WO2017155337A1 - Anti-reflection film - Google Patents

Abstract

The present invention relates to an anti-reflection film comprising: a hard coating layer; and a low refractive layer comprising a binder resin, and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, wherein the low refractive layer comprises a first layer comprising at least 70 volume% of the total of the solid inorganic nanoparticles, and a second layer comprising at least 70 volume% of the total of the hollow inorganic nanoparticles. The anti-reflection film satisfies a predetermined condition when the ellipticity of polarization, measured by ellipsometry with respect to the first layer and/or the second layer included in the low refractive layer, is fitted by a Cauchy model.

Description

 【Specification】

 [Name of invention]

 Antireflection film

 [Technical Field] Cross Citation with Related Application (s)

 This application is filed with the Korean Patent Application No. 10-2016-0028468 filed March 9, 2016, the Korean Patent Application No. 10-2016-0029336 filed March 11, 2016, and the Korean Patent Application No. 10-2016 dated March 14, 2016. -0030395, and the benefit of priority based on Korean Patent Application No. 10-2017-0029953 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 antireflection film, and more particularly, to a high anti-reflective and antifouling property while having a low reflectance and a high light transmittance. will be.

 [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 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. 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 interlayer adhesion (interface adhesion) as a separate process of forming each layer.

 In addition, in order to improve 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 lowering the reflectance of the low refractive index layer, and the antifouling property of the low refractive layer surface is large due to the nanometer size particles. Degraded.

 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, the hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

 The 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 total hollow inorganic nanoparticles,

When optimizing the ellipticity of the polarization measured by el lsosometry for the second layer included in the low refractive index layer by the Cauchy model of Formula 1, the following A is 1.0 to 1.50 and B is from 0 to 0.007 and C is provided with a 0 to 1 *, the anti-reflection film satisfying the condition of ^10-3. [Formula 1]

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

 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 total hollow inorganic nanoparticles,

 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 Formula 1, the following A is 1.0 to

An antireflection film, which is 1.65, is provided. In addition, in the present specification, the hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

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

When the ellipticity of the polarization measured by ellipsometry for each of the first layer and the second layer included in the low refractive layer is optimized by the Cauchy model of Formula 1, An antireflection film is provided, wherein the difference between the A value for the first layer and the A value for the second layer is 0.100 to 0.200. Hereinafter, an antireflection film according to specific embodiment (s) of the present invention will be described in more detail. In the present specification, the 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 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.

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

In addition, silica hollow particles are silica particles derived from a silicon compound or an organosilicon compound, and mean particles having a void space on the surface and / or inside of the silica particles. According to one embodiment of the invention, the hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, wherein the low refractive layer is 70% by volume or more of the total solid inorganic nanoparticles. The first layer included and the second layer containing at least 70% by volume of the entire hollow inorganic nanoparticles, the second layer included in the low refractive index layer of the polarization measured by ellipsometry when the ellipticity hayeoteul Kosh the model of formula 1 as optimization (Cauchy model) (fitting), to a of 1.0 to 1.50 and B is from 0 to 0.007 and C is to satisfy the condition of 0 to 1 x ^10-3, the reflection Prevention films may be provided. 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.

Accordingly, the present inventors proceed with a study on the antireflection film, 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, high scratch resistance and antifouling property can be simultaneously realized while having low reflectance and high light transmittance. It was confirmed through the experiment to complete the invention.

 Specifically, the anti-reflection film may include 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; It may include a first layer containing at least 70% by volume of the total solid inorganic nanoparticles and a second layer containing at least 70 volume ¾> of the entire hollow inorganic nanoparticles.

 Ellipsometry is a low refraction layer comprising a first layer containing at least 70 vol% of the solid inorganic nanoparticles and a second layer containing at least 70 vol% of the entire hollow inorganic nanoparticles. ), When the ellipticity of the polarization is measured and fitted to a Cauchy model, it may represent an inherent Kosh parameter value.

Specifically, when the ellipticity of the polarization measured by ellipsometry of the second 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 1.50 and B is from 0 to 0.007, and C may satisfy the condition of 0 to 1 x ^10-3. In addition, with respect to the second layer included in the low refractive layer, the following A is 1.10 to 1.40, or 1.20 to 1.35, or 1.211 to 1.349, the following B is 0 to 0.007, or 0 to 0.00550, or 0 to 0.00513 , C may satisfy a condition of 0 to 1 * 1 (Γ ³ , or 0 to 5.0 * 10− ⁴ , or 0 to 4.8685 * 1 (Γ ⁴ ).

