KR102216567B1 - Anti-reflective film - Google Patents

Abstract

The present invention, a hard coating layer; And a low refractive layer including a binder resin and a hollow inorganic nanoparticle and a solid inorganic nanoparticle dispersed in the binder resin, wherein the ratio of the particle diameter of the solid particle to the particle diameter of the hollow particle is 0.26 to 0.55 It relates to an anti-reflective film.

Description

Anti-reflective film {ANTI-REFLECTIVE FILM}

The present invention relates to an anti-reflection film, and more particularly, to an anti-reflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having low reflectivity and high light transmittance, and improving the clarity of the screen of a display device.

In general, flat panel display devices such as PDPs and LCDs are equipped with anti-reflection films to minimize reflection of light incident from the outside.

As a method for minimizing reflection of light, a method of coating a base film by dispersing a filler such as inorganic fine particles in a resin and providing irregularities (anti-glare: AG coating); There is a method of using interference of light by forming a plurality of layers having different refractive indices on the base film (anti-reflection: AR coating) or a method of mixing them.

Among them, in the case of the AG coating, the absolute amount of reflected light is equivalent to that of a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by using scattering of light through irregularities. However, since the AG coating decreases the sharpness of the screen due to surface irregularities, many studies on AR coating have recently been conducted.

As a film using the AR coating, a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film is commercially available. 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 the process of forming each layer is separately performed.

In addition, previously, in order to improve the scratch resistance of the low refractive index layer included in the antireflection film, a method of adding various particles of nanometer size (eg, particles such as silica, alumina, zeolite, etc.) has been mainly attempted. However, in the case of using nanometer-sized particles as described above, there is a limitation in that it is difficult to simultaneously increase scratch resistance while lowering the reflectance of the low refractive layer, and the antifouling properties of the surface of the low refractive layer are large due to nanometer-sized particles. Fell down.

Accordingly, many studies have been conducted to reduce the absolute reflection amount of light incident from the outside and to improve the scratch resistance of the surface as well as antifouling properties, but the degree of improvement of physical properties accordingly is insufficient.

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

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

In addition, in the present specification, a hard coating layer including a binder resin and organic or inorganic fine particles dispersed in the binder resin; And a low refractive layer comprising a binder resin and a hollow inorganic nanoparticle and a solid inorganic nanoparticle dispersed in the binder resin, wherein the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.15 to It is 0.55, and 70% by volume or more of the total solid inorganic nanoparticles are present within 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer. An antireflection film is provided.

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

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

In addition, the fluorine-containing compound means a compound containing at least one or more fluorine elements among the compounds.

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

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

In addition, hollow silica particles (silica hollow particles) are silica particles derived from a silicon compound or an organosilicon compound, and refers to particles in a form in which empty spaces exist on the surface and/or inside of the silica particles.

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

The average particle diameter of the hollow particles and the average particle diameter of the solid particles are the average values obtained by measuring and calculating the particle diameters of the hollow particles and the solid particles identified in the TEM photograph (eg, 25,000 times magnification) of the antireflection film, respectively. I can.

The present inventors conducted research on an antireflection film, and the antireflection film including a low refractive index layer including hollow particles and solid particles having a specific average particle diameter ratio described above has a lower reflectance and a high light transmittance while having a high scratch resistance. Through an experiment, it was confirmed through an experiment that both resistance and antifouling properties can be realized and the invention was completed.

In the manufacturing process of the low refractive layer, various factors affecting the distribution of the hollow particles and the solid particles, for example, manufacturing conditions or the weight or density of the particles may be considered. It was confirmed that when the difference in particle diameter is adjusted to the above-described ratio, improved scratch resistance and antifouling properties can be realized while securing a lower reflectance in the final antireflection film.

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

As described above, as the regions in which the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, the low refractive layer has a unique internal structure and an arrangement pattern of components, thereby having a lower reflectance. In addition, as the regions in which the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, the surface characteristics of the low refractive layer are also changed, so that more improved scratch resistance and antifouling properties can be realized.

On the other hand, when the difference between the particle diameter of the hollow particles included in the low refractive layer and the particle diameter of the solid particles is not so large, the hollow particles and the solid particles are agglomerated with each other, or uneven distribution or distribution according to the particle type does not occur, so that the reflection Not only is it difficult to significantly lower the reflectivity of the prevention film, but it may be difficult to achieve the required scratch resistance and stain resistance.

As described above, the characteristic effects of the anti-reflection film of the embodiment, for example, a low reflectivity and a high transmittance, while simultaneously realizing high scratch resistance and antifouling properties, and improving the clarity of the screen of the display device are described in detail above. It is according to the ratio of the average particle diameter between one hollow particle and a solid particle.

The solid inorganic nanoparticles refer to particles having no empty space therein.

In addition, the hollow inorganic nanoparticles refer to particles in which empty spaces exist on the surface and/or inside.

