KR101919128B1 - Anti-refractive film - Google Patents

Abstract

The present invention relates to a hard coating layer, And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, wherein the low refraction layer contains not less than 70% by volume of the total of the solid inorganic nanoparticles And a second layer containing at least 70% by volume of the total of the hollow inorganic nanoparticles, wherein the first layer and / or the second layer included in the low refractive layer are ellipsometry ) Is fitted to a ellipticity of a polarized light by a Cauchy model. The present invention relates to an antireflection film satisfying a predetermined condition.

Description

ANTI-REFRACTIVE FILM

The present invention relates to an antireflection film, and more particularly, to an antireflection film capable of simultaneously realizing high scratch resistance and antifouling property while having a low reflectance and a high transmittance, and capable of enhancing the clarity of a screen of a display device.

Generally, a flat panel display device such as a PDP or an LCD is equipped with an antireflection film for minimizing reflection of light incident from the outside.

As a method for minimizing the reflection of light, a method in which a filler such as an inorganic fine particle is dispersed in a resin and is coated on a substrate film to impart irregularities (anti-glare: AG coating); A method of forming a plurality of layers having different refractive indexes on a base film to use interference of light (anti-reflection (AR coating)) or a method of mixing them.

In the case of the AG coating, the absolute amount of the reflected light is equivalent to 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 the irregularities. However, since the AG coating deteriorates the sharpness of the screen due to the surface irregularities, much research on AR coating has been conducted recently.

As the film using the AR coating, a multi-layer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a substrate film has been commercialized. However, the method of forming a plurality of layers as described above is disadvantageous in that the interlayer adhesion force (interfacial adhesion) is weak and scratch resistance is deteriorated by separately performing the steps of forming each layer.

In order to improve the scratch resistance of the low refraction layer previously contained in the antireflection film, a method of adding various particles of nanometer size (for example, particles of silica, alumina, zeolite, etc.) has been mainly tried. However, in the case of using nanometer-sized particles as described above, there is a limit in increasing the scratch resistance while lowering the reflectance of the low refractive layer, and the antifouling property of the surface of the low refractive layer due to the nanometer- .

Accordingly, much research has been conducted to reduce the absolute reflection amount of light incident from the outside and to improve scratch resistance of the surface as well as to improve the antifouling property. However, the degree of improvement of the physical properties is insufficient.

An object of the present invention is to provide an antireflection film capable of simultaneously realizing high scratch resistance and antifouling property while having a low reflectance and a high light transmittance and capable of enhancing the clarity of a screen of a display device.

In this specification, the term " hard coat layer " And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, wherein the low refraction layer has a first region exhibiting a refractive index of at least 1.420 at 550 nm and a second region exhibiting a refractive index of 550 And a second region exhibiting a refractive index of 1.400 or less at a wavelength of 400 nm or less.

The first region may contain 70 vol% or more of the total solid nanoparticles, and the second region may include 70 vol% or more of the hollow nanoparticles.

The first region may be located closer to the interface between the hard coating layer and the low refractive layer than the second region.

The first region may have a refractive index of 1.420 to 1.600 at 550 nm and the second region may have a refractive index of 1.210 to 1.400 at 550 nm.

When the ellipticity of the polarized light measured by ellipsometry with respect to the second region included in the low refraction layer is fitted to a Cauchy model of the following Formula 1, A is 1.0 to 1.50 B is from 0 to 0.007, and C is from 0 to 1 * 10 ^-3 .

[Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

When the ellipticity of the polarized light measured by ellipsometry with respect to the first region included in the low refraction layer is fitted to a Cauchy model of the following Formula 1, the following A is 1.0 to 1.65 B is 0.0010 to 0.0350, and C is 0 to 1 * 10 ^-3 .

 [Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

The solid inorganic nanoparticles may have a density of 0.50 g / cm < 3 > or more higher than that of the hollow inorganic nanoparticles.

The binder resin contained in the low refraction layer may include a crosslinked (co) polymer of a fluoropolymer compound containing a (co) polymer of a photopolymerizable compound and a photoreactive functional group.

The low refraction 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.

The fluorinated compounds containing the photoreactive functional groups may each have a weight average molecular weight of 2,000 to 200,000.

The binder resin may contain 20 to 300 parts by weight of a fluorine-containing compound containing the photoreactive functional group per 100 parts by weight of the (co) polymer of the photopolymerizable compound.

The hard coating layer may include a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin. The organic fine particles may have a particle diameter of 1 to 10 mu m, and the inorganic fine particles may have a particle diameter of 1 nm to 500 nm.

Further, in this specification, the term " hard coat layer " And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, wherein the low refraction layer contains not less than 70% by volume of the total of the solid inorganic nanoparticles And a second layer containing at least 70% by volume of the hollow inorganic nanoparticles in total, wherein the second layer contained in the low refractive layer is a polarized Wherein A is from 1.0 to 1.50, B is from 0 to 0.007, and C is from 0 to 1 * 10 ^-3 when the ellipticity of the cemented carbide is optimized by a Cauchy model of the following general formula (1) An antireflection film is provided.

[Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

Further, in this specification, the term " hard coat layer " And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles,

Wherein the low refraction layer comprises a first layer containing not less than 70% by volume of the entire solid inorganic nanoparticles and a second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles,

When the ellipticity of the polarized light measured by ellipsometry is fitted to the Cauchy model of the general formula 1 with respect to the first layer included in the low refractive layer, , Is provided.

Further, in this specification, the term " hard coat layer " And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles,

Wherein the low refraction layer comprises a first layer containing not less than 70% by volume of the entire solid inorganic nanoparticles and a second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles,

When the ellipticity of the polarized light measured by the ellipsometry method for each of the first layer and the second layer included in the low refraction layer is fitted to the Cauchy model of the general formula 1, 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.

The antireflection film according to the specific embodiment (s) of the present invention will be described in more detail below.

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

Further, the fluorinated compound means a compound containing at least one fluorine element in the compound.

Also, (meth) acryl [meth] acryl is meant to include both acryl and methacryl.

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

Also, the term "hollow silica particles" refers to silica particles derived from a silicon compound or an organosilicon compound, in which voids are present on the surface and / or inside of the silica particles.