[Formula 1]

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

In addition, 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), the following A is 1.0 to 1.65 and B is 0.0010 to 0.0350, and C may satisfy the condition of 0 to 1 x ^10-3.

In addition, with respect to one layer contained in the low refractive layer, the following A is 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511, while the following B is 0 to 0.005, or 0 to 0.00580, or 0 to 0.00573 , to C it may satisfy the 0-1 * ^10-3, or from 0 to 5.0 * ^10-4, or from 0 to 4.1352 · ^10-4 conditions.

The ellipticity of the polarization and related data (Ellipsometry data ( ⁱ P, A)) measured by the ellipsometry can be measured using conventionally known methods and devices. For example, for the first layer and the second layer included in the low refractive layer, JA Woo 11 am Co. Using the device of the M-2000, it is possible to apply an angle of incidence of 70 ° and measure linearly polarized light in the wavelength range of 380 nm to 1000 ran. The measured linear light measurement data (Ellipsometry (1 ^ 3 (Ψ, Δ)) is divided into the first layer and the second layer by a Cauchy model of Formula 1 using the Complete EASE software. Can be optimized so that the MSE is 3 or less.

 The Kosh parameters A, B, and C in each of the first and second layers included in the low refractive index layer described above relate to changes in refractive index and extinction coefficient according to wavelengths, respectively, When the layer satisfies the Kosh parameters A, B, and C ranges as a result of the fitting to the above-described Cauchy model of Formula 1, it is possible to maintain an optimized electron density and refractive index distribution therein. As a result, a lower reflectance may be realized and a relatively stable structure may be prevented from scratches or external contaminants.

Specifically, the Kosh parameter A is related to the refractive index at the maximum wavelength, and B and C are related to the degree of decrease in the refractive index with increasing wavelength. Accordingly, each of the first layer and the second layer included in the low refractive layer is described above. When the Kosher parameters A, B, and C ranges obtained by the fitting of the Cauchy model of Formula 1 are satisfied, the above-described effects may be further improved and maximized. In addition, according to another embodiment of the invention, the hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

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

 When the ellipticity of the polarization measured by ellipsometry with respect to the first layer included in the low refractive index layer is optimized by the Cauchy model of the following general formula (1), the following A is 1.0 to An antireflection film, which is 1.65, may be provided.

[General Formula

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

 The Kosh parameter A relates to the refractive index at the maximum wavelength, as the Kosh parameter A for the first layer is 1.0 to 1.65, or 1.30 to 1.55, or 1.40 to 1.52, or 1.480 to 1.515, or 1.491 to 1.511. In addition, the anti-reflection film of the embodiment may maintain an optimized refractive index distribution therein, and thus may implement a lower reflectance in a required wavelength range.

The ellipticity of the polarization and related data (Ellipsometry data (, A)) measured by the ellipsometry may be measured and confirmed by the method described above with respect to the antireflection film according to one embodiment. More specifically, the ellipticity of the polarization measured by the ellipsometry can be determined by applying an incident angle of 70 ^ο and measuring linearly polarized light in the wavelength range of 380 nm to 1000 nm. In addition, according to another embodiment of the invention, the hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

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

 The ellipticity of the polarization measured by ellipsometry for each of the first and second layers included in the low refractive index layer was optimized by a Cauchy model of the following general formula (1). time,

 An antireflection film may be provided in which the difference between the A value for the first layer and the A value for the second layer is 0.100 to 0.200.

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

 The Kosh parameter A relates to the refractive index at the maximum wavelength, wherein the difference between the A value for the first layer and the A value for the second layer is 0.100 to 0.200, or 0.120 to 0.190, or 0.140 to 0.180, or 0.145. To 0.177, the anti-reflection film of the embodiment can greatly improve the mechanical properties of the outer surface while maintaining an optimized refractive index distribution, thereby realizing a lower reflectivity, and relative to scratches or external contaminants It may have a stable structure.

