KR101973197B1 - Anti-reflective film - Google Patents

Abstract

The present invention, a hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, wherein the ratio of the particle diameter of the solid particles to the particle diameter of the hollow particles is 0.26 to 0.55. It relates to an antireflection film.

Description

Anti-reflective film {ANTI-REFLECTIVE FILM}

The present invention relates to an anti-reflection film, and more particularly, to an anti-reflection film that can simultaneously realize high scratch resistance and antifouling property while having a low reflectance and a high light transmittance, and can increase the sharpness of a screen of 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 the reflection of light, a method of dispersing a filler such as inorganic fine particles in a resin is coated on a base film and imparts irregularities (anti-glare: AG coating); There are a method of forming a plurality of layers having different refractive indices on the base film to use interference of light (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 may be obtained by reducing the amount of light entering the eye by scattering light through unevenness. However, since the AG coating has poor screen clarity due to surface irregularities, many studies on AR coatings have recently been made.

As the film using the AR coating, a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film is commercialized. However, the method of forming a plurality of layers as described above has a disadvantage in that scratch resistance is inferior due to weak adhesion between the layers (interfacial adhesion) as the process of forming each layer separately.

In addition, in order to improve the scratch resistance of the low refractive layer included in the antireflection film, a method of adding various particles having a nanometer size (for example, particles of silica, alumina, zeolite, etc.) has been mainly attempted. However, in the case of using the nanometer size particles as described above, there was a limit that it is difficult to simultaneously increase the scratch resistance while reducing the reflectance of the low refractive index layer, and due to the nanometer size particles, the antifouling property of the low refractive layer surface is greatly increased. Degraded.

Accordingly, many studies have been made to reduce the absolute reflection amount of light incident from the outside and to improve the antifouling property together with the scratch resistance of the surface. However, the improvement of the physical properties is insufficient.

The present invention is to provide an anti-reflection film having a low reflectance and a high light transmittance and at the same time can implement a high scratch resistance and antifouling resistance and can increase the sharpness of the screen of the display device.

In the present specification, the hard coating layer; And a low refractive layer comprising a binder resin, hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, wherein the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.26 to 0.55, and at least 70% by volume of the total solid inorganic nanoparticles present within 50% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer is provided.

In addition, in the present specification, a hard coating layer containing a binder resin and organic or inorganic fine particles dispersed in the binder resin; And a low refractive layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, wherein the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.15 to 0.15. 0.55, and at least 70% by volume of the total solid inorganic nanoparticles is present within 50% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer.

Hereinafter, an antireflection film according to a specific embodiment of the present invention will be described in detail.

In the present specification, a photopolymerizable compound is collectively referred to as a compound that causes a polymerization reaction when light is irradiated, for example, visible light or ultraviolet light.

In addition, a fluorine-containing compound means the compound in which at least 1 or more fluorine element is contained in a compound.

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

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

Further, silica hollow particles are silica particles derived from a silicon compound or an organosilicon compound, and mean particles having a void space on the surface and / or inside of the silica particles.

According to one embodiment of the invention, the hard coating layer; And a low refractive layer comprising a binder resin, hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, wherein the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.26 to 0.55 and 70% by volume or more of the entire solid inorganic nanoparticles may be provided within 50% of the total thickness of the low refractive index layer from an interface between the hard coating layer and the low refractive index layer.

The average particle diameter of the hollow particles and the average particle diameter of the solid particles are average values obtained by measuring and calculating the particle diameters of the hollow particles and the solid particles, respectively, which are found in the TEM photograph (for example, 25,000 times magnification) of the antireflection film. Can be.

The present inventors have conducted research on the antireflection film, so that the antireflection film including the low refractive index layer including the hollow particles and the solid particles having the specific average particle diameter ratio described above has a lower reflectance and a high light transmittance and high scratch resistance. The experiment confirmed that the castle and antifouling can be implemented at the same time, and completed the invention.

Various factors influencing the distribution of the hollow particles and the solid particles in the manufacturing process of the low refractive index layer, for example, manufacturing conditions or the weight or density of the particles, etc. can be considered. When the difference in particle diameter is controlled at the above ratio, it was confirmed that the scratch resistance and the antifouling property can be realized while securing a lower reflectance in the antireflection film to be manufactured.

More specifically, the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles in the low refractive layer is less than 0.55, or 0.15 to 0.55, or 0.26 to 0.55, or 0.27 to 0.40, or 0.280 to 0.380 In the low refractive layer, the hollow particles and the solid particles may exhibit different localization and distribution patterns. For example, a position where the hollow particles and the solid particles are mainly distributed is between the hard coating layer and the low refractive layer. The distance may be different based on the interface.

As such, as the areas where the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, the low refractive layer may have a unique internal structure and an arrangement of components, thereby having a lower reflectance. In addition, as the area where the hollow particles and the solid particles are mainly distributed in the low refractive layer is changed, the surface characteristics of the low refractive layer are also changed, thereby improving scratch and antifouling properties.

On the contrary, when the difference between the particle diameters of the hollow particles and the solid particles included in the low refractive index layer is not so large, the hollow particles and the solid particles do not aggregate together or do not occur ubiquitous or distributed according to particle types. Not only is it difficult to significantly lower the reflectance of the prevention film, but it may be difficult to achieve the required scratch and antifouling properties.

As such, the inherent effects of the anti-reflection film of the embodiment, for example, having a low reflectance and a high light transmittance, can simultaneously realize high scratch resistance and antifouling property, and can improve the screen sharpness of the display device. It depends on the average particle diameter ratio between one hollow particle and a solid particle.

The solid inorganic nanoparticle refers to a particle having no empty space therein.

In addition, the hollow inorganic nanoparticles mean particles in the form of empty spaces on the surface and / or inside thereof.

As the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles described above is 0.55 or less, the antireflection film may have high reflectance and antifouling resistance while having a lower reflectance and a high light transmittance.

Hollow particles and solid particles having a predetermined average particle diameter may be used to more easily adjust the properties of such an antireflection film and to meet the properties required in the application field.

For example, in order for the anti-reflection film to have a lower reflectance and a high light transmittance, and to improve the scratch resistance and antifouling property, the average particle diameter of the hollow particles may be within a range of 40 nm to 100 nm. In addition, the average particle diameter of the solid particles may be within the range of 1 nm to 30 nm.

When the average particle diameter of the hollow particle and the solid particle satisfies the above-described ratio or the size range described above, the range of the specific particle size is not limited to a large extent. However, in order to have a more uniform and improved quality of the anti-reflection film, the particle diameter of the hollow particles may be within the range of 10 nm to 200 nm, or 30 nm to 120 nm, or 38 nm to 80 nm, The particle diameter of the solid particles may be within the range of 0.1 nm to 100 nm, or 0.5 nm to 50 nm, or 2 nm to 25 nm.

The diameter of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may refer to the longest diameter identified in the particle cross section.

Meanwhile, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may be selected from the group consisting of a hydroxyl group, a (meth) acrylate group, an epoxide group, a vinyl group (Vinyl), and a thiol group (Thiol) on a surface thereof. It may contain the above reactive functional group. As the solid inorganic nanoparticles and the hollow inorganic nanoparticles each contain the reactive functional groups described above on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby ensuring more scratch resistance and antifouling resistance. can do. Each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may have a hydroxyl group on the surface when there is no separate substituent.

