WO2017155335A1 - Anti-reflective film - Google Patents

Abstract

The present invention relates to an anti-reflective film which has one extremum appearing at a 35 nm to 55 nm thickness and one extremum appearing at a 85 nm to 105 nm thickness on a graph showing the result of a Fourier transform analysis for an X-ray reflectivity result measured using a Cu-Kα ray.

Description

 【Specification】

 [Name of invention]

 Antireflection film

 Technical Field

 Cross Citation with Related Application (s)

 This application is filed with Korean Patent Application No. 1, 2016-0028468, filed March 9, 2016, Korean Patent Application No. 10-2016-0029336, filed March 11, 2016, and Korean Patent Application No. 10-2016, March 14, 2016. -0030395, and the benefit of priority based on Korean Patent Application No. 10-2017-0029954 dated March 9, 2017, all the contents disclosed in the documents of the relevant Korean patent applications are incorporated as part of this specification.

 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.

 [Technique to become background of invention]

 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 fillers such as inorganic fine particles in resin and coating on a base film and imparting irregularities (ant i ^¬ glare: AG coating); The method of using the interference of light by forming a plurality of layers having different refractive indices on the base film (AR coating), or a common method thereof.

 Among them, in the case of the AG coating, the absolute amount of reflected light is equivalent to that of a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by using light scattering through unevenness. However, since the AG coating has poor screen clarity due to surface irregularities, much research has recently been conducted on AR coatings.

The AR coating film may be a multi-layered structure in which a hard coating layer (high refractive index layer) and a low reflection coating layer are laminated on a base film. It 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 (interface adhesion force) as a separate process of forming each layer.

 In addition, in order to improve the scratch resistance of the low refractive index 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, and the antifouling property of the surface of the low refractive layer due to the nanometer size particles is greatly reduced. It became.

 Accordingly, many studies have been made to reduce the absolute reflection 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.

 [Content of invention]

 Problem to be solved

 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. [Measures of problem]

 In the present specification, in the Fourier transform analysis results graph for X-ray reflectance measurement results by Cu-K α-rays, one extreme value is determined at a thickness of 35 nm to 55 ran from the surface. And an antireflection film is provided that exhibits one extreme at a thickness of 85 ran to 105 ran from the surface.

Hereinafter, an antireflection film according to a specific embodiment of the present invention will be described in detail. In the present specification, the photopolymerizable compound is collectively referred to as a compound that causes polymerization reaction when light is irradiated, for example, visible light or ultraviolet light. In addition, a fluorine-containing compound means the compound containing at least 1 or more fluorine elements among the compounds.

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

 In addition, (co) polymer is meant to include both copolymers and homopolymers.

 In addition, the hollow silica particles (si l ica hol low part icles) is a silica particle derived from a silicon compound or an organosilicon compound, means a particle in the form of an empty space on the surface and / or inside of the silica particles. do .

According to one embodiment of the invention, the thickness of 35 ran to 55 nm from the surface of the Cu-K c (Four ier transform analysis results of X-ray reflectance measurement results by rays) An antireflection film can be provided that exhibits one extreme at and one extreme at a thickness of 85 nm to 105 ran from the surface.

 Accordingly, the present inventors have conducted research on the antireflection film, and from the results of Fourier transform analysi s on the X-ray reflectance measurement result by Cu-K α-ray, 35 nm to 55 from the surface. An antireflection film exhibiting one extreme value in the thickness of the ran and one extreme value in the thickness of 85 nm to 105 ran from the surface has high scratch resistance and antifouling property with low reflectance and high light transmittance. Experiments confirmed that it can be implemented at the same time and completed the invention.

 Specifically, the Fourier transform analysis results of the X-ray reflectance measurement results by Cu— κ α for the anti-reflection film are graphs of the Y axis versus the thickness of the film on the X axis. Fourier transform magni tude.

The extreme value of the Fourier transform intensity is related to the change of the electron density in the thickness direction, and from 35 ran to 55 ran from the surface described above. If the extremes of one Fourier transform intensity in thickness and the extremes of one Fourier transform intensity in thickness between 85 ηπ and 105 nm from the surface, two layers with different electron densities in the film thickness direction While present, it is possible to realize a lower reflectance and to improve scratch resistance and antifouling properties.

 Specifically, the anti-reflection film is one in the thickness of 35 nm to 55 nm from the surface in the Fourier transform analysis (Fourier transform analysis) results graph for the X-ray reflectance measurement results by Cu-K α-rays By exhibiting an extreme value and one extreme value from a thickness of 85 nm to 105 nm from the surface, it is possible to maintain an optimized internal electron density and refractive index distribution, thus realizing lower reflectance, scratch or external It may have a relatively stable structure against contaminants.

 The extreme value is convex in the direction of the Fourier transform analysis intensity of the reflectance corresponding to the y-axis in the Fourier transform analysis result graph of the X-ray reflectance measurement result by the Cu-K α ray for the antireflection film. It means the point that appears.