More specifically, with respect to the first layer included in the low refractive layer When the ellipticity of the polarization measured by ellipsometry is optimized by the Cauchy model of Formula 1, A is A for the first layer included in the low refractive layer. 1.0 to 1.65, or 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511.

 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 May be 1.0 to 1.50, or 1.10 to 1.40, or 1.20 to 1.35, or 1.211 to 1.349.

The ellipticity of the polarization and related data (Ellipsometry data ( ⁱ P, Z)) measured by the ellipsometry may be measured and confirmed by the method described above with respect to the antireflection film according to one embodiment.

 More specifically, the ellipticity of the polarization measured by the ellipsometry may be determined by applying an incident angle of 70 ° and measuring linearly polarized light in the wavelength range of 380 nm to 1000 ran. Hereinafter, specific contents of the antireflective film of the above-described embodiment (s) will be described.

 In the anti-reflection film of the above-described embodiment (s), the low refractive layer has a volume of at least 70 vol% of the first layer and at least 70 vol% of the entire hollow inorganic nanoparticles. It may include a second layer included, 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 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. A region in which the inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed may form an independent layer that is visible in the low refractive layer.

Specifically, the hard coating layer of the low refractive layer of the anti-reflection film And in the case of mainly distributing solid inorganic nanoparticles near the interface between the low refractive layers and mainly distributing hollow inorganic nanoparticles toward the opposite side of the interface, to the actual reflectivity previously obtainable using the inorganic particles. Compared with this, a lower reflectance can be achieved, and the low refractive index layer can realize both scratch resistance and antifouling resistance. In addition, the first layer including more than 70 volume ¾> of the total solid inorganic nanoparticles may be located within the total thickness of the low refractive index layer 5 from the interface between the hard coating layer and the low refractive index layer. More specifically, there may be a first layer including 70 volume 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, 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% 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. 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.

 '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. 70% by volume or more of the total solid inorganic nanoparticles may be confirmed by measuring the volume of the whole solid inorganic nanoparticles.

In addition, as described above, it can be visually confirmed that each of the first layer and the second layer, which is a region in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, is present in the low refractive layer. For example, it is possible to visually confirm that each of the first layer and the second layer exists in the low refractive layer by using a transmission electron microscope [Scanning Electron Microscope] or the like. Also The ratio of the solid inorganic nanoparticles and the hollow inorganic nanoparticles distributed in the first layer and the second layer in the low refractive 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 can 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 Equation 1. , B and C, and thus, the first layer and the second layer may be distinguished from each other. In addition, since the ellipticity of the polarization measured by ellipsometry is optimized by the Cauchy model of Formula 1, the thicknesses of the first and second layers can also be derived. The first layer and the second layer can be defined in the low refractive layer.

 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 in one layer. It may be an average value of. Accordingly, in the case where 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 crab layers overlap. However, even in this case, the thickness and position of the first layer and the second layer may be specified according to an area satisfying the average values of the Cosch parameters A, B, and C of the first layer and the second layer, respectively. .

 On the other hand, whether the hollow inorganic nanoparticles and solid inorganic nanoparticles are present in the specified region is determined by whether each of the hollow inorganic nanoparticles or solid inorganic nanoparticles are present in the specified region, Particles that exist across the interface of the particular region are determined to be excluded.

Among the low refractive layers 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. Therefore, 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 photocurable resin composition for forming a low refractive index layer containing two kinds of nanoparticles can be obtained by adjusting the dry silver.

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 / orf to 1.50 g / cin ³ , or 0.60 g / cin ³ 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 later, despite the difference in density between the two particles, a predetermined drying temperature and time should 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 reflectance of 1.5% or less, or 1.0% or less, or 0.50 to 1.0%, or 0.60% to 0.70%, or 0.62% to 0.67% in the visible light wavelength range of 380 nm to 780 nm. Can be represented.

 On the other hand, the first layer is 1 nm to 50 nm, or 2 nm to 40 nm, or

Having a thickness of 3 nm to 30 nm, and the second layer is 5 nm to 300 ran, or 10 nm to 200 nm, or 20 nm to 150 nm, or 25 nm to 120 nm, 30 nm It may have a thickness of 100 ran.