As described above, the anti-reflection film comprises a hard coating layer; And a low refractive layer including a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

Specifically, in the anti-reflection film, the solid inorganic nanoparticles may be distributed more than the hollow inorganic nanoparticles near the interface between the hard coating layer and the low refractive layer.

Previously, an excessive amount of inorganic particles was added to increase scratch resistance of the antireflective film, but there was a limit in improving scratch resistance of the antireflective film, but there was a problem in that reflectance and antifouling property were lowered.

On the contrary, when the hollow inorganic nanoparticles and the solid inorganic nanoparticles are distributed so as to be distinguished from each other in the low refractive layer included in the antireflection film, they have high scratch resistance and antifouling resistance while having low reflectance and high light transmittance. Can be implemented at the same time.

Specifically, in the case of mainly distributing the solid inorganic nanoparticles near the interface between the hard coating layer and the low refractive index of the low refractive layer of the anti-reflection film and the hollow inorganic nanoparticles mainly toward the opposite side of the interface It is possible to achieve a lower reflectance than the actual reflectance previously obtained using inorganic particles, and the low refractive index layer can realize both scratch resistance and stain resistance.

As described above, the low refractive layer includes a binder resin, hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, and may be formed on one surface of the hard coating layer, the solid inorganic nano At least 70% by volume of the total particles may be present within 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.

'70% by volume or more of the entire solid inorganic nanoparticles are present in a specific region 'is defined as meaning that the solid inorganic nanoparticles are mostly present in the specific region in the cross-section of the low refractive index layer. More than 70% by volume of the total solid inorganic nanoparticles may be confirmed by measuring the volume of the entire solid inorganic nanoparticles, and may also be confirmed through photographs such as a transmission electron microscope (TEM).

Whether the hollow inorganic nanoparticles and the solid inorganic nanoparticles are present in the specified region is determined by whether each of the hollow inorganic nanoparticles or the solid inorganic nanoparticles is present in the specified region and wherein the specific It is determined by excluding particles that exist across the interface of the region.

In addition, as described above, hollow inorganic nanoparticles may be mainly distributed toward the opposite surface of the interface between the hard coating layer and the low refractive layer in the low refractive layer. Volume%, or 50% by volume or more, or 70% by volume or more may be present at a greater distance in the thickness direction of the low refractive layer from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles.

From the interface between the hard coating layer and the low refractive layer more than 50% of the total thickness of the low refractive layer (from the point of exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer 30 volume%, 50 volume% or more, or 70 volume% or more of the entire hollow inorganic nanoparticle may be present in the region up to the other surface of the low refractive layer facing the interface.

In addition, 70% by volume or more of the total solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer. In addition, 70 vol% or more of the entire hollow inorganic nanoparticles may be present in an area of more than 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.

In the low refractive layer of the antireflection film, the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer, and the hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface. Two or more portions or two or more layers having different refractive indices may be formed in the low refractive layer, and thus the reflectance of the antireflection film may be lowered.

Specific distribution of the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the low refractive index layer in the specific manufacturing method described below, the ratio of the average particle diameter between the solid inorganic nanoparticles and hollow inorganic nanoparticles The photocurable resin composition for forming a low refractive layer including the two kinds of nanoparticles may be obtained by controlling a drying temperature.

When the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer among the low refractive layers of the antireflection film, and the hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface, It is possible to realize reflectance lower than that which could be obtained using inorganic particles. Specifically, the reflective ring film is 1.5% or less, or 1.0% or less, or 0.50 to 1.0%, 0.7% or less, or 0.60% to 0.70%, or 0.62% to 0.67% in the visible light wavelength range of 380 nm to 780 nm. It can represent the average reflectance of.

On the other hand, in the anti-reflection film of the embodiment, the low refractive layer is a first layer containing at least 70% by volume of the total solid inorganic nanoparticles and 70% by volume or more of the entire hollow inorganic nanoparticles It may include two layers, the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the second layer.

As described above, in the low refractive layer of the antireflection film, solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer, and hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface. In this case, an area in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed may form an independent layer which is visible in the low refractive layer.

In addition, the first layer including 70% by volume or more of the total solid inorganic nanoparticles may be located within 50% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer. More specifically, the first layer including 70% by volume or more of the total solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer.

In addition, as described above, hollow inorganic nanoparticles may be mainly distributed toward the opposite surface of the interface between the hard coating layer and the low refractive layer in the low refractive layer. At least 50% by volume, or at least 50% by volume, or at least 70% by volume may be present at a greater distance in the thickness direction of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer than the entire solid inorganic nanoparticle. . Accordingly, as described above, the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the second layer.

In addition, as described above, it can be visually confirmed that each of the first layer and the second layer, which are regions in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, is present in the low refractive layer. For example, the transmission and electron microscope [Transmission Electron Microscope] or the scanning electron microscope [Scanning Electron Microscope], etc. can be visually confirmed that each of the first layer and the second layer in the low refractive layer, and also low refractive index The ratio of solid inorganic nanoparticles and hollow inorganic nanoparticles distributed in each of the first and second layers in the layer can also be confirmed.

Meanwhile, each of the first layer including 70% by volume or more of the solid inorganic nanoparticles and the second layer including 70% or more by volume of the hollow inorganic nanoparticles all share common optical properties in one layer. It may be defined as a single layer accordingly.

More specifically, each of the first layer and the second layer has a specific Kosh parameter A when the ellipticity of the polarity measured by ellipsometry is optimized by the Cauchy model of Formula 1. , B and C, whereby the first layer and the second layer can be distinguished from each other. In addition, since the ellipticity of the polarization measured by the ellipsometry can be derived from the Caching model of Formula 1, the thicknesses of the first layer and the second layer can also be derived. The first layer and the second layer can be defined in the low refractive layer.

[Formula 1]

)는

파장에서의 굴절율(refractive index)이고,

는 300 ㎚ 내지 1800㎚의 범위이고, A, B 및 C는 코쉬 파라미터이다. In the general formula 1, n (

)

Refractive index at the wavelength,

Is in the range of 300 nm to 1800 nm, and A, B and C are the Kosch parameters.

Meanwhile, the Kosh parameters A, B, and C derived when the ellipticity of the polarization measured by the ellipsometry is optimized by the Cauchy model of Equation 1 are calculated in one layer. It may be an average value. Accordingly, when an interface exists between the first layer and the second layer, there may be a region where the Kosh parameters A, B, and C of the first layer and the second layer overlap. However, even in this case, the thickness and position of the first layer and the second layer may be specified according to the region satisfying the average values of the Cosch parameters A, B, and C of each of the first layer and the second layer. .

For example, when the ellipticity of the polarization measured by ellipsometry with respect to the first layer included in the low refractive layer is optimized by the Cauchy model of the following general formula (1), Is 1.0 to 1.65, B is 0.0010 to 0.0350, and C may satisfy a condition of 0 to 1 * 10 ⁻³ , and for the first layer included in the low refractive layer, A is 1.30 to 1.55, or 1.40 To 1.52, or 1.491 to 1.511, wherein B is 0 to 0.005, or 0 to 0.00580, or 0 to 0.00573, wherein C is 0 to 1 * 10 ⁻³ , or 0 to 5.0 * 10 ⁻⁴ , or 0 to It can satisfy the condition of 4.1352 * 10 ^-4 .

