JP2022069431A - Optical laminate - Google Patents

Abstract

To provide an optical laminate capable of having high transmissivity, achieving simultaneously high scratch resistance and anti fouling property, achieving low reflectance and having colorless transparent properties, a polarizer including the optical laminate, a display unit containing the optical laminate, and an organic light emission diode display unit including the optical laminate.SOLUTION: An optical laminate comprises: a polymer resin layer; and an optical functional layer which is formed on one surface of the polymer resin layer and includes a binder resin and hollow type organic nano particles and solid type organic nano particles dispersed in the binder resin. The optical laminate has a specific volume ratio of a zirconium element to a silicon element in a portion from an interface between the polymer resin layer and the optical functional layer to a thickness 5 nm to 10 nm region of the optical functional layer and a portion from the interface between the polymer resin layer and the optical functional layer to a thickness of 50 nm to 150 nm of the optical functional layer. There are also provided a polarizer comprising the same optical laminate, a display device, and an organic light emission diode display unit.SELECTED DRAWING: Figure 1

Description

[Mutual citation with related applications]
This application is for Korean Patent Application No. 10-2020-0138549 dated October 23, 2020, Korean Patent Application No. 10-2020-0138548 dated October 23, 2020, and Korean Patent Application No. 10-2020 dated November 3, 2020. All content disclosed in the literature of the Korean patent application claiming the benefit of priority under 014548 is included as part of this specification.

The present invention relates to an optical laminate, and more specifically, it has low reflectance and high light transmittance, and can simultaneously realize high scratch resistance and antifouling property, and enhances the sharpness of the screen of a display device. Regarding the obtained optical laminate.

Generally, a flat plate display device such as a PDP or an LCD is equipped with an optical film for minimizing the reflection of light incident from the outside. As a method for minimizing the reflection of light, a method of dispersing a filler such as inorganic fine particles in a resin and coating it on a base film to give unevenness (anti-glare: AG coating); on the base film. There are a method of forming a large number of layers having different refractive indexes and using light interference (anti-reflection: AR coating), or a method of mixing these.

Among them, in the case of the AG coating, the absolute amount of reflected light is at the same level as that of a general hard coat, but the low reflection effect is achieved by reducing the amount of light entering the eyes by using light scattering due to unevenness. Obtainable. However, since the sharpness of the screen of the AG coating is reduced due to the surface unevenness, much research has been conducted on the AR coating recently.

As a film using the AR coating, a film having a multilayer structure in which a high refractive index layer, a low reflection coating layer and the like are laminated on a base film has been commercialized. However, the method of forming a large number of layers as described above has a disadvantage that the scratch resistance is lowered because the interlayer adhesion force (interfacial adhesive force) is weak due to the step of forming each layer separately.

Previously, in order to improve the scratch resistance of the AR coating, a method of adding various nanometer-sized particles (for example, particles of silica, alumina, zeolite, etc.) was mainly attempted. However, when nanometer-sized particles are used as described above, it is difficult to reduce the reflectance and simultaneously increase the scratch resistance, and the nanometer-sized particles have an antifouling property on the surface of the optical film. Has dropped significantly.

Therefore, many studies have been conducted to reduce the absolute reflection amount of light incident from the outside and to improve the scratch resistance and antifouling property of the surface, but the degree of improvement in physical properties accompanying this is insufficient. Is.

The present invention provides an optical laminate having high light transmittance, high scratch resistance and antifouling property at the same time, and having colorless and transparent properties while achieving low reflectance. ..

The present invention also provides a polarizing plate containing the optical laminate.

The present invention also provides a display device including the optical laminate.

The present invention also provides an organic light emitting diode display device including the optical laminate.

The present specification includes a polymer resin layer; and an optical functional layer formed on one surface of the polymer resin layer and containing a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin. The volume ratio of the zirconium element to the silicon element is less than 2.6 in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 5 nm to 10 nm, and the polymer resin layer. An optical laminate having a volume ratio of a zirconium element to a silicon element of 1.62 or more is provided in a region having a thickness of 50 nm to 150 nm from the interface between the optical functional layer and the optical functional layer.

Further, in the present specification, a polarizing plate including the optical laminate and a polarizing element is provided.

Further, in the present specification, a display device including the optical laminate is provided.

Further, the present specification provides an organic light emitting diode display device including the optical laminate.

Hereinafter, the optical laminate, the polarizing plate, the display device, and the organic light emitting diode display device according to the specific embodiment of the present invention will be described in more detail.

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

Further, the fluorine-containing compound means a compound containing at least one fluorine element among the compounds.

Further, (meth) acrylic [(Meth) acrylic] means to include both acrylic (acryl) and methacrylate (Methacrylic).

Further, the (co) polymer means that both a copolymer (co-polymer) and a homopolymer (homo-polymer) are included.

Further, hollow silica particles mean silica particles derived from a silicon compound or an organic silicon compound, in which an empty space exists on the surface and / or inside of the silica particles.

According to one embodiment of the invention, an optical function including a polymer resin layer; and hollow inorganic nanoparticles and solid inorganic nanoparticles formed on one surface of the polymer resin layer and dispersed in the binder resin and the binder resin. The volume ratio of the zirconium element to the silicon element is less than 2.6 in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 5 nm to 10 nm. Provided is an optical laminate in which the volume ratio of the zirconium element to the silicon element is 1.62 or more in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 50 nm to 150 nm. Can be done.

When the optical film including the optical functional layer has a low refractive index, the reflectance in the blue color region is higher than the reflectance in the green region. As a result, the film may be blue in color and have a degree of opacity or color that is not suitable for application to a polarizing plate or a display device.

Therefore, the present inventors conducted research on an optical laminate, and obtained that the optical functional layer containing hollow inorganic nanoparticles and solid inorganic nanoparticles contained silicon element and zirconium element in a specific region in a specific volume ratio. The invention was completed by experimentally confirming that it is possible to improve the black appearance while achieving low reflectance and haze, and to significantly reduce the degree of bluish tint so that it has colorless and transparent properties. ..

Further, the optical laminate can have a high light transmittance in addition to the above-mentioned characteristics, and can have a feature that can simultaneously realize high scratch resistance and antifouling property.

Specifically, the volume ratio of the zirconium element to the silicon element is less than 2.6, 0.5 in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 5 nm to 10 nm. It can be ~ 2.0, 1.0 ~ 1.8 or 1.2 ~ 1.6.

The volume ratio of the zirconium element to the silicon element is 1.62 or more and 1.70 to 2.5 in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 50 nm to 150 nm. It can be 1.75 to 2.3 or 1.80 to 2.0.

The volume ratio of the zirconium element to the silicon element in the above-mentioned region corresponds to the arithmetic mean value of the volume ratio in the above-mentioned region.

Further, by satisfying the above-mentioned range in the volume ratio of the zirconium element to the silicon element in the above-mentioned region, it has a colorless and transparent property while realizing a low reflectance, has a higher light transmittance, and has a high resistance. Scratch property and antifouling property can be realized at the same time.

When the volume ratio of the zirconium element to the silicon element is 2.6 or more in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 5 nm to 10 nm, low reflectance is realized. Difficult or difficult to exhibit colorless and transparent properties.

Low reflectance is achieved if the volume ratio of the zirconium element to the silicon element is less than 1.62 in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 50 nm to 150 nm. Difficult to do or difficult to exhibit colorless and transparent properties.

The optical functional layer contained in the optical laminate according to the above embodiment has high light transmittance by containing both hollow inorganic nanoparticles and solid inorganic nanoparticles, and has high scratch resistance and antifouling property. Can be realized at the same time. Further, the solid type inorganic nanoparticles may include both solid type silica nanoparticles and solid type zirconia nanoparticles. As a result, the optical laminate can improve the black appearance while exhibiting a low haze.

For example, the optical functional layer contains a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, solid silica nanoparticles, and solid zirconia nanoparticles, and the solid zirconia nanoparticles relative to the solid silica nanoparticles. The weight ratio can be 10 or more, 15-40, 20-30, or 23-28.

By containing the solid-type zirconia nanoparticles in a weight ratio of 10 or more with respect to the solid-type silica nanoparticles, it is possible to simultaneously realize high scratch resistance and antifouling property while having high reflectance. While achieving low reflectance and haze, it is possible to improve the black appearance and exhibit colorless and transparent characteristics.

On the other hand, when the weight ratio of the solid-type zirconia nanoparticles to the solid-type silica nanoparticles is less than 10, the thickness of the particle-mixed layer may increase, and an appropriate refractive index difference cannot be imparted. Increases reflectance and haze.

In the optical functional layer, there may be a particle mixed layer in which the hollow inorganic nanoparticles and the solid inorganic nanoparticles are both present and have a thickness of 25 to 100 nm.

Due to the presence of the particle mixed layer, the optical laminate may have colorless and transparent properties while achieving low reflectance, but the optical functional layer contains hollow inorganic nanoparticles and solid inorganic nanoparticles. Therefore, it has a high reflectance and can simultaneously realize high scratch resistance and antifouling property.