More specifically, the extremal value is the thickness of the X-axis that appears in the graph of the Fourier transform analysis of the Cu-K c (X-ray reflectance measurement result by the ray for the antireflection film ( Fourier transform magnitude on the Y axis for the thickness) is the largest or smallest value compared to the surrounding function, for example, the Fourier transform strength on the Y axis for the thickness of the X axis. (Fourier transform magnitude) means a point at which the value differentiating the function of ¹ is 0. In addition, the extreme value may mean a local maximum.

X-ray reflectance measurement by the Cu-K α-rays was measured using a Cu-K α-ray having a wavelength of 1.5418 A for the antireflection film having a size of 1 cm * l cm (horizontal * vertical). It can be measured. Specifically, after adjusting the sample stage so that the value of 2theta (29) becomes 0, checking the hal f-cut of the sample, and then performing reflectance measurement with the incident angle and the reflecting angle satisfying the specular condition, thereby performing the X-ray reflectance pattern Measure

Fourier transform analysis of the X-ray reflectance measurement result by the Cu-K α-rays can be performed using the X 'pert reflective avi ty program of PANalytical. Specifically, Fourier transform input values include start angle, end angle, and cr iti cal angle.For example, start angle is set to 0.01 °, end angle is set to 1.2 °, and cr it ical angle is set. You can enter 0. 163 ⁰ or 0. 18 °. . On the other hand, the Fourier transform analysis result of the X-ray reflectance measurement by Cu-K α-ray shows one extreme value at a thickness of 35 ran to 55 nm in the graph of the results of Fourier transform analysis. The antireflection film exhibiting one extreme value in the thickness of the ran may be achieved by adjusting components, optical properties, surface properties, internal properties, and the like included in the antireflection film.

 The antireflection film of the embodiment may comprise a conventionally known detailed configuration, for example the antireflection film may comprise a hard coating layer; And a low refractive layer formed on the hard coating layer, and may further include one or more layers having other characteristics as necessary.

 A thickness of 35 nm to 55 ran and a thickness of 85 nm to 105 nm, respectively, from the surface are defined or measured from the surface of the antireflective film, and as described above, the antireflective film may include a hard coating layer; And a low refractive layer formed on the hard coating layer, each of the thickness of 35 nm to 55 ηπι and the thickness of 85 ran to 105 nm may be the thickness from the surface of the low refractive layer.

More specifically, the anti-reflection film is a hard coating layer; And hollow inorganic nanoparticles and solid particles dispersed in the binder resin and the binder resin. It may include; low refractive index layer containing inorganic nanoparticles.

 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 antireflection film, but there was a limit in improving scratch resistance of the antireflection film, but there was a problem in that reflectance and antifouling property were lowered.

 On the contrary, in the case of distributing the hollow inorganic nanoparticles and the solid inorganic nanoparticles 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 where 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 achieve a lower reflectance compared to the actual reflectivity previously obtained using inorganic particles, and the low refractive index layer can realize a significantly improved scratch resistance and antifouling resistance. In addition, the Fourier transform analysis result of the X-ray reflectance measurement by Cu-K α-ray shows one extreme value at a thickness of 35 ran to 55 nm in the graph of the results of Fourier transform analysis. The anti-radiation film exhibiting one extreme value in the thickness of nm may be due to the surface or internal characteristics of the low refractive layer.

As described above, the anti-reflection film has a thickness of 35 ran to 55 ran in a Fourier transform analysis (F _0ur i _er transform analysi s) result graph for X-ray reflectance measurement results by Cu-K α-rays. By representing one extreme value at) and one extreme value at a thickness of 85 nm to 105 nm, an optimized internal electron density and refractive index distribution can be maintained, thereby realizing a lower reflectance. It may have a relatively stable structure against scratches or external contaminants. 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 More than 70 volume ¾ »of the total particles 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.

^{1 at} least 70% by volume of the total solid inorganic nanoparticles is 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, the 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 index layer. The volume% or more, 50 volume% or more, or 70 volume% or more may be present at a distance farther 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 nanoparticles.

 More specifically, 70% by volume or more of the entire 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, at least 70% by volume ¾> of the entire hollow inorganic nanoparticle may be present in an area of more than 30% of the total thickness of the low refractive index layer from an interface between the hard coating layer and the low refractive index 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 parts or two having different refractive indices in the low refractive layer The above layer may be formed, and thus the reflectance of the anti-reflection film may be lowered.

 The 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 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 / cin ³ or more higher than the hollow inorganic nanoparticles, and the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles may be 0.50 g / crf to 1.50 g / cin ³ , or 0.60 g / cirf to 1.00 g / cin 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 must be applied to implement the distribution pattern of the 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 has an average of 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 ran. It can indicate reflectance.

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

 As described above, 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 index, and the hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface. In addition, a region in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed may form an independent layer that is visually identified in the low refractive layer.