According to one embodiment of the invention, a hard coat layer is provided; And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles, wherein the low refraction layer contains not less than 70% by volume of the total of the solid inorganic nanoparticles And a second layer containing at least 70% by volume of the hollow inorganic nanoparticles in total, wherein the second layer contained in the low refractive layer is a polarized Wherein A is from 1.0 to 1.50, B is from 0 to 0.007, and C is from 0 to 1 * 10 ^-3 , when the ellipticity of the cemented carbons is fitted to the cauchy model of the general formula (1) An antireflection film may be provided.

Previously, in order to increase the scratch resistance of the antireflection film, an excessive amount of inorganic particles was added. However, the antireflection film had a limitation in enhancing the scratch resistance, and the reflectance and antifouling properties were lowered.

Accordingly, the inventors of the present invention conducted research on an antireflection film. When the hollow inorganic nanoparticles and the solid inorganic nanoparticles are distributed so as to be distinguishable from each other in the low refractive layer included in the antireflection film, And that high scratch resistance and antifouling property can be simultaneously realized while having a high light transmittance, and have completed the invention through experiments.

Specifically, the antireflection film comprises a hard coat layer; And a low refraction layer comprising a binder resin and hollow inorganic nanoparticles dispersed in the binder resin and solid inorganic nanoparticles, wherein the low refraction layer comprises 70 vol% or more of the solid inorganic nanoparticles, Or more of the hollow inorganic nanoparticles and a second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles.

The low refraction layer including a first layer containing not less than 70% by volume of the total solid inorganic nanoparticles and a second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles is subjected to ellipsometry, And the ellipticity of the polarization is measured by a Cauchy model, it is possible to represent a unique value of the COSH parameter.

Specifically, when the ellipticity of the polarized light measured by ellipsometry on the second layer included in the low refractive layer is fitted to a Cauchy model of the following general formula (1), the following equation 1.0 to 1.50, B is 0 to 0.007, and C is 0 to 1 * 10 ^-3 . The following A is from 1.10 to 1.40, or from 1.20 to 1.35, or from 1.211 to 1.349, and the following B is from 0 to 0.007, or from 0 to 0.00550, or from 0 to 0.00513, with respect to the second layer included in the low refractive layer , And C is 0 to 1 * 10 ^-3 , or 0 to 5.0 * 10 ^-4 , or 0 to 4.8685 * 10 ^-4 .

[Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

When the ellipticity of the polarized light measured by ellipsometry on the first layer included in the low refractive index layer is fitted to a Cauchy model of the following general formula 1, To 1.65, B is 0.0010 to 0.0350, and C is 0 to 1 * 10 ^-3 .

Further, the following layer A is 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511, and the layer B is 0 to 0.005, or 0 to 0.00580, or 0 to 0.00573, with respect to the first layer included in the low refractive layer , And C is 0 to 1 * 10 ^-3 , or 0 to 5.0 * 10 ^-4 , or 0 to 4.1352 * 10 ^{- 4} .

The ellipticity and related data (Ellipsometry data (Ψ, Δ)) of the polarization measured by the ellipsometry can be measured using a commonly known method and apparatus. For example, the first layer and the second layer included in the low refractive layer may be prepared by a method described in J. A. Woollam Co. Using an apparatus of M-2000, it is possible to measure linearly polarized light in a wavelength range of 380 nm to 1000 nm by applying an incident angle of 70 °. The measured Eulipsometry data (Ψ, Δ) is divided into the first layer and the second layer using a Cauchy model of the general formula 1 using Complete EASE software, 3 or less.

The cushion parameters A, B and C in each of the first layer and the second layer included in the low refraction layer described above relate to changes in refraction index and extinction coefficient depending on wavelengths, When the layer satisfies the ranges of the cose parameters A, B and C according to the result of fitting with the Cauchy model of the general formula 1 described above, it is possible to maintain the electron density and the refractive index distribution optimized therein , Thus providing a lower reflectance and having a relatively stable structure against scratches or external contaminants.

Specifically, the cose parameter A is related to the refractive index at the maximum wavelength, and B and C are related to the degree of reduction of the refractive index with the wavelength increase.

Accordingly, when the first layer and the second layer included in the low refraction layer respectively satisfy the ranges of the cushion parameters A, B, and C according to the result of fitting to the Cauchy model of the general formula 1 When satisfied, the above-described effect can be further improved and maximized.

According to another embodiment of the present invention, there is also provided a hard coat layer; And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles,

Wherein the low refraction layer comprises a first layer containing not less than 70% by volume of the entire solid inorganic nanoparticles and a second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles,

When the ellipticity of a polarized light measured by ellipsometry is fitted to a Cauchy model of the following general formula 1 with respect to the first layer included in the low refractive layer, An anti-reflection film may be provided.

 [Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

The crossover parameter A is related to the refractive index at the maximum wavelength where the cushion 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 , The antireflection film of this embodiment can maintain an optimized refractive index distribution therein, thereby realizing a lower reflectance in a required wavelength range.

The ellipticity and related data (Ellipsometry data (?,?)) Of the polarization measured by the ellipsometry can be measured and confirmed by the method described above with respect to the antireflection film of one embodiment.

More specifically, the ellipticity of the polarized light measured by the ellipsometry can be determined by measuring the linearly polarized light in a wavelength range of 380 nm to 1000 nm by applying an incident angle of 70 °.

According to another embodiment of the present invention, there is also provided a hard coat layer; And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles,

Wherein the low refraction layer comprises a first layer containing not less than 70% by volume of the entire solid inorganic nanoparticles and a second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles,

When the ellipticity of the polarization of each of the first and second layers included in the low refractive index layer measured by ellipsometry is fitted to a Cauchy model of the following general formula (1)

An anti-reflection film having a 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 the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

The crosstalk parameter A is related to the refractive index at the maximum wavelength where the difference between the A value for the first layer and the A value for the second layer is from 0.100 to 0.200, or 0.120 to 0.190, or 0.140 to 0.180, or 0.145 To 0.177, the antireflection film of this embodiment can greatly improve the mechanical properties of the outer surface while maintaining an optimized refractive index distribution, thereby realizing a reflectance lower than this and providing a relatively low refractive index relative to scratch or external contaminants It can have a stable structure.

More specifically, when the ellipticity of the polarized light measured by ellipsometry is fitted to the Cauchy model of the general formula 1 with respect to the first layer included in the low refractive layer, For the first layer included in the refraction layer, A may be 1.0 to 1.65, or 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511.