 The thickness of the first layer and the second layer can also be confirmed by optimizing the ellipticity of the polarity measured by ellipsometry (F i tt ting) with a Cauchy model of the following general formula (1).

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

 In addition, the hollow inorganic nanoparticles mean a particle having a maximum diameter of 200 ran 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 50 ran or 5 to 30 ran, or 10 to 20 nm.

 The hollow inorganic nanoparticles may have a diameter of 1 to 200 ran, or 10 to 100 ran, or 20 to 80 ran, or 40 to 70 nm.

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

 On the other hand, in the antireflection 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 ran. have.

 Measurement of the above-mentioned 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.

 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 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 (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, Dipentaerythri nuclei "(meth) acrylate, tripentaerythrib hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane polyethoxy tri (meth) acrylate, trimethyl to propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more thereof Compounds or urethane modified acrylate oligomers, epoxides Acrylate oligomers, etheracrylate oligomers, dendritic acrylate oligomers, or combinations of two or more thereof. It is preferable that molecular weight is 1,000-10,000.

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

 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-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-based monomer or oligomer include at least one compound after selection from the group consisting of the following formulas (11) to (15).

 [Formula 11]

In Formula 11, 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 12]

In Chemical Formula 12, c is an integer of 1 to 10.

 [Formula 13]

In Formula 13, d is an integer of 1 to 11.

[Formula 14]

In Formula 14, e is an integer of 1 to 5.

 15]

In Formula 15, f is an integer of 4 to 10.

On the other hand, the low refractive index layer containing fluorine-containing functional groups Portions derived from the compound may be included.

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

 Each of the ambles compound including the photo-banung 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. have.

 If 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, but are positioned inside the low refractive layer to be 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-reflective functional group is too high, the 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 photo-reflective functional group is i) an aliphatic compound or aliphatic ring compound in which at least one photo-reflective functional group is substituted, at least one fluorine is substituted in at least one carbon; ii) hetero aliphatic compounds or heteroaliphatic ring compounds 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 silicon; iv) 1 And polyether compounds substituted with the above photo-banung functional groups 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 20 to 300 parts by weight of the fluorine-containing compound including the photobanung functional group based on 100 parts by weight of the photopolymerizable compound.

 When the fluorine-containing compound containing the photoreactive functional group is added to the photopolymerizable compound in an excessive amount, 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 excellent durability or scratch resistance. You may not have a last name. In addition, when the amount of the ambleo 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 photobanung functional group may further include silicon or a silicon compound. That is, the fluorine-containing compound including the photo-banung functional group may optionally contain a silicon or silicon compound, specifically, the content of silicon in the fluorine-containing compound containing the photo-banung functional group may be 0.1 to 20% by weight> have.

 Silicon contained in the fluorine-containing compound including the photo-banung functional group can increase the compatibility with other components included in the photocurable coating composition of the embodiment, and thus it is observed that haze is generated in the final refractive layer. 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 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 hollow inorganic nanoparticles and solid inorganic nanoparticles in the low refractive index layer is excessive, phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not occur sufficiently in the manufacturing process of the low refractive index layer As a result, the reflectance may be increased, and surface irregularities may occur excessively, thereby degrading antifouling properties. In addition, when the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles of the low refractive index layer is too small, many of the solid inorganic nanoparticles are located in an area close to an 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 significantly increased.

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

 On the other hand, as the hard coating layer, a conventionally known hard coating layer may 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 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 dipentaerythrite nucliacrylate, dipentaerythroxy hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythriri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylic Laterate, trimethylpropane ethoxy triacrylate, 1, 6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol It may include one or more selected from the group of polyfunctional acrylate monomers consisting of diacrylate and ethylene glycol diacrylate.

 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, and the inorganic particles may have a particle size of 1 nm to 500 nm, or lnm to 300 nm. . 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 layer 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, It may be an inorganic fine particle 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 layer, a binder resin of a photocurable resin; And an antistatic agent dispersed in the binder resin.

