KR101973196B1 - Anti-reflective film - Google Patents

Abstract

The present invention, in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the small angle scattering by X-ray irradiation, antireflection, showing one or more peaks in the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 It is about a 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, in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the small angle scattering by X-ray irradiation, antireflection, which shows one or more peaks in the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 . A film is provided.

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, in the graph of the log value of the scattering intensity for the scattering vector defined in the incineration scattering by X-ray irradiation, one or more peaks in the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 Indicative, antireflection film can be provided.

Accordingly, the present inventors have conducted research on the antireflection film, and in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the incineration scattering by X-ray irradiation, the scattering vector (q _max) of 0.0758 to 0.1256 nm ^-1 is shown. The antireflection film that satisfies the condition showing one or more peaks at) has been confirmed through experiments to achieve a high scratch resistance and antifouling properties while having a low reflectance and a high light transmittance, and completed the invention.

Specifically, in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the incineration scattering by X-ray irradiation, the antireflection film has a scattering intensity of at least one scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 . Whether a log value peak can be exhibited may be related to the internal structure of the antireflection film, for example, the average distance between organic or inorganic particles included in the antireflection film.

In the graph of the log value of the scattering intensity with respect to the scattering vector defined in the small angle scattering by X-ray irradiation, the antireflection film satisfying the condition showing one or more peaks in the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 . May maintain an optimized refractive index value, and thus the antireflection film may realize a low reflectance.

For example, when the peak in the scattering vector of less than 0.0758 nm ^-1 in the graph of the log value of the scattering intensity for the scattering vector defined in the incineration scattering by the X-ray irradiation, the organic or included in the antireflection film The refractive index of the antireflection film may be increased due to the distance between the inorganic particles being too far, and thus the reflectance may be greatly increased.

On the other hand, in the graph of the log value of the scattering intensity with respect to the scattering vector defined by the incineration scattering by the X-ray irradiation, when the peak first appears in the scattering vector of more than 0.1256 nm ^-1 , the organic or inorganic contained in the antireflection film The distance between the particles may be so small that the roughness of the antireflective film may be increased and the scratch resistance and the antifouling property may be reduced.

The peak is an extreme value in which the log value of the scattering intensity is convex upward in a 'graph of the log value of the scattering intensity with respect to the scattering vector defined in the incineration scattering by X-ray irradiation'. This extreme value or inflection point may be a point at which scattering is maximized by an arrangement of organic or inorganic particles included in the antireflection film.

As described above, the anti-reflection film of the embodiment is ^{1 in} the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the small angle scattering by X-ray irradiation. More than one peak may be indicated. More specifically, the range of the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 in the graph of the log value of the scattering intensity for the scattering vector defined in the small angle scattering by X-ray irradiation to the anti-reflection film of the embodiment May be the point where the peak of the log value of the scattering intensity for the scattering vector first appears.

The scattering vector defined in incineration scattering by X-ray irradiation is defined by the following general formula A.

[Formula A]

q = 4π sinθ / λ

In the general formula A, q is a scattering vector, θ is a half value of the scattering angle, and λ is a wavelength of irradiated X-rays.

Specifically, the incineration scattering by the X-ray irradiation means a transmission mode or grazing angle X-ray incineration scattering, for example, 0.63 Å to 1.54 Å for an antireflection film having a size of 1 cm * 1 cm (width * length) It can measure by irradiating X-ray of the wavelength of in 4m distance.

For example, Small Angle X-ray Scattering (SAXS) may be performed by measuring the scattering intensity according to a scattering vector q by transmitting X-rays to a sample in a Pohang accelerator 4C beamline. More specifically, the incineration scattering measurement can be measured by injecting X-rays with a sample placed about 4m away from the detector, using an X-ray having a vertical size of 0.023 mm and a horizontal size of 0.3 mm, 2D mar CCD can be used as a detector. In addition, the scattered 2D diffraction pattern can be obtained as an image, calibrated using the sample-to-detector distance obtained through the standard sample, and the scattering intensity according to the scattering vector q can be converted through the circular average.

On the other hand, in the graph of the log value of the scattering intensity for the scattering vector defined in the small angle scattering by X-ray irradiation to the anti-reflection film, at least one peak in the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 The conditions to be shown can be achieved by adjusting the component contained in the antireflection film which is a characteristic of the said antireflection film, an optical characteristic, a surface characteristic, an internal characteristic, etc.