When the ellipticity of the polarization measured by ellipsometry is fitted to the Cauchy model of the general formula 1 with respect to the second layer included in the low refractive layer, 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 and related data (Ellipsometry data (?,?)) Of the polarization measured by the ellipsometry can be measured and confirmed by the method described above with respect to the antireflection film of one embodiment.

More specifically, the ellipticity of the polarized light measured by the ellipsometry can be determined by measuring the linearly polarized light in a wavelength range of 380 nm to 1000 nm by applying an incident angle of 70 °.

Hereinafter, the specific contents of the antireflection film of the above embodiment (s) will be described.

In the antireflection film of the above-described embodiment (i), the low refraction layer comprises a first layer containing not less than 70% by volume of the total of the solid inorganic nanoparticles and not less than 70% by volume of the whole hollow inorganic nanoparticles 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 refraction 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 surface of the interface. It is possible to form an independent layer in which regions where the inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed are visually confirmed in the low refractive layer.

Specifically, when the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer in the low refractive index layer of the antireflection film and the hollow inorganic nanoparticles are mainly distributed on the opposite side of the interface , It is possible to achieve a lower reflectance than the actual reflectance that could be obtained by using the inorganic particles previously, and the low refraction layer can also achieve greatly improved scratch resistance and antifouling properties.

In addition, the first layer containing not less than 70% by volume of the total solid inorganic nanoparticles may be located within 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer. More specifically, from the interface between the hard coating layer and the low refraction layer, a first layer containing not less than 70% by volume of the entire solid inorganic nanoparticles may be present within the total thickness of the low refraction layer within 30%.

As described above, the hollow inorganic nanoparticles may be mainly distributed on the opposite side of the interface between the hard coating layer and the low refractive layer in the low refractive layer. Specifically, 30 At least 50 vol.%, Or at least 70 vol.% May be present at a greater distance from the interface between the hard coat layer and the low refractive layer than from the entire solid inorganic nanoparticle in the thickness direction of the low refractive layer . 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.

That 70% by volume or more of the solid type 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 layer, More than 70% by volume of the solid type inorganic nanoparticles can be identified by measuring the volume of the entire solid type inorganic nanoparticles.

As described above, it can be visually confirmed that each of the first layer and the second layer, in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, is present in the low refractive layer. For example, it can be visually confirmed that each of the first layer and the second layer is present in the low refractive layer by using a transmission electron microscope or a scanning electron microscope, The ratio of the solid inorganic nanoparticles and the hollow inorganic nanoparticles distributed in the first layer and the second layer in the layer can also be confirmed.

On the other hand, each of the first layer containing not less than 70% by volume of the total solid inorganic nanoparticles and the second layer containing not less than 70% by volume of the whole hollow inorganic nanoparticles share a common optical property in one layer And thus can be defined as a single layer.

More specifically, when the ellipticity of the polarization measured by ellipsometry is fitted to the Cauchy model of the general formula (1), each of the first layer and the second layer has a specific coherence parameter A , B and C, so that the first layer and the second layer can be distinguished from each other. Also, since the thicknesses of the first layer and the second layer can be derived by fitting the ellipticity of the polarization measured by the ellipsometry to the Cauchy model of the general formula 1, The definition of the first layer and the second layer in the low refraction layer becomes possible.

On the other hand, when the ellipticity of the polarization measured by the ellipsometry is fitted to the Cauchy model of the general formula 1, the derived coke parameters A, B, May be an average value. Accordingly, when an interface exists between the first layer and the second layer, there may be a region where the first layer and the second layer overlap with the cushion parameters A, B, and C, respectively. However, even in this case, the thickness and the position of the first layer and the second layer can be specified along the region that satisfies the average value of the cushion parameters A, B, and C of each of the first layer and the second layer .

Whether or not the hollow inorganic nanoparticles and the solid inorganic nanoparticles are present in the specified region determines whether each of the hollow inorganic nanoparticles or the solid inorganic nanoparticles exists in the specified region, Except for the particles existing over the boundary surface of the specific region.

The solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer in the low refractive index layer of the antireflection film and the hollow inorganic nanoparticles are mainly distributed on the opposite side of the interface, Two or more portions or two or more layers having different refractive indexes may be formed in the low refraction layer, so that the reflectance of the antireflection film may be lowered.

The specific distribution of the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the low refractive layer can be controlled by controlling the density difference between the solid inorganic nanoparticles and the hollow inorganic nanoparticles in the specific manufacturing method described below, A photocurable resin composition for forming a low refractive index layer containing nanoparticles of the species can be obtained by controlling the drying temperature.

Specifically, the solid type inorganic nanoparticles may have a density of 0.50 g / cm 3 or more higher than that of the hollow inorganic nanoparticles, and the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles is 0.50 g / cm3 to 1.50 g / cm3, or 0.60 g / cm3 to 1.00 g / cm3.

Due to such a difference in density, 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 from the production methods and examples to be described later, it is necessary to effect the drying temperature and time at a predetermined temperature despite the difference in density between the two kinds of particles to realize the distribution pattern of the particles in the low refractive layer .

When the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer in the low refraction layer of the antireflection film and the hollow inorganic nanoparticles are mainly distributed on the opposite surface of the interface, It is possible to realize a reflectance lower than that which can be obtained by using inorganic particles. Specifically, the reflection 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 band region of 380 nm to 780 nm .

On the other hand, the first layer has a thickness of 1 nm to 50 nm, or 2 nm to 40 nm, or 3 nm to 30 nm, and the second layer has a thickness of 5 nm to 300 nm, or 10 nm to 200 nm, 20 nm to 150 nm, or 25 nm to 120 nm, and 30 nm to 100 nm.

The thicknesses of the first layer and the second layer can be confirmed by fitting the ellipticity of the polarized light measured by ellipsometry to a Cauchy model of the following general formula (1).

The solid type inorganic nanoparticle means a particle having a maximum diameter of 100 nm or less and no void space therein.

The hollow inorganic nanoparticles mean particles having a maximum diameter of 200 nm or less and having voids 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 nm, or 5 to 30 nm, or 10 to 20 nm.

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

The diameter of each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may mean the longest diameter of the nanoparticles identified on the cross section.