Specifically, the optical functional layer can be formed on one surface of the polymer resin layer, and the particle mixed layer can be located at a distance of 50 nm or more from one surface of the polymer resin layer, or the particles. The mixed layer may be located at a distance of 50 nm to 250 nm, 60 nm to 220 nm, 70 nm to 200 nm, 80 nm to 180 nm, 90 nm to 150 nm, or 100 nm to 120 nm from one surface of the polymer resin layer.

By locating the particle mixed layer at a distance of 50 nm or more from one surface of the polymer resin layer, the particle mixed layer plays a role of alleviating a sudden difference in the refractive index between the layers in the optical functional layer, and at the wavelength of 550 nm. The absolute value of the inclination of the reflectance pattern in the short wavelength region of the optical laminate having the reflectance of 0.5% or less becomes low.

When the particle mixed layer is located in a region of less than 50 nm from one surface of the polymer resin layer, the effect of reducing the difference in the refractive index between the layers in the optical functional layer is limited, so that the reflectance at the wavelength of 550 nm is limited. It is not possible to sufficiently find the absolute value of the inclination of the reflectance pattern of the optical laminate having a value of 0.5% or less.

The distance between the particle mixed layer and the polymer resin layer is the shortest distance between one surface of the polymer resin layer and the particle mixed layer with reference to the surface direction of the polymer resin layer. Alternatively, the distance between the particle mixed layer and the polymer resin layer can be defined by the thickness of the region between one surface of the polymer resin layer and the particle mixed layer.

The existence of a region between one surface of the polymer resin layer and the particle mixed layer can be confirmed by an ellipsometry method. The ellipticity of the polarization measured by the ellipsometry for each region between one surface of the particle mixed layer and the polymer resin layer and the particle mixed layer is optimized by a Cauchy model (Cauchy model). When fitting), the specific Cauchy parameters A, B and C are obtained, so that the regions between one surface of the particle mixed layer and the polymer resin layer and the particle mixed layer are separated from each other.

Specifically, regarding the optical functional layer, J. A. Woollam Co. Using the M-2000 device, line polarization can be measured in the wavelength range of 380-1000 nm by applying an incident angle of 70 °. The measured linear polarization measurement data (Ellipsometry data (Ψ, Δ)) is optimized by the Cauchy model of the following general formula 2 for the detailed layer in the optical functional layer using the Complete EASE software (Cauchy model). Fitting) can be done.

In the general formula 2, n (λ) is the refractive index at the λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B and C are Cauchy parameters.

Further, the particles are mixed by optimizing (fitting) the ellipticity of the polarization measured by the elliptical polarization method (Cauchy model) and the diffusion layer model (Diffuse Layer Model) of the general formula 2. Since the thickness of each region between the particle mixed layer can be derived from one surface of the layer or the polymer resin layer, the particle mixed layer can be derived from one surface of the particle mixed layer or the polymer resin layer in the optical functional layer. It is possible to define each of the areas between.

Further, in the optical laminate having a reflectance of 0.5% or less at a wavelength of 550 nm, the ratio of the reflectance at a wavelength of 400 nm to the reflectance at a wavelength of 550 nm is 5 or more, 5 to 20, 5.5 to 5. It can be 15, or 6-12.

By satisfying the property that the ratio of the reflectance at a wavelength of 400 nm to the reflectance at a wavelength of 550 nm is 5 or more, or 5 to 20, or 5.5 to 15, or 6 to 12, the optical laminate is satisfied. The optical laminate can have an optical characteristic that the reflectance in the blue color region is lower than the reflectance in the green region, and therefore, it can have a colorless and transparent property while realizing a low reflectance.

When the ratio of the reflectance at a wavelength of 400 nm to the reflectance at a wavelength of 550 nm is less than 5, the optical laminate having a reflectance of 0.5% or less at a wavelength of 550 nm has a blue color. It becomes opaque or chromatic to a degree unsuitable for application to polarizing plates or display devices. In particular, in the case of an optical laminate in which the ratio of the reflectance at a wavelength of 400 nm to the reflectance at a wavelength of 550 nm is less than 5, the color reproduction power of the organic light emitting diode display device is lowered.

The ratio of the reflectance at a wavelength of 400 nm to the reflectance at a wavelength of 550 nm of the optical laminate having a reflectance of 0.5% or less at a wavelength of 550 nm is 5 or more, or 5 to 20, or 5.5 to 5. The reflectance of the optical laminate at a wavelength of 550 nm is 0.05% to 5.0%, or 0.06 to 4.0%, or is within the range of 15 or 6 to 12. It can be 0.07 to 3.0% or 0.08% to 0.3%.

Further, the reflectance of the optical laminate at 400 nm may be 0.5% to 3.50%, or 0.80% to 2.0%.

The optical laminate may have a characteristic that the ratio of the reflectance at a wavelength of 700 nm is 5 or more, or 5 to 20, or 6 to 15, or 7 to 12 with respect to the reflectance at a wavelength of 550 nm. Therefore, the optical laminate can have optical characteristics in which the reflectance in the blue color region is lower than the reflectance in the green region, and therefore, it can have colorless and transparent characteristics while realizing low reflectance. can. When the reflectance at a wavelength of 700 nm is excessively high as compared with the reflectance at a wavelength of 550 nm, the reflectance in the red light region becomes relatively high and the corresponding optical film looks yellow or red.

On the other hand, the optical laminate having a reflectance of 0.5% or less at a wavelength of 550 nm includes a particle mixed layer having the predetermined thickness in the optical functional layer, and the reflectance at a wavelength of 550 nm is 0. The ratio of the reflectance at a wavelength of 400 nm to the reflectance at a wavelength of 550 nm of an optical laminate of 5.5% or less can be 5 or more, or 5 to 20, or 5.5 to 15, or 6 to 12. However, the optical laminate can therefore have the property that the absolute value of b * is 4 or less, 3 or less, or 2 or less, or 1.5 or less in the CIE Lab color space.

Each numerical value in the CIE Lab color space can be measured by applying a general method for measuring each coordinate of the color space, for example, having a detector in the form of an integration zone at the measurement position. After the equipment (spectrophotometer) (eg CM-2600d, KONICA MINORTA) is positioned, it can be measured according to the manufacturer's manual. In one example, each coordinate of the CIE Lab color space can be measured with the splitter or the polarizing plate attached to the liquid crystal panel, for example, the highly reflective liquid crystal panel, with respect to the splitter or the polarizing plate itself. It can also be measured.

The CIE Lab color space is a color space obtained by non-linearly transforming the CIE XYZ color space based on the antagonistic theory of human vision. In such a color space, the L * value indicates brightness, when the L * value is 0, it indicates a black color, and when the L * value is 100, it indicates white. If the a * value is a negative number, the color is biased toward green, and if it is a positive number, the color is biased toward red. If the b * value is a negative number, the color is biased toward blue, and if the b * value is a positive number, the color is biased toward yellow.

That is, the optical laminate has a characteristic that the absolute value of the b * value is 4 or less, 3 or less, 2 or less, or 1.5 or less in the CIE Lab color space, thereby realizing low reflectance. It can also have colorless and transparent properties by significantly reducing the degree of redness and blueness.

More specifically, the reflectance of the optical laminate at a wavelength of 550 nm can be 0.5% or less, and the absolute value of the b * value in the CIE Lab color space can be achieved while achieving such a low reflectance. It can have characteristics of 4 or less, or 3 or less, or 2 or less, or 1.5 or less.

Thus, by achieving low reflectance and maintaining a low level of absolute b * values in the CIE Lab color space, the optical laminate is readily applied to displays with high contrast ratio and brightness. , Performance with high color reflectance can be realized.

In order to have the above-mentioned characteristics of the optical laminate, the optical functional layer contains both hollow inorganic nanoparticles and solid inorganic nanoparticles, and is 25 to 100 nm, or 35 nm to 90 nm, or 40 nm to 85 nm, or 50 nm. There can be a mixed particle layer with a thickness of ~ 80 nm, or 60 nm ~ 75 nm.

If the thickness of the particle mixed layer is too small, the scratch resistance of the optical functional layer is lowered. On the other hand, if the thickness of the particle mixed layer is too thick, the optical characteristics such as the transparency of the optical laminate may be deteriorated.

The refractive index and thickness of the mixed particle layer can be confirmed by various optical measurement methods. For example, the ellipticity of the polarized pole measured by the ellipsometry method is measured by a diffusion layer model (Diffuse layer model). It can also be confirmed by using a method of optimizing (fitting).

The ellipsometry ellipsometry and related data (Ellipsometry data (Ψ, Δ)) measured by the ellipsometry can be measured using commonly known methods and devices. For example, with respect to the particle mixed layer or other regions contained in the optical functional layer, J. A. Woollam Co. Using the M-2000 device, line polarization can be measured in the wavelength range of 380-1000 nm by applying an incident angle of 70 °.