 In addition, the first layer containing 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, there may be a first layer including 70 vol ¾ or more of the entire solid inorganic nanoparticles 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, the 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. The volume% or more, or 50 volume ¾> or more, or 70 volume% or more may be present at a distance farther 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. have. 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 crab 2 layer, which are areas in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, is present in the low refractive layer. For example, using the transmission electron microscope [Scanning Electron Mi croscope] or the scanning electron microscope [Scanning Electron Mi croscope], etc. can be visually confirmed that each of the first layer and the second layer in the low refractive layer, In addition, the ratio of the solid inorganic nanoparticles and the hollow inorganic nanoparticles distributed in each of the crab 1 layer and the crab 2 layer in the low refractive layer can also be confirmed.

On the other hand, more than 70 vol ¾> of the solid inorganic nanoparticles in total Each of the first and second layers including at least 70% by volume of the entire hollow inorganic nanoparticles may share common optical properties in one layer, and thus may be defined as one layer.

 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 the general formula (1). , B and C, so that the first layer and the second layer can be distinguished from each other. In addition, since the thickness of the first layer and the second layer of the crab can be derived by fitting the ellipticity of the polarization measured by the ellipsometry to the Cauchy model of the following general formula (1), In the low refractive layer, definition of a crab layer and a crab layer is possible.

[Formula 1]

In Formula 1, nO is a refractive index at lambda wavelength, lambda is in the range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

 On the other hand, the coarse parameters A, B, and (:) obtained when the ellipticity of the polarization measured by the ellipsometry is optimized by the Cauchy model of Equation 1 Accordingly, when an interface exists between the first and second crab layers, there may be a region where the Kosh parameters A, B, and C of the first and second layers overlap. However, even in such a case, the thicknesses and positions of the first and second layers may be specified according to the regions satisfying the average values of the Cosch parameters A, B and () of the first and second layers, respectively. Can be.

For example, when the ellipticity of the polarization measured by ellipsometry of the system 1 layer included in the low refractive layer is optimized by the Cauchy model of the following general formula (1), the following A Is 1.0 to 1.65 and B is 0.0010 to 0.0350, and C is from 0 to 1 x may satisfy the condition of ^10-3, but also with respect to the said first layer comprises a low refractive index layer, and A is 1.30 to 1.55, or from 1.40 to 1.52, or 1.491 to 1.511, yet, the B is from 0 to 0.005, or from 0 to 0.00580, or yet from 0 to 0.00573, the C is from 0 to 1 × 10 ^_3 eu or 0 to 5.0 * ^10-4, or from 0 to 4.1352 * ^10-4 can be satisfied with the conditions.

In addition, when the ellipticity of the polarization measured by el lsosometry (el l ipsometry) for the two layers included in the low refractive index layer is optimized (Cauchy model) of Formula 1 (fi tt ing), The A is 1.0 to 1.50, the B is 0 to 0.007 and the C may satisfy the condition of 0 to 1 * 1 (Γ ³ , and for the two layers included in the low refractive layer, the A is 1. 10. yet to 1.40, or 1.20 to 1.35, or 1.211 to 1.349, and the B is from 0 to 0.007, or from 0 to about 0.00550, or from 0 to 00 513 while flying, the C is from 0 to 1 * ^10-3, or from 0 to 5.0 * 10 — ⁴ , or 0 to 4.8685 * 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 crab layer 2 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 ran. 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 conventionally known method, for example, the elliptical polarization measured at a wavelength of 380 nm to 1,000 nm for each of the first layer and the second layer included in the low refractive layer; The Cauchy model can be used to calculate and determine the refractive index at 550 nm.

 On the other hand, the solid-type inorganic nanoparticles mean a particle having a maximum diameter of less than 100 ran and there is no empty space therein.

In addition, the hollow inorganic nanoparticles have a maximum diameter of less than 200 ran and the particles having a form having an empty space on the surface and / or inside thereof it means.

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

 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.

 On the other hand, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles are at least one half selected from the group consisting of (meth) acrylate group, epoxide group, vinyl group (Vinyl) and thio group (Thiol) on the surface It may contain male functional groups. As each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles contain the semi-functional functional groups described above on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby improving scratch and antifouling properties. It can be secured.

 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, a hollow inorganic nanoparticle, a solid inorganic nanoparticle, and a photoinitiator.

Accordingly, the binder resin contained in the low refractive index layer may comprise a crosslinked (co) polymer between the authentication box containing (co) polymer and a functional group of the photopolymerizable compound male flare fluoride ^"compound.

 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 (meth) acrylate or vinyl group of one or more, or two or more, or three or more.

Specific examples of the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipenta erythri nucleus (meth) acrylate, tripentaerythri Hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, trimethyl propanetrimethacryl Ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more kinds thereof, or urethane modified acrylate oligomers, epoxide acrylate oligomers, Etheracrylate oligomers, dendritic acrylate oligomers, or combinations of two or more thereof. 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 particularly 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 anti-reflection film to be produced finally May be from 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.