By satisfying the condition that the ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.55 or less, the antireflection film can simultaneously implement high scratch resistance and antifouling properties while having a lower reflectance and a high light transmittance.

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

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

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

The diameters of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may mean the longest diameter found in the cross section of the particles.

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

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

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

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

On the other hand, when the hollow inorganic nanoparticles and the solid inorganic nanoparticles are distributed so that they can be distinguished from each other in the low refractive index layer included in the antireflection film, they have low reflectance and high light transmittance, while having high scratch resistance and antifouling resistance. Can be implemented simultaneously.

Specifically, when 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 hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface , It is possible to achieve a lower reflectance compared to the actual reflectance that was previously obtained using the inorganic particles, and also realize the low refractive index layer with significantly improved scratch resistance and stain resistance.

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

"At least 70% by volume of the solid inorganic nanoparticles are present in a specific region" is defined as meaning that most of the solid inorganic nanoparticles are present in the specific region in the cross section of the low refractive layer. More than 70% by volume of the total solid inorganic nanoparticles can be confirmed by measuring the volume of the entire solid inorganic nanoparticle, and can also be confirmed through photographs such as a transmission electron microscope (TEM).

Whether the hollow inorganic nanoparticles and the solid inorganic nanoparticles are present in the specified region is determined by whether each hollow inorganic nanoparticles or the solid inorganic nanoparticles are present in the specified region, and the specific Particles present across the boundary of the region are excluded.

In addition, as described above, hollow inorganic nanoparticles may be mainly distributed from the low refractive layer to the opposite side of the interface between the hard coating layer and the low refractive layer, specifically, 30 of the hollow inorganic nanoparticles. Volume%, or 50% by volume or more, or 70% by volume or more may be present at a greater distance in the thickness direction of the low refractive layer from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles.

A region exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer (from a point exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer) In an area up to the other surface of the low refractive layer facing the interface), 30% by volume, 50% by volume or more, or 70% by volume or more of the total hollow inorganic nanoparticles may be present.

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

Among the low refractive layers 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. Two or more portions or two or more layers having different refractive indices may be formed in the low refractive layer, and thus the reflectivity 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 is in a specific manufacturing method to be described later, by adjusting the ratio of the average particle diameter between the solid inorganic nanoparticles and the hollow inorganic nanoparticles It can be obtained by controlling the drying temperature of the photocurable resin composition for forming a low refractive index layer including the two kinds of nanoparticles.

In the case where 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 hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface, previously It is possible to achieve a reflectance lower than that that could be obtained using inorganic particles. Specifically, the reflective ring film is 1.5% or less, or 1.0% or less, or 0.50 to 1.0%, 0.7% or less, or 0.60% to 0.70%, or 0.62% to 0.67% in the visible light wavelength range of 380 nm to 780 nm Can represent the average reflectance of

Meanwhile, in the anti-reflection film of the embodiment, the low refractive layer includes a first layer containing at least 70% by volume of the total solid inorganic nanoparticles, and a first layer containing at least 70% by volume of the total hollow inorganic nanoparticles. It may include two layers, 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.

As described above, in the low refractive layer of the anti-reflection 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. However, a region in which each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed may form an independent layer that is visible in the low refractive layer.

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

In addition, as described above, hollow inorganic nanoparticles may be mainly distributed from the low refractive layer to the opposite side of the interface between the hard coating layer and the low refractive layer, specifically, 30 of the hollow inorganic nanoparticles. Volume% or more, or 50% by volume or more, or 70% by volume or more may be present at a greater distance in the thickness direction of the low refractive layer from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles. . Accordingly, as described above, the first layer may be positioned closer to the interface between the hard coating layer and the low refractive layer than the second layer.

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

Meanwhile, each of the first layer containing 70 vol% or more of the total solid inorganic nanoparticles and the second layer containing 70 vol% or more of the hollow inorganic nanoparticles share common optical properties within one layer. Can be, and thus can be defined as one layer.

More specifically, when the ellipticity of the polarization measured by the ellipsometry of each of the first and second layers is optimized by the Cauchy model of the general formula 1, a specific Coch parameter A , B and C, and thus the first layer and the second layer can be distinguished from each other. In addition, since the thickness of the first layer and the second layer can be derived by optimizing the ellipticity of the polarization measured by the ellipsometry with the Cauchy model of the following general formula 1, The first layer and the second layer can be defined within the low refractive layer.

[General Formula 1]

)는

파장에서의 굴절율(refractive index)이고,

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

) Is

Is the refractive index at wavelength,

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

Meanwhile, the Cauchy parameters A, B and C derived when the ellipticity of the polarization measured by the ellipsometry is optimized with the Cauchy model of the general formula 1 are It can be an average value. Accordingly, when an interface exists between the first layer and the second layer, there may be a region where the coch parameters A, B, and C of the first layer and the second layer overlap. However, even in this case, the thickness and location of the first layer and the second layer may be specified according to the region that satisfies the average values of the coch parameters A, B and C of each of the first layer and the second layer. .