The measured linear polarization measurement data (Ellipsometry data (Ψ, Δ)) uses the Complete EASE software, a diffusion layer model (Diffuse layer model) for the particle mixture layer, and the following for the lower and upper layers of the particle mixture layer. According to the Cauchy model of the general formula 2, the two layers can be applied separately and optimized (fitting) so that the MSE is 5 or less.

In the general formula 2, n (λ) is the refractive index at the λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B and C are Cauchy parameters.

When the range of the thickness and the refractive index of the particle mixed layer contained in the optical functional layer satisfies the above-mentioned range, the sharp difference in the refractive index between the layers can be alleviated, and therefore the optical laminate is low. It enables the absolute value of the b * value to be maintained at a low level in the CIE Lab color space while achieving the reflectance.

On the other hand, the composition of the binder resin contained in the optical functional layer, the type and content of particles, the specific process at the time of forming the optical functional layer (for example, coating speed, coating method or drying conditions), characteristics of the polymer resin layer. The particle mixed layer can be formed in the optical functional layer by adjusting the above.

Such an example is an example of a method or means for forming the particle mixed layer, and only when the method or means is used at the same time, the particle mixed layer is not formed in the optical functional layer, but an optical function. It can be adjusted according to the detailed materials forming the layer and their contents, the thickness of the optical functional layer, the detailed materials of the polymer resin layer and their contents, the surface characteristics and thickness of the polymer resin layer, and the like. It is possible. That is, the existence of the particle mixed layer in the optical functional layer and the effect thereof can be realized based on the description of the specification and the examples.

For example, the polymer resin layer contained in the optical laminate may contain a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin; and a binder resin on such a polymer resin layer. And when the optical functional layer containing the hollow type inorganic nanoparticles and the solid type inorganic nanoparticles is formed under predetermined conditions, the particle mixed layer may exist.

Further, the polymer resin layer contained in the optical laminate may have a surface energy of 34 mN / m or more, 34 mN / m to 60 mN / m, or 35 mN / m to 55 mN / m. When an optical functional layer containing a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles is formed on a polymer resin layer having a range of surface energy, the surface in the optical functional layer due to the high surface energy of the interface is formed. The above-mentioned particle mixed layer can be formed in the process of energy optimization.

The surface energy of the polymer resin layer can be obtained by adjusting the surface characteristics of the polymer resin layer. For example, the surface energy of the polymer resin layer can be adjusted by adjusting the surface hardening degree, drying conditions, and the like of the polymer resin layer.

Specifically, the degree of curing of the polymer resin layer is adjusted by adjusting the curing conditions such as the amount of light irradiation or the intensity of light irradiation and the flow rate of injected nitrogen in the process of forming the polymer resin layer. be able to. For example, the polymer resin layer is subjected to nitrogen purge to apply nitrogen atmospheric conditions, and the resin composition forming the polymer resin layer is 5 to 100 mJ / cm ² or 10 to 25 mJ / cm ² . It is obtained by irradiating ultraviolet rays with an exposure amount.

The surface energy is an average value obtained by measuring the contact angles of di-water (Gebhardt) and di-iodomethane (Owens) at 10 points using a commonly known measuring device, for example, a DSA-100 contact angle measuring device manufactured by Kruss. The average contact angle is converted into surface energy and measured. Specifically, in the measurement of the surface energy, the Dropshape Analysis software is used, and the following general formula 1 of the OWRK (Owen, Wendt, Rable, Kaelble) method is applied on the program to convert the contact angle into the surface energy.

Further, as will be described later, the particle mixed layer is formed by applying a drying temperature, air volume adjustment, or the like at the time of forming the optical functional layer.

Specifically, the air volume can be adjusted in the drying process by adjusting the drying conditions, for example, the intake air or the exhaust volume in the process of forming the optical functional layer. For example, in the post-coating drying process of the optical functional layer, the air volume is 0.5 m / s or more, 0.5 m / s to 10 m / s, or 0.5 m / s to 8 m / s, or 0.5 m / s to. It can also be done at 5 m / s.

More specifically, the optical functional layer is formed on one surface of the polymer resin layer, and the optical functional layer may contain hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in a binder resin, at this time. In the optical functional layer, 50% by volume or more, 60% by volume or more, or 70% by volume or more, or the numerical value or more or 95% by volume or less of the whole solid type inorganic nanoparticles is from one surface of the polymer resin layer. It may exist between the particle mixed layers.

As described above, the solid-type inorganic nanoparticles are mainly distributed in the region between one surface of the polymer resin layer and the mixed particle layer, so that the solid inorganic nanoparticles are mainly distributed between one surface of the polymer resin layer and the mixed particle layer. The region has a refractive index of 1.46 to 1.75 at a wavelength of 550 nm.

"50% by volume or more of the whole solid-type inorganic nanoparticles are present in a specific region" is defined in the sense that most of the solid-type inorganic nanoparticles are present in the specific region in the cross section of the optical functional layer. Specifically, 70% by volume or more of the total volume of the solid type inorganic nanoparticles can be confirmed by measuring the volume of the entire solid type inorganic nanoparticles.

For example, it can be visually recognized that each of the regions in which the solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles are mainly distributed exists in the optical functional layer. For example, a transmission electron microscope [Transmission Electron Microscope] or a scanning electron microscope [Scanning Electron Microscope] can be used to visually confirm that each individual layer or individual region exists in the optical functional layer, and the optical function can be confirmed. The ratio of solid-type inorganic nanoparticles and hollow-type inorganic nanoparticles distributed in the corresponding layer or the corresponding region in the functional layer can also be confirmed.

Further, in the optical functional layer, 50% by volume or more, 60% by volume or more, or 70% by volume or more, or the numerical value or more or 95% by volume or less of the whole hollow inorganic nanoparticles is said from the particle mixed layer. It may exist in the region up to one surface of the optical functional layer facing the polymer resin layer. One surface of the optical functional layer facing the polymer resin layer means another surface located in the direction opposite to the surface in contact with the polymer resin layer.

As described above, the hollow inorganic nanoparticles are mainly distributed in the region from the particle mixed layer to one surface of the optical functional layer facing the polymer resin layer, whereby the particle mixed layer to the polymer resin layer. The region up to one surface of the optical functional layer facing the surface can have a refractive index of 1.0 to 1.40 at a wavelength of 550 nm.

In the optical functional layer of the optical laminate, the above-mentioned particle mixed layer exists, and solid-type inorganic nanoparticles are mainly distributed near the interface between the polymer resin layer and the optical functional layer, and the solid inorganic nanoparticles are mainly distributed at the interface. Hollow-type inorganic nanoparticles are mainly distributed on the opposite side, but regions in which the solid-type inorganic nanoparticles and hollow-type inorganic nanoparticles are mainly distributed are visually confirmed in the optical functional layer. Layers can be formed.

Specifically, among the optical functional layers of the optical laminate, solid-type inorganic nanoparticles are mainly distributed near the interface between the polymer resin layer and the optical functional layer, and the opposite surface of the interface is mainly distributed. When hollow inorganic nanoparticles are mainly distributed, lower reflectance can be achieved compared to the actual reflectance previously obtained using inorganic particles, and the resistance is greatly improved. Both scratch property and antifouling property can be realized.

In the optical laminate of the embodiment, the region where the solid inorganic nanoparticles and the hollow inorganic nanoparticles are unevenly distributed in the optical functional layer is divided based on the particle mixed layer. Therefore, the optical laminate has a wavelength of 550 nm. The reflectance of is 0.5% or less, and the absolute value of the b * value in the CIE Lab color space is 4 or less, 3 or less, 2 or less, or 1.5 or less, so that the reflectance is low. While realizing it, it is possible to have a colorless and transparent property by significantly reducing the degree of tinging with a blue color.

Further, the region between one surface of the polymer resin layer and the mixed particle layer and the region from the mixed particle layer to one surface of the optical functional layer facing the polymer resin layer can be distinguished into individual layers, as described above. As described above, the volume ratios of the silicon element and the zirconium element distributed in these individual layers can also be distinguished.

More specifically, the ellipticity of the polarization measured by the ellipsometry with respect to the region between one surface of the polymer resin layer and the particle mixed layer is the Cauchy model of the following general formula 2. ), The following A is 1.00 to 1.65, B is 0.0010 to 0.0350, and C satisfies the condition of 0 to 1 * 10 ^-3 . Further, with respect to the region between one surface of the polymer resin layer and the particle mixed layer, the following A is 1.25 to 1.55, 1.30 to 1.52, or 1.45 to 1.51. Yes, B below is 0.0010 to 0.0150, 0.0010 to 0.0080, or 0.0010 to 0.0050, and C below is 0 to 8.0 * 10 ^-4 , 0 to 5. The conditions of 0.0 * 10 ^-4 or 0 to 4.1352 * 10 ^-4 can be satisfied.

In the general formula 2, n (λ) is the refractive index at the λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B and C are Cauchy parameters.