In addition, when the ellipticity of the polarity measured by ellipsometry of the second layer included in the low refractive index layer is optimized by a Cauchy model of Formula 1, A is 1.0. To 1.50, B is 0 to 0.007, C may satisfy a condition of 0 to 1 * 10 ⁻³ , and A is 1.10 to 1.40, or 1.20 to 1.35 for the second layer included in the low refractive layer. , Or 1.211 to 1.349, wherein B is 0 to 0.007, or 0 to 0.00550, or 0 to 0.00513, wherein C is 0 to 1 * 10 ^-3 , or 0 to 5.0 * 10 ^-4 , or 0 to 4.8685 * The condition of 10 ^-4 can be satisfied.

On the other hand, in the anti-reflection film of the above-described embodiment (s), the first layer and the second layer included in the low refractive layer may have a different refractive index.

More specifically, the first layer included in the low refractive layer may have a refractive index of 1.420 to 1.600, or 1.450 to 1.550, or 1.480 to 1.520, or 1.491 to 1.511 at 550 nm. In addition, the second layer included in the low refractive layer may have a refractive index of 1.200 to 1.410, or 1.210 to 1.400, or 1.211 to 1.375 at 550 nm.

Measurement of the above-described refractive index may use a commonly known method, for example, the elliptical polarization and the Cauchy model measured at a wavelength of 380 nm to 1,000 nm for each of the first and second layers included in the low refractive index layer. It can be determined by calculating the refractive index at 550nm using.

Meanwhile, the above-described low refractive layer may be prepared from a photocurable coating composition including a photopolymerizable compound, a fluorine-containing compound including a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles, and a photoinitiator.

Accordingly, the binder resin included in the low refractive index layer may include a cross-linked (co) polymer between the (co) polymer of the photopolymerizable compound and the fluorine-containing compound including the photoreactive functional group.

The photopolymerizable compound included in the photocurable coating composition of the embodiment may form a base material of the binder resin of the low refractive index layer to be prepared. Specifically, the photopolymerizable compound may include a monomer or oligomer including a (meth) acrylate or a vinyl group. More specifically, the photopolymerizable compound may include a monomer or oligomer containing at least one, or at least two, or at least three (meth) acrylate or vinyl groups.

Specific examples of the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth). ) Acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylic Latex, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate or a mixture of two or more thereof, or a urethane-modified acrylate oligomer, epoxy Side acrylate oligo , There may be mentioned ether acrylate oligomers, the dendritic acrylate oligomer, or a mixture of these two or more kinds. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.

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

Although the content of the photopolymerizable compound in the photocurable coating composition is not significantly limited, the content of the photopolymerizable compound in the solid content of the photocurable coating composition in consideration of the mechanical properties of the low refractive index layer or the antireflection film to be produced finally May be 5% to 80% by weight. Solid content of the photocurable coating composition means only the components of the solid except the components of the liquid, for example, an organic solvent that may be optionally included as described below in the photocurable coating composition.

Meanwhile, the photopolymerizable compound may further include a fluorine (meth) acrylate monomer or oligomer in addition to the monomer or oligomer described above. When the fluorine-based (meth) acrylate monomer or oligomer is further included, the weight ratio of the fluorine-based (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group is 0.1% to May be 10%.

Specific examples of the fluorine-based (meth) acrylate monomers or oligomers may include at least one compound selected from the group consisting of the following Chemical Formulas 1 to 5.

[Formula 1]

In Formula 1, R ¹ is a hydrogen group or an alkyl group having 1 to 6 carbon atoms, a is an integer of 0 to 7, b is an integer of 1 to 3.

[Formula 2]

In Formula 2, c is an integer of 1 to 10.

[Formula 3]

In Formula 3, d is an integer of 1 to 11.

[Formula 4]

In Chemical Formula 4, e is an integer of 1 to 5.

[Formula 5]

In Formula 5, f is an integer of 4 to 10.

On the other hand, the low refractive index layer may include a portion derived from the fluorine-containing compound including the photoreactive functional group.

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 the polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light. Means functional groups. The photoreactive functional group may include various functional groups known to be able to participate in a polymerization reaction by irradiation of light, and specific examples thereof may include (meth) acrylate groups, epoxide groups, vinyl groups, or thiol groups ( Thiol).

Each of the fluorine-containing compounds 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 in the photocurable coating composition may not be uniformly and effectively arranged on the surface, and thus are located inside the low refractive layer that is finally manufactured. Accordingly, the antifouling property of the surface of the low refractive index layer is lowered, and the crosslinking density of the low refractive index layer is lowered, so that mechanical properties such as overall strength and scratch resistance may be reduced.

In addition, when the weight average molecular weight of the fluorine-containing compound including the photoreactive functional group is too high, compatibility with other components in the photocurable coating composition may be lowered, thereby increasing the haze of the low refractive layer to be produced Light transmittance may be lowered, and the strength of the low refractive index layer may also be lowered.

Specifically, the fluorine-containing compound including the photoreactive functional group may include: i) an aliphatic compound or an aliphatic ring compound in which one or more photoreactive functional groups are substituted and at least one fluorine is substituted for at least one carbon; ii) a heteroaliphatic compound or a heteroaliphatic ring compound substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; iii) polydialkylsiloxane polymers (eg, polydimethylsiloxane polymers) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicone; iv) polyether compounds substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine, or mixtures of two or more of the above i) to iv) or copolymers thereof.

The photocurable coating composition may include 20 to 300 parts by weight of the fluorine-containing compound including the photoreactive functional group with respect to 100 parts by weight of the photopolymerizable compound.

When the fluorine-containing compound containing the photoreactive functional group is added in excess of the photopolymerizable compound, the coating property of the photocurable coating composition of the embodiment is reduced or the low refractive layer obtained from the photocurable coating composition has sufficient durability or scratch resistance. May not have In addition, when the amount of the fluorine-containing compound including the photoreactive functional group relative to the photopolymerizable compound is too small, the low refractive index layer obtained from the photocurable coating composition may not have sufficient mechanical properties such as antifouling 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 a silicon or silicon compound, specifically, the content of silicon in the fluorine-containing compound containing the photoreactive functional group is 0.1% to 20% by weight Can be.

Silicon contained in the fluorine-containing compound including the photoreactive functional group can increase the compatibility with other components included in the photocurable coating composition of the embodiment, and thus haze (haze) is generated in the refractive layer to be manufactured It can play a role of increasing transparency by preventing. On the other hand, when the content of silicon in the fluorine-containing compound containing the photoreactive functional group is too large, the compatibility between the other components included in the photocurable coating composition and the fluorine-containing compound may be rather deteriorated, thereby resulting in low Since the refractive layer or the antireflection film does not have sufficient light transmittance or antireflection performance, the antifouling property of the surface may also be reduced.