On the other hand, each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may have at least one reactive group selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group, and a thiol group, Functional groups. As each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles contains the above-mentioned reactive functional group on the surface, the low refractive layer can have a higher degree of crosslinking, thereby ensuring more improved scratch resistance and antifouling property can do.

On the other hand, in the antireflection film of the embodiment (s) described above, the first layer and the second layer included in the low refractive layer may have refractive indexes in different ranges.

More specifically, the first layer included in the low refraction layer may have a refractive index of 550 nm to 1.420 to 1.600, or 1.450 to 1.550, or 1.480 to 1.520, or 1.491 to 1.511.

Further, the second layer included in the low refractive layer may have a refractive index of 550 nm to 1.200 to 1.410, or 1.210 to 1.400, or 1.211 to 1.375.

The refractive index can be measured by a commonly known method. For example, the elliptically polarized light and the Cauchy model 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 Can be determined by calculating the refractive index at 550 nm.

On the other hand, the above-mentioned low refraction layer can be produced from a photocurable coating composition including a photopolymerizable compound, a fluorine compound containing a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles, and a photoinitiator.

Accordingly, the binder resin contained in the low refraction layer may include a crosslinked (co) polymer of a fluoropolymer compound containing a (co) polymer of a photopolymerizable compound and a photoreactive functional group.

The photopolymerizable compound contained in the photocurable coating composition of this embodiment can form the base of the binder resin of the low refractive layer to be produced. Specifically, the photopolymerizable compound may include a monomer or an oligomer containing a (meth) acrylate or a vinyl group. More specifically, the photopolymerizable compound may comprise monomers or oligomers containing one or more, or two or more, or three or more (meth) acrylates or vinyl groups.

Specific examples of the monomer or oligomer including (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, trimethylolpropane tri (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol hexa Butyl methacrylate, butyl methacrylate, or a mixture of two or more thereof, or a urethane-modified acrylate oligomer, epoxidized acrylate oligomer, Side acrylate oligomer , There may be mentioned ether acrylate oligomers, the dendritic acrylate oligomer, or a mixture of these two or more kinds. 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.

The content of the photopolymerizable compound in the photocurable coating composition is not particularly limited, but the content of the photopolymerizable compound in the solid content of the photocurable coating composition, considering the mechanical properties of the low refractive index layer and the antireflection film, May be from 5% to 80% by weight. The solids content of the photocurable coating composition refers only to components of the solids in the photocurable coating composition, excluding components of the liquid phase, such as, for example, organic solvents that may optionally be included as described below.

Meanwhile, the photopolymerizable compound may further include a fluorine-based (meth) acrylate monomer or an oligomer in addition to the monomer or oligomer described above. When the fluorine-based (meth) acrylate monomer or oligomer is further contained, 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% 10%. ≪ / RTI >

Specific examples of the fluorine-based (meth) acrylate-based monomer or oligomer include at least one compound selected from the group consisting of the following formulas (11) to (15).

(11)

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

[Chemical Formula 12]

In the above formula (12), c is an integer of 1 to 10.

[Chemical Formula 13]

In the above formula (13), d is an integer of 1 to 11.

[Chemical Formula 14]

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

[Chemical Formula 15]

In the above formula (15), f is an integer of 4 to 10.

On the other hand, the low refraction layer may include a portion derived from a fluorinated compound containing the photoreactive functional group.

The fluorinated compound containing the photoreactive functional group may contain at least one photoreactive functional group, and the photoreactive functional group may participate in the polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light. ≪ / RTI > The photoreactive functional group may include various functional groups known to be capable of participating in the polymerization reaction by irradiation of light. Specific examples thereof include a (meth) acrylate group, an epoxide group, a vinyl group or a thiol group Thiol).

Each of the fluorinated compounds containing the photoreactive functional group may have a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by GPC method) of 2,000 to 200,000, preferably 5,000 to 100,000.

If the weight average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too small, the fluorine-containing compounds in the photocurable coating composition can not be uniformly and effectively arranged on the surface, The antifouling property of the surface of the low refraction layer is lowered and the cross-linking density of the low refraction layer is lowered, so that the mechanical properties such as the overall strength and the crush resistance can be deteriorated.

In addition, if the weight average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too high, the compatibility with other components in the photocurable coating composition may be lowered, and thus the haze of the low refractive index layer The light transmittance may be lowered, and the strength of the low refractive index layer may also be lowered.

Specifically, the fluorinated compound containing the photoreactive functional group may be selected from i) an aliphatic compound or an aliphatic cyclic compound in which at least one photoreactive functional group is substituted and at least one fluorine is substituted for at least one carbon; ii) a heteroaliphatic compound or heteroaliphatic ring compound substituted with at least one photoreactive functional group, at least one hydrogen substituted with fluorine and at least one carbon substituted with silicon; iii) a polydialkylsiloxane-based polymer (for example, a polydimethylsiloxane-based polymer) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted for at least one silicon; iv) a polyether compound which is substituted by at least one photoreactive functional group and at least one of which is substituted by fluorine, or a mixture of at least two of i) to iv), or a copolymer thereof.

The photocurable coating composition may include 20 to 300 parts by weight of a fluorine compound containing the photoreactive functional group per 100 parts by weight of the photopolymerizable compound.

When the fluorine-containing compound containing the photoreactive functional group is added in excess to the photopolymerizable compound, the coating properties of the photocurable coating composition of the embodiment may be deteriorated or the low refractive layer obtained from the photocurable coating composition may have sufficient durability or scratch resistance . ≪ / RTI > If the amount of the fluorine-containing compound containing the photoreactive functional group is too small as compared with the photopolymerizable compound, the low refractive layer obtained from the photocurable coating composition may not have sufficient mechanical properties such as antifouling property and scratch resistance.

The fluorinated compound containing the photoreactive functional group may further contain silicon or a silicon compound. That is, the fluorinated compound containing the photoreactive functional group may optionally contain silicon or a silicon compound. Specifically, the silicon content of the fluorinated compound containing the photoreactive functional group may be 0.1 wt% to 20 wt% .