Further, the ellipticity of the polarization measured by the ellipsometry method for the region from the particle mixed layer to one surface of the optical functional layer facing the polymer resin layer is determined by the Cauchy model of the general formula 2. When optimized by the polymer), A is 1.00 to 1.50, B is 0 to 0.007, and C satisfies the conditions of 0 to 1 * 10 ^-3 . Further, the A is 1.00 to 1.30, 1.00 to 1.20, 1.00 to the region from the particle mixed layer to one surface of the optical functional layer facing the polymer resin layer. 1.09, or 1.00 to 1.05, and B is 0 to 0.0060, 0 to 0.0055, or 0 to 0.00513, and C is 0 ^to 8 * 10-. ⁴ , 0 to 5.0 * 10 ^-4 , or 0 to 4.8685 * 10 ^-4 is satisfied.

Further, when the ellipticity of the polarization measured with respect to the particle mixed layer by the elliptical polarization method is optimized (fitting) by the Cauchy model of the general formula 2, the A is 1.100. It is 1.200, 1.130 to 1.199, 1.150 to 1.198, or 1.180 to 1.195, and B is 0 to 0.007, 0 to 0.006, 0 to 0. It is 005 or 0 to 0.004, and C is 0 to 1 * 10 ^-3 , 0 to 8 * 10 ^-4 , 0 to 5.0 * 10 ^-4 , or 0 to 4.8685 * 10 ^-4 . Meet the conditions.

On the other hand, each of the particle mixed layer, the region between one surface of the polymer resin layer and the particle mixed layer, and the region from the particle mixed layer to one surface of the optical functional layer facing the polymer resin layer is one layer. It is possible to share common optical properties within, and therefore it can be defined as one layer.

More specifically, the region between the particle mixed layer, one surface of the polymer resin layer and the particle mixed layer, and the region from the particle mixed layer to one surface of the optical functional layer facing the polymer resin layer, respectively. Has specific Cauchy parameters A, B and C when the ellipticity of the polarization measured by the ellipsometry is optimized by the Cauchy model of the general formula 2. Therefore, the areas are separated from each other. Further, by optimizing (fitting) the ellipticity of the polarization measured by the ellipsometry method by the Cauchy model of the general formula 2, the thickness of each region is also derived, so that the optical function is described. Each region can be defined within the layer.

On the other hand, the Cauchy parameters A, B and C derived when the ellipticity of the polarization measured by the ellipsometry is optimized (fitting) by the Cauchy model of the general formula 2 are one region. Can be the average value within. Therefore, when an interface exists between the respective regions, the Cauchy parameters A, B, and C of the respective regions overlap. However, even in such a case, the thickness and position of the respective regions are specified according to the regions satisfying the average values of the Cauchy parameters A, B, and C possessed by the respective regions.

On the other hand, whether or not the hollow inorganic nanoparticles and the solid inorganic nanoparticles are present in the specified region is determined by the presence of the hollow inorganic nanoparticles or the solid inorganic nanoparticles in the specified region. It is determined by whether or not, and the particles existing over the boundary surface of the specific region are excluded.

The optical functional layer including the above-mentioned particle mixed layer may have a lower average refractive index than the polymer resin layer. For example, the optical functional layer has an average refractive index of 1.46 or less and 1.43 or less at a wavelength of 550 nm. , 1.40 or less, or 1.39 to 1.30. Further, the polymer resin layer may have an average refractive index of more than 1.46, 1.47 or more, or 1.49 to 1.52 at a wavelength of 550 nm.

On the other hand, as described above, even in the optical functional layer, "the region between one surface of the polymer resin layer and the particle mixture layer has a refractive index of 1.46 to 1.75 at a wavelength of 550 nm", and "the particle mixture". The region from the layer to one surface of the optical functional layer facing the polymer resin layer has a refractive index of 1.0 to 1.40 at a wavelength of 550 nm, but the average refractive index of the optical functional layer is such a region. It means the average value of the refractive index of the entire optical functional layer including all the mixed particles. Similarly, the average refractive index of the polymer resin layer also means the average value of the refractive indexes measured in the entire layer.

The specific distribution of the solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles in the optical functional layer is the drying temperature of the photocurable resin composition for forming the optical functional layer containing the above-mentioned nanoparticles in a specific production method described later. , The method of adjusting the dry air volume, the drying time, etc., and the above-mentioned method of forming the particle mixed layer.

When the hollow inorganic nanoparticles and the solid inorganic nanoparticles are selected because the optical laminate has a reflectance of 0.5% or less at a wavelength of 550 nm, a type having a large refractive index difference between them is selected. do.

More specifically, the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles is 0.7 to 8.5 g / cm ³ , 0.8 to 7.5 g / cm ³ , 0. It can be 9 to 6.5 g / cm ³ , 1.1 to 5.5 g / cm ³ , 1.20 to 4.5 g / cm ³ or 1.24 to 4.27 g / cm ³ .

When the difference in density between the solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles is excessively large, the region where the solid-type inorganic nanoparticles are densely packed in the polymer resin layer and the hollow-type inorganic nanoparticles are mainly distributed. An intermediate layer in which particles are substantially absent can be formed between the regions where solid-type inorganic nanoparticles and hollow-type inorganic nanoparticles are mainly distributed. In this way, the solid-type inorganic particles may be concentrated and gathered at the interface between the optical functional layer and the polymer resin layer, or the movement and uneven distribution of the particles may not be smooth in the process of forming the optical functional layer, and the surface of the optical functional layer may not be smooth. The transparency may decrease due to the occurrence of stains or a large increase in haze of the optical functional layer.

Further, when the difference in density between the solid type inorganic nanoparticles and the hollow type inorganic nanoparticles is too small, the above-mentioned solid type inorganic nanoparticles and the hollow type inorganic nanoparticles do not appear unevenly distributed, so that the reflectance is greatly increased. Colorless and transparent properties do not appear.

Therefore, the optical functional layer included in the optical laminate of the above embodiment contains the above-mentioned inorganic particles having a density difference, has a high reflectance, and simultaneously realizes high scratch resistance and antifouling property. It is possible to improve the black appearance and have colorless and transparent characteristics while achieving low reflectance and haze.

More specifically, the solid-type inorganic nanoparticles can have a higher density than the hollow-type inorganic nanoparticles, for example, the solid-type inorganic nanoparticles are 1.2 to 10.5 g / cm ³ , 3. The hollow inorganic nanoparticles can have a density of 2.0 to 7.5 g / cm ³ or 3.0 to 5.5 g / cm ³ , and the hollow inorganic nanoparticles are 0.50 g / cm ³ to 2.00 g / cm ³ , It can have a density of 0.70 g / cm ³ to 1.80 g / cm ³ or 1.00 g / cm ³ to 1.60 g / cm ³ .

Specific types of the solid-type inorganic nanoparticles include zirconia, titania, antimony pentoxide, silica, tin oxide, and the like, and may include, for example, solid-type silica nanoparticles and solid-type zirconia nanoparticles. At this time, the solid zirconia nanoparticles may have a density of 3 to 7 g / cm ³ or 5 to 6 g / cm ³ , and the solid silica nanoparticles have a density of 2 to 4 g / cm ³ or 2.5 to 3. It can be 0 g / cm ³ .

Moreover, as a specific kind of the hollow type inorganic nanoparticles, hollow silica and the like can be mentioned.

On the other hand, the optical functional layer may contain a binder resin, hollow inorganic nanoparticles dispersed in the binder resin, and solid inorganic nanoparticles.

The photopolymerizable compound contained in the photocurable coating composition of the embodiment can form a base material for a binder resin of the optical functional layer to be produced.

Specifically, the photopolymerizable compound may include a (meth) acrylate or a monomer or oligomer containing a vinyl group. More specifically, the photopolymerizable compound may include a monomer or oligomer containing one or more, two or more, or three or more (meth) acrylates or vinyl groups.

Specific examples of the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (. Meta) acrylate, tripentaerythritol hepta (meth) acrylate, tolylene diisocyanate, xylenedi isocyanate, hexamethylene diisocyanate, trimethylol propanetri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylol propanetrimethacrylate, Ethylene glycol dimethacrylate, butanediol dimethacrylate, hexaethylmethacrylate, butylmethacrylate or a mixture of two or more thereof, or a urethane-modified acrylate oligomer, epoxided acrylate oligomer, ether acrylate oligomer, dendric acrylate oligomer, or a mixture thereof. Examples include a mixture of two or more. At this time, the molecular weight of the oligomer is preferably 1,000 to 10,000.

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

The content of the photopolymerizable compound in the photocurable coating composition is not largely limited, but the mechanical properties of the finally produced optical functional layer and optical laminate are taken into consideration. The content of the photopolymerizable compound in the solid content of the photocurable coating composition can be 5% by weight to 80% by weight. The solid content of the photocurable coating composition means only the solid component excluding the liquid phase component in the photocurable coating composition, for example, a component such as an organic solvent that may be selectively contained as described later. do.

The solid-type inorganic nanoparticles have a maximum diameter of 100 nm or less, and mean particles in a form in which no empty space exists inside.