The low refractive layer may include 10 to 400 parts by weight of the hollow inorganic nanoparticles and 10 to 400 parts by weight of the solid inorganic nanoparticles relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.

When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive index layer is excessive, the phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not sufficiently occur in the low refractive layer manufacturing process is mixed Therefore, the reflectance may be increased, and surface irregularities may be excessively generated, thereby preventing the antifouling property. In addition, when the content of the hollow inorganic nanoparticles and solid inorganic nanoparticles in the low refractive index layer is too small, many of the solid inorganic nanoparticles are located in a region close to the interface between the hard coating layer and the low refractive layer. It may be difficult to, and the reflectance of the low refractive layer may be significantly increased.

The low refractive layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 nm, or 85 nm to 300 nm.

On the other hand, as the hard coating layer, a conventionally known hard coating layer can be used without great limitation.

An example of the hard coating layer may include a hard resin layer including a binder resin and organic or inorganic fine particles dispersed in the binder resin.

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

The organic or inorganic fine particles are not particularly 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 size 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 film are not limited. For example, the organic or inorganic fine particles may be organic fine particles made of acrylic resin, styrene resin, epoxide resin and nylon resin or silicon oxide. And inorganic fine particles consisting 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.

The high molecular weight (co) polymer may be one or more selected from the group consisting of cellulose polymers, acrylic polymers, styrene polymers, epoxide polymers, nylon polymers, urethane polymers, and polyolefin polymers.

On the other hand, as another example of the hard coating film, a binder resin of a photocurable resin; And the hard coat film containing the antistatic agent disperse | distributed to the said binder resin is mentioned.

The photocurable resin included in the hard coat layer is a polymer of a photocurable compound that may cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be conventional in the art. However, preferably, the photocurable compound may be a polyfunctional (meth) acrylate-based monomer or oligomer, wherein the number of (meth) acrylate-based functional groups is 2 to 10, preferably 2 to 8, more preferably Preferably, 2 to 7 is advantageous in terms of securing physical properties of the hard coating layer. More preferably, the photocurable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Erythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxy It may be at least one selected from the group consisting of tri (meth) acrylates.

The antistatic agent is a quaternary ammonium salt compound; Pyridinium salts; Cationic compounds having from 1 to 3 amino groups; Anionic compounds such as sulfonic acid base, sulfate ester base, phosphate ester base and phosphonic acid base; Positive compounds, such as an amino acid type or amino sulfate ester type compound; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Two or more reactants or polymerized compounds 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 a molecule, and may use a low molecular type or a polymer type without limitation.

Moreover, as said antistatic agent, a conductive polymer and metal oxide fine particles can also be used. Examples of the conductive polymer include aromatic conjugated poly (paraphenylene), polypyrrole of heterocyclic conjugated system, polythiophene, polyacetylene of aliphatic conjugated system, polyaniline of conjugated example containing a hetero atom, poly of mixed form conjugated system ( Phenylene vinylene), a double-chain conjugated compound which is a conjugated system having a plurality of conjugated chains in a molecule, and a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain to a saturated polymer. Further, the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminium oxide, antimony doped tin oxide, aluminum doped zinc oxide, and the like.

Binder resin of the photocurable resin; And an antistatic agent dispersed in the binder resin may further include one or more compounds selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers.

The alkoxy silane compound may be conventional in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be one or more compounds selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.

In addition, the metal alkoxide-based oligomer may be prepared through a sol-gel reaction of a composition comprising a metal alkoxide-based compound and water. The sol-gel reaction can be carried out by a method similar to the method for producing an alkoxy silane oligomer described above.

However, since the metal alkoxide compound may react with water rapidly, the sol-gel reaction may be performed by diluting the metal alkoxide compound in an organic solvent and slowly dropping water. At this time, in consideration of the reaction efficiency and the like, the molar ratio (metal ion reference) of the metal alkoxide compound to water is preferably adjusted within the range of 3 to 170.

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

On the other hand, the hard coating layer may have a thickness of 0.1㎛ to 100㎛.

It may further include a substrate bonded to the other side of the hard coating layer. The specific kind or thickness of the substrate is not particularly limited, and a substrate known to be used for the production of a low refractive index layer or an antireflection film can be used without great limitation. For example, a polycarbonate, a cycloolefin polymer, polyester, or triacetyl cellulose etc. are mentioned as said base material.

On the other hand, the low refractive index layer may further include a silane compound containing at least one reactive functional group selected from the group consisting of vinyl groups and (meth) acrylate groups.

The silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may increase the mechanical properties of the low refractive index layer, for example, scratch resistance, due to the reactive functional group. . In addition, as the low refractive layer includes a silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group, it is possible to secure more improved scratch resistance.

In addition, the internal characteristics of the low refractive index layer may be improved due to the silane functional group or silicon atom included in the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group. More specifically, as the silane functional groups or silicon atoms included in the silane-based compound are uniformly distributed in the low refractive layer, a lower average reflectance may be realized, and due to the silane functional groups or silicon atoms, The uniformly distributed inorganic fine particles may be uniformly combined with the photopolymerizable compound to improve scratch resistance of the antireflective film to be manufactured.

As described above, as the silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group has a chemical structure simultaneously containing the reactive functional group and the silicon atom The low refractive index layer may be optimized for lowering the refractive index. Accordingly, the low refractive index layer may realize a low reflectance and a high light transmittance, and also obtain a uniform crosslink density to provide more excellent wear resistance or scratch resistance. It can be secured.

Specifically, the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may contain 100 to 1000 g / mol equivalents of the reactive functional group.

If the content of the reactive functional group is too small in the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group, the scratch resistance and the mechanical properties of the low refractive index layer It can be difficult to raise enough.

On the other hand, if the content of the reactive functional group in the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is too high, homogeneous or inorganic fine in the low refractive layer The dispersibility of the particles may be lowered, and thus the light transmittance of the low refractive index layer may be lowered.

The silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group has a weight average molecular weight of 100 to 5,000, or 200 to 3,000 (in terms of polystyrene measured by GPC method). Weight average molecular weight).

Specifically, the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is at least one reactive functional group 1 selected from the group consisting of a vinyl group and a (meth) acrylate group. As described above, an organic functional group including at least one trialkoxysilane group having an alkylene group having 1 to 10 carbon atoms and a urethane functional group may be included. The trialkoxysilane group may be a functional group in which three alkoxy having 1 to 3 carbon atoms are substituted with a silicon compound.

Although the specific chemical structure of the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is not limited, specific examples thereof include the compounds represented by the following Chemical Formulas 11 to 14 have.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

이며, In Formula 14, R ¹

Is,

X is hydrogen, a monovalent moiety derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxycarbonyl group having 1 to 4 carbon atoms,

Y is a single bond, -CO- or -COO-,

R ² is a divalent moiety derived from an aliphatic hydrocarbon having 1 to 20 carbon atoms, or at least one hydrogen of the divalent moiety is a divalent moiety substituted with a hydroxyl, carboxyl or epoxy group, or at least one of the divalent moieties. -CH ₂ -is a divalent residue substituted with -O-, -CO-O-, -O-CO- or -O-CO-O- so that the oxygen atoms are not directly connected,

A is either of hydrogen and monovalent residues derived from aliphatic hydrocarbons having 1 to 6 carbon atoms, B is any of monovalent residues derived from aliphatic hydrocarbons having 1 to 6 carbon atoms, and n is an integer of 0 to 2.