 On the other hand, the photopolymerizable compound may further include a fluorine-based (meth) acrylate monomer or oligomer in addition to the above-described monomer or oligomer. When the fluorine (meth) acrylate monomer or oligomer further comprises, the weight ratio of the fluorine (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group is 0.1. % To 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 6 to 6 carbon atoms and an integer of 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 photo-reflective 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 groups may participate in the polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light. Means a functional group. The photoreactive functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include (meth) acrylate groups, epoxide groups, vinyl groups, or thiol groups ( Thiol) is mentioned.

 Each of the fluorine-containing compounds including the photo-cyclic functional groups 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. have.

 If the increase average molecular weight of the fluorine-containing compound including the photo-reflective functional group is too small, the fluorine-containing compounds in the photocurable coating composition may not be uniformly and effectively arranged on the surface of the fluorine-containing compound, 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, if the weight average molecular weight of the fluorine-containing compound containing the photo-banung functional group is too high, different from the photocurable coating composition The compatibility with the components may be lowered, and thus the haze of the low refractive layer to be produced may be increased or the light transmittance may be lowered, and the strength of the low refractive layer may be lowered.

 Specifically, the fluorine-containing compound including the photo-cyclic functional group is i) an aliphatic compound or aliphatic ring compound in which at least one photo-cyclic functional group is substituted, at least one fluorine is substituted in at least one carbon; i i) a heteroaliphatic compound or a heteroaliphatic ring compound substituted with one or more photocyclic functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; i i i) 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 silicon; iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine, or a mixture of two or more of the above i) to iv) or a copolymer thereof.

 The photocurable coating composition may include 300 parts by weight of the inside of the fluorine-containing compound 20 including the photobanung functional group based on 100 parts by weight of the photopolymerizable compound.

 When the excess amount of the habso compound containing the photo-banung functional group compared to the photopolymerizable compound is reduced in the coating property of the photocurable coating composition of the embodiment or the low refractive index layer obtained from the photocurable coating composition has a durable durability or scratch You may not have a last name. In addition, when the amount of the fluorine-containing compound containing the photo-reflective functional group relative to the photopolymerizable compound is too small, the low refractive index layer obtained from the photocurable coating composition may not have mechanical properties such as layered antifouling or scratch resistance. . The fluorine-containing compound including the photobanung 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 therein, specifically, the content of silicon in the fluorine-containing compound including the additive photo-banung functional group is from 0.1 to ¾ to 20 Weight%.

Silicon contained in the fluorine-containing compound containing the photo-banung functional group is It can increase the compatibility with other components included in the photocurable coating composition of the embodiment and thus may act to increase the transparency by preventing the generation of haze (haze) in the refractive layer to be finally produced. 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 lowered, 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 thickened inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive index layer becomes excessive, phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not sufficiently occur in the low refractive layer manufacturing process. As a result, the reflectance may be increased, and surface irregularities may occur excessively, thereby degrading antifouling properties. Also, when the content of the hollow inorganic nanoparticles and the 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 index layer may be greatly increased.

 The low refractive index layer may have a thickness of Iran to 300 ran ᅳ or 50ran 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.

As an example of the said hard coat layer, the hard coat layer containing the binder resin containing photocurable resin, and the organic or inorganic fine particle disperse | distributed to the said binder resin; The photocurable resin included in the hard coating layer is a polymer of a photocurable compound that can cause polymerization reaction when irradiated with light such as ultraviolet rays, It may be conventional in the art. Specifically, the photocurable resin is a semi-aromatic acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol nucleoacrylate, dipentaerythroxy hydroxy pentaacrylate, pentaerythriri tetraacrylate, pentaerythriri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol Multifunctional acryl consisting of triacrylate, trimethylpropane ethoxy triacrylate, 1, 6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may include one or more selected from the group of the rate monomers.

 The organic or inorganic fine particles are not particularly limited in particle size, for example, the organic fine particles may have a particle size of 1 to 10 mm 3, and the inorganic particles may have a particle size of 1 ran to 500 nm or Iran to 300 ran. 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 or oxidized or composed of acrylic resin, styrene resin, epoxide resin and nylon resin. It may be an inorganic fine particle consisting of silicon, 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-based polymers, acrylic polymers, styrene-based polymers, epoxide-based polymers, nylon-based polymers, urethane-based polymers, and polyolefin-based 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 coating layer is a polymer of a photocurable compound that may cause polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art. However, preferably, the photocurable compound may be a polyfunctional (meth) acrylate-based monomer or an oligomer, wherein the number of the (meth) acrylate-based functional groups is 2 to 10, preferably 2 to 8, Preferably 2 to 7, it 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, dipentaerythrite nucleus ( Meth) acrylate, dipentaerythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri (meth ) Acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate may be one or more selected from the group consisting of. 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 chelating ^"compounds such as acetyl acetonate salt of the organic metal compound; Two or more semi-ungmuls or polymerized compounds of these compounds; It may be a combination of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium salt groups in the molecule, it can be used without limitation low molecular type or polymer type. In addition, a conductive polymer and metal oxide fine particles may also be used as the antistatic agent. Examples of the conductive polymer include aromatic conjugated poly (paraphenylene), polycyclic heterocyclic conjugated polyolefin, polythiophene, aliphatic conjugated polyacetylene, and heteroanimal polyaniline conjugated conjugated system. Poly (phenylene vinylene), having a plurality of conjugated chains in a molecule And conjugated double-chain conjugated compounds, conductive composites obtained by grafting or block copolymerizing conjugated polymer chains to saturated polymers. 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, methoxy triethoxysilane, methacryloxy It may be at least one compound selected from the group consisting of propyltrimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.