Further, the hollow inorganic nanoparticles have a maximum diameter of 200 nm or less, and mean particles having an empty space on the surface and / or inside thereof.

The solid inorganic nanoparticles can have a diameter of 0.5-100 nm, or 1-50 nm, or 5-30 nm, or 10-20 nm.

The hollow inorganic nanoparticles can have a diameter of 1 to 200 nm, or 10 to 100 nm, or 50 to 120 nm, or 30 to 90 nm, or 40 to 80 nm.

The diameter of the hollow inorganic nanoparticles and the diameter of the solid inorganic nanoparticles may be different.

Further, the diameter of the hollow inorganic nanoparticles may be larger than the diameter of the solid inorganic nanoparticles.

The diameters of the solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles each mean the longest diameter of the nanoparticles confirmed in the cross section.

On the other hand, each of the solid type inorganic nanoparticles and the hollow type inorganic nanoparticles is one or more selected from the group consisting of a (meth) acrylate group, an epoxide group, a vinyl group (Vinyl) and a thiol group (Tiol) on the surface. Can contain reactive functional groups of. By containing the above-mentioned reactive functional groups on the surface of each of the solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles, the optical functional layer can have a higher degree of cross-linking, and therefore, the scratch resistance is further improved. Sexuality and antifouling property can be ensured.

The optical functional layer is obtained by applying the photocurable coating composition on a predetermined substrate and photocuring the applied product. The specific type and thickness of the base material are not largely limited, and a base material known to be used for producing an optical functional layer or an optical laminate can be used without major restrictions.

The methods and devices commonly used for applying the photocurable coating composition can be used without particular limitation, for example, a bar coating method such as Meyer bar, a gravure coating method, a 2 roll reverse coating method, a vacuum slot. A die coating method, a 2-roll coating method, or the like can be used.

The optical functional layer can have a thickness of 20 nm to 240 nm, or 50 nm to 200 nm, or 80 nm to 180 nm.

At the stage of photocuring the photocurable coating composition, ultraviolet rays having a wavelength of 200 to 400 nm or visible light can be irradiated, and the exposure amount at the time of irradiation is preferably 100 to 4,000 mJ / cm ² . The exposure time is not particularly limited, and can be appropriately changed depending on the exposure apparatus used, the wavelength of the irradiation light beam, or the exposure amount.

Further, at the stage of photocuring the photocurable coating composition, nitrogen purging or the like can be performed in order to apply nitrogen atmospheric conditions.

On the other hand, the binder resin contained in the optical functional layer may contain a (co) polymer of a photopolymerizable compound and a crosslinked (co) polymer between a fluorine-containing compound containing a photoreactive functional group.

The above-mentioned optical functional layer is produced from a photocurable coating composition containing a photopolymerizable compound, a fluorine-containing compound containing a photoreactive functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles and a photoinitiator. Can be done. Therefore, the binder resin contained in the optical functional layer may contain a (co) polymer of a photopolymerizable compound and a crosslinked (co) polymer between a fluorine-containing compound containing a photoreactive functional group.

The hydrophobicity of the binder resin containing the fluorine-containing compound and the hydrophilicity of the polymer resin layer due to the high surface energy affect the speed at which the fluorine-containing compound moves to the surface of the coat layer during the drying process of the optical laminate. As a result, convection is formed in the solvent, and the fine particles that are evenly distributed in the solvent behave differently depending on the characteristics of the particles. In particular, in this process, each particle can form a plurality of layers different from each other, and when the evaporation of the solvent is completed during the formation of each layer, the above-mentioned particle mixed layer is formed.

The surface rise of the fluorine-containing compound can induce the surface rise of the hollow inorganic nanoparticles, and the solid inorganic nanoparticles having a relatively small size are less affected by the surface rise, so that phase separation of each particle occurs. However, when the evaporation of the solvent in the process is completed and the fluidity of the particles disappears, the particles are formed in the optical functional layer having a predetermined thickness of the above-mentioned mixed layer.

The photopolymerizable compound may further contain a fluorine-based (meth) acrylate-based monomer or oligomer in addition to the above-mentioned monomer or oligomer. When the fluorine-based (meth) acrylate-based monomer or oligomer is further contained, 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. Can be 0.1% to 10%.

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

In the chemical formula 11, R ¹ is a hydrogen group or an alkyl group having 1 to 6 carbon atoms, a is an integer of 0 to 7, and b is an integer of 1 to 3.

In the chemical formula 12, c is an integer of 1 to 10.

In the chemical formula 13, d is an integer of 1 to 11.

In the chemical formula 14, e is an integer of 1 to 5.

In the chemical formula 15, f is an integer of 4 to 10.

On the other hand, the optical functional layer may contain a portion derived from the fluorine-containing compound containing the photoreactive functional group.

The fluorine-containing compound containing the photoreactive functional group may contain or be substituted with one or more photoreactive functional groups, the photoreactive functional group being irradiated with light, for example by irradiation with visible light or ultraviolet rays. It means a functional group that can participate in a polymerization reaction. The photoreactive functional group may contain various functional groups known to be able to participate in the polymerization reaction by irradiation with light, and specific examples thereof include (meth) acrylate group, epoxide group and vinyl group (Vinyl). Alternatively, a thiol group can be mentioned.

Each of the fluorine-containing compounds containing a photoreactive functional group has a weight average molecular weight of 2,000 to 200,000, preferably 5,000 to 100,000 (polystyrene-equivalent weight average molecular weight measured by the GPC method). be able to.

If the weight average molecular weight of the fluorine-containing compound containing the photoreactive functional group is too small, the fluorine-containing compound is not uniformly and effectively arranged on the surface in the photocurable coating composition, and is finally produced. Although it is located inside the optical functional layer, the antifouling property of the surface of the optical functional layer is lowered, the crosslink density of the optical functional layer is lowered, and mechanical properties such as overall strength and scratch resistance are deteriorated. Can be reduced.

Further, if the weight average molecular weight of the fluorine-containing compound containing the photoreactive functional group is excessively high, the compatibility with other components in the photocurable coating composition becomes low, and therefore the final product is produced. The haze of the optical functional layer may increase or the light transmittance may decrease, and the intensity of the optical functional layer may also decrease.

Specifically, the fluorine-containing compound containing the photoreactive functional group is i) an aliphatic compound in which one or more photoreactive functional groups are substituted and at least one carbon is substituted with one or more fluorine. Aliphatic compounds; ii) heteroaliphatic compounds or heteros substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine and one or more carbons substituted with silicon. (Hetero) Aliphatic ring compounds; iii) Polydialkylsiloxane-based polymers in which one or more photoreactive functional groups are substituted and at least one silicon is substituted with one or more fluorines (eg, polydimethylsiloxane-based). Polymer); 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 the above i) to iv), or their co-weight. Coalescence is mentioned.

The photocurable coating composition may contain 20 to 300 parts by weight of the fluorine-containing compound containing the photoreactive functional group with respect to 100 parts by weight of the photopolymerizable compound.

When the fluorine-containing compound containing the photoreactive functional group is excessively added to the photopolymerizable compound, the coating property of the photocurable coating composition of the embodiment is deteriorated or the photocurable coating composition is formed. The optical functional layer obtained from the above cannot have sufficient durability and scratch resistance. Further, if the amount of the fluorine-containing compound containing the photoreactive functional group is too small with respect to the photopolymerizable compound, the optical functional layer obtained from the photocurable coating composition has sufficient antifouling property and resistance. It cannot have mechanical properties such as scratch properties.

The fluorine-containing compound containing a photoreactive functional group may further contain silicon or a silicon compound. That is, the fluorine-containing compound containing the photoreactive functional group may selectively contain silicon or a silicon compound inside, and specifically, the content of silicon in the fluorine-containing compound containing the photoreactive functional group. Can be from 0.1% by weight to 20% by weight.

The silicon contained in the fluorine-containing compound containing the photoreactive functional group can enhance compatibility with other components contained in the photocurable coating composition of the embodiment, and is therefore finally produced. It is possible to prevent haze from being generated in the refracting layer and to increase the transparency. On the other hand, when the content of silicon in the fluorine-containing compound containing the photoreactive functional group is excessively large, the compatibility between the other components contained in the photocurable coating composition and the fluorine-containing compound becomes high. On the contrary, it may be lowered, and therefore the antifouling property of the surface may also be lowered because the finally manufactured optical functional layer or optical laminate cannot have sufficient translucency and antireflection performance.

The optical functional layer may be contained in an amount of 10 to 400 parts by weight, 20 to 350 parts by weight, or 50 to 300 parts by weight of the hollow inorganic nanoparticles with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound. .. Further, the optical functional layer is contained in an amount of 10 to 400 parts by weight, 20 to 350 parts by weight, or 50 to 300 parts by weight of the solid type inorganic nanoparticles with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound. It can be.