As an example of the compound of Formula 14, there may be mentioned a compound of Formula 15.

[Formula 15]

In Formula 15, R ₁ , R ₂ and R ₃ is an alkoxy group having 1 to 3 carbon atoms or hydrogen, X is a straight or branched chain alkylene group having 1 to 10 carbon atoms, and R 4 is 1 to 3 carbon atoms. Alkyl group or hydrogen.

The low refractive layer may include 2 to 40 parts by weight of a silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group relative to 100 parts by weight of the photopolymerizable compound included therein. Can be.

When the content of the silane compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is too small compared to the photopolymerizable compound, sufficient scratch resistance of the low refractive layer is ensured. It can be difficult to do. In addition, when the content of the silane compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group compared to the photopolymerizable compound is too large, other components included in the low refractive layer Compatibility with these materials may be greatly reduced, so that haze may occur in the low refractive index layer or the anti-reflection film or transparency thereof may be lowered, and scratch resistance may be lowered.

On the other hand, the anti-reflection film of the embodiment, a photocurable compound or a (co) polymer thereof, a resin for forming a low refractive index layer containing a fluorine-containing compound, a photoinitiator, a hollow inorganic nanoparticles and a solid inorganic nanoparticles, including photoreactive functional groups Applying the composition on a hard coat layer and drying at a temperature of 35 ° C. to 100 ° C .; And photocuring the dried material of the resin composition.

Specifically, the anti-reflection film provided by the method of manufacturing the anti-reflection film is distributed in the low refractive layer so that the hollow inorganic nanoparticles and the solid inorganic nanoparticles can be distinguished from each other, thereby providing a low reflectance and a high light transmittance. It can have high scratch resistance and antifouling at the same time.

More specifically, the anti-reflection film is a hard coating layer; And a low refractive layer formed on one surface of the hard coating layer, the hollow refractive inorganic nanoparticles and the solid inorganic nanoparticles dispersed in the binder resin, between the hard coating layer and the low refractive index layer. At least 70% by volume of the total solid inorganic nanoparticles may be present within 50% of the total thickness of the low refractive layer from an interface.

In addition, at least 30% by volume of the entire hollow inorganic nanoparticles may be present at a greater distance in the thickness direction of the low refractive layer than the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles.

In addition, 70% by volume or more of the total solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer. In addition, 70 vol% or more of the entire hollow inorganic nanoparticles may be present in an area of more than 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.

In addition, in the anti-reflection film provided by the method for manufacturing the anti-reflection film, the low refractive index layer of the first layer and 70% by weight of the total of the solid inorganic nanoparticles and the entire hollow inorganic nanoparticles It may include a second layer containing more than 70% by weight, the first layer may be located closer to the interface between the hard coating layer and the low refractive index than the second layer.

The low refractive index layer comprises a photocurable compound or a (co) polymer thereof, a fluorine-containing compound including a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and a resin composition for forming a low refractive index layer including solid inorganic nanoparticles on a hard coating layer. It can be formed by applying to and drying at a temperature of 35 ℃ to 100 ℃, or 40 ℃ to 80 ℃.

When the temperature for drying the low refractive index layer-forming resin composition applied on the hard coating layer is less than 35, antifouling properties of the low refractive index layer may be greatly reduced. In addition, when the temperature of drying the low refractive layer forming resin composition applied on the hard coating layer is more than 100, the phase separation between the hollow inorganic nanoparticles and solid-type inorganic nanoparticles does not sufficiently occur in the low refractive layer manufacturing process. By being mixed, not only the scratch resistance and the antifouling property of the low refractive layer may be lowered, but also the reflectance may be greatly increased.

Low refractive index layer having the above-described characteristics by controlling the density difference between the solid inorganic nanoparticles and the hollow inorganic nanoparticles with the drying temperature in the process of drying the resin composition for forming the low refractive index layer applied on the hard coating layer Can be formed. The solid inorganic nanoparticles may have a density of 0.50 g / cm3 or more higher than that of the hollow inorganic nanoparticles, and due to the density difference, the solid inorganic nanoparticles may be formed in the low refractive layer formed on the hard coating layer. It may be located closer to the hard coating layer.

On the other hand, the step of drying the resin composition for forming the low refractive index layer applied on the hard coating layer at a temperature of 35 ℃ to 100 ℃ may be performed for 10 seconds to 5 minutes, or 30 seconds to 4 minutes.

When the drying time is too short, phase separation between the solid inorganic nanoparticles and the hollow inorganic nanoparticles described above may not sufficiently occur. In contrast, when the drying time is too long, the formed low refractive index layer may erode the hard coating layer.

Meanwhile, the low refractive layer may be prepared from a photocurable coating composition including a photocurable compound or a (co) polymer thereof, a fluorine-containing compound including a photoreactive functional group, a hollow inorganic nanoparticle, a solid inorganic nanoparticle, and a photoinitiator. .

The low refractive layer can be obtained by applying the photocurable coating composition on a predetermined substrate and photocuring the applied resultant. The specific kind or thickness of the substrate is not particularly limited, and a substrate known to be used for the production of a low refractive index layer or an antireflection film can be used without great limitation.

Methods and apparatuses conventionally used to apply the photocurable coating composition may be used without particular limitation, for example, bar coating such as Meyer bar, gravure coating, 2 roll reverse coating, vacuum slot die coating Method, 2 roll coating method and the like can be used.

The low refractive layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 nm. Accordingly, the thickness of the photocurable coating composition applied on the predetermined substrate may be about 1 nm to 300 nm, or 50 nm to 200 nm.

In the step of photocuring the photocurable coating composition may be irradiated with ultraviolet light or visible light having a wavelength of 200 to 400nm, the exposure dose is preferably 100 to 4,000 mJ / ㎠. Exposure time is not specifically limited, either, According to the exposure apparatus used, wavelength of an irradiation light, or exposure amount, it can change suitably.

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

Details of the photocurable compound, the hollow inorganic nanoparticles, the solid inorganic nanoparticles, and the fluorine-containing compound including the photoreactive functional group include the aforementioned contents with respect to the antireflection film of the embodiment.

Each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles may be included in the composition in the form of a colloid dispersed in a predetermined dispersion medium. Each colloidal phase including the hollow inorganic nanoparticles and the solid inorganic nanoparticles may include an organic solvent as a dispersion medium.

The colloidal phase of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in consideration of the content range of the hollow inorganic nanoparticles and the solid inorganic nanoparticles or the viscosity of the photocurable coating composition in the photocurable coating composition Heavy content may be determined, for example, the solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the colloidal phase may be 5% by weight to 60% by weight.

Herein, examples of the organic solvent in the dispersion medium include alcohols such as methanol, isopropyl alcohol, ethylene glycol and butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Dimethylformamide. Amides such as dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or mixtures thereof.

The photopolymerization initiator may be used without limitation as long as it is a compound known to be used in the photocurable resin composition. Specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or the like. Mixtures of two or more thereof can be used.