The silicon contained in the fluorine-containing compound containing the photoreactive functional group can increase the compatibility with other components contained in the photocurable coating composition of the embodiment, and thus haze is generated in the finally produced refractive layer Thereby enhancing transparency. On the other hand, if the content of silicon among the fluorinated compounds containing the photoreactive functional group is too large, compatibility between the other components contained in the photocurable coating composition and the fluorinated compound may be lowered, The refractive layer or the antireflection film does not have sufficient transparency and antireflection performance, and the antifouling property of the surface may also be deteriorated.

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

When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive index layer is excessively large, phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not sufficiently take place in the process of producing the low refractive index layer, And the reflectance may be increased, and the surface irregularity may be excessively generated and the antifouling property may be lowered. When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive index layer is excessively small, a majority of the solid inorganic nanoparticles are located in a region near the interface between the hard coating layer and the low refractive index layer. And the reflectance of the low refraction layer can be greatly increased.

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

On the other hand, as the hard coat layer, a commonly known hard coat layer can be used without any limitation.

As an example of the hard coating layer, there can be mentioned a hard coating layer comprising a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin.

The photocurable resin included in the hard coat layer is a polymer of a photocurable compound which can cause a polymerization reaction upon irradiation with light such as ultraviolet rays, and may be conventional in the art. Specifically, the photo-curable resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethyl propane ethoxy tri At least one member selected from the group consisting of polyfunctional acrylate monomers consisting of acrylate, 1,6-hexanediol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate . ≪ / RTI >

For example, the organic fine particles may have a particle diameter of 1 to 10 mu m, and the inorganic particles may have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm Lt; / RTI > The particle diameter of the organic or inorganic fine particles may be defined as a volume average particle diameter.

For example, the organic or inorganic fine particles may be organic fine particles composed of an acrylic resin, a styrene resin, an epoxide resin and a nylon resin, or may be an organic fine particle such as silicon oxide, Titanium dioxide, indium oxide, tin oxide, zirconium oxide, and zinc oxide.

The binder resin of the hard coat layer may further comprise 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 at least one selected from the group consisting of a cellulosic polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer.

As another example of the hard coating layer, a binder resin of a photocurable resin; And a hard coat layer comprising an antistatic agent dispersed in the binder resin.

The photocurable resin included in the hard coat layer is a polymer of a photocurable compound which can cause a polymerization reaction upon irradiation with light such as ultraviolet rays, and may be conventional in the art. Preferably, however, the photocurable compound may be a polyfunctional (meth) acrylate monomer or an oligomer, wherein the number of (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably Is preferably from 2 to 7 in terms of ensuring the physical properties of the hard coat layer. More preferably, the photocurable compound is selected from the group consisting of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, Tri (meth) acrylate, and tri (meth) acrylate.

The antistatic agent is a quaternary ammonium salt compound; Pyridinium salts; A cationic compound having 1 to 3 amino groups; Anionic compounds such as sulfonic acid bases, sulfuric acid ester bases, phosphoric acid ester bases, and phosphonic acid bases; Amphoteric or aminosulfuric ester compounds; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; A metal chelate compound such as an acetylacetonate salt of the organometallic compound; Two or more reactants or polymers of such compounds; Or a mixture of two or more of such compounds. Here, the quaternary ammonium salt compound may be a compound having at least one quaternary ammonium salt group in the molecule, and a low molecular weight or polymer type may be used without limitation.

As the antistatic agent, a conductive polymer and metal oxide fine particles may also be used. Examples of the conductive polymer include an aromatic conjugated poly (paraphenylene), a heterocyclic conjugated polypyrrole, a polythiophene, an aliphatic conjugated polyacetylene, a conjugated polyaniline containing a heteroatom, a mixed poly Phenylene vinylene), a double bond type conjugated compound which is a conjugated system having a plurality of conjugated chains in the molecule, and an electrically conductive complex in which a conjugated polymer chain is grafted or block copolymerized with a saturated polymer. Examples of the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminum oxide, antimony doped tin oxide, and aluminum doped zinc oxide.

A binder resin of the photocurable resin; And an antistatic agent dispersed in the binder resin may further include at least one compound selected from the group consisting of an alkoxysilane-based oligomer and a metal alkoxide-based oligomer.

The alkoxysilane-based compound may be one that is conventional in the art, but preferably includes tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl At least one compound selected from the group consisting of trimethoxysilane, glycidoxypropyltrimethoxysilane, and glycidoxypropyltriethoxysilane.

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

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

Here, the metal alkoxide 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 탆 to 100 탆.

And a substrate bonded to the other surface of the hard coating layer. The specific type and thickness of the substrate are not limited to a great extent, and descriptions known to be used in the production of a low refractive layer or an antireflection film can be used without any limitations.

On the other hand, the antireflection film of the embodiment is a resin for forming a low refractive layer including a photo-curing compound or its (co) polymer, a fluorine compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles Applying the composition onto the hard coat layer and drying at a temperature of from 35 캜 to 100 캜; And a step of photocuring the dried product of the resin composition.

Specifically, the antireflection film provided by the method for producing an antireflection film is characterized in that the hollow inorganic nanoparticles and the solid inorganic nanoparticles are distributed so as to be distinguishable from each other in the low refractive layer, and accordingly, a low reflectance and a high transmittance High scratch resistance and antifouling property can be realized at the same time.

More specifically, in the antireflection film provided by the method for producing an antireflection film, the low refractive layer comprises a first layer containing not less than 70% by weight of the total solid inorganic nanoparticles and the first layer containing the hollow inorganic nano- The first layer may include a second layer containing at least 70% by weight of the total particles, and the first layer may be positioned closer to the interface between the hard coat layer and the low refractive layer than the second layer.

Wherein the low refraction layer comprises a resin composition for forming a low refraction layer containing a photo-curable compound or its (co) polymer, a fluorine compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles on a hard coat layer And drying at a temperature of from 35 캜 to 100 캜, or from 40 캜 to 80 캜.

If the temperature for drying the resin composition for forming a low refraction layer coated on the hard coat layer is less than 35 占 폚, the antifouling property of the formed low refraction layer may be greatly lowered. When the temperature for drying the resin composition for forming a low refraction layer coated on the hard coating layer is more than 100 ° C., the phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles occurs sufficiently during the production of the low refraction layer So that the scratch resistance and antifouling property of the low refraction layer are lowered and the reflectance can be greatly increased.