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

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

Meanwhile, in the antireflection film of the embodiment(s) described above, the first layer and the second layer included in the low refractive index layer may have different ranges of refractive indices.

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

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

Meanwhile, the above-described low refractive layer may be prepared from a photo-curable 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 layer may include a crosslinked (co)polymer between a (co)polymer of a photopolymerizable compound and a fluorine-containing compound including a photoreactive functional group.

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

Specific examples of the monomer or oligomer including the (meth)acrylate include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate. )Acrylate, tripentaerythritol hepta(meth)acrylate, triethylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylic Rate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethyl methacrylate, butyl methacrylate, or a mixture of two or more thereof, or urethane-modified acrylate oligomer, epoxide Side acrylate oligomers, ether acrylate oligomers, dendritic acrylate oligomers, or mixtures of two or more thereof. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.

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

The content of the photopolymerizable compound in the photocurable coating composition is not largely limited, but 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 layer or antireflection film to be finally prepared May be from 5% to 80% by weight. The solid content of the photocurable coating composition refers to only solid components excluding liquid components, for example, components such as organic solvents that may be selectively included as described below in the photocurable coating composition.

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

Specific examples of the fluorine-based (meth)acrylate-based monomer or oligomer may include one or more compounds selected from the group consisting of the following Chemical Formulas 1 to 5.

[Formula 1]

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

[Formula 2]

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

[Formula 3]

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

[Formula 4]

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

[Formula 5]

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

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

The fluorinated compound including the photoreactive functional group may contain or be substituted with at least one photoreactive functional group, and the photoreactive functional group may participate in the polymerization reaction by irradiation of light, for example, irradiation with visible or ultraviolet light. It 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 a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl), or a thiol group ( Thiol).

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

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 cannot be uniformly and effectively arranged on the surface and are located inside the final low refractive index layer. Accordingly, the antifouling property of the surface of the low refractive layer is lowered, and the crosslinking density of the low refractive layer is lowered, so that mechanical properties such as overall strength and scratch resistance may be lowered.

In addition, if the weight average molecular weight of the fluorinated compound including the photoreactive functional group is too high, compatibility with other components in the photocurable coating composition may be lowered, and accordingly, the haze of the finally prepared low refractive layer may increase or The light transmittance may be lowered, and the strength of the low refractive layer may also be lowered.

Specifically, the fluorine-containing compound including a photoreactive functional group is i) an aliphatic compound or an alicyclic compound in which at least one photoreactive functional group is substituted and at least one carbon is substituted with at least one fluorine; ii) a hetero aliphatic compound or a heteroaliphatic ring compound in which at least one photoreactive functional group is substituted, at least one hydrogen is substituted with fluorine, and at least one carbon is substituted with silicon; iii) a polydialkylsiloxane polymer (eg, polydimethylsiloxane polymer) in which at least one photoreactive functional group is substituted and at least one silicone is substituted with at least one fluorine; iv) a polyether compound substituted with one or more photoreactive functional groups and at least one hydrogen substituted with fluorine, or a mixture of two or more of i) to iv), or a copolymer thereof.

The photocurable coating composition may include 20 to 300 parts by weight of the fluorinated compound including the photoreactive functional group based on 100 parts by weight of the photopolymerizable compound.

When the fluorine-containing compound including the photoreactive functional group is added in an excessive amount compared to the photopolymerizable compound, the coatability of the photocurable coating composition of the embodiment is lowered, or the low refractive layer obtained from the photocurable coating composition has sufficient durability or scratch resistance. May not have. In addition, if the amount of the fluorine-containing compound including the photoreactive functional group is too small compared to the photopolymerizable compound, the low refractive layer obtained from the photocurable coating composition may not have sufficient antifouling properties or mechanical properties such as scratch resistance.

The fluorinated compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorinated compound including the photoreactive functional group may optionally contain silicon or a silicon compound therein, and specifically, the content of silicon in the fluorine-containing compound including the photoreactive functional group is 0.1% to 20% by weight. I can.

Silicon included in the fluorine-containing compound including the photoreactive functional group can increase compatibility with other components included in the photocurable coating composition of the embodiment, and accordingly, haze is generated in the finally prepared refractive layer. It can play a role of increasing transparency by preventing. On the other hand, if the content of silicon in the fluorinated compound including the photoreactive functional group is too large, the compatibility between the other components included in the photocurable coating composition and the fluorinated compound may be rather lowered. 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 decrease.

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

When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive layer is excessive, the phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not occur sufficiently during the manufacturing process of the low refractive layer and is mixed As a result, reflectance may be increased, and antifouling properties may be deteriorated due to excessive occurrence of surface irregularities. In addition, when the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the low refractive layer is insufficient, many of the solid inorganic nanoparticles are located in a region close to the interface between the hard coating layer and the low refractive layer. It may be difficult to do, and the reflectance of the low refractive layer may be greatly increased.