When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the optical functional layer is too large, the phase between the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the manufacturing process of the optical functional layer. Separation does not occur sufficiently and the particles are mixed to increase the reflectance, and the antifouling property may decrease due to the excessive occurrence of surface irregularities. When the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the optical functional layer is too small, the solid inorganic nanoparticles are located in a region close to the interface between the polymer resin layer and the optical functional layer. It is difficult to position a large number of nanoparticles, and the reflectance of the optical functional layer becomes very high.

Each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles can be contained in the composition in the form of colloids dispersed in a predetermined dispersion medium. Each colloidal form containing the hollow inorganic nanoparticles and the solid inorganic nanoparticles may contain an organic solvent as a dispersion medium.

The hollow inorganic nanoparticles and the solid in consideration of the range of the contents of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the photocurable coating composition, the viscosity of the photocurable coating composition, and the like. The content of each of the type inorganic nanoparticles in the colloid can be determined, for example, the solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the colloid is 5% by weight to 60% by weight. possible.

Here, among the dispersion media, the organic solvent includes 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. , Dimethylacetamides, amides such as N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate, γ-butyrolactone; ethers such as tetrahydrofuran, 1,4-dioxane; or mixtures thereof.

As the photopolymerization initiator, any compound known to be usable in a photocurable resin composition can be used without major restrictions, and specifically, a benzophenone-based compound, an acetophenone-based compound, and biimidazole. A system compound, a triazine system compound, an oxime system compound, or a mixture of two or more thereof can be used.

The photopolymerization initiator is used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. If the amount of the photopolymerization initiator is too small, uncured and residual substances may be generated in the photocuring step of the photocurable coating composition. If the amount of the photopolymerization initiator is too large, the unreacted initiator remains as an impurity, the crosslink density becomes low, the mechanical properties of the produced film deteriorate, and the reflectance becomes very high.

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

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

Specific examples of such organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, i-. Alcohols such as 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 mixtures of two or more thereof. Can be mentioned.

The organic solvent is added to the photocurable coating composition at the time of mixing each component contained in the photocurable coating composition, or by adding each component in a dispersed or mixed state in the organic solvent. Can be included. If the content of the organic solvent in the photocurable coating composition is too small, defects such as stripes may occur in the finally produced film due to a decrease in the flowability of the photocurable coating composition. .. Further, when the organic solvent is excessively added, the solid content content becomes low, and the physical properties and surface characteristics of the film may be deteriorated due to insufficient coating and film formation, and defects may occur in the drying and curing processes. .. Therefore, the photocurable coating composition may contain an organic solvent so that the concentration of the total solid content of the contained components is 1% by weight to 50% by weight, or 2 to 20% by weight.

On the other hand, the optical laminate of the above embodiment contains a photocurable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles. An optical laminate comprising a step of applying a resin composition for forming an optical functional layer containing the resin composition on a polymer resin layer and drying at a temperature of 35 ° C. to 100 ° C.; and a step of photocuring the dried product of the resin composition. Provided by the manufacturing method of.

The optical functional layer forms an optical functional layer containing a photocurable compound or a (co) polymer thereof, a fluorine-containing compound containing a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles and solid inorganic nanoparticles. It can be formed by applying a resin composition for use on a polymer resin layer and drying it at a temperature of 35 ° C to 100 ° C or 40 ° C to 80 ° C.

When the temperature at which the resin composition for forming an optical functional layer coated on the polymer resin layer is dried is less than 35 ° C., the antifouling property of the formed optical functional layer may be significantly reduced. When the temperature at which the resin composition for forming an optical functional layer coated on the polymer resin layer is dried exceeds 100 ° C., the hollow inorganic nanoparticles and the solid inorganic nanoparticles are formed in the process of manufacturing the optical functional layer. Not only the scratch resistance and antifouling property of the optical functional layer are lowered but also the reflectance is very high because the phase separation between the particles does not occur sufficiently and is mixed.

In the process of drying the resin composition for forming an optical functional layer applied on the polymer resin layer, the density difference between the solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles is adjusted together with the drying temperature. It is possible to form an optical functional layer having the above-mentioned characteristics.

On the other hand, the step of drying the resin composition for forming an optical functional layer applied on the polymer resin layer at a temperature of 35 ° C. to 100 ° C. is 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 solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles described above does not sufficiently occur. On the other hand, if the drying time is too long, the formed optical functional layer erodes the polymer resin layer.

The polymer resin layer can have a thickness of 0.1 μm to 100 μm.

Examples of the polymer resin layer include a binder resin containing a photocurable resin and a polymer resin layer containing organic or inorganic fine particles dispersed in the binder resin.

The photocurable resin contained in the polymer resin layer can be a normal polymer in the art as a polymer of a photocurable compound that can cause a polymerization reaction when irradiated with light such as ultraviolet rays. Specifically, the photocurable resin is a reactive acrylate oligomer group consisting of a urethane acrylate oligomer, an epoxide acrylate oligomer, a polyester acrylate, and a polyether acrylate; and dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, and pentaerythritol. Tetraacrylate, pentaerythritol triacrylate, trimethylenepropyltriacrylate, propoxylated glycerol triacrylate, trimethylpropaneethoxytriacrylate, 1,6-hexanediol diacrylate, propoxylated glycerotriacrylate, tripropylene glycol diacrylate, and It may contain one or more selected from the polyfunctional acrylate monomer group consisting of ethylene glycol diacrylate.

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

Further, the organic or inorganic fine particles are not limited to specific examples of the organic or inorganic fine particles contained in the polymer resin layer, but for example, the organic or inorganic fine particles are organic composed of an acrylic resin, a styrene resin, an epoxy resin and a nylon resin. It can be fine particles or inorganic fine particles composed of silicon oxide, titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide.

The binder resin of the polymer resin layer may further contain a high molecular weight (co) polymer having a weight average molecular weight of 10,000 or more.

The high molecular weight (co) polymer may be one or more selected from the group consisting of a cellulose-based polymer, an acrylic-based polymer, a styrene-based polymer, an epoxide-based polymer, a nylon-based polymer, a urethane-based polymer, and a polyolefin-based polymer.

On the other hand, as another example of the polymer resin layer, a binder resin of a photocurable resin; and a polymer resin layer containing an antistatic agent dispersed in the binder resin can be mentioned.

The photocurable resin contained in the polymer resin layer can be a normal polymer in the art as a polymer of a photocurable compound that can cause a polymerization reaction when irradiated with light such as ultraviolet rays. However, preferably, the photocurable compound may be a polyfunctional (meth) acrylate-based monomer or oligomer, and at this time, the number of (meth) acrylate-based functional groups is 2 to 10, preferably 2 to 8. , More preferably 2 to 7, which is advantageous from the aspect of ensuring the physical properties of the polymer resin layer. More preferably, the photocurable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol hepta (meth). ) Acrylate, tripentaerythritol hepta (meth) acrylate, tolylene diisocyanate, xylenedi isocyanate, hexamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane polyethoxytri (meth) acrylate. Can be more than a seed.

The antistatic agent is a quaternary ammonium salt compound; a pyridinium salt; a cationic compound having 1 to 3 amino groups; an anionic compound such as a sulfonic acid base, a sulfate ester base, a phosphoric acid ester base, and a phosphonic acid base; amino acids. Amphoteric compounds such as system or aminosulfate ester compounds; nonionic compounds such as imino alcohol compounds, glycerin compounds, polyethylene glycol compounds; organic metal compounds such as metal alkoxide compounds containing tin or titanium; It can be a metal chelating compound such as an acetylacetonate salt of a compound; two or more reactants or polymerized compounds of such a compound; or a mixture of two or more of such compounds. Here, the quaternary ammonium salt compound can be a compound having one or more quaternary ammonium bases in the molecule, and a low molecular weight form or a high molecular weight form can be used without limitation.

Further, as the antistatic agent, a conductive polymer and metal oxide fine particles can also be used. Examples of the conductive polymer include aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, conjugated polyaniline containing a hetero atom, and mixed-form conjugated poly. (Phenylene vinylene), a double-chain type conjugated system compound which is a conjugated system having a plurality of conjugated chains in a molecule, a conductive composite obtained by grafting or block-copolymerizing a conjugated polymer chain on a saturated polymer, and the like. 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.

The binder resin of the photocurable resin; and the polymer resin layer containing the antistatic agent dispersed in the binder resin may further contain one or more compounds selected from the group consisting of alkoxysilane-based oligomers and metal alkoxide-based oligomers. ..

The alkoxysilane-based compound may be a conventional one in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacrypropyltrimethoxysilane, and grease. It can be one or more compounds selected from the group consisting of sidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane.

Further, the metal alkoxide-based oligomer can be produced by a sol-gel reaction of a composition containing a metal alkoxide-based compound and water. The sol-gel reaction can be carried out by a method according to the above-mentioned method for producing an alkoxysilane-based oligomer.

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

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.

The optical laminate may further include a light transmissive substrate layer formed on the other surface of the polymer resin layer so as to face the optical functional layer.

The light-transmitting substrate layer may have a transmittance of 50% or more, 75% or more, 85% or more, or 95% or more at a wavelength of 300 nm or more.