For example, the anti-reflection film may include 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, in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the small angle scattering by X-ray irradiation on the antireflection film, one in the scattering vector (q _max ) of 0.0758 to 0.1256 nm ^-1 . By satisfying the conditions representing the above peaks, the film can simultaneously realize high scratch resistance and antifouling resistance while having low reflectance and high light transmittance.

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. At least 70% by volume of the total solid inorganic nanoparticles may be confirmed by measuring the volume of the whole solid inorganic nanoparticles.

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. At least 50% by volume, 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 layer from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticle.

More specifically, 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 a specific manufacturing method to be described later, the density difference between the solid inorganic nanoparticles and hollow inorganic nanoparticles and the 2 The photocurable resin composition for forming a low refractive layer including the nanoparticles of a species can be obtained by controlling the drying temperature.

Specifically, the solid inorganic nanoparticles may have a density of 0.50 g / cm 3 or more higher than the hollow inorganic nanoparticles, and the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles is 0.50. g / cm 3 to 1.50 g / cm 3, or 0.60 g / cm 3 to 1.00 g / cm 3. Due to the density difference, the solid inorganic nanoparticles may be located closer to the hard coating layer in the low refractive layer formed on the hard coating layer. However, as can be seen in the manufacturing methods and examples described below, despite the difference in density between the two particles, a predetermined drying temperature and time should be applied to implement the distribution of particles in the above-described low refractive layer. Can be.

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 may exhibit an average reflectance of 0.7% or less, or 0.50 to 0.7%, or 0.60% to 0.70%, or 0.62% to 0.67% in the visible light wavelength range of 380 nm to 780 nm.

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.

[Class 1]

In Formula 1, n (λ) is the refractive index at the λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B and C are Kosh 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 polarization measured by ellipsometry with respect to 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.

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

In addition, the hollow inorganic nanoparticle refers to a particle having a maximum diameter of 200 nm or less and having a void space on the surface and / or inside thereof.

The solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, or 1 to 30 nm.

The hollow inorganic nanoparticles may have a diameter of 1 to 200 nm, or 10 to 100 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 have at least one reactive group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (Vinyl), and a thiol group (Thiol) on a surface thereof. It may contain functional groups. 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.

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 degraded.

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.

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

As an example of the hard coating layer, a hard resin layer including a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder 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, sulfuric acid 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.

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.

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., or 40 ° C. to 80 ° 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 of drying the resin composition for forming the low refractive index layer applied on the hard coating layer is less than 35 ° C., the antifouling property of the formed low refractive layer may be greatly reduced. In addition, when the temperature of drying the resin composition for forming the low refractive index layer 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. Without being mixed, the scratch resistance and antifouling property of the low refractive index layer may be lowered, and 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.

Specifically, the solid inorganic nanoparticles may have a density of 2.00 g / cm 3 to 4.00 g / cm 3, and the hollow inorganic nanoparticles may have a density of 1.50 g / cm 3 to 3.50 g / cm 3.

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 ~ 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.

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

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.

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 anti-reflection film of Example 1.
Figure 2 shows a cross-sectional TEM photograph of the anti-reflection film of Example 2.
Figure 3 shows a cross-sectional TEM photograph of the anti-reflection film of Example 3.
Figure 4 shows a cross-sectional TEM photograph of the anti-reflection film of Example 4.
Figure 5 shows a cross-sectional TEM photograph of the anti-reflection 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 anti-reflection film of Comparative Example 1.
Figure 8 shows a cross-sectional TEM photograph of the anti-reflection film of Comparative Example 2.
Figure 9 shows a cross-sectional TEM photograph of the anti-reflection film of Comparative Example 3.
FIG. 10 is a graph of log values of scattering intensities with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 1. FIG.
FIG. 11 shows a graph of log values of scattering intensities with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 2. FIG.
12 shows a graph of log values of scattering intensities with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 3. FIG.
FIG. 13 shows a graph of log values of scattering intensities with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 4. FIG.
FIG. 14 shows a graph of log values of scattering intensities with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 5. FIG.
FIG. 15 shows a graph of log values of scattering intensity with respect to a scattering vector defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 6. FIG.
FIG. 16 shows a graph of log values of scattering intensity with respect to a scattering vector defined in small angle scattering obtained by irradiating an anti-reflection film of Comparative Example 1 with X-rays.
Fig. 17 shows a graph of log values of scattering intensities with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Comparative Example 2. FIG.
Fig. 18 shows a graph of log values of scattering intensities with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Comparative Example 3. FIG.