With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight. 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 have a low crosslinking density, thereby lowering mechanical properties or significantly increasing reflectance of the film.

Meanwhile, the photocurable coating composition may further include an organic solvent.

Non-limiting examples of the organic solvent include ketones, alcohols, acetates and ethers, or mixtures of two or more thereof.

Specific examples of such organic solvents include ketones such as methyl ethyl kenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more 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, defects may occur, such as streaks in the final manufactured film due to reduced flowability of the photocurable coating composition. In addition, when the excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation is not enough, the physical properties and surface properties of the film may be lowered, and defects may occur in the drying and curing process. Accordingly, the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1% by weight to 50% by weight, or 2 to 20% by weight.

The hard coating layer may be used without any limitation as long as it is a material known to be used for the antireflection film.

Specifically, the method of manufacturing the anti-reflection film may further include applying a photocurable compound or a polymer resin composition for forming a hard coating layer including the (co) polymer on the substrate and photocuring the above step, Through the hard coating layer can be formed.

The components used to form the hard coat layer are the same as described above with respect to the antireflection film of the embodiment.

In addition, the polymer resin composition for forming the hard coating layer may further include at least one compound selected from the group consisting of an alkoxy silane oligomer and a metal alkoxide oligomer.

Methods and apparatuses conventionally used to apply the polymer resin composition for forming the hard coating layer may be used without particular limitation, for example, bar coating method such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum Slot die coating, 2 roll coating, etc. can be used.

In the step of photocuring the polymer resin composition for forming the hard coating layer may be irradiated with ultraviolet rays or visible light having a wavelength of 200 ~ 400nm, the exposure dose is preferably 100 to 4,000 mJ / ㎠. Exposure time is not specifically limited, either, According to the exposure apparatus used, wavelength of an irradiation light, or exposure amount, it can change suitably. In addition, in the step of photocuring the polymer resin composition for forming a hard coating layer may be purged with nitrogen in order to apply nitrogen atmospheric conditions.

On the other hand, according to another embodiment of the invention, a hard coating layer comprising a binder resin and organic or inorganic fine particles dispersed in the binder resin; And a low refractive layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, wherein the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.15 to 0.15. 0.55, and an antireflection film having 70% by volume or more of the entire solid inorganic nanoparticles may be provided within 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.

The present inventors have conducted research on the antireflection film, so that the antireflection film including the low refractive index layer including the hollow particles and the solid particles having the specific average particle diameter ratio described above has a lower reflectance and a high light transmittance and high scratch resistance. The experiment confirmed that the castle and antifouling can be implemented at the same time, and completed the invention.

More specifically, the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles in the low refractive layer is less than 0.55, or 0.15 to 0.55, or 0.26 to 0.55, or 0.27 to 0.40, or 0.280 to 0.380 In the low refractive layer, the hollow particles and the solid particles may exhibit different localization and distribution patterns. For example, a position where the hollow particles and the solid particles are mainly distributed is between the hard coating layer and the low refractive layer. The distance may be different based on the interface.

As such, as the areas where the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, the low refractive layer may have a unique internal structure and an arrangement of components, thereby having a lower reflectance. In addition, as the area where the hollow particles and the solid particles are mainly distributed in the low refractive layer is changed, the surface characteristics of the low refractive layer are also changed, thereby improving scratch and antifouling properties.

Specific contents of the solid inorganic nanoparticles and the hollow inorganic nanoparticles include the above-mentioned contents in the anti-reflection film of the embodiment of the present invention.

In the low refractive layer of the antireflection film, the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer, and the hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface. Two or more portions or two or more layers having different refractive indices may be formed in the low refractive layer, and thus the reflectance of the antireflection film may be lowered.

Specific distribution of the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the low refractive index layer in the specific manufacturing method described below, the ratio of the average particle diameter between the solid inorganic nanoparticles and hollow inorganic nanoparticles The photocurable resin composition for forming a low refractive layer including the two kinds of nanoparticles may be obtained by controlling a drying temperature.

The low refractive layer may include a binder resin, hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, and may be formed on one surface of the hard coating layer. More than% may be present within 50% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer.

In addition, as described above, hollow inorganic nanoparticles may be mainly distributed toward the opposite surface of the interface between the hard coating layer and the low refractive layer in the low refractive layer. Volume%, or 50% by volume or more, or 70% by volume or more may be present at a greater distance in the thickness direction of the low refractive layer from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles.

From the interface between the hard coating layer and the low refractive layer more than 50% of the total thickness of the low refractive layer (from the point of exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer 30 volume%, 50 volume% or more, or 70 volume% or more of the entire hollow inorganic nanoparticle may be present in the region up to the other surface of the low refractive layer facing the interface.

In addition, 70% by volume or more of the total solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer. In addition, 70 vol% or more of the entire hollow inorganic nanoparticles may be present in an area of more than 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.

It may include a hard coating layer comprising a binder resin containing the photocurable resin and organic or inorganic fine particles dispersed in the binder resin.

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.

The content of the binder resin and the organic or inorganic fine particles of the hard coating layer includes the above-described content of the anti-reflection film of the embodiment of the present invention.

In addition, except for the above-described details in the anti-reflection film of the other embodiment includes more details with respect to the anti-reflection film of the embodiment of the present invention.

According to the present invention, it is possible to provide an anti-reflection film and a method of manufacturing the anti-reflection film which can simultaneously realize high scratch resistance and antifouling property while having a low reflectance and a high light transmittance and can increase the sharpness of the screen of the display device. .

Figure 1 shows a cross-sectional TEM photograph of the antireflection film of Example 1.
Figure 2 shows a cross-sectional TEM photograph of the antireflection film of Example 2.
Figure 3 shows a cross-sectional TEM photograph of the antireflection film of Example 3.
Figure 4 shows a cross-sectional TEM photograph of the antireflection film of Example 4.
Figure 5 shows a cross-sectional TEM photograph of the antireflection film of Example 5.
Figure 6 shows a cross-sectional TEM photograph of the anti-reflection film of Example 6.
Figure 7 shows a cross-sectional TEM photograph of the antireflection film of Comparative Example 1.
Figure 8 shows a cross-sectional TEM photograph of the antireflection film of Comparative Example 2.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

<Production example>

Preparation Example: Production of Hard Coating Film

KYOEISHA salt type antistatic hard coating solution (50 wt% solids, product name: LJD-1000) was coated on a triacetyl cellulose film with # 10 mayer bar and dried at 90 minutes for 1 minute, and then irradiated with 150 mJ / ㎠ To prepare a hard coat film having a thickness of about 5 ~ 6㎛.

<Examples 1 to 5: Preparation of an antireflection film>

Example 1

(1) Preparation of photocurable coating composition for low refractive layer production

281 parts by weight of hollow silica nanoparticles (diameter range: about 44 nm to 61 nm, manufactured by JSC catalyst and chemicals), 100 parts by weight of pentaerythritol triacrylate (PETA), solid silica nanoparticles (diameter range) About 12.7 nm to 17 nm) 63 parts by weight, 131 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu), 19 parts by weight of the second fluorine-containing compound (RS-537, DIC), initiator ( 31 parts by weight of Irgacure 127, Ciba Co., Ltd. were diluted in a MIBK (methyl isobutyl ketone) solvent so as to have a solid content concentration of 3% by weight.