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

Meanwhile, as the hard coating layer, a conventionally known hard coating layer may be used without great limitation.

As an example of the hard coating layer, a hard coating layer including a binder resin and organic or inorganic fine particles dispersed in the binder resin may be mentioned.

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

The organic or inorganic fine particles are not specifically limited in particle diameter, for example, the organic fine particles may have a particle diameter of 1 to 10 µm, and the inorganic particles may have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm. Can have. The particle size of the organic or inorganic fine particles may be defined as a volume average particle size.

In addition, specific examples of the organic or inorganic fine particles included in the hard coating film are not limited, for example, the organic or inorganic fine particles are organic fine particles composed of acrylic resin, styrene resin, epoxide resin, and nylon resin, or silicon oxide , Titanium dioxide, indium oxide, tin oxide, zirconium oxide, and may be inorganic fine particles composed of 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 at least one selected from the group consisting of a cellulose polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer.

Meanwhile, as another example of the hard coating film, a binder resin of a photocurable resin; And a hard coating film including an antistatic agent dispersed in the binder resin.

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

The antistatic agent is a quaternary ammonium salt compound; Pyridinium salt; Cationic compounds having 1 to 3 amino groups; Anionic compounds such as a sulfonic acid base, a sulfuric acid ester base, a phosphoric acid ester base, and a phosphonic acid base; Amphoteric compounds such as amino acid or amino sulfuric acid 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; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Reactants or polymers of two or more of these compounds; It may be a mixture of two or more of these compounds. Here, the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium base groups in the molecule, and a low molecular or high molecular type may be used without limitation.

In addition, a conductive polymer and metal oxide fine particles may be used as the antistatic agent. The conductive polymers include aromatic conjugated poly(paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing conjugated polyaniline, mixed conjugated poly( Phenylene vinylene), a conjugated multi-chain conjugated compound having a plurality of conjugated chains in a molecule, and a conductive composite obtained by grafting or block copolymerizing a conjugated polymer chain onto a saturated polymer. Further, 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, aluminum-doped zinc oxide, and the like.

A binder resin of the photocurable resin; And the hard coating film including the antistatic agent dispersed in the binder resin may further include one or more compounds selected from the group consisting of alkoxy silane-based oligomers and metal alkoxide-based oligomers.

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

In addition, the metal alkoxide oligomer may be prepared through a sol-gel reaction of a composition comprising a metal alkoxide compound and water. The sol-gel reaction may be performed in a manner similar to the method for preparing the alkoxysilane oligomer described above.

However, since the metal alkoxide-based compound may react rapidly with water, the sol-gel reaction may be performed by slowly dropping water after diluting the metal alkoxide-based compound in an organic solvent. At this time, in consideration of reaction efficiency, etc., 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 one or more compounds selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.

Meanwhile, the hard coating layer may have a thickness of 0.1 μm to 100 μm.

It may further include a substrate bonded to the other side of the hard coating layer. The specific type or thickness of the substrate is not largely limited, and a substrate known to be used for manufacturing a low refractive index layer or an antireflection film may be used without significant limitation. For example, the base material may include polycarbonate, cycloolefin polymer, polyester or triacetyl cellulose.

Meanwhile, the low refractive layer may further include a silane-based compound including at least one reactive functional group selected from the group consisting of a vinyl group and a (meth)acrylate group.

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

In addition, due to the silane functional group or silicon atom contained in the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth)acrylate group, the internal characteristics of the low refractive layer may be improved. More specifically, as the silane functional groups or silicon atoms included in the silane-based compound are uniformly distributed inside the low refractive layer, a lower average reflectance can be implemented, and also, due to the silane functional group or silicon atoms, the low refractive layer Since the uniformly distributed inorganic fine particles are uniformly combined with the photopolymerizable compound, the scratch resistance of the final antireflection film may be improved.

As described above, as the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth)acrylate group has a chemical structure including the reactive functional group and the silicon atom simultaneously , The internal characteristics of the low refractive layer can be optimized to lower the refractive index, and accordingly, the low refractive layer can implement a low reflectance and high light transmittance, and also secure a uniform crosslinking density to provide more excellent wear resistance or scratch resistance. Can be secured.

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

If the content of the reactive functional group in the silane-based compound containing one or more one or more reactive functional groups selected from the group consisting of the vinyl group and the (meth)acrylate group is too small, the scratch resistance or mechanical properties of the low refractive layer It can be difficult to raise enough.

On the other hand, if the content of the reactive functional group in the silane-based compound containing one or more reactive functional groups selected from the group consisting of the vinyl group and the (meth)acrylate group is too high, homogeneity or inorganic fineness in the low refractive layer Since the dispersibility of the particles is lowered, the light transmittance of the low refractive layer may rather decrease.