 In addition, the metal alkoxide-based oligomer may be prepared through the sol-gel reaction of the 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 ΐ ″ may be rapidly reacted with water, 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 reaction efficiency, the molar ratio of the metal alkoxide compound to water (based on metal ions) 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 0.01 / 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 in the manufacture 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 its

A resin composition for forming a low refractive index layer including a (co) polymer, a fluorine-containing compound including a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and solid inorganic nanoparticles is applied on a hard coating layer, and then 35 ° C to 100 ° C. Drying at a temperature of; And photocuring the dried product 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 index layer formed on one surface of the hard coating layer, the binder resin and hollow inorganic nanoparticles dispersed in the binder resin and solid inorganic nanoparticles; and between the hard coating layer and the low refractive layer. 70 volume ¾> or more of the entire solid inorganic nanoparticle 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, more than 70 vol 3> of the 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, the hollow type in an area of more than 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 At least 70% by volume of the total inorganic nanoparticles may be present.

 In addition, in the anti-reflection film provided by the method for manufacturing the anti-reflection film, the low refractive index layer is a crab layer and the entire hollow inorganic nanoparticles containing at least 70% by weight of the total solid inorganic nanoparticles. The crab may include two layers of 70 wt% or more, and the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the two layers of crabs.

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 ° C to 100 ° C, or 40 ° C to 80 ⁰ C.

When the temperature for drying the low refractive index layer-forming resin composition applied on the hard coating layer is less than 35 ⁰ C, antifouling property of the low refractive index layer may be greatly reduced. In addition, if the temperature of drying the resin composition for forming the low refractive index layer applied on the hard coating layer is more than 100 ^o C, phase separation between the hollow inorganic nanoparticles and solid inorganic nanoparticles in the low refractive layer manufacturing process layer It is not common to occur, so that 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 / cin ³ or more higher than that of the hollow inorganic nanoparticles, and due to the density difference, the solid inorganic nanoparticles in the low refractive layer formed on the hard coating layer. May be located closer to the hard coating layer.

Specifically, the solid inorganic nanoparticles are 2.00 g / cin ³ to 4.00 It has a density of g / crf, the hollow inorganic nanoparticles may have a density of 1.50 g / cirf to 3.50 g / orf.

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 ° C to 100 ⁰ C 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 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 in the manufacture of a low refractive index layer or an antireflection film can be used without great care.

 The method and apparatus conventionally used to apply the photocurable coating composition may be used without particular limitation, for example, bar coating method such as Meyer bar, gravure coating method, 2 rol l reverse coating method, vacuum s lot die coating, 2 roll coating, and the like can be used.

 The low refractive layer may have a thickness of lnm to 300 ran, or 50ηηι to 200 rai. Accordingly, the thickness of the photocurable coating composition applied on the predetermined substrate may be about Iran to 300 ran, or 50nm 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 amount is preferably from 100 to 4,000 mJ / crf. Exposure time is also special It is not limited, It can change suitably according to the exposure apparatus used, the wavelength of irradiation light, or an exposure amount.

 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 above-described contents with respect to the anti-reflection 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-methylpyridone; Esters such as ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or combinations thereof.

The photopolymerization initiator may be used without any limitation as long as it is a compound known to be used in the photocurable resin composition, and specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or the like. Two or more kinds 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, it is uncured in the photocuring step of the photocurable coating composition Residual material may be issued. If the amount of the photopolymerization initiator is too large, the non-aqueous initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or reflectance of the film.

 Meanwhile, the photocurable coating composition may further include an organic solvent. Non-limiting examples of the organic solvents include ketones, alcohols, acetates and ethers, or combinations 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 two or more kinds thereof.

 The organic solvent may be included in the photocurable coating composition while being added at the time of mixing each component included in the photocurable coating composition or in the state in which each component is dispersed or mixed 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 resulting film due to the flowability of the photocurable coating composition is reduced. In addition, the solid content is lowered when the excessive amount of the organic solvent is added, the coating and film formation is not divided, the physical properties and surface properties of the film may be lowered, and a poor amount may occur during 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 for producing the anti-reflection film may further include applying a photocurable compound or a polymer resin composition for forming a hard coating layer including a (co) polymer, a photoinitiator, and an antistatic agent on a substrate and photocuring the same. Through the above steps, a hard coating layer may 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 commonly used to apply the polymer resin composition for forming the hard coating layer may be used without particular limitation, for example, a bar coating method such as Meyer bar, gravure coating method, 2 roll l reverse coating method, Vacuum slot die coating and 2 roll coating can be used. In the step of photocuring the polymer resin composition for forming the hard coating layer may be irradiated with ultraviolet light or visible light having a wavelength of 200 ~ 400nm, the amount of exposure during irradiation is preferably 100 to 4,000 mJ / cin ² . 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 the hard coating layer may be purged with nitrogen in order to apply nitrogen atmospheric conditions.