In the course of drying the resin composition for forming a low refractive index layer coated on the hard coat layer, the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles is adjusted together with the drying temperature to obtain a low refractive index layer having the above- Can be formed. The solid inorganic nanoparticles may have a density higher than that of the hollow inorganic nanoparticles by 0.50 g / cm 3 or more. Due to such a difference in density, the solid inorganic nanoparticles in the low refractive layer, which is formed on the hard coating layer, And can be located closer to the hard coat layer side.

Specifically, the solid inorganic nanoparticles may have a density of 2.00 g / cm3 to 4.00 g / cm3, and the hollow inorganic nanoparticles may have a density of 1.50 g / cm3 to 3.50 g / cm3.

On the other hand, the step of drying the resin composition for forming a low refraction layer coated on the hard coat layer 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, the above-mentioned solid type inorganic nanoparticles and hollow inorganic nanoparticles may not sufficiently undergo phase separation phenomenon. On the other hand, if the drying time is too long, the formed low refraction layer may erode the hard coating layer.

On the other hand, the low refraction layer can be prepared from a photocurable coating composition comprising a photocurable compound or its (co) polymer, a fluorine compound containing a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles and a photoinitiator .

The low refraction layer can be obtained by applying the photocurable coating composition onto a predetermined substrate and photocuring the coated resultant. The specific type and thickness of the substrate are not limited to a great extent, and descriptions known to be used in the production of a low refractive layer or an antireflection film can be used without any limitations.

The method and apparatus commonly used for applying the photocurable coating composition may be used without limitation, and examples thereof include a bar coating method such as Meyer bar, a gravure coating method, a 2 roll reverse coating method, a vacuum slot die coating A 2 roll coating method, or the like can be used.

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

In the step of photocuring the photocurable coating composition, ultraviolet rays or visible rays having a wavelength of 200 to 400 nm may be irradiated, and an exposure dose of 100 to 4,000 mJ / cm 2 is preferable. The exposure time is not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiation light, or the exposure dose.

In the step of photo-curing the photocurable coating composition, nitrogen purging or the like may be applied to apply nitrogen atmosphere conditions.

Specific details regarding the fluorinated compound containing the photocurable compound, the hollow inorganic nanoparticle, the solid inorganic nanoparticle, and the photoreactive functional group include the above-described contents of the antireflection film of one embodiment.

Each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles may be contained in a composition in a colloidal state dispersed in a predetermined dispersion medium. Each of the colloidal phases 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 each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the photocurable coating composition and the viscosity of the photo- The solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the colloidal phase may be 5 wt% to 60 wt%, for example.

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

The photopolymerization initiator may be any compound known to be usable in the photocurable resin composition. The photopolymerization initiator may be a benzophenone based compound, an acetophenone based compound, a nonimidazole based compound, a triazine based compound, a oxime based compound, Mixtures of two or more of these may be used.

The photopolymerization initiator may be used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the photopolymerizable compound. If the amount of the photopolymerization initiator is too small, the photocurable coating composition may be uncured in the photocuring step to produce a residual material. If the amount of the photopolymerization initiator is too large, the unreacted initiator may remain as an impurity or the crosslinking density may be lowered, so that the mechanical properties of the produced film may be deteriorated or the reflectance may be greatly increased.

On the other hand, the photocurable coating composition may further include an organic solvent.

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

Specific examples of such an organic solvent include ketones such as methyl ethyl ketone, 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; Ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more thereof.

The organic solvent may be added to the photocurable coating composition at the time of mixing the components contained in the photocurable coating composition, or may be added to the photocurable coating composition while the components are dispersed or mixed in an organic solvent. If the content of the organic solvent in the photocurable coating composition is too low, the flowability of the photocurable coating composition may be deteriorated, resulting in defects such as streaks on the finally produced film. In addition, when the organic solvent is added in an excess amount, the solid content is lowered and the coating and film formation are not sufficiently performed, so that the physical properties and surface characteristics of the film may be deteriorated, and defects may occur during the drying and curing process. Accordingly, the photocurable coating composition may comprise an organic solvent such that the concentration of the total solids of the components involved is between 1 wt% and 50 wt%, or between 2 wt% and 20 wt%.

The hard coat layer can be used without any limitations as long as it is a material known to be usable for the antireflection film.

Specifically, the manufacturing method of the antireflection film may further include coating a substrate with a polymer resin composition for forming a hard coating layer containing a photocurable compound or a (co) polymer thereof, a photoinitiator, and an antistatic agent, and photo- , The hard coat layer can be formed through the above steps.

The components used for forming the hard coat layer are as described above with respect to the antireflection film of one embodiment.

The hard coating layer-forming polymeric resin composition may further comprise at least one compound selected from the group consisting of an alkoxysilane-based oligomer and a metal alkoxide-based oligomer.

For example, a bar coating method such as a Meyer bar method, a gravure coating method, a 2 roll reverse coating method, a vacuum coating method, or a vacuum coating method may be used. slot die coating method, 2 roll coating method and the like can be used.

In the step of photo-curing the hard coat layer-forming polymer resin composition, ultraviolet rays or visible rays having a wavelength of 200 to 400 nm may be irradiated, and an exposure dose of 100 to 4,000 mJ / cm 2 is preferable. The exposure time is not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiation light, or the exposure dose. In the step of photo-curing the hard coat layer-forming polymer resin composition, nitrogen purging or the like may be performed to apply nitrogen atmosphere conditions.

According to the present invention, there can be provided an antireflection film and a method of manufacturing the antireflection film which can simultaneously realize high scratch resistance and antifouling property while having a low reflectance and a high light transmittance, and can improve the sharpness of the screen of a display device .

Fig. 1 is a cross-sectional TEM photograph of the antireflection film of Example 1. Fig.
Fig. 2 is a cross-sectional TEM photograph of the antireflection film of Example 2. Fig.
Fig. 3 is a cross-sectional TEM photograph of the antireflection film of Example 3. Fig.
4 is a cross-sectional TEM photograph of the antireflection film of Example 4. Fig.
Fig. 5 is a cross-sectional TEM photograph of the antireflection film of Example 5. Fig.
6 is a cross-sectional TEM photograph of the antireflection film of Example 6. Fig.
7 is a cross-sectional TEM photograph of the antireflection film of Comparative Example 1. Fig.
8 is a cross-sectional TEM photograph of the antireflection film of Comparative Example 2. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

<Production Example>

Production Example: Production of hard coat layer (HD1)

KYOEISHA anti-static hard coating solution (solid content: 50% by weight, product name: LJD-1000) was coated on a triacetylcellulose film with a # 10 mayer bar and dried at 90 ° C. for 1 minute. Ultraviolet rays of 150 mJ / To prepare a hard coat layer having a thickness of about 5 mu m.