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

Specifically, the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth)acrylate group is one or more reactive functional groups selected from the group consisting of a vinyl group and a (meth)acrylate group 1 As described above, it may include an organic functional group including at least one trialkoxysilane group to which an alkylene group having 1 to 10 carbon atoms is bonded and a urethane functional group. The trialkoxysilane group may be a functional group in which 3 alkoxy having 1 to 3 carbon atoms is substituted with a silicone compound.

The specific chemical structure of the silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and the (meth)acrylate group is not limited, but specific examples thereof include compounds of Formulas 11 to 14 below. have.

[Formula 11]

[Chemical Formula 12]

[Formula 13]

[Formula 14]

이며, In Formula 14, R ¹ is

Is,

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

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

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

A is any one of hydrogen and a monovalent residue derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, B is any one of a monovalent residue derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, and n is an integer of 0 to 2.

One example of the compound of Formula 14 may be a compound of Formula 15 below.

[Formula 15]

In Formula 15, R ₁ , R ₂ and R ₃ are an alkoxy group having 1 to 3 carbon atoms or hydrogen, X is a linear or branched alkylene group having 1 to 10 carbon atoms, and R 4 is a carbon number of 1 to 3 It is an alkyl group or hydrogen.

The low refractive layer includes 2 to 40 parts by weight of a silane-based compound including at least one reactive functional group selected from the group consisting of the vinyl group and (meth)acrylate group relative to 100 parts by weight of the photopolymerizable compound contained therein. I can.

When the content of the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth)acrylate group is too small compared to the photopolymerizable compound, the scratch resistance of the low refractive layer is sufficiently secured. It can be difficult to do. In addition, when the content of the silane-based compound containing at least one reactive functional group selected from the group consisting of the vinyl group and the (meth)acrylate group is too large compared to the photopolymerizable compound, other components included in the low refractive layer Due to the large decrease in compatibility with the low-refractive-index layer or the anti-reflection film, haze may occur or its transparency may decrease, and scratch resistance may rather decrease.

On the other hand, the antireflection film of the embodiment is a photocurable compound or a (co)polymer thereof, a fluorine-containing compound including a photoreactive functional group, a photoinitiator, a resin for forming a low refractive index layer including hollow inorganic nanoparticles and solid inorganic nanoparticles Applying the composition on the hard coating layer and drying at a temperature of 35°C to 100°C; And photo-curing the dried product of the resin composition. It may be provided through a method of manufacturing an anti-reflection film comprising.

Specifically, the antireflection film provided by the method of manufacturing the antireflection film is distributed so that the hollow inorganic nanoparticles and the solid inorganic nanoparticles can be distinguished from each other in the low refractive index layer, thereby providing low reflectivity and high light transmittance. While having, high scratch resistance and stain resistance can be implemented at the same time.

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

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

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

In addition, in the antireflection film provided by the method of manufacturing the antireflection film, the low refractive layer includes a first layer containing 70% by weight or more of the total solid inorganic nanoparticles and the hollow inorganic nanoparticles. A second layer containing 70% by weight or more may be included, and the first layer may be located closer to an interface between the hard coating layer and the low refractive layer than the second layer.

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

When the temperature for drying the resin composition for forming a low refractive layer applied on the hard coating layer is less than 35, the antifouling property of the formed low refractive layer may be greatly reduced. In addition, if the temperature for drying the resin composition for forming a low refractive layer applied on the hard coating layer is greater than 100, phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not occur sufficiently during the manufacturing process of the low refractive layer. Since they are mixed, not only the scratch resistance and stain resistance of the low refractive layer may be reduced, but also the reflectance may be greatly increased.

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

Meanwhile, the step of drying the resin composition for forming a low refractive index layer applied on the hard coating 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.

If the drying time is too short, the phase separation phenomenon between the above-described solid inorganic nanoparticles and hollow inorganic nanoparticles may not occur sufficiently. On the other hand, when the drying time is too long, the formed low refractive layer may erode the hard coating layer.

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

The low refractive layer may be obtained by applying the photocurable coating composition on a predetermined substrate and photocuring the applied result. The specific type or thickness of the substrate is not largely limited, and a substrate known to be used for manufacturing a low refractive index layer or an antireflection film may be used without significant limitation.

The method and apparatus commonly used to apply the photocurable coating composition can be used without any other limitation. For example, bar coating method such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum slot die coating Method, two roll coating method, etc. can be used.

The low refractive index 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 or visible light having a wavelength of 200 to 400 nm may be irradiated, and the exposure amount during irradiation is preferably 100 to 4,000 mJ/cm 2. The exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiated light, or the amount of exposure.

In addition, in the step of photocuring the photocurable coating composition, nitrogen purging may be performed to apply a nitrogen atmosphere.

Specific details of the photocurable compound, the hollow inorganic nanoparticles, the solid inorganic nanoparticles, and the fluorine-containing compound including a photoreactive functional group include the above-described information with respect to the antireflection film of the embodiment.