The light-transmitting substrate layer may contain a transparent plastic resin. Specific examples of the plastic resin include polyester resin, cellulose resin, polycarbonate resin, acrylic resin, styrene resin, polyolefin resin, polyimide resin, polyether sulfone resin, sulfone resin and the like. , Any one or a mixture of two or more of these is used.

More specifically, the light-transmitting substrate layer is made of polyethylene terephthalate (polyetheretherketone, PET), cyclic olefin copolymer (COC), polyacrylate (PAC), polycarbonate (polycarbonate, PC), polyethylene. (Polyetherketone, PE), polymethylmethacrylate (PMMA), polyetheretherketone (PEEK), polyethylenenaphthalate (polyetherepine, PEN), polyetherimide (polyetherimide) It may contain at least one of polyamimidide (PAI) and triacetylcellulose (TAC).

On the other hand, the light-transmitting base material layer may be a single layer, or may have a multi-layer structure of two or more layers made of the same or different substances from each other. As an example, the supporting substrate may be a multilayer structure of polyethylene terephthalate (PET), a multilayer structure formed by coextrusion of polymethylmethacrylate (PMMA) / polycarbonate (PC), or polymethylmethacrylate (PMMA) and polycarbonate (PC). ) Can be a single layer structure containing a copolymer.

Further, the light-transmitting base material layer may be plasma-treated as needed, and the method is not particularly limited and can be carried out by a usual method.

Further, if the thickness of the light-transmitting base material layer is excessively thick or thin, there is a problem of surface hardness, deterioration of impact resistance, or folding characteristics. Therefore, it is preferable to appropriately set the range. As an example, the light transmissive substrate can have a thickness of 20-200 μm, 30-150 μm, or 50-120 μm.

According to another embodiment of the invention, a polarizing plate including the optical laminate can be provided.

The polarizing plate may include a polarizing element and an optical laminate formed on at least one surface of the polarizing element.

The material and manufacturing method of the stator are not particularly limited, and ordinary materials and manufacturing methods known in the art can be used. For example, the splitter can be a polyvinyl alcohol-based modulator.

The polarizing element and the optical laminate are interleaved with an adhesive such as a water-based adhesive or a non-water-based adhesive.

According to still another embodiment of the invention, a display device including the above-mentioned optical laminate can be provided.

Specific examples of the display device are not limited, and are devices such as a liquid crystal display device (Liquid Crystal Display), a plasma display device, an organic light emitting diode display device, and a flexible display device. obtain.

In the display device, the optical laminate is provided on the outermost surface of the display panel on the observer side or the backlight side.

In the display device including the optical laminate, the optical laminate may be located on one surface of the polarizing plate, which is relatively far from the backlight unit in the pair of polarizing plates.

Further, the display device may include a display panel, a polarizing element provided on at least one surface of the panel, and an optical functional layer provided on an opposite side surface in contact with the panel of the polarizing element.

According to still another embodiment of the invention, an organic light emitting diode display device including the optical laminate can be provided.

Generally, an organic light emitting diode display device has high resolution and high color reproduction ability, but in the case of an optical laminate having a characteristic that a high color value, for example, an absolute value of b * exceeds 4 in the CIE Lab color space, the organic light emitting diode is used. It reduces the color reproduction of the display device.

On the other hand, the optical laminate of the above embodiment has a low color value with an absolute value of b * of 4 or less in the CIE Lab color space while achieving high translucency and low reflectance, and is colorless and transparent. Therefore, it is possible to realize the effect of maintaining or enhancing the color reproducibility of the organic light emitting diode display device as it is.

According to the present invention, an optical laminate having high light transmittance, high scratch resistance and antifouling property at the same time, and having colorless and transparent properties while achieving low reflectance, can be obtained. A polarizing plate including a polarizing plate, a display device, and an organic light emitting diode display device can be provided.

It is a photograph which took the cross section of the optical laminated body of Example 1 with a transmission electron microscope (TEM). 3 is a TEM-EDS map photograph of the silicon element and the zirconium element in the cross section of the optical laminate of Example 1. It is a photograph which took the cross section of the optical laminated body of the comparative example 1 with a transmission electron microscope. It is a TEM-EDS map photograph for the silicon element and the zirconium element of the cross section of the optical laminate of the comparative example 1. FIG. It is a photograph which took the cross section of the optical laminated body of the comparative example 2 with a transmission electron microscope. 2 is a TEM-EDS map photograph of the silicon element and the zirconium element in the cross section of the optical laminate of Comparative Example 2. It is a graph which shows the reflectance for each wavelength of Example 1, Comparative Example 1 and Comparative Example 2.

The invention will be described in more detail with reference to the following examples. However, the following examples merely exemplify the present invention, and the content of the present invention is not limited to the following examples.

Production Example 1: Production of Polymer Resin Layer A coating liquid for forming a polymer resin layer was produced by diluting the solid content of LAS-1467KR (Toyo-ink) with a cyclohexanone solvent so that the solid content concentration was 40% by weight. .. The diluted polymer resin layer forming coating liquid was coated on a triacetyl cellulose film with # 10 mayer bar, dried at an ultraviolet intensity of 25 mJ / cm ² , and photocured while purging with nitrogen, and had a thickness of 4 μm. A molecular resin layer was produced.

Example 1: Production of Optical Laminate (1) Production of Photocurable Coating Composition for Production of Optical Functional Layer Hollow Silica Nanoparticles (Density) with respect to 100 parts by weight of Trimethylol Propaneethoxytriacrylate (M3190, MIWON) : Approximately 70-80 nm, Density: 1.41 g / cm ³ , JSC catalyst and chemicals) 297 parts by weight, Solid zirconia nanoparticles (Diameter: Approx. 11 nm, Density: 5.68 g / cm ³ , Daiken) 1326 weight , Solid type silica nanoparticles (diameter: about 10 to 15 nm, density: 2.65 g / cm ³ , Nissan chemical) 51.75 parts by weight, silane coupling agent (KBM-503, ShinEtsu silicone) 146 parts by weight, 1st fluorine-containing compound (KY-1207, ShinEtsu) 183 parts by weight, 2nd fluorine-containing compound (RS-4137, Egyeong Chemical Co., Ltd.) 74.5 parts by weight, initiator (SPI-02, Samyan Co., Ltd.) 12.9 By weight, methyl isobutyl ketone (MIBK): diacetone alcohol (DAA): isopropyl alcohol (IPA): methyl ethyl ketone (MEK): ethanol (EtOH) 26.32: 6.12: 24.23: 25.33: The solvent was diluted with a weight ratio of 9.49 so as to have a solid content concentration of 8% by weight.

(2) Production of Optical Functional Layer and Optical Laminate The photocurable coating composition obtained above is coated on the polymer resin layer of Production Example 1 with # 4 mayer bar so as to have a thickness of about 150 nm. Then, it was dried at a wind speed of 0.5 m / s or more and a temperature of 90 ° C. for 1 minute, and cured while purging with nitrogen at an ultraviolet intensity of 254 mJ / cm ² .

<Comparative example: Manufacturing of optical laminate>

Comparative Example 1
The optical laminate was prepared in the same manner as in Example 1 except that solid-type zirconia nanoparticles were used in an amount of 1440 parts by weight without using solid-type silica nanoparticles in the photocurable coating composition for producing an optical functional layer. Manufactured.

Comparative Example 2
The same method as in Example 1 except that solid silica nanoparticles were used in an amount of 145 parts by weight and solid zirconia nanoparticles were used in an amount of 1133 parts by weight in the photocurable coating composition for producing an optical functional layer. An optical laminate was manufactured.

<Experimental example: Measurement of physical properties of optical laminate>
Experiments on the following items were performed on the optical laminates obtained in the above Examples and Comparative Examples, and the results are shown in Table 1 below.

1. 1. Volume ratio of zirconium element to silicon element in the optical functional layer For the optical functional layer obtained in each of the examples and comparative examples, a thin piece is manufactured using a microtome, and then a transmission electron microscope (TEM), product name: H. -7650), STEM EDS map analysis was performed with FETEM Bright field mode (acceleration voltage: 100 kV).

The volumes of silicon (Si) element and zirconium (Zr) element in the optical functional layer obtained by the above analysis are measured by the pixels (pixel) occupied by each element with respect to the total pixels (total) using the OPEN-CV program. The volume of was quantified.

Using the result data in which the volume of each element in the optical functional layer is quantified, "the thickness of the optical functional layer from the interface between the polymer resin layer and the optical functional layer is 5 nm to 10 nm" and "polymer resin". The volume ratio (arithmetic average value) of the zirconium (Zr) element to the silicon (Si) element was calculated within the region where the thickness of the optical functional layer is 50 nm to 150 nm from the interface between the layers and the optical functional layer.

