example 2: low refractive index Preparation of coating solution for forming

The components shown in Table 1 were mixed and mixed to prepare a coating solution (C1 to C9) for forming a low refractive index layer.

(Unit: g) C1 C2 C3 C4 C5 C6 C7 TMPTA 0.107 0.127 0.149 0.1068 0.132 0.163 0.091 Hollow Silica Particle Dispersion (20% in MIBK) 0.7 0.9 0.84 0.7 0.9 0.84 1.10 Solid silica particle dispersion (40.6% in MIBK) 0.333 0.261 0 0.333 0.261 0 0 KBM-5103 0.084 0.054 0 0.084 0.054 0 0 RS-923 Dispersion
(40% in MIBK) 0.024 0.039 0.064 0.0179 0.026 0.027 0.083 Irgacure 127 0.005 0.03 0.02 0.005 0.03 0.02 0.02 MIBK 2.87 4 3.827 2.87 4.01 3.96 3.34 DAA 0.754 1.004 0.804 0.6767 1.023 0.663 1.045 IPA 5.532 6.997 6.202 5.493 7.006 6.192 5.673 2-BuOH 0 0 3.20 0 0 3.20 2.90 t-BuOH 0 3.66 0 3.33 3.66 0 0

TMPTA: Trimethylolpropane triacrylate hollow silica particle dispersion: about 42 nm to 66 nm in diameter, manufactured by JSC catalyst and chemicals (20% in MIBK)

Solid silica particle dispersion: about 12 nm to 19 nm in diameter (40.6% in MIBK)

KBM-5103: Silane coupling agent, Shin-Etsu Silicone

RS-923 Dispersion: Fluorine-containing compound, DIC (40% in MIBK)

Irgacure 127: photopolymerization initiator, Ciba

MIBK: methyl isobutyl ketone

DAA: Diacetone alcohol

IPA: Isopropyl alcohol

2-BuOH: 2-Butanol

t-BuOH: tert-Butanol

< Example and comparative example : Preparation of anti-reflection film>

Polyethylene terephthalate (thickness 2㎛, SRF PET, Toyobo Co.) was coated with the coating solution for forming the hard coat layer of Preparation Example 1 and dried to form a hard coat layer, and the low refractive index layer described in Table 2 below was formed on the hard coat layer An anti-reflection film was prepared by coating and drying the coating solution.

Specifically, after coating the prepared coating solution for forming a hard coating layer on the polyethylene terephthalate with #12 mayer bar, drying at a temperature of 60° C. for 2 minutes, and UV curing to obtain a hard coating layer (coating thickness is 5 μm) formed 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 48mJ/cm ² .

On the hard coating layer, the coating solution (C1 to C7) for forming the low refractive index layer was coated to have a thickness of about 110 to 120 nm with #4 mayer bar, and dried and cured at a temperature of 90° C. for 1 minute. During the curing, the dried coating solution was irradiated with ultraviolet rays of 294 mJ/cm 2 under nitrogen purge.

evaluation

1. Average reflectance evaluation

The average reflectance of the antireflection films obtained in Examples and Comparative Examples in the visible light region (380 to 780 nm) was measured using Solidspec 3700 (SHIMADZU) equipment, and the results are shown in Table 2 below.

2. Antifouling evaluation

On the surface of the anti-reflection film obtained in Examples and Comparative Examples, a straight line was drawn under a load of 50 g using a black name pen (for medium text) from Monami Corporation, and dewetting droplets formed using an optical microscope (Olympus, BX51) ) was measured 10 or more times, and the antifouling property was determined based on the following arithmetic mean value, and the results are shown in Table 2 below.

On the other hand, FIGS. 1 to 3 are photographs taken with an optical microscope of the antifouling property evaluation results of Examples 2 and Comparative Examples 1 and 4, respectively.

<Judgment Criteria>

○: The arithmetic mean value of the spacing between dewetting droplets exceeds 200 μm

△: The arithmetic mean value of the spacing between dewetting droplets is 200 μm or less and exceeds 50 μm

X: The arithmetic mean value of the spacing between dewetting droplets is 50 μm or less, or there is no dewetting

low refractive index Average Reflectance (%) antifouling Example 1 Coating liquid (C1) 1.41 ○ Example 2 Coating liquid (C2) 1.39 ○ Example 3 Coating liquid (C3) 1.26 ○ Comparative Example 1 Coating liquid (C4) 2.23 △ Comparative Example 2 Coating liquid (C5) 1.43 △ Comparative Example 3 Coating liquid (C6) 1.41 X Comparative Example 4 Coating liquid (C7) 1.16 X

According to Table 2, Examples 1 to 3 had a low average reflectance of 1.41% or less, and it was confirmed that the antifouling property was remarkably excellent compared to Comparative Examples 1 to 4.

Claims (13)

hard coating layer; and
A (co)polymer of a photopolymerizable compound, a hollow inorganic particle, and a low refractive layer comprising a fluorine-containing compound including a photoreactive functional group;
The content of the hollow inorganic particles with respect to the total weight of the low refractive layer is 29 to 50% by weight,
The content of the fluorine-containing compound including a photoreactive functional group with respect to the total weight of the low refractive layer is 1 to 7% by weight,
An antireflection film, wherein the content (F) of the fluorine-containing compound including the photoreactive functional group and the content (V) of the hollow inorganic particles satisfy Equation 1 below:
[Equation 1]
F ≥ 0.26V-6.11
According to claim 1,
The average diameter of the hollow inorganic particles is 10 to 200 nm, anti-reflection film.
According to claim 1,
The low refractive layer includes solid inorganic particles,
The content of the solid inorganic particles with respect to 100 parts by weight of the hollow inorganic particles is 1 to 50 parts by weight, anti-reflection film.
According to claim 1,
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 wherein 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 wherein 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 silicone is substituted with at least one fluorine; and iv) a polyether compound substituted with one or more photoreactive functional groups and wherein at least one hydrogen is substituted with fluorine.
According to claim 1,
The low refractive index layer further comprises a cross-linked polymer between a photopolymerizable compound, a fluorine-containing compound including a photoreactive functional group, and polysilsesquioxane substituted with one or more reactive functional groups.
6. The method of claim 5,
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.
According to claim 1,
The low refractive index layer further comprises a photoinitiator, anti-reflection film.
According to claim 1,
The hard coating layer includes a binder resin including a photocurable resin, and organic or inorganic fine particles dispersed in the binder resin.
According to claim 1,
The anti-reflection film further comprising a light-transmitting substrate positioned on one surface of the hard coating layer to face the low-refractive layer.
10. The method of claim 9,
The light-transmitting substrate is a cycloolefin polymer film, a poly (meth) acrylate film, a polycarbonate film, a triacetyl cellulose (TAC) film, a polynorbornene (polynorbornene) film, a polyester film, and polyethylene tere An anti-reflection film comprising at least one selected from the group consisting of phthalate (PET) films.
According to claim 1,
The anti-reflection film exhibits an average reflectance of 2% or less in a visible light wavelength region of 380 nm to 780 nm.
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