Each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles may be included in the composition in a colloidal form dispersed in a predetermined dispersion medium. Each colloidal phase including the hollow inorganic nanoparticles and the solid inorganic nanoparticles may contain 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 or the viscosity of the photocurable coating composition. The weight 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% to 60% by weight.

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

As the photoinitiator, any compound known to be used in a photocurable resin composition may be used without limitation, and specifically, a benzophenone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or A mixture of two or more of these may be used.

With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight. If the amount of the photopolymerization initiator is too small, a material that remains uncured 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 remains as an impurity or the crosslinking density is low, so that the mechanical properties of the produced film may decrease or the reflectance may be greatly increased.

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

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

Specific examples of such an organic solvent include ketones such as methyl ethylkenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or a mixture of two or more of these may be mentioned.

The organic solvent may be added at the time of mixing each component included in the photocurable coating composition or may be included in the photocurable coating composition while each component is added in a dispersed or mixed state in an organic solvent. If the content of the organic solvent in the photocurable coating composition is too small, the flowability of the photocurable coating composition decreases, and thus defects such as streaks may occur in the final film. In addition, when an excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation are not sufficiently performed, so that physical properties or surface properties of the film may be deteriorated, and defects may occur during drying and curing. Accordingly, the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1% to 50% by weight, or 2 to 20% by weight.

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

Specifically, the method of manufacturing the antireflection film may further include applying a polymer resin composition for forming a hard coating layer including a photocurable compound or a (co)polymer thereof on a substrate and photocuring, the step of Through it can form a hard coating layer.

Components used for forming the hard coating layer are as described above with respect to the antireflection film of the embodiment.

In addition, the polymer resin composition for forming the hard coating layer may further include one or more compounds selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers.

The method and apparatus commonly used to apply the polymer resin composition for forming the hard coating layer can be used without any other limitation. For example, a bar coating method such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum Slot die coating method, 2 roll coating method, etc. can be used.

In the step of photocuring the polymer resin composition for forming the hard coating layer, ultraviolet or visible light having a wavelength of 200 to 400 nm may be irradiated, and the exposure amount during irradiation is preferably 100 to 4,000 mJ/cm 2. The exposure time is also not particularly limited, and can be appropriately changed according to the exposure apparatus used, the wavelength of the irradiated light, or the amount of exposure. In addition, in the step of photocuring the polymer resin composition for forming the hard coating layer, nitrogen purging may be performed to apply a nitrogen atmosphere.

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

The present inventors conducted research on an antireflection film, and the antireflection film including a low refractive index layer including hollow particles and solid particles having a specific average particle diameter ratio described above has a lower reflectance and a high light transmittance while having a high scratch resistance. Through an experiment, it was confirmed through an experiment that both resistance and antifouling properties can be realized and the invention was completed.

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

As described above, as the regions in which the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, the low refractive layer has a unique internal structure and an arrangement pattern of components, thereby having a lower reflectance. In addition, as the regions in which the hollow particles and the solid particles are mainly distributed in the low refractive layer are different, the surface characteristics of the low refractive layer are also changed, so that more improved scratch resistance and antifouling properties can be realized.

Specific details on the solid inorganic nanoparticles and the hollow inorganic nanoparticles include the above-described information in the antireflection film of the embodiment of the present invention.

Among the low refractive layers 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. Two or more portions or two or more layers having different refractive indices may be formed in the low refractive layer, and thus the reflectivity 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 is in a specific manufacturing method to be described later, by adjusting the ratio of the average particle diameter between the solid inorganic nanoparticles and the hollow inorganic nanoparticles It can be obtained by controlling the drying temperature of the photocurable resin composition for forming a low refractive index layer including the two kinds of nanoparticles.

The low refractive layer includes a binder resin, hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, and may be formed on one surface of the hard coating layer, wherein 70 volumes of the total solid inorganic nanoparticles % Or more may exist within 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.

In addition, as described above, hollow inorganic nanoparticles may be mainly distributed from the low refractive layer to the opposite side of the interface between the hard coating layer and the low refractive layer, specifically, 30 of the hollow inorganic nanoparticles. Volume%, or 50% by volume or more, or 70% by volume or more may be present at a greater distance in the thickness direction of the low refractive layer from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles.

A region exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer (from a point exceeding 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer) In an area up to the other surface of the low refractive layer facing the interface), 30% by volume, 50% by volume or more, or 70% by volume or more of the total hollow inorganic nanoparticles may be present.

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

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

The organic fine particles may have a particle diameter of 1 to 10 μm, and the inorganic particles may have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm.

The contents of the binder resin and the organic or inorganic fine particles of the hard coating layer include the above-described contents with respect to the anti-reflection film of the embodiment of the present invention.

In addition, more specific information except for the above-described information in the antireflection film of the other embodiment includes the above description with respect to the antireflection film of the embodiment of the present invention.

According to the present invention, an antireflection film capable of simultaneously realizing high scratch resistance and antifouling properties while having low reflectance and high light transmittance and increasing the clarity of a screen of a display device, and a method of manufacturing the antireflection film can be provided. .