(2) Preparation of low refractive index layer and antireflection film

On the hard coat film of the above production example, the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at a temperature and time shown in Table 1 below to form a low refractive layer. It formed and the antireflection film was produced. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cm 2 under nitrogen purge.

In addition, 100 to 170 longest diameters of the hollow silica nanoparticles and the solid silica nanoparticles contained in the formed low refractive layer were measured using a transmission electron microscope (TEM), and the hollow silica was repeated 10 times. The average particle diameter of the nanoparticles and the solid silica nanoparticles was obtained [average diameter of the hollow silica nanoparticles: 55.9 nm, average diameter of the solid silica nanoparticles: 14.5 nm].

Example 2

(1) Preparation of photocurable coating composition for low refractive layer production

283 parts by weight of hollow silica nanoparticles (diameter range: about 42 nm to 66 nm, manufactured by JSC catalyst and chemicals) based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA), solid silica nanoparticles (diameter) Range: about 12 nm to 19 nm) 59 parts by weight, 115 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu), 15.5 parts by weight of the second fluorine-containing compound (RS-537, DIC), initiator 10 parts by weight (Irgacure 127, Ciba Co., Ltd.) was diluted in a MIBK (methyl isobutyl ketone) solvent so as to have a solid content concentration of 3% by weight.

(2) Preparation of low refractive index layer and antireflection film

On the hard coat film of the above production example, the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at a temperature and time shown in Table 1 below to form a low refractive layer. It formed and the antireflection film was produced. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cm 2 under nitrogen purge.

In addition, 100 to 170 longest diameters of the hollow silica nanoparticles and the solid silica nanoparticles contained in the formed low refractive layer were measured using a transmission electron microscope (TEM), and the hollow silica was repeated 10 times. The average particle diameter of the nanoparticles and the solid silica nanoparticles was obtained [average diameter of hollow silica nanoparticles: 54.9 nm, average diameter of solid silica nanoparticles: 14.5 nm].

Example 3

(1) Preparation of photocurable coating composition for low refractive layer production

281 parts by weight of hollow silica nanoparticles (diameter range: about 43 nm to 71 nm, manufactured by JSC catalyst and chemicals), 100 parts by weight of pentaerythritol triacrylate (PETA), solid silica nano particles (diameter range) : About 13 nm to 16 nm) 63 parts by weight, 111 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu), 30 parts by weight of the second fluorine-containing compound (RS-537, DIC), initiator (Irgacure 127, Ciba) 23 parts by weight was diluted in a MIBK (methyl isobutyl ketone) solvent so as to have a solid content concentration of 3% by weight.

(2) Preparation of low refractive index layer and antireflection film

On the hard coat film of the above production example, the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at a temperature and time shown in Table 1 below to form a low refractive layer. It formed and the antireflection film was produced. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cm 2 under nitrogen purge.

In addition, 100 to 170 longest diameters of the hollow silica nanoparticles and the solid silica nanoparticles contained in the formed low refractive layer were measured using a transmission electron microscope (TEM), and the hollow silica was repeated 10 times. The average particle diameter of the nanoparticles and the solid silica nanoparticles was obtained [average diameter of the hollow silica nanoparticles: 54.5 nm, average diameter of the solid silica nanoparticles: 19.5 nm].

Example 4

(1) Preparation of photocurable coating composition for low refractive layer production

264 parts by weight of hollow silica nanoparticles (diameter range: about 38 nm to 82 nm, manufactured by JSC catalyst and chemicals), 100 parts by weight of trimethylolpropane triacrylate (TMPTA), solid silica nano particles (diameter) Range: about 15 nm to 19 nm) 60 parts by weight, 100 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu), 50 parts by weight of the second fluorine-containing compound (RS-537, DIC), initiator (Irgacure 127, Ciba Co., Ltd.) 30 parts by weight was diluted in a MIBK (methyl isobutyl ketone) solvent so as to have a solid content concentration of 3% by weight.

(2) Preparation of low refractive index layer and antireflection film

On the hard coat film of the above production example, the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at a temperature and time shown in Table 1 below to form a low refractive layer. It formed and the antireflection film was produced. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cm 2 under nitrogen purge.

In addition, 100 to 170 longest diameters of the hollow silica nanoparticles and the solid silica nanoparticles contained in the formed low refractive layer were measured using a transmission electron microscope (TEM), and the hollow silica was repeated 10 times. The average particle diameter of the nanoparticles and the solid silica nanoparticles was obtained [average diameter of the hollow silica nanoparticles: 55.4 nm, average diameter of the solid silica nanoparticles: 17.1 nm].

Example 5

(1) Preparation of photocurable coating composition for low refractive layer production

414 parts by weight of hollow silica nanoparticles (diameter range: about 43 nm to 81 nm, manufactured by JSC catalyst and chemicals), 100 parts by weight of pentaerythritol triacrylate (PETA), solid silica nanoparticles (diameter range) About 14 nm to 19 nm) 38 parts by weight, fluorine-containing compound (RS-537, DIC) 167 parts by weight, initiator (Irgacure 127, Ciba) 33 parts by weight, and 3-methacryloxypropylmethyldimethoxysilane (Molecular weight: 234.3) 110 parts by weight was diluted in an IBK (methyl isobutyl ketone) solvent so as to have a solid concentration of 3.2% by weight.

(2) Preparation of low refractive index layer and antireflection film

On the hard coat film of the above production example, the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at a temperature and time shown in Table 1 below to form a low refractive layer. It formed and the antireflection film was produced. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cm 2 under nitrogen purge.

In addition, 100 to 170 longest diameters of the hollow silica nanoparticles and the solid silica nanoparticles contained in the formed low refractive layer were measured using a transmission electron microscope (TEM), and the hollow silica was repeated 10 times. The average particle diameter of the nanoparticles and the solid silica nanoparticles was obtained [average diameter of the hollow silica nanoparticles: 55.5 nm, average diameter of the solid silica nanoparticles: 17.1 nm].

Example 6

(1) Preparation of Hard Coating Layer (HD2)

After uniform mixing of 30 g of pentaerythritol triacrylate, 2.5 g of high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000), 20 g of methyl ethyl ketone and 0.5 g of leveling agent (Tego wet 270) As a fine particle of 1.525, 2 g of an acrylic-styrene copolymer (volume average particle diameter: 2 μm, manufacturer: Sekisui Plastic) was added to prepare a hard coating composition.

The hard coating composition thus obtained was coated with a # 10 mayer bar on a triacetylcellulose film and dried at 90 ° C. for 1 minute. 150 mJ / cm 2 was irradiated to the dried material to prepare a hard coating layer having a thickness of 5 μm.

(2) Preparation of low refractive index layer and antireflection film

283 parts by weight of hollow silica nanoparticles (diameter range: about 40 nm to 68 nm, manufactured by JSC catalyst and chemicals), based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA), solid silica nanoparticles (diameter) Range: about 14 nm to 17 nm) 59 parts by weight, 115 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu), 15.5 parts by weight of the second fluorine-containing compound (RS-537, DIC), initiator 10 parts by weight (Irgacure 127, Ciba Co., Ltd.) was diluted in a MIBK (methyl isobutyl ketone) solvent to have a solid content of 3% by weight to prepare a photocurable coating composition for producing a low refractive layer.