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 monomer or oligomer, wherein the number of (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably Preferably 2 to 7, in terms of securing physical properties of the hard coating layer It is advantageous . More preferably, the photocurable compound is pentaerythroxy tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythride nucleus (Meth) acrylate, dipentaerythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri ( Meth) acrylate, and trimethyl may be one or more selected from the group consisting of propane polyethoxy tri (meth) acrylate. 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; Non-different 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 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 may be used without limitation low molecular 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 an aromatic conjugated poly (paraphenylene), a polycyclic ring having a heterocyclic conjugate, polythiophene, a polyacetylene having an aliphatic conjugate, and a polyaniline conjugated with a hetero atom. Poly (phenylene vinylene), a conjugated compound having a plurality of conjugated chains in a molecule, and a conjugated conjugated compound, a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain to a saturated polymer. In addition, 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 dispersed in the binder resin The hard coating layer including the antistatic agent may further include at least one compound selected from the group consisting of an alkoxy silane oligomer and a metal alkoxide oligomer.

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

 In addition, the metal alkoxide-based oligomer may be prepared through 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-based oligomer described above.

 However, since the metal alkoxide compound may react rapidly 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 0.1 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 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 a (co) polymer thereof, a fluorine-containing compound including a photobanung functional group, photoinitiator, hollow Applying a resin composition for forming a low refractive index layer including inorganic nanoparticles and solid inorganic nanoparticles on a hard coating layer and drying at a temperature of 35 ^° C. to 100 ^° C .; And photocuring the dried material of the resin composition.

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

 More specifically, in the antireflection film provided by the method for manufacturing the antireflection film, the low refractive layer is the first layer and 70% by weight of the total solid inorganic nanoparticles and the hollow inorganic nano The second layer may include a second layer including 70% by weight or more of the whole particles, and the first layer may be located closer to the interface between the hard coating layer and the low refractive layer 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 ^° C to 100 V, or 40 ^° C to 80 ^° C.

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 low refractive index layer-forming resin composition applied on the hard coating layer is more than 100 ^° C, phase separation between the hollow inorganic nanoparticles and solid-type inorganic nanoparticles during the low refractive layer manufacturing process is sufficient. It does not occur and is common, and not only the scratch resistance and antifouling property of the low refractive index layer is lowered, but also the reflectance can be greatly increased.

The solid inorganic nanoparticles together with the drying temperature in the process of drying the resin composition for forming a low refractive index layer applied on the hard coating layer And by adjusting the density difference between the hollow inorganic nanoparticles can form a low refractive layer having the above characteristics. 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 may have a density of 2.00 g / cirf to 4.00 g / cuf, and the hollow inorganic nanoparticles may have a density of 1.50 g / cin ³ to 3.50 g / cirf.

 On the other hand, the resin composition for forming a low refractive index layer coated on the hard coating layer

Drying at a temperature of 35 ^° C to 100 ^° 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 sufficiently occur. The ^'hand, when the drying time is too long, the low refractive index layer in which the formation can be eroded hard coating layer.

 On the other hand, the low refractive layer is a photocurable compound or a (co) polymer thereof, photoreactive. It can be prepared from a photocurable coating composition comprising a fluorine-containing compound containing a functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles 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 limitation.

 Methods and apparatuses 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, etc. may be used.

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

 In the step of photocuring the photocurable coating composition may be irradiated with ultraviolet light or visible light of a wavelength of 200 ~ 400nm, the exposure dose is preferably from 100 to 4,000 mJ / cu '. Exposure time is not specifically limited, either, The exposure apparatus used can be changed suitably according to the wavelength or exposure amount of irradiation light.

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

 Details of the fluorine-containing compound including the photocurable compound hollow inorganic nanoparticles, solid inorganic nanoparticles, and photoreactive functional groups include the above-described contents with respect to the anti-reflection film of the embodiment.

 Each of the vaporized 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 of ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or mixtures thereof.

The photopolymerization initiator may be used in the photocurable resin composition As long as it is a known compound, it can be used without a restriction | limiting, specifically, a benzophenone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, an oxime type compound, or these 2 or more types of mixtures can be used. For 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 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 methane, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butane, 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 monomethylyl 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 excess amount of the organic solvent is added, the coating and film formation is not enough, the physical properties and surface properties of the film may be lowered, and defects 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 wt% to 50 wt%, or 2 to 20 wt%. 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 (co) polymer thereof, a polymer resin composition for forming a hard coating layer including a photoinitiator and an antistatic agent on a substrate and photocuring the same. , Through the above steps can form a hard coating layer.