2. 2. Measurement of surface energy of polymer resin layer Example and Comparative Example The surface energy of each polymer resin layer is measured by di-water (Gebhardt) and di-iodomethane (Owens) using DSA-100 contact angle measurement equipment manufactured by Kruss. ) Was measured at 10 points to obtain an average value, and then the average contact angle was converted into surface energy and measured. In the measurement of the surface energy, the following general formula 1 of the OWRK (Owen, Wendt, Rable, Kaelble) method was applied to the program using the Drophape Analysis software, and the contact angle was converted into the surface energy.

3. 3. Measurement of average reflectance of optical laminate and a value and b * value in CIE Lab color space For the optical laminate obtained in Examples and Comparative Examples, at each wavelength in the visible light region (380 to 780 nm). The reflectance, a value and b * value of the above were measured using the Solidspec 3700 (SHIMADZU) equipment. The test piece was scanned from a wavelength of 380 to 780 nm to measure the reflectance at each wavelength, and then the average reflectance and the a value and the b * value were derived using the UV-2401PC Color Analysis program.

4. Measurement of scratch resistance A load was applied to steel wool (# 0000) and reciprocated 10 times at a speed of 27 rpm to rub the surface of the optical laminates obtained in Examples and Comparative Examples. The maximum load observed below one scratch of 1 cm or less observed with the naked eye was measured.

5. Measurement of Ellipsometry The ellipsometry of the polarization was measured for the optical functional layers obtained in each of the above Examples and Comparative Examples by ellipsometry.

Specifically, with respect to the optical functional layers obtained in each of the above-mentioned Examples and Comparative Examples, J. A. Woollam Co. Using the M-2000 device, line polarization was measured in the wavelength range of 38-1000 nm by applying an incident angle of 70 °. The measured linear polarization measurement data (Ellipsometry data (Ψ, Δ)) is subjected to the Complete EASE software so that the MSE becomes 3 or less by the Cauchy model of the following general formula 2 for the optical functional layer. Optimized for (fitting).

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

6. Measurement of reflectance Using elliptically polarized light measured at a wavelength of 380 nm to 1,000 nm and a Cauchy model for the particle mixed layer contained in the optical functional layer obtained in the above Examples and Comparative Examples, the wavelength is 550 nm and the wavelength is 400 nm. And the reflectance of each was calculated at a wavelength of 700 nm.

7. Haze measurement A 4 cm × 4 cm test piece was prepared from the optical laminates obtained in the above Examples and Comparative Examples, and measured three times with a haze measuring machine (HM-150, A light source, Murakamisha) to obtain the average value. It was calculated and this was calculated as the total haze value. At this time, haze was measured according to JIS K 7136 standard.

8. Evaluation of Black Visibility Evaluation of black visual perception was performed based on the CIElab color space and haze value evaluated for the optical laminates obtained in Examples and Comparative Examples.

<Evaluation criteria>
Good: Absolute values of CIE lab a * and b * are less than 2 and less than 3, respectively, and haze value (JIS K7136 standard) is less than 0.6% decrease: Absolute values of CIE lab a * and b * are 2 respectively. Above and above and 3 or above, or haze value (JIS K7136 standard) of 0.6% or above

As shown in Table 1, the volume ratio of the zirconium element to the silicon element is less than 2.6 in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 5 nm to 10 nm. The optical functional layer of Example 1 in which the volume ratio of the zirconium element to the silicon element is 1.62 or more in the region from the interface to the thickness of the optical functional layer of 50 nm to 150 nm is 0.2% or less at a wavelength of 550 nm. It was confirmed that the absolute values of a * and b * are 2 or less in the CIE Lab color space, the color values are low, and the color values can be colorless and transparent while realizing the reflectance of.

Further, the optical laminate of the embodiment includes a particle mixed layer having a thickness of 25 to 100 nm in the optical functional layer, and a region in which hollow inorganic nanoparticles and solid inorganic nanoparticles are mainly distributed is divided. As described above, the absolute values of a * and b * are 2 or less in the CIE Lab color space, and the color values are low, and the color is colorless and transparent, but the black appearance is good. It was confirmed that excellent scratch resistance was realized.

On the other hand, the comparative example does not satisfy the volume ratio of the zirconium element to the specific silicon element in the above-mentioned region, and thus the comparative example 1 does not use the solid silica particles, so that in the CIE Lab color space of the optical laminate. It was confirmed that the absolute value of a * exceeds 2 and becomes reddish, and the haze value is large, so that the black appearance is lowered and the scratch resistance is also lowered. Further, in Comparative Example 2, the hollow type inorganic nanoparticles and the solid type inorganic nanoparticles are each divided into regions mainly distributed and are not unevenly distributed (phase separation), and there is a particle mixed layer having an excessive thickness. The mixed particle layer is located too close to the polymer resin layer, which causes the absolute value of b * to exceed 2 and become blue in color, making it unsuitable for application to polarizing plates or display devices. It was confirmed that it had (high haze) or colorability.

Claims (24)

A polymer resin layer; and an optical functional layer formed on one surface of the polymer resin layer and containing a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin;
The volume ratio of the zirconium element to the silicon element is less than 2.6 in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 5 nm to 10 nm.
An optical laminate in which the volume ratio of the zirconium element to the silicon element is 1.62 or more in the region from the interface between the polymer resin layer and the optical functional layer to the thickness of the optical functional layer of 50 nm to 150 nm. The optical laminate according to claim 1, wherein both the hollow inorganic nanoparticles and the solid inorganic nanoparticles are present, and a particle mixed layer having a thickness of 25 to 100 nm is present in the optical functional layer. The optical laminate according to claim 2, wherein the particle mixed layer is located at a distance of 50 nm or more from one surface of the polymer resin layer. The optics according to claim 2, wherein the thickness of the mixed particle layer is determined by optimizing (fitting) the ellipticity of the polarization measured by the ellipsometry method with a diffusion layer model. Laminated body. When the ellipticity of the polarization measured by the ellipsometry with respect to the particle mixed layer is optimized (fitting) by the Cauchy model of the following general formula 2, A is 1.100 to 1. The optical laminate according to claim 2, wherein B is 200 to 0.007, C is 0 to 1 * 10 ^-3 :

In the general formula 2, n (λ) is the refractive index at the λ wavelength, λ is in the range of 300 nm to 1800 nm, and A, B and C are Cauchy parameters. The optical laminate according to claim 1, wherein the solid-type inorganic nanoparticles include solid-type silica nanoparticles and solid-type zirconia nanoparticles. The optical laminate according to claim 6, wherein the weight ratio of the solid zirconia nanoparticles to the solid silica nanoparticles is 10 or more. The optical laminate according to claim 1, wherein the optical functional layer has a thickness of 20 to 240 nm. The optical laminate according to claim 1, wherein the optical laminate has a reflectance of 0.5% or less at a wavelength of 550 nm. The optical laminate according to claim 1, wherein the ratio of the reflectance at a wavelength of 400 nm to the reflectance of the optical laminate at a wavelength of 550 nm is 5 or more. The optical laminate according to claim 1, wherein the polymer resin layer has a surface energy of 34 mN / m or more. The polymer resin layer has an average refractive index exceeding 1.46 at a wavelength of 550 nm.
The optical laminate according to claim 1, wherein the optical functional layer has a wavelength of 550 nm and an average refractive index of 1.46 or less. The optical laminate according to claim 2, wherein 50% by volume or more of the total solid inorganic nanoparticles in the optical functional layer are present between one surface of the polymer resin layer and the particle mixed layer. The optical laminate according to claim 2, wherein the region between one surface of the polymer resin layer and the particle mixed layer has a refractive index of 1.46 to 1.75 at a wavelength of 550 nm. The second aspect of the present invention, wherein 50% by volume or more of the total hollow inorganic nanoparticles in the optical functional layer are present in the region from the particle mixed layer to one surface of the optical functional layer facing the polymer resin layer. Optical laminate. The optical laminate according to claim 2, wherein the region from the particle mixed layer to one surface of the optical functional layer facing the polymer resin layer has a refractive index of 1.0 to 1.40 at a wavelength of 550 nm. The solid inorganic nanoparticles have a diameter of 0.5 to 100 nm and have a diameter of 0.5 to 100 nm.
The optical laminate according to claim 1, wherein the hollow inorganic nanoparticles have a diameter of 1 to 200 nm. The optical laminate according to claim 1, wherein the difference in density between the solid-type inorganic nanoparticles and the hollow-type inorganic nanoparticles is 0.7 to 8.5 g / cm ³ . The optical according to claim 1, wherein the binder resin contained in the optical functional layer contains a (co) polymer of a photopolymerizable compound and a crosslinked (co) polymer between a fluorine-containing compound containing a photoreactive functional group. Laminated body. The optical laminate according to claim 1, wherein the polymer resin layer contains a binder resin containing a photocurable resin and organic or inorganic fine particles dispersed in the binder resin. The optical laminate according to claim 1, further comprising a light-transmitting base material layer formed on another surface of the polymer resin layer so as to face the optical functional layer. A polarizing plate comprising the optical laminate and a polarizing element according to claim 1. A display device comprising the optical laminate according to claim 1. An organic light emitting diode display device including the optical laminate according to claim 1.

Images