 【Effects of the Invention】

 According to the present invention, an anti-reflection film and a method of manufacturing the anti-reflection film can be provided 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 the screen of the display device. .

 [Brief Description of Drawings]

 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.

 7 shows a cross-sectional TEM photograph of the antireflective film of Comparative Example 1. FIG.

 8 shows a cross-sectional TEM photograph of the antireflective film of Comparative Example 2. FIG.

 9 shows a cross-sectional TEM photograph of the antireflective film of Comparative Example 3. FIG.

 FIG. 10 shows a graph obtained by Fourier transform analysis of the results of measuring X-ray reflectance by Cu-K α-rays for the antireflection film of Example 1. FIG.

 FIG. 11 shows a graph obtained by Fourier transform analysis of the result of measuring X-ray reflectance by Cu-K α-rays for the antireflection film of Example 2. FIG.

 FIG. 12 shows a graph obtained by Fourier transform analysis of the results of measuring X-ray reflectance by Cu-K α-rays for the antireflection film of Example 3. FIG.

 FIG. 13: shows the graph which carried out the Fourier transform analysis of the X-ray reflectance measurement result by Cu-K (alpha) ray about the antireflection film of Example 4. FIG.

 FIG. 14 shows a graph obtained by Fourier transform analysis of the results of measuring X-ray reflectance by Cu-K α-rays for the antireflection film of Example 5. FIG.

FIG. 15 shows a graph obtained by Fourier transform analysis of X-ray reflectance measurement results using Cu-K α rays for the antireflection film of Example 6. FIG. FIG. 16: shows the graph which carried out the Fourier transform analysis of the X-ray reflectance measurement result by Cu-K (alpha) ray about the antireflective film of the comparative example 1. FIG.

 FIG. 17 shows a graph obtained by Fourier transform analysis of X-ray reflectance measurement results using Cu-K α-rays for the antireflection film of Comparative Example 2. FIG.

 FIG. 18 shows a graph obtained by Fourier transform analysis of X-ray reflectance measurement results using Cu-K α rays for the antireflection film of Comparative Example 3.

 [Specific contents to carry out invention]

 The invention is explained in more detail in the following examples. However, the following examples are only for exemplifying the present invention, and the contents of the present invention are not limited to the following examples. <Production example>

 Preparation Example: Preparation of Hard Coating Film

 KY0EISHA salt type antistatic hard coating solution (50 wt% solids, product name: LJD-1000) was coated on a triacetyl cellulose film with # 10 mayer bar.

After drying at 90 ^o C for 1 minute, 150 mJ / cin ^! Was irradiated with UV light to prepare a hard coat film having a thickness of about 5 to 6 / mm 3.

<Examples 1 to 5: Preparation of Anti-reflection Films>

 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 ran, density: 1.96 g / citf, manufactured by JSC catalyst and chemi cal s) based on 100 parts by weight of pentaerythritol triacrylate (PETA), Solid silica nanoparticles (Diameter: about 12 ran, Density: 2.65 g / cirf) 63 parts by weight, Crab 1 fluorine compound (X-71-1203M, ShinEtsu Co., Ltd.) 131 parts by weight, crab 2-fluorine compound (RS-537, DIC) 19 parts by weight, initiator (Irgacure 127, Ciba) 31 parts by weight, solid content concentration of 3% by weight in a solvent of methyl i-butyl ketone Dilute to

 (2) Preparation of low refractive 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 ran, and dried and cured at the temperatures and times shown in Table 1 below. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / ciif 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 ran, density: 1.96 g / cin ¹ , manufactured by JSC catalyst and chemi cals) based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA), Solid silica nanoparticles (Diameter: about 12 ran, Density: 2.65 g / citf) 55 parts by weight, Crab 1 fluorine compound (X-71-1203M, ShinEtsu) 144 parts by weight, second fluorine-containing compound (RS- 537, DIC Corp.) 21 parts by weight, and 31 parts by weight of an initiator (Irgacure 127, Ciba) were diluted so as to have a solid concentration of 3% by weight in a MIBK (methyl i sobutyl ketone) solvent.