 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 coat layer may further include at least one compound selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers.

 The method and apparatus conventionally used to apply the polymer coating composition for forming the hard coating layer can 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 etc. can be used.

In the step of photocuring the polymer resin composition for forming a hard coating layer may be irradiated with ultraviolet light or visible light of a wavelength of 200 ~ 400nm, the exposure amount is preferably 100 to 4, 000 mJ / cin ² when irradiation. Exposure time is not specifically limited, either, The exposure apparatus used can be changed suitably according to the wavelength or exposure amount of irradiation light. 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.

 【Effects of the Invention】

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

 [Brief Description of Drawings]

1 shows a cross-sectional TEM photograph of the antireflective film of Example 1. FIG. Figure 2 shows a cross-sectional TEM photograph of the anti-reflection film of Example 2.

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

 4 shows a cross-sectional TEM photograph of the antireflective film of Example 4. FIG.

 Figure 5 shows a cross-sectional TEM photograph of the anti-reflection film of Example 5.

 6 shows a cross-sectional TEM photograph of the antireflective film of Example 6. FIG.

 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.

 [Specific contents to carry out invention]

 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: Preparation of Hard Coating Layer (HD1)

Antistatic hard coating solution of KYOEISHA salt type (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, and then 150 mJ / cin ² Ultraviolet rays were irradiated to prepare a hard coating layer having a thickness of about 5.

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

 Examples 1-4

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

Pentaerythritol to 100 parts by weight of triacrylate (PETA) Hollow silica nanoparticles (diameter: about 50 to 60 ran, density: 1.96 g / cin ³ , manufactured by JSC catalyst and chemicals) 281 parts by weight, solid silica nanoparticles (diameter: about 12 ran, density: 2.65 g / cin ³ ) 63 parts by weight, 131 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu), 19 parts by weight of the second fluorine-containing compound (RS-537, DIC), initiator (Irgacure 127, Ciba) ) 31 parts by weight of methyl isobutyl ketone (MIBK): diacetone alcohol (DM): isopropyl alcohol in a weight ratio of 3: 3: 4: was diluted in a mixed solvent to a solid content of 3 weight ¾.

 (2) manufacture of low refractive and antireflection films

 On the hard coating layer of the above preparation, the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 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 / cuf 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 / cirf, manufactured by JSC catalyst and chemicals) based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA) Silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cu) 55 parts by weight, 1 fluorine-containing compound (X-71-1203M, ShinEtsu) 144 parts by weight, 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) to a solid content of 3% by weight.

 (2) Preparation of low refractive layer and antireflection film

On the hard coating layer of the above preparation, the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at 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 / cin ² under nitrogen purge.

TABLE 1 Drying temperature Drying time Example 1 40 ^° C 1 min

Example 2 60 ^° C 1 min

Example 3 80 ^° C 1 min

Example 4 60 ^° C 2 minutes

Example 5 60 ^° C 3 minutes Example 6

 (1) Preparation of Hard Coating Layer (HD2)

 After pentaeryeri was uniformly mixed with 30 g of 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 having a refractive index of 1.525, an acrylic-styrene copolymer (volume average particle diameter: 2 manufacturer: Sekisui Plastic) ¾ was added to prepare a hard coating composition.

The hard coating composition thus obtained was coated on a triacetylsalose film with # 10 mayer bar and dried at 90 ^° C. for 1 minute. 150 mJ / cui ² 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

100 parts by weight of pentaerythritol triacrylate (PETA), 135 parts by weight of expanded silica nanoparticles (diameter: about 50 to 60 ran, density: 1.96 g / cirf, manufactured by JGC catalyst and chemicals) 88 parts by weight of silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cin ¹ ), 38 parts by weight of the first fluorine-containing compound (X-71-1203M, ShinEtsu), 2nd fluorine-containing compound (RS-537 .DI) 11 parts by weight, initiator (Irgacure 127, 7 parts by weight of Ciba, methyl isobutyl ketone (MIBK): diacetone alcohol (DM): isopropyl alcohol solids in a solvent mixed in a weight ratio of 3: 3: 4 Dilution to a concentration of 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 obtained above is coated with a # 4 mayer bar to a thickness of about 110 to 120 nm, and dried at a temperature of 60 ^° C for 1 minute. And cured. At the time of curing, the dried coating was subjected to 252 mJ / cuf under nitrogen purge. Ultraviolet rays were irradiated.