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 ° C for 1 minute, followed by 150 mJ / ㎠ Irradiation produced a hard coat film having a thickness of about 5-6 μm.

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

Examples 1-4

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

281 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cm 3, manufactured by JSC catalyst and chemicals) with respect to 100 parts by weight of pentaerythritol triacrylate (PETA), solid silica 63 parts by weight of nanoparticles (diameter: about 12 nm, density: 2.65 g / cm 3), 131 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu Co., Ltd.), second fluorine-containing compound (RS-537, DIC G) 19 parts by weight and 31 parts by weight of an initiator (Irgacure 127, Ciba) were diluted in a MIBK (methyl isobutyl ketone) solvent so as to have a solid content of 3% by weight.

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

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

Example 5

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

268 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cm 3, manufactured by JSC catalyst and chemicals) with respect to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) 55 parts by weight of silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cm 3), 144 parts by weight of a first fluorine-containing compound (X-71-1203M, ShinEtsu Co., Ltd.), a second fluorine-containing compound (RS-537, 21 parts by weight of DIC) and 31 parts by weight of an initiator (Irgacure 127, Ciba) were diluted in a solvent of methyl isobutyl ketone (MIBK) so that the solid content concentration was 3% by weight.

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

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

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 ℃ 3 minutes

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

135 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cm 3, manufactured by JGC catalyst and chemicals) with respect to 100 parts by weight of pentaerythritol triacrylate (PETA), solid silica 88 parts by weight of nanoparticles (diameter: about 12 nm, density: 2.65 g / cm 3), 38 parts by weight of a first fluorine-containing compound (X-71-1203M, ShinEtsu Co., Ltd.), a second fluorine-containing compound (RS-537, DI G) 11 parts by weight, 7 parts by weight of an initiator (Irgacure 127, Ciba), methyl isobutyl ketone (MIBK): diacetone alcohol (DAA): isopropyl alcohol in a solvent mixed with a weight ratio of 3: 3: 4 Dilution to 3% by weight to prepare a photocurable coating composition for producing a low refractive index 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 Cured. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cm 2 under nitrogen purge.

Comparative Example: Production of Anti-Reflection Film

Comparative Example 1

The antireflection film was prepared in the same manner as in Example 1 except that the photocurable coating composition for preparing the low refractive index layer was dried and dried at room temperature (25 ° C.).

Comparative Example 2

Except for replacing 63 parts by weight of the solid silica nanoparticles used in Example 1 with 63 parts by weight of pentaerythritol triacrylate (PETA), the photocurable coating composition for producing a low refractive index layer in the same manner as in Example 1 In the same manner as in Example 1, an antireflection film was prepared.

Comparative Example 3

An antireflective film was prepared in the same manner as in Example 5 except that the photocurable coating composition for preparing the low refractive index layer was applied and dried at 140 ° C.

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.

<Metrics>

O: erase time is 10 times or less

Δ: 11-20 times

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.

4. Measurement of refractive index

The refractive index at 550 nm was calculated using the Cauchy model and the elliptical polarization measured at a wavelength of 380 nm to 1,000 nm for the phase-separated regions of the low refractive layers obtained in the above examples.

Specifically, for the low refractive layer obtained in each of the above examples, J. A. Woollam Co. Using the apparatus of the M-2000, an angle of incidence of 70 ° was applied and linearly polarized light was measured in the wavelength range of 380 nm to 1000 nm. The measured linear light measurement data (Ellipsometry data (Ψ, Δ)) by using the Complete EASE software for the first and second layers (Layer 1, Layer 2) of the low refractive index layer of the general formula (1) Cauchy model) to fit the MSE to 3 or less (fitting).