On the prepared hard coating layer (HD2), the photocurable coating composition for producing a low refractive index layer is coated with a # 4 mayer bar to a thickness of about 110 to 120nm, dried for 1 minute at a temperature of 60 ℃ and It hardened | cured and the low refractive layer was formed and the antireflection film was produced. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cm 2 under nitrogen purge.

In addition, 100 to 170 longest diameters of the hollow silica nanoparticles and the solid silica nanoparticles contained in the formed low refractive layer were measured using a transmission electron microscope (TEM), and the hollow silica was repeated 10 times. The average particle diameter of the nanoparticles and the solid silica nanoparticles was obtained [average diameter of the hollow silica nanoparticles: 55.4 nm, average diameter of the solid silica nanoparticles: 14.7 nm].

Drying temperature (℃) Drying time Example 1 40 1 minute Example 2 60 1 minute Example 3 80 1 minute Example 4 60 2 minutes Example 5 60 1 minute Example 6 60 1 minute

Comparative Example 1 Preparation of Antireflection Film Comparative Example 1

An anti-reflection film was prepared in the same manner as in Example 1 except for using solid silica nanoparticles (diameter: about 34 nm to 80 nm).

Using a transmission electron microscope (TEM) to measure the longest diameter of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive index layer, and repeated 10 times to repeat the hollow silica nanoparticles And the average particle diameter of the solid silica nanoparticles (average diameter of the hollow silica nanoparticles: 54.6 nm, average diameter of the solid silica nanoparticles: 53.2 nm).

Comparative Example 2

An anti-reflection film was prepared in the same manner as in Example 2, except that solid silica nanoparticles (diameter: about 36 nm to 48 nm) were used.

Using a transmission electron microscope (TEM) to measure the longest diameter of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive index layer, and repeated 10 times to repeat the hollow silica nanoparticles And the average particle diameter of the solid silica nanoparticles (average diameter of the hollow silica nanoparticles: 54.5 nm, average diameter of the solid silica nanoparticles: 41.1 nm).

Experimental Example: Measurement of Physical Properties of Anti-Reflection Film

The antireflection films obtained in the Examples and Comparative Examples were subjected to the experiments as follows.

1.Measure the average reflectance of the antireflective film

The average reflectance which the antireflective film obtained by the Example and the comparative example shows in visible region (380-780 nm) was measured using the Solidspec 3700 (SHIMADZU) apparatus.

2. Antifouling measurement

A 5 cm long straight line was drawn with a black name pen on the surface of the antireflective films obtained in Examples and Comparative Examples, and the antifouling properties were measured by checking the number of times erased when rubbed using a dust-free cloth.

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O: erase time is 10 times or less

: 11 to 20 times erased

X: Cleared more than 20 times

3. Scratch resistance measurement

The steel wool was loaded and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in Examples and Comparative Examples. The maximum load at which one scratch or less of 1 cm or less observed with the naked eye was observed was measured.

Average reflectance (%) Scratch resistance
(g) Antifouling Phase separation Example 1 0.63 500 O O Example 2 0.62 500 O O Example 3 0.67 500 O O Example 4 0.64 500 O O Example 5 0.63 500 O O Example 6 0.65 500 0 0 Comparative Example 1 0.80 50 X X Comparative Example 2 0.82 50 X X

As shown in Table 2, the ratio of the particle size of the solid particles to the particle size of the hollow particles included in the low refractive layer of the antireflection films of Examples 1 to 6 is 0.55 or less, and therefore 0.70% or less in the visible light region. It is confirmed that high scratch resistance and antifouling property can be simultaneously realized while showing low reflectance. 1 to 6, hollow inorganic nanoparticles and solid inorganic nanoparticles are phase-separated in the low refractive layer of the antireflection film of Examples 1 to 4, and the solid inorganic nanoparticles are It is confirmed that most of them exist and are concentrated toward the interface between the hard coating layer and the low refractive layer of the anti-reflection film, and the hollow inorganic nanoparticles are mostly present and crowded away from the hard coating layer.

As shown in Table 2, in the low refractive layer of the antireflection films of Comparative Examples 1 and 2, the ratio of the particle size of the solid particles to the particle size of the hollow particles exceeded 0.55, and as shown in FIGS. It is confirmed that the inorganic nanoparticles and the solid inorganic nanoparticles are mixed without phase separation.

And, as shown in Table 2, it was confirmed that each exhibits a relatively high scratch resistance and low scratch resistance and stain resistance.

Claims (12)

Hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
The ratio of the average particle diameter of the solid inorganic nanoparticles to the average particle diameter of the hollow inorganic nanoparticles is 0.26 to 0.55,
The low refractive layer includes a first layer containing at least 70% by volume of the total solid inorganic nanoparticles and a second layer containing at least 70% by volume of the entire hollow inorganic nanoparticles,
Anti-reflection film.
The method of claim 1,
And the first layer is located closer to the interface between the hard coat layer and the low refractive layer than the second layer.
The method of claim 1,
The anti-reflection film of which the average particle diameter of the hollow inorganic nanoparticles is within a range of 40 nm to 100 nm.
The method of claim 1,
The anti-reflection film of which the average particle diameter of the said solid type inorganic nanoparticle is in the range of 1 nm-30 nm.
The method of claim 1,
The binder resin included in the low refractive index layer comprises an anti-reflective film comprising a cross-linked (co) polymer between a (co) polymer of a photopolymerizable compound and a fluorine-containing compound including a photoreactive functional group.
The method of claim 5,
The low refractive index layer comprises 10 to 400 parts by weight of the hollow inorganic nanoparticles and 10 to 400 parts by weight of the solid inorganic nanoparticles relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
The method of claim 1,
The hard coating layer comprises a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin; Antireflection film comprising a.
The method of claim 7, wherein
The hard coating layer is a binder resin containing a photocurable resin; And organic fine particles having a particle size of 1 to 10 μm or inorganic fine particles having a particle size of 1 nm to 500 nm.
The method of claim 1,
The low refractive index layer comprises the hollow inorganic nanoparticles at a higher weight than the solid inorganic nanoparticles, anti-reflection film.
The method of claim 1,
The antireflective film has an average reflectance of 0.7% or less in the visible light wavelength range of 380 nm to 780 nm.
A hard coating layer comprising a binder resin and organic or inorganic fine particles dispersed in the binder resin; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
The ratio of the average particle diameter of the solid inorganic nanoparticles to the average particle diameter of the hollow inorganic nanoparticles is 0.26 to 0.55,
The low refractive layer includes a first layer containing at least 70% by volume of the total solid inorganic nanoparticles and a second layer containing at least 70% by volume of the entire hollow inorganic nanoparticles,
Anti-reflection film.
The method of claim 11,
The organic fine particles included in the hard coating layer has a particle diameter of 1 to 10 ㎛
Inorganic fine particles contained in the hard coating layer has a particle size of 1 nm to 500 nm, antireflection film.

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