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. 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 of the antireflective films obtained in Examples and Comparative Examples in the visible light region (380 to 780 nm) was measured using a Sol idspec 3700 (SHIMADZU) instrument.

2. Antifouling measurement

 A 5 cm long straight line was drawn with a black name pen on the surface of the antireflective film 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.

 <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 was loaded on and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in the Examples and Comparative Examples. The maximum load at which 1 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 antireflective 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 exist. 5. Ellipsometry Measurements

 The ellipticity of the polarization was measured by ellipsometry on the low refractive index layer obtained in each of the above Examples and Comparative Examples.

Specifically, for the low refractive index layer obtained in each of the above Examples and Comparative Examples, JA Wool lam Co. Using the device of the M-2000, an angle of incidence of 70 ° was applied and linearly polarized light was measured in the wavelength range of 380 ran to 1000 ran. The measured Coplanar Measurement data (Ellipsometry data (¾ ^f , Z) is used for the first and second layers (Layer 1, Layer 2) of the low refractive index layer using the Complete EASE software. Cauchy model) to fit the MSE to 3 or less (fitting).

[Formula 1]

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

5. Measurement of the refractive index

 The refractive index at 550 nm was calculated using a Cauchy model measured at a wavelength of 380 nm to 1,000 nm for each of the first included in the low refractive index layer obtained in the above examples.

TABLE 2

 TABLE 3

As shown in FIGS. 1 to 6, it is confirmed that the hollow inorganic nanoparticles and the solid inorganic nanoparticles are phase separated in the low refractive layer of the antireflection film of Examples 1 to 6.

 Specifically, as confirmed by the analysis results of FIGS. 1 to 6, the low refractive index layer is 70% of the first layer and the entire hollow inorganic nanoparticles, including 70% by volume or more of the total solid inorganic nanoparticles. And a second layer having a volume of at least ¾>, wherein the solid inorganic nanoparticles are mostly present and flocked toward the interface between the hard coating layer and the low refractive layer of the antireflection film, and the hollow inorganic nanoparticles are hard It is confirmed that the first layer containing at least 70% by volume of the total solid inorganic nanoparticles is within 50% of the total thickness of the low refractive index layer from the interface between the low refractive index layers. Will be located.

In addition, when the ellipticity of the polarization measured by the ellipsometry (el l ipsometry) with respect to the second layer included in the low refractive index layer is optimized (Cauchy model) of the general formula 1 (fi tt ing), and a is from 1.0 to 1.50 and B is from 0 to 0.007, and C was confirmed in that it satisfies the condition of 0 to 1 x ^10-3. In addition, when the ellipticity of the polarization measured by el l ipsometry with respect to the first layer included in the low refractive index layer (fitt ing) by the Cauchy model of the general formula (1), a 1.0 to 1.65 and B is 0.0010 to 0.0350, and C must satisfy the condition of 0 to 1 x ^10-3.

 In addition, as shown in Table 2, it was confirmed that the anti-reflection film of the embodiment can realize a high scratch resistance and antifouling at the same time while showing a low reflectance of 0.70% or less in the visible light region.

 In addition, as shown in Table 3, the first layer and the second layer included in the low refractive layer of the embodiment has a different refractive index range, specifically, the first layer of the low refractive layer has a refractive index of 1.420 or more It was confirmed that the second layer of the low refractive layer exhibits a refractive index of 1.400 or less.

In contrast to this, as shown in FIGS. 6 and 7, Comparative Example 1 It is confirmed that hollow inorganic nanoparticles and solid inorganic nanoparticles are common without being separated in the low refractive layer of the antireflection film of the invention. In addition, the antireflection films of Comparative Examples 1 and 2 were measured with an antireflection film of Example when the ellipticity of the polarization measured by elliptical polarization (eUipsometry) was optimized by the Cauchy model of Formula 1. In the results and the fitting results by the Cauchy model, it was confirmed that they exhibit different ranges and also have relatively high reflectance and low scratch resistance and antifouling resistance.

Claims

[Patent Claims]

 [Claim 1]

 And 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.