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

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

Table 11

Example 6

(1) Preparation of hard coating layer (HD2) Pentaerythritol triacrylate 30 g, high molecular weight copolymer (BEAMSET 371, Era, Epoxy Acrylate, molecular weight 40,000) 2.5 g, methyl ethyl ketone 20 g and leveling agent (Tego wet 270) ) After uniformly mixing 0.5 g), 2 g of an acrylic-styrene copolymer (volume average particle diameter: 2 μm, manufacturer: Sekisui Plastic) was added as fine particles having a refractive index of 1.525 to prepare a hard coating composition. The hard coating composition thus obtained was coated on a triacetylcell film with # 10 mayer bar and dried at 90 ^° C. for 1 minute. 150 mJ / crf was irradiated to the dried material to prepare a hard coating layer having a thickness of 5.

(2) Preparation of low refractive index layer and antireflection film Hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cirf, JGC) based on 100 parts by weight of pentaerythritol triacrylate (PETA) catalyst and chemicals) 135 parts by weight, solid silica nanoparticles (diameter: about 12 nm, density: 2.65 g / arf) 88 parts by weight, first fluorine-containing compound (X-71-1203M, ShinEtsu) 38 parts by weight 11 parts by weight of the second fluorine-containing compound (RS-537, DI), 7 parts by weight of the initiator (Irgacure 127, Ciba), methyl isobutyl ketone (MIBK): diacetone alcohol (DM): isopropyl alcohol A photocurable coating composition for producing a low refractive index layer was prepared by diluting the solvent to a weight ratio of 3: 3: 4 to a solid content concentration of 3 wt%. On the prepared hard coating layer (HD2), the photocurable coating composition for preparing the low refractive index layer obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 ran, dried at a temperature of 60 X for 1 minute, and Cured. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge. Comparative Example: Preparation of Antireflection 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 To prepare a, antireflection film was prepared in the same manner as in Example 1. Comparative Example 3

The antireflection film was prepared in the same manner as in Example 5 except that the photocurable coating composition for preparing the low refractive layer was dried and dried at about 140 ^° C.

Experimental Example: Measurement of Physical Properties of Antireflection Film

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

1. Reflectance measurement of antireflection 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 Sol idspec 3700 (SHIMADZU) apparatus.

2. Antifouling measurement

When a straight line of 5 cm length was drawn with a black name pen on the surface of the antireflective film obtained in Examples and Comparative Examples, and rubbed using a dust-free cloth. Checking the number of times to erase the antifouling properties.

 <Measurement standard>

 0: It is less than ten times to be erased

 Δ: 11 to 20 erase points

 X ： The erase point exceeds 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. Check for phase separation

 In the cross-sections of the antireflection films of FIGS. 1 to 7, it was determined that phase separation occurred when 70 volumes ¾> of all the solid inorganic nanoparticles (solid nano silica particles) used within 30 nm from the hard coating layer were present.

5. 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 index layers obtained in the above examples. Specifically, for the low refractive index layer obtained in each of the above examples, J. A. Woo 11 am Co. Using the device of 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 (1 ^ 3 (Ψ, Δ)) was applied to the first and second layers (Layer 1, Layer 2) of the low refractive index layer by using the Complete EASE software. A Cauchy model was used to fit the MSE to 3 or less.

[Formula 1]

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

6. Fourier transform analysis of X-ray reflectance measurement results by Cu-K α-ray

 X-ray reflectivity is about lcm * lcm (horizontal * vertical) sized antireflection film,

It measured by irradiating Cu-K (alpha) ray of the wavelength of 1.5418A. Specifically, the device used was a PANalytical X'Pert Pro MRD XRD, and applied a voltage of 45 kV and a current of 40 mA. The optics used are as follows.

 -Incident beam opt ic ： Primary mirror, Auto Attenuator, 1/16 ° FDS

Diffracted beam optic: Parallel plate col 1 imator (PPC) with silt (0.27)

 -Soller slit (0.04 rad), Xe counter

After adjusting the sample stage so that the value of 2theta (29) becomes 0, check the half-cut of the sample, and then set the angle of incidence and the angle of reflection to satisfy the specular condition, and perform Z Omega Z alignment to perform X- Ready to measure the line reflectance, 2Θ is measured at intervals of 0.004 ° from 0.2 ° to 3.2 °. Through this, the X-ray reflectance pattern was measured.

The Fourier transform analysis on the X-ray reflectance measurement result by the Cu-K α-ray was performed using PANalytical's X'pert Reflectivity program, and the input angle during the Fourier transform was 0.Γ ⁵ as the start angle. Input was 1.2 ° for end angle and 0.163 ° for critical angle.

Table 2

 [PI] and [P2] are thicknesses in which the poles of the Fourier transform intensity of the Y-axis appear in the Fourier transform analysis result graph for the X-ray reflectance measurement results by Cu-K α rays, respectively.

[Table 3]

Examples 1 to 6 of the antireflective film, as confirmed in Figs. 10 to 15, in the graph of Fourier transform analysis of the X-ray reflectance measurement results by Cu-K α-rays, 35 nm An extreme value of one Fourier transform intensity at a thickness of 55 nm to 55 nm and an extreme value of one Fourier transform intensity at a thickness of 85 ran to 105 ran, as shown in Table 2 above. Film is thorns It has been confirmed that high scratch resistance and antifouling property can be realized simultaneously with low reflectance of 70% or less in the light ray region.

