KR102040301B1 - Antireflection film, polarizing plate comprising the same and optical display apparatus comprising the same - Google Patents

Abstract

The base layer, the first layer and the second layer is an antireflection film sequentially stacked, the second layer is formed directly on the first layer, the first layer has a surface energy of 20 dyne / cm to 25 ℃ 23 dyne / cm, the second layer includes an air hole, and the anti-reflection film is provided with an anti-reflection film having a reflectance of 0.3% or less, a polarizing plate including the same, and an optical display device including the same.

Description

Anti-reflective film, polarizing plate including the same, and optical display including the same {ANTIREFLECTION FILM, POLARIZING PLATE COMPRISING THE SAME AND OPTICAL DISPLAY APPARATUS COMPRISING THE SAME}

The present invention relates to an antireflection film, a polarizing plate including the same, and an optical display device including the same.

An optical display device is used under an environment in which external light is incident. Incident of external light may degrade the screen display quality of the optical display device. Therefore, in the optical display device, an antireflection film is generally used. The antireflection film usually has a structure in which a high refractive index layer and a low refractive index layer are repeated on a substrate layer. The antireflection film generally lowers the refractive index of the low refractive layer to lower the reflectance.

Since the anti-reflection film is located outside the optical display device, it is preferable to further have a hard coat function and an antistatic function. Therefore, in recent years, a technology for manufacturing an antireflection film by including a hard coating layer having a hard coating function and an inorganic particle on a substrate layer and sequentially laminating a high refractive layer having a high refractive index and an antistatic function and a low refractive layer has been developed. However, this consisted of three coating layers which made the production of antireflective films complicated. If there is no hard coating layer, there is a problem that the hardness and the external shocks are vulnerable, there is a limit to lower the reflectance of the antireflection film in the absence of a high refractive index layer. Increasing the ratio of the inorganic hollow particles to the low refractive index layer in order to lower the reflectance of the antireflection film, the reflectance is reduced, but there is a problem that is difficult to apply due to the weak mechanical properties.

Background art of the present invention is disclosed in Korea Patent Publication No. 2015-0135662.

The problem to be solved by the present invention is to provide an antireflection film having excellent adhesion between the second layer and the first layer including an air hole and having a significantly low reflectance.

Another object of the present invention is to provide an antireflection film having a low surface roughness of a second layer including hollow particles and air holes.

Another object of the present invention is to provide an antireflection film including an air hole, a second layer having excellent pencil hardness and excellent scratch resistance.

Another object of the present invention is to provide a polarizing plate and an optical display device comprising an anti-reflection film of the present invention.

In the antireflection film of the present invention, a base layer, a first layer, and a second layer are sequentially stacked, the second layer is directly formed on the first layer, and the first layer has a surface energy of 20 dyne at 25 ° C. / cm to 23 dyne / cm, the second layer includes an air hole, the antireflection film may have a reflectance of 0.3% or less.

The polarizing plate of the present invention may include the antireflective film of the present invention.

The optical display device of the present invention may include the antireflection film of the present invention.

The present invention provides an antireflection film having excellent adhesion between the second layer and the first layer including air holes and having a significantly low reflectance.

The present invention provides an antireflection film having a low surface roughness of a second layer including hollow particles and air holes.

The present invention provides an antireflection film including an air hole and a second layer having excellent pencil hardness and excellent scratch resistance.

The present invention provides a polarizing plate and an optical display device including the antireflection film of the present invention.

1 is a conceptual view of a cross-sectional view of a portion in the thickness direction of the antireflective film according to an embodiment of the present invention.
2 is a conceptual view of a part of the top plan view of the second layer of the antireflective film according to an embodiment of the present invention.
3 is a SEM measurement result of the antireflection film according to Example 1.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and the same names are used for the same or similar elements throughout the specification.

In the present specification, "upper" and "lower" are defined based on the drawings, and according to a viewpoint, "upper" may be changed to "lower" and "lower" to "upper", and "on" or What is referred to as “on” may include not only the above but also intervening other structures in the middle. On the other hand, what is referred to as "directly on" or "directly on" indicates that there is no intervening structure in between.

As used herein, "(meth) acryl" refers to acrylic and / or methacryl.

In the present specification, the "reflectivity" of the antireflection film is a spectrophotometer (Spectrophotometer, Konica Minolta, CM-3600A) for a specimen prepared by laminating a black acrylic sheet (CLAREX, Nitto Jushi Kogyo Co., Ltd.) on the back side of the base layer of the antireflection film. In the SCI reflection mode (light source: D65 light source, light source aperture: φ8 mm), the value of Y (D65) is measured among reflectances measured at a wavelength of 360 nm to 740 nm.

In the antireflection film according to the embodiment of the present invention, the base layer, the first layer, and the second layer are sequentially stacked, and the first layer is directly formed with the second layer. The term "directly formed" means that no other adhesive layer, adhesive layer or adhesive layer is formed between the first layer and the second layer.

The first layer has a surface energy of 20 dyne / cm to 23 dyne / cm at 25 ° C. Therefore, although the degree of formation of air holes is increased in the second layer, the bonding strength between the first layer and the second layer due to excessive air hole formation is increased by increasing the adhesion between the first layer and the second layer. At the same time, the degree of air hole formation in the second layer may be increased, and the refractive index of the second layer may be significantly lowered than that of the first layer, thereby significantly lowering the reflectance of the antireflection film. The antireflective film may have a reflectance of 0.3% or less. Within this range, the screen quality improvement effect may be great when used as an antireflection film in the optical display device. In particular, when the second layer includes hollow particles or a mixture of hollow particles and non-hollow particles, the particles may come into contact with the first layer, thereby decreasing the adhesion. The adhesion may be controlled by adjusting the surface energy of the first layer to the above range. At the same time, the air hole was well formed to lower the reflectance. When the surface energy of the first layer is out of the above range, the air hole itself may not be formed, and thus adhesion may be good, but since the air hole is not formed, the reflectance may not be low.