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

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

<Production Example>

Preparation Example: Preparation of hard coating film

KYOEISHA's salt-type antistatic hard coating solution (solid content 50% by weight, product name: LJD-1000) is coated on a triacetyl cellulose film with #10 mayer bar, dried at 90 for 1 minute, and irradiated with ultraviolet rays of 150 mJ/㎠ Thus, a hard coating film having a thickness of about 5 to 6 μm was prepared.

<Examples 1 to 5: Preparation of antireflection film>

Example 1

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

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

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

On the hard coating film of Preparation Example, the photocurable coating composition obtained above was coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at the temperature and time of Table 1 below to form a low refractive layer. Formed, and an anti-reflection film was prepared. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating under nitrogen purge.

And, using a transmission electron microscope (TEM) to measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer, and repeat this 10 times to the hollow silica The average particle diameters of the nanoparticles and solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 55.9 nm, average diameter of solid silica nanoparticles: 14.5 nm].

Example 2

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

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

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

On the hard coating film of Preparation Example, the photocurable coating composition obtained above was coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at the temperature and time of Table 1 below to form a low refractive layer. Formed, and an anti-reflection film was prepared. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating under nitrogen purge.

And, using a transmission electron microscope (TEM) to measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer, and repeat this 10 times to the hollow silica The average particle diameters of the nanoparticles and solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 54.9 nm, average diameter of solid silica nanoparticles: 14.5 nm].

Example 3

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

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

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

On the hard coating film of Preparation Example, the photocurable coating composition obtained above was coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at the temperature and time of Table 1 below to form a low refractive layer. Formed, and an anti-reflection film was prepared. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating under nitrogen purge.

And, using a transmission electron microscope (TEM) to measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer, and repeat this 10 times to the hollow silica The average particle diameters of the nanoparticles and solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 54.5 nm, average diameter of solid silica nanoparticles: 19.5 nm].

Example 4

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

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

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

On the hard coating film of Preparation Example, the photocurable coating composition obtained above was coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at the temperature and time of Table 1 below to form a low refractive layer. Formed, and an anti-reflection film was prepared. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating under nitrogen purge.

And, using a transmission electron microscope (TEM) to measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer, and repeat this 10 times to the hollow silica The average particle diameters of the nanoparticles and solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 55.4 nm, average diameter of solid silica nanoparticles: 17.1 nm].

Example 5

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

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

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

On the hard coating film of Preparation Example, the photocurable coating composition obtained above was coated with a #4 mayer bar to a thickness of about 110 to 120 nm, and dried and cured at the temperature and time of Table 1 below to form a low refractive layer. Formed, and an anti-reflection film was prepared. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating under nitrogen purge.

And, using a transmission electron microscope (TEM) to measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer, and repeat this 10 times to the hollow silica The average particle diameters of the nanoparticles and solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 55.5 nm, average diameter of solid silica nanoparticles: 17.1 nm].

Example 6

(1) Preparation of hard coating layer (HD2)

After uniformly mixing 30 g of pentaerythritol triacrylate, 2.5 g of high molecular weight copolymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000), 20 g of methyl ethyl ketone and 0.5 g of a leveling agent (Tego wet 270), the refractive index is A hard coating composition was prepared by adding 2 g of an acrylic-styrene copolymer (volume average particle diameter: 2 μm, manufacturer: Sekisui Plastic) as 1.525 fine particles.

The obtained hard coating composition was coated on a triacetylcellulose film with #10 mayer bar and dried at 90°C for 1 minute. A hard coating layer having a thickness of 5 μm was prepared by irradiating the dried product with ultraviolet rays of 150 mJ/cm 2.

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

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

On the prepared hard coating layer (HD2), the photocurable coating composition for producing a low refractive index layer obtained above was coated with a #4 mayer bar to a thickness of about 110 to 120 nm, dried at a temperature of 60° C. for 1 minute, and By curing to form a low refractive layer, an antireflection film was prepared. During the curing, ultraviolet rays of 252 mJ/cm 2 were irradiated to the dried coating under nitrogen purge.

And, using a transmission electron microscope (TEM) to measure the longest diameter of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer, and repeat this 10 times to the hollow silica The average particle diameters of the nanoparticles and solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 55.4 nm, average diameter of solid silica nanoparticles: 14.7 nm].

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

<Comparative Example: Preparation of antireflection film> Comparative Example 1

An antireflection film was prepared in the same manner as in Example 1, except that solid silica nanoparticles (diameter range: about 34 nm to 80 nm) were used.

Using a transmission electron microscope (TEM), the longest diameters of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer were measured, and the hollow silica nanoparticles were repeated 10 times. And the average particle diameter of the solid silica nanoparticles were determined [average diameter of hollow silica nanoparticles: 54.6 nm, average diameter of solid silica nanoparticles: 53.2 nm].