[Formula 1]

In Formula 1, n (λ) is the refractive index at the λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

5. Measurement of scattering intensity according to scattering vector in incineration scattering by X-ray irradiation

EXAMPLES AND COMPARATIVE EXAMPLES A 1 cm * 1 cm (horizontal * vertical) specimen obtained from each of the antireflection films can be irradiated with an X-ray having a wavelength of 1.54 kHz at a distance of 4 m to measure scattering vector and scattering intensity.

Specifically, the scattering angle was measured by scattering intensity according to the scattering vector (q) by transmitting the X-ray through the sample in the Pohang accelerator 4C beamline. More specifically, the incineration scattering measurement was performed by placing the sample at a position about 4 m away from the detector and measuring the incident X-rays, using an X-ray having a vertical size of 0.023 mm and a horizontal size of 0.3 mm. 2D mar CCD was used. The scattered 2D diffraction pattern was obtained as an image, calibrated using a sample-to-detector distance obtained through a standard sample, and the scattering intensity according to the scattering vector q was converted through a circular average.

[Formula A]

q = 4π sinθ / λ

In the general formula A, q is a scattering vector, θ is a half value of the scattering angle, and λ is a wavelength of irradiated X-rays.

And based on the measurement result, the value (q _max ) of the scattering vector from which the first peak appears in the graph of the log value of scattering intensity with respect to the scattering vector defined by the incineration scattering by X-ray irradiation was calculated | required.

Average reflectance
(%) Scratch resistance
(g) Antifouling Phase separation q _max
( Nm ^-1 ) Example 1 0.63 500 O O 0.12 Example 2 0.62 500 O O 0.121 Example 3 0.67 500 O O 0.119 Example 4 0.64 500 O O 0.12 Example 5 0.65 500 O O 0.12 Example 6 0.67 500 O O 0.106 Comparative Example 1 0.78 150 X X 0.0739 Comparative Example 2 0.8 200 △ X 0.0127 Comparative Example 3 0.75 200 X X 0.0722

Refractive index Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 First area 1.502 1.505 1.498 1.491 1.511 1.505 Second area 1.35 1.349 1.321 1.346 1.211 1.375

As confirmed in Table 2 and FIGS. 10 to 15, the antireflection films of Examples 1 to 6 are 0.0758 to 0.1256 nm in a graph of log values of scattering intensities for scattering vectors defined in incineration scattering by X-ray irradiation. It was confirmed that high scratch resistance and antifouling property can be simultaneously realized while exhibiting one or more peaks in the scattering vector of ^-1 and also having a low reflectance of 0.70% or less in the visible light region as shown in Table 2 above. 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 6, 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.

In addition, as shown in Table 3, in the low refractive layer of the embodiment, the first and second regions in which the hollow inorganic nanoparticles and the solid inorganic nanoparticles are separated from each other in phases exhibit different refractive indices, specifically, solids. It was confirmed that the first region in which the inorganic type nanoparticles were mainly distributed showed a refractive index of 1.420 or more, and the second region in which the hollow inorganic nanoparticles were mainly distributed showed a refractive index of 1.400 or less.

In contrast, as shown in Table 2 and FIGS. 16 to 18, in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the small angle scattering by X-ray irradiation for the antireflection films of Comparative Examples 1 to 3 It was found that no peak appeared in the scattering vector range of 0.0758 to 0.1256 nm ^-1 , and the antireflective films of Comparative Examples 1 to 3 each exhibited low scratch resistance and antifouling resistance with relatively high reflectance.

7 and 9, in the low refractive layer of the antireflection films of Comparative Examples 1 to 3, it is confirmed that the hollow inorganic nanoparticles and the solid inorganic nanoparticles are mixed without phase separation.

Claims (7)

A hard coating layer having a thickness of 0.1 μm to 100 μm; And
And a low refractive index layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
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 total hollow inorganic nanoparticles,
The anti-reflection film which shows one or more peaks in the scattering vector (q _max ) of 0.0758-0.256 nm < ^-1 > in the graph of the log value of scattering intensity with respect to the scattering vector defined by the incineration scattering by X-ray irradiation.
delete 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 first layer is in contact with the interface between the hard coating layer and the low refractive index layer, the second layer is in contact with the other surface of the first layer, the anti-reflection film.
The method of claim 1,
And the first layer is located within 50% of the total thickness of the low refractive layer from an interface between the hard coating layer and the low refractive layer.
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.
The method of claim 1,
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 binder resin, antireflection film.

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