Examples 1 to 5: Preparation of antireflection film [

Examples 1 to 4

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

281 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cm 3, manufactured by JSC catalyst and chemicals) were added to 100 parts by weight of pentaerythritol triacrylate (PETA) 63 parts by weight of nanoparticles (diameter: about 12 nm, density: 2.65 g / cm3), 131 parts by weight of the first fluorine compound (X-71-1203M, ShinEtsu), the second fluorine compound (RS- 19 parts by weight of an initiator (Irgacure 127, manufactured by Ciba), 31 parts by weight of a mixture of methyl isobutyl ketone (MIBK), diacetone alcohol (DAA) and isopropyl alcohol in a weight ratio of 3: 3: 4: And diluted to a solid concentration of 3% by weight.

(2) Production of low refraction layer and antireflection film

The photocurable coating composition obtained above was coated on the hard coating layer of the above production example to a thickness of about 120 nm with a # 4 mayer bar and dried and cured at the temperature and time shown in Table 1 below. At the time of curing, ultraviolet rays of 252 mJ / cm 2 were irradiated to the dried coating under nitrogen purge.

Example 5

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

268 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cm 3, manufactured by JSC catalyst and chemicals) were added to 100 parts by weight of trimethylolpropane triacrylate (TMPTA) 55 parts by weight of silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cm3), 144 parts by weight of a first fluorine compound (X-71-1203M, ShinEtsu) 21 parts by weight of DIC) and 31 parts by weight of an initiator (Irgacure 127, manufactured by Ciba) were diluted with a solvent of methyl isobutyl ketone (MIBK) to a solid concentration of 3% by weight.

(2) Production of low refraction layer and antireflection film

The photocurable coating composition obtained above was coated on the hard coating layer of the above preparation example to a thickness of about 110 to 120 nm with a # 4 mayer bar and dried and cured at the temperature and time shown in Table 1 below. At the time of curing, ultraviolet rays of 252 mJ / cm 2 were irradiated to the dried coating under nitrogen purge.

Drying temperature Drying time Example 1 40 ℃ 1 minute Example 2 60 ° C 1 minute Example 3 80 ℃ 1 minute Example 4 60 ° C 2 minutes Example 5 60 ° C 3 minutes

Example  6

(1) Production of hard coat layer (HD2)

30 g of pentaerythritol triacrylate, 2.5 g of high molecular weight copolymer (BEAMSET 371, Arakawa Co., Epoxy Acrylate, molecular weight 40,000), 20 g of methyl ethyl ketone and 0.5 g of leveling agent (Tego wet 270) Hard coating composition was prepared by adding 2 g of acrylic-styrene copolymer (volume average particle diameter: 2 탆, manufacturer: Sekisui Plastic) as fine particles having a particle diameter of 1.525.

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

(2) Production of low refraction layer and antireflection film

135 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 nm, density: 1.96 g / cm 3, manufactured by JGC catalyst and chemicals) were added to 100 parts by weight of pentaerythritol triacrylate (PETA) 88 parts by weight of nanoparticles (diameter: about 12 nm, density: 2.65 g / cm3), 38 parts by weight of the first fluorine compound (X-71-1203M, ShinEtsu), the second fluorine compound (RS- 7 parts by weight of an initiator (Irgacure 127, manufactured by Ciba), 11 parts by weight of an initiator (manufactured by Ciba Chemical Industries, Ltd.) were mixed in a solvent mixture of methyl isobutyl ketone (MIBK): diacetone alcohol (DAA): isopropyl alcohol in a weight ratio of 3: And diluted to a concentration of 3% by weight to prepare a photocurable coating composition for producing a low refractive layer.

The photo-curable coating composition for producing a low refractive index layer obtained above was coated on the hard coating layer (HD2) so as to have a thickness of about 110 to 120 nm with a # 4 mayer bar, dried at a temperature of 60 ° C for 1 minute, And cured. At the time of curing, ultraviolet rays of 252 mJ / cm 2 were irradiated to the dried coating under nitrogen purge.

&Lt; Comparative Example: Preparation of antireflection film >

Comparative Example 1

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

Comparative Example 2

Except that 63 parts by weight of solid silica nanoparticles used in Example 1 were replaced with 63 parts by weight of pentaerythritol triacrylate (PETA), a photocurable coating composition for preparing a low refractive layer was prepared in the same manner as in Example 1 And an antireflection film was prepared in the same manner as in Example 1. [

<Experimental Example: Measurement of Physical Properties of Antireflection Film>

The following items were tested on the antireflection films obtained in the above Examples and Comparative Examples.

One. Reflectance measurement of anti-reflection film

The average reflectance of the antireflection film obtained in Examples and Comparative Examples in a visible light region (380 to 780 nm) was measured using a Solidspec 3700 (SHIMADZU) equipment.

2. Antifouling measurement

Antifouling properties were measured by confirming the number of times the antireflection film obtained in Examples and Comparative Examples was rubbed with a black name pen to a straight line having a length of 5 cm and rubbed with a nonwoven fabric.

<Measurement Standard>

O: 10 times or less to be erased

?: 11 to 20 times of erasing

X: More than 20 times to erase

3. Measurement of scratch resistance

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

4. Confirm phase separation

In the cross section of the antireflection film of FIGS. 1 to 7, it was determined that phase separation occurred when 70% by volume of the entire solid type inorganic nanoparticles (solid type nano silica particles) used within 30 nm from the hard coat layer was present.

5. Ellipsometry measurement

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

Specifically, the low-refractive-index layer obtained in each of the above Examples and Comparative Examples was measured with a spectrophotometer of J. A. Woollam Co. Using a M-2000 apparatus, an incident angle of 70 ° was applied and linearly polarized light was measured in a wavelength range of 380 nm to 1000 nm. (1, 2) of the low refractive index layer by using the measured Eulipsometry data (Ψ, Δ) using Complete EASE software. Cauchy model) was fitted with an MSE of 3 or less.

[Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.

5. Measurement of refractive index

The refractive index at 550 nm was calculated using elliptically polarized light and a Cauchy model measured at wavelengths of 380 nm to 1,000 nm for each of the first layer and the second layer included in the low refractive index layer obtained in the above embodiments.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Average reflectance
(%) 0.63 0.62 0.67 0.64 0.65 0.67 0.78 0.66 Scratch resistance
(g) 500 500 500 500 500 500 150 50 Antifouling 0 0 0 0 0 0 X X Whether phase separation 0 0 0 0 0 0 X X Ellipsometry measurement Layer
One A 1.502 1.505 1.498 1.491 1.511 1.505 1.25 1.206 B 0.00351 0.00464 0.00311 0.00573 0.001924 0.00316 0.00192 0.07931 C 4.1280 * 10 ^-4 3.4882 * 10 ^-4 4.1352 * 10 ^-4 3.9821 * 10 ^-4 2.6729 * 10 ^-4 0 0.003 -0.004 Layer
2 A 1.35 1.349 1.321 1.346 1.211 1.375 1.33 1.32 B 0.00513 0.00304 0.00312 0 0.00253 0.00178 0.00786 0.00040374 C 2.5364 * 10 ^-4 0 4.1280 * 10 ^-4 4.8685 * 10 ^-4 1.6421 * 10 ^-4 1.2131 * 10 ^-5 0.000953 0.000782

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

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.

1 to 6, the low refraction layer is composed of a first layer containing not less than 70% by volume of the entire solid inorganic nanoparticles and a second layer containing not less than 70% of the entire hollow inorganic nanoparticles Wherein the solid inorganic nanoparticles are present mainly on the interface between the hard coating layer and the low refractive layer of the antireflection film and the hollow inorganic nanoparticles are contained in the hard coating layer The first layer including not less than 70% by volume of the total of the solid inorganic nanoparticles is located within 50% of the total thickness of the low refractive layer from the interface between the low refractive layers, .

When the ellipticity of the polarized light measured by ellipsometry on the second layer included in the low refraction layer is fitted to the Cauchy model of the general formula 1, To 1.50, B is 0 to 0.007, and C is 0 to 1 * 10 ^-3 . When the ellipticity of the polarized light measured by the ellipsometry method is fitted to the Cauchy model of the general formula 1 with respect to the first layer included in the low refractive layer, To 1.65, B is 0.0010 to 0.0350, and C satisfies the condition of 0 to 1 * 10 ^-3 .

Further, as shown in Table 2, it was confirmed that the antireflection films of the Examples exhibited a low reflectance of 0.70% or less in the visible light region, and simultaneously had high scratch resistance and antifouling properties.

In addition, as shown in Table 3, the first layer and the second layer included in the low refraction layer of the embodiment exhibit different refractive indexes. Specifically, the first layer of the low refraction layer exhibits a refractive index of 1.420 or more, And the second layer of the low refraction layer exhibited a refractive index of 1.400 or less.

On the other hand, as shown in FIGS. 6 and 7, it was confirmed that the hollow inorganic nanoparticles and the solid inorganic nanoparticles were mixed in the low refraction layer of the antireflection film of Comparative Examples 1 and 2 without being phase-separated.

When the ellipticity of the polarized light measured by ellipsometry was fitted to the Cauchy model of the general formula 1, the antireflection films of Comparative Examples 1 and 2 and the antireflection film of Example And the results of fitting by the Cauchy model show different ranges, and it has been confirmed that it has relatively high reflectance and low scratch resistance and antifouling property.

Claims (13)

Hard coating layer; And a low refraction layer comprising a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles,
Wherein the low refraction layer includes a first region exhibiting a refractive index of 1.420 or more at 550 nm and a second region exhibiting a refraction index of less than 1.400 at 550 nm,
Wherein the first region includes at least 70% by volume of the total of the solid inorganic nanoparticles,
Wherein the second region contains not less than 70% by volume of the entire hollow inorganic nanoparticles,
Wherein the first region is located closer to the interface between the hard coating layer and the low refractive layer than the second region,
Antireflection film.
delete delete The method according to claim 1,
When the ellipticity of the polarized light measured by ellipsometry with respect to the second region included in the low refraction layer is fitted to a Cauchy model of the following Formula 1, A is 1.0 to 1.50 , B is from 0 to 0.007, and C is from 0 to 1 * 10 ^-3 .
[Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.
The method according to claim 1,
When the ellipticity of the polarized light measured by ellipsometry with respect to the first region included in the low refraction layer is fitted to a Cauchy model of the following Formula 1,
Wherein A is from 1.0 to 1.65, B is from 0.0010 to 0.0350, and C is from 0 to 1 * 10 ^-3 .
[Formula 1]

In the above general formula (1), n (?) Is a refractive index at a? Wavelength,? Is in a range of 300 nm to 1800 nm, and A, B and C are Kosh parameters.
The method according to claim 1,
Wherein the solid inorganic nanoparticles have a density higher than that of the hollow inorganic nanoparticles by at least 0.50 g / cm &lt; 3 &gt;.
The method according to claim 1,
Wherein the binder resin contained in the low refraction layer comprises a crosslinked (co) polymer of a fluoropolymer compound containing a (co) polymer of a photopolymerizable compound and a photoreactive functional group.
The method according to claim 1,
Wherein the low refraction 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 with respect to 100 parts by weight of the binder resin.
8. The method of claim 7,
Wherein the fluorinated compound containing the photoreactive functional group each has a weight average molecular weight of 2,000 to 200,000.
8. The method of claim 7,
Wherein the binder resin comprises 20 to 300 parts by weight of a fluorinated compound containing the photoreactive functional group per 100 parts by weight of the (co) polymer of the photopolymerizable compound.
The method according to claim 1,
Wherein the hard coat layer comprises a binder resin comprising a photo-curing resin; And an organic or inorganic fine particle dispersed in the binder resin.
12. The method of claim 11,
Wherein the organic fine particles have a particle diameter of 1 to 10 mu m and the inorganic fine particles have a particle diameter of 1 nm to 500 nm.
The method according to claim 1,
Wherein the first region has a refractive index of 1.420 to 1.600 at 550 nm,
And the second region has a refractive index of 1.210 to 1.400 at 550 nm.

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