Comparative Example 2

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

Using a transmission electron microscope (TEM), the longest diameters of each of 100 to 170 hollow silica nanoparticles and solid silica nanoparticles contained in the formed low refractive layer were measured, and the hollow silica nanoparticles were repeated 10 times. And the average particle diameter of the solid silica nanoparticles were determined [average diameter of the hollow silica nanoparticles: 54.5 nm, and the average diameter of the solid silica nanoparticles: 41.1 nm].

<Experimental Example: Measurement of physical properties of an antireflection film>

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

1.Measurement of average reflectance of antireflective film

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

2. Antifouling property measurement

Antifouling properties were measured by drawing a 5 cm long straight line on the surface of the antireflection film obtained in Examples and Comparative Examples with a black name pen, and checking the number of times it was erased when rubbed with a dust-free cloth.

<Measurement criteria>

O: 10 times or less when erased

: The time point to be erased is 11 to 20 times

X: Time to be erased exceeds 20 times

3. Scratch resistance measurement

A load was applied to the steel wool, reciprocated 10 times at a speed of 27 rpm, and the surfaces of the antireflection films obtained in Examples and Comparative Examples were rubbed. The maximum load at which no more than 1 scratch of 1 cm or less observed with the naked eye was observed was measured.

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

As shown in Table 2, the ratio of the particle diameter of the solid particles to the particle diameter of the hollow particles included in the low refractive layer of the antireflection films of Examples 1 to 6 is 0.55 or less, and thus 0.70% or less in the visible light region. It is confirmed that it can simultaneously implement high scratch resistance and antifouling properties while showing low reflectance. In addition, as shown in FIGS. 1 to 6, in the low refractive layer of the antireflection film of Examples 1 to 4, the hollow inorganic nanoparticles and the solid inorganic nanoparticles are phase separated, and the solid inorganic nanoparticles are It is confirmed that most of the hollow inorganic nanoparticles are present and concentrated toward the interface between the hard coating layer of the antireflection film and the low refractive layer, and the hollow inorganic nanoparticles are mostly present and concentrated on the far side from the hard coating layer.

As shown in Table 2, in the low refractive layer of the antireflection film of Comparative Examples 1 and 2, the ratio of the particle diameter of the solid particles to the particle diameter of the hollow particles exceeds 0.55, and as shown in FIGS. 7 and 8 It is confirmed that the inorganic nanoparticles and the solid inorganic nanoparticles are not phase separated and are mixed.

And, as shown in Table 2, it was confirmed that each exhibited relatively high reflectivity and low scratch resistance and antifouling property.

Claims (12)

A hard coating layer comprising a binder resin and organic or inorganic fine particles dispersed in the binder resin; And
Including; a binder resin and a low refractive index layer including hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin,
The ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.55 or less,
The low refractive layer includes a first layer having a refractive index of 1.420 or more at 550 nm and a second layer having a refractive index of 1.410 or less at 550 nm, and the first layer is the hard coating layer and the low refractive index compared to the second layer. Located closer to the interface between layers,
The first layer contains at least 70% by volume of the total solid inorganic nanoparticles,
The second layer contains at least 70% by volume of the total of the hollow inorganic nanoparticles,
The solid inorganic nanoparticles include solid silica nanoparticles,
The hollow inorganic nanoparticles include hollow silica nanoparticles,
Anti-reflective film.
delete The method of claim 1,
The antireflection film, wherein the average particle diameter of the hollow particles is within a range of 40 nm to 100 nm.
The method of claim 1,
The antireflection film, wherein the average particle diameter of the solid particles is within the range of 1 nm to 30 nm.
The method of claim 1,
The ratio of the average particle diameter of the solid particles to the average particle diameter of the hollow particles is 0.15 to 0.55, the anti-reflection film.
The method of claim 1,
The reflective ring film exhibits an average reflectance of 0.7% or less in a visible light wavelength range of 380 nm to 780 nm.
The method of claim 1,
The antireflection film, wherein the solid inorganic nanoparticles have a higher density of 0.50 g/cm3 or more than that of the hollow inorganic nanoparticles.
The method of claim 1,
Each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles has at least one reactive group selected from the group consisting of a hydroxyl group, a (meth)acrylate group, an epoxide group, a vinyl group (Vinyl), and a thiol group (Thiol) on the surface. An antireflection film containing a functional group.
The method of claim 1,
The binder resin included in the low refractive layer includes a crosslinked (co)polymer between a (co)polymer of a photopolymerizable compound and a fluorine-containing compound containing a photoreactive functional group.
The method of claim 1,
The low refractive layer includes 10 to 400 parts by weight of the hollow inorganic nanoparticles and 10 to 400 parts by weight of the solid inorganic nanoparticles relative to 100 parts by weight of the binder resin, antireflection film.
delete The method of claim 1,
The organic fine particles have a particle diameter of 1 to 10 μm,
The inorganic fine particles have a particle diameter of 1 nm to 500 nm, antireflection film.

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