 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 the hollow inorganic nanoparticles are concentrated and existed toward the interface between the hard coating layer and the low refractive index layer of the anti-reflection film.

 In addition, as shown in Table 3, in the low refractive layer of the embodiment, the hollow U nanoparticles and the second region in which the hollow inorganic nanoparticles and the solid inorganic nanoparticles are separated from each other by phases exhibit different refractive indices. It was confirmed that the first region in which the inorganic inorganic 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 had a refractive index of 1.400 or less.

 As described above, as shown in FIGS. 7 to 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 common without being separated. In addition, as shown in Table 2 and FIGS. 16 to 18, the low refractive layer of the antireflective films of Comparative Examples 1 to 3 may have a Fourier transform analysis (Four) on Cu-K c (X-ray reflectance measurement results by rays). ier transform analysi s) In the graph of results, both the thickness of 35 nm to 55 ran and the two thickness ranges of 85 nm to 105 nm do not exhibit poles, and also show relatively high reflectance and low It has been confirmed that it has scratch resistance and antifouling resistance.

Claims

 [Claim]

 [Claim 11

 In the graph of Fourier transform analysis of the results of X-ray reflectance measurement by Cu-K α-ray,

 Showing one extreme at a thickness of 35 nm to 55 nm from the surface and one extreme at a thickness of 85 ran to 105 nm from the surface,

 Anti-reflection film.

[Claim 2]

 The method of claim 1,

 Fourier transform analysis results of the X-ray reflectance measurement results by Cu-K α-rays for the anti-reflection film (Fourier transform strength (Four) ier transform magni tude).

[Claim 3]

 According to claim 1,

 X-ray reflectance measurement by the Cu-K α-rays is measured using a Cu-K α-ray having a wavelength of 1.5418 A for the antireflection film having a size of 1 cm * lcm (horizontal * length).

 Anti-reflection film.

[Claim 4]

 According to claim 1,

 The anti-reflection film is a hard coating layer; And a low refractive layer formed on the hard coating layer,

35 ran to 55 ran thickness and 85 ran to 105 ran from the surface Each being a thickness from the surface of the low refractive layer.

[Claim 5]

 In U,

 The anti-reflection film includes a hard coating layer; and a low refractive index layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

[Claim 6]

 The method of claim 5,

 Anti-reflection film, wherein the solid inorganic nanoparticles are distributed more than the hollow inorganic nanoparticles near the interface between the hard coating layer and the low refractive index layer

[Claim 7]

 The method of claim 6,

 The anti-reflection film of 70% or more 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.

[Claim 8]

 The method of claim 6,

 30% by volume or more of the entire hollow inorganic nanoparticles are present at a distance farther 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. .

[Claim 9]

 According to claim 6,

The low refractive index layer from the interface between the low refractive index _layer: The hard coat layer and An antireflective film, wherein at least 70% by volume of the total solid inorganic nanoparticles is present within a total thickness of 30¾>.

[Claim 10]

 The method of claim 9,

 The antireflection film of more than 70% by volume of the whole of the enhanced inorganic nanoparticles is present in the region of the total thickness of the low refractive index layer more than 3 from the interface between the hard coating layer and the low refractive index layer.

[Claim 11]

 The method of claim 6,

 The low refractive layer includes a first layer containing at least 70 volume ¾> of the total solid inorganic nanoparticles and a second layer containing at least 70 volume% of the entire hollow inorganic nanoparticles,

 The anti-reflection film of claim 1, wherein the crab layer is located closer to the interface between the hard coating layer and the low refractive layer than the crab layer 2.

[Claim 12]

 The method of claim 11,

 The first layer containing at least 70% by volume of the total solid inorganic nanoparticles is 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, anti-reflection film.

[Claim 13]

 The method of claim 5,

 The anti-reflection film of claim 1, wherein the solid inorganic nanoparticles have a density higher than or equal to 0.50 g / orf compared to the hollow inorganic nanoparticles.

[Claim 14] The method of claim 5,

 Each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may have at least one reactive functional 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. Containing, antireflection film.

[Claim 15]

 The method of claim 5,

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

[Claim 16]

 The method of claim 15,

 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.

[Claim 17]

 The method of claim 15,

 The fluorine-containing compound containing the photo-banung functional groups are each 2,000 to

An antireflection film having a weight average molecular weight of 200, 000.

[Claim 18] _.

 The method of claim 15,

 The binder resin comprises an anti-reflective film containing 20 to 300 parts by weight of the fluorine-containing compound containing the photo-banung functional group with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound.

[Claim 19] The method according to claim 5,

 The hard coating layer comprises a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin;

[Claim 20]

 The method of claim 19,

 The organic fine particles have a particle diameter of 1 to 10 ^,

 The inorganic particles have a particle size of 1 nm to 500 ran, anti-reflection film.