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

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 the Cauchy model of the following general formula (1), the following A is 1.0 to 1.50 and B is 0 to 0.007 and C is to satisfy the condition of 0 to 1 x ^10-3, the anti-reflection film:

[Formula 1]

In Formula 1, η (λ) is a refractive index at λ wavelength, λ is in the range of 300 ran to 1800 nm, and A, Β and C are Kosh parameters. [Claim 2]

 Hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

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

The ellipticity of the polarization measured by ellipsotnetry with respect to the crab 1 layer included in the low refractive index layer was When fitted with the Cauchy model,

 An antireflection film having the following A of 1.0 to 1.65:

[Formula 1]

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

[Claim 3]

 Hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.

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

 When the ellipticity of the polarization measured by ellipsometry of each of the first layer and the second layer included in the low refractive layer is optimized by the Cauchy model of the following general formula (1),

 The antireflection film, wherein the difference between the A value for the first layer and the A value for the second layer is 0.100 to 0.200:

[Formula 1] + ^:: :: /. In Formula 1, η (λ) is the refractive index at the λ wavelength, λ is in the range of 300 ran to 1800 nm, and A, B and C are Kosh parameters. [Claim 4]

 The method according to any one of claims 1 to 3,

 The ellipticity of the polarization measured by the ellipsometry is determined by applying an angle of incidence of 70 ° and measuring linearly polarized light in the wavelength range of 380 ran to 1000 nm.

[Claim 5]

 The method of claim 1,

 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),

A to 1.0 to 1.65 and B is 0.0010 to 0.0350, and C is to satisfy the condition of 0 to 1 x ^10-3, the anti-reflection film:

[Formula 1]

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

[Claim 6]

 The method according to any one of claims 1 to 3,

 And the first layer is located closer to the interface between the hard coat layer and the low refractive layer than the second layer.

[Claim 7]

 According to claim 16,

70% by volume or more of the total solid inorganic nanoparticles The first layer is located within 50% of the total thickness of the low refractive index layer from the plane between the hard coating layer and the low refractive index layer, antireflection film.

[Claim 8]

 The method according to any one of claims 1 to 3,

 The first layer has a thickness of l nm to 50 ran,

 The second layer has a thickness of 5 nm to 300 nm.

[Claim 9]

 The method according to any one of claims 1 to 3,

 The solid inorganic nanoparticles have a diameter of 0.5 to 100 nm, the hollow inorganic nanoparticles have a diameter of 1 to 200 nm, antireflection film. [Claim 10]

 The method according to any one of claims 1 to 3,

 The reflective ring film exhibits an average reflectance of 1.5% or less in the visible light wavelength range of 380 nm to 780 ran. [Claim 11]

 The method according to any one of claims 1 to 3,

The anti-reflection film of claim ^1, wherein the solid inorganic nanoparticles have a density higher than or equal to 0.50 g / cin ³ as compared to the hollow inorganic nanoparticles. [Claim 12]

 The method according to any one of claims 1 to 3,

Each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may have at least one semi-ungsung 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 13]

 The method according to any one of claims 1 to 3,

 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 14]

 The method of claim 13,

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

Anti-reflection film having a weight average molecular weight of 200, 000.

[Claim 15]

 The method of claim 13,

 The binder resin is a (co) polymer of the photopolymerizable compound

An anti-reflection film comprising 20 to 300 parts by weight of a ambleso compound containing the photo-banung functional group per 100 parts by weight.

[Claim 16]

 The method according to any one of claims 1 to 3,

 The first layer included in the low refractive layer has a refractive index of 1.420 to 1.600 at 550 nm, anti-reflection film.

[Claim 17]

 The method of claim 16,

 The second layer included in the low refractive index layer has a refractive index of 1.200 to 1.410 at 550 nm, anti-reflection film.

[Claim 18]

The method according to any one of claims 1 to 3, And the hard coat layer comprises a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin.

[Claim 19]

 The method of claim 18, wherein the organic fine particles have a particle size of 1 to 10,

 The inorganic particles have a particle diameter of 1 nm to 500 nm, antireflection film.

[Claim 20]

 The method according to any one of claims 1 to 3,

 The hard coating layer is a binder resin of photocurable resin; And an antistatic agent dispersed in the binder resin.