The air hole may have an air pillar shape. The air pillar is not formed sporadically in the second layer, the interface between the first layer and the second layer is referred to as the bottom surface of the second layer and the bottom surface of the second layer among the second layers. When the opposite surface is referred to as the upper surface of the second layer, it means that the pillars formed of air having a predetermined cross-sectional area are continuously formed in the thickness direction of the second layer from the lower surface of the second layer to the upper surface of the second layer. . The air pillar may be well formed by having a surface energy of 20 dyne / cm to 23 dyne / cm at 25 ° C. of the first layer.

1 and 2, an anti-reflection film according to an embodiment of the present invention will be described. 1 is a conceptual view of a cross-sectional view of a portion in the thickness direction of the antireflective film according to an embodiment of the present invention. 2 is a conceptual view of a part of the top plan view of the second layer of the antireflective film according to an embodiment of the present invention.

Referring to FIG. 1, the antireflective film 100 includes a first layer 110 and a second layer 120 formed directly on the first layer 110. In FIG. 1, the base layer of the antireflection film is omitted.

The second layer 120 may include an air hole 121. The air hole 121 has a predetermined end area and has an air pillar shape continuously formed in the thickness direction of the second layer 120 from the bottom surface of the second layer 120 to the top surface of the second layer 120. . Through this, the refractive index of the second layer compared to the first layer can be significantly lowered to lower the reflectance of the antireflection film. When the air pillar is formed in a volume similar to the case in which the air hole is sporadically formed, the refractive index of the second layer may be lowered, and the reflectance may be lowered.

1 illustrates a case where the first layer 110 is one plane. However, in the antireflective film of the present invention, the first layer may be one plane or a curved surface. The first layer 110 may have a surface energy of 20 dyne / cm to 23 dyne / cm at 25 ° C., thereby lowering the surface roughness of the second layer 120 even if the first layer is curved.

Referring to FIG. 2, the second layer includes a region composed of an air hole 121 and a region composed of hollow particles 122, non-hollow particles 124, and a cured product 123 of a curable compound. The second layer 120 may include hollow particles 122 and a cured product 123 of a curable compound.

1 and 2 illustrate a case where the non-hollow particles 124 are included in the second layer 120. However, non-hollow particles 124 may not be included. The hollow particles, the cured product of the curable compound, and the non-hollow particles will be described in detail below.

The antireflective film can lower the surface roughness of the second layer by adjusting the surface energy of the first layer in the above range and including hollow particles and a curable compound as described below. The antireflection film may have a surface roughness of 50 nm or less, for example, 15 nm to 50 nm, measured in the second layer. In the above range, there may be a water and oil repelling effect. Surface roughness is the value measured in the second layer of the antireflective film.

The second layer

The second layer is formed directly on the first layer. The second layer includes air holes, so that the refractive index is significantly lower than that of the first layer. Thus, the second layer can lower the reflectance of the antireflective film. Specifically, the second layer may have a refractive index of 1.30 or less, for example, 1.20 to 1.30, specifically 1.29 to 1.30. Within this range, the reflectance of the antireflective film can be significantly lowered.

The second layer may be formed of a composition for a second layer including hollow particles, a curable compound, and an initiator. The air hole in the second layer is not formed by the composition of the composition for the second layer or the content of the constituents, but may be well formed by making the surface energy at 25 ° C. of the first layer from 20 dyne / cm to 23 dyne / cm. have.

The air hole may be sporadically formed in the second layer, but preferably, may be formed in the shape of an air column as shown in FIG. 1 to significantly lower the refractive index of the second layer. The air hole may have a minimum average particle diameter of 200 nm or less, for example, 100 nm to 200 nm. Within this range, the refractive index reduction effect of the second layer can be great while maintaining an excellent appearance.

The air hole may be formed surrounded by hollow particles. Alternatively, the air hole may be formed surrounded by hollow particles and non-hollow particles. This relates to the formation of air holes by the curable compound catching hollow particles and non-hollow particles with each other. As a result, a perfect air hole may be formed, and the reflectance may be reduced due to the decrease in the refractive index of the second layer.

The hollow particles may lower the refractive index of the second layer while increasing the hardness of the second layer in comparison with the case of only the air holes. The pencil hardness of the antireflection film may be 1H or more, for example, 2H to 3H. In the above range, it can be used on the outer side of the optical display device. In addition, the hollow particles may be included at least in part on the surface of the second layer to increase scratch resistance of the second layer.

The hollow particles may have a hollow structure to lower the refractive index of the second layer. The refractive index of the hollow particles may be 1.40 or less, for example, 1.10 to 1.30. The hollow particles may include one or more of organic hollow particles and inorganic hollow particles. Preferably, the hollow particles may be hollow silica. The hollow particles may be untreated hollow particles that are not surface treated, but by using hollow particles that are surface treated with a curable functional group (such as a UV curable functional group), the hardness of the second layer may be further increased through a curing reaction with the curable compound. Can be. The hollow particles may include particles such as spherical and amorphous. The average particle diameter (D50) of the hollow particles may be 30 nm to 150 nm, for example, 60 nm to 120 nm. In the above range, it can be included in the second layer, and can improve optical characteristics such as haze and transmittance.

The average particle diameter of the air holes in the second layer may be larger than the average particle diameter of the hollow particles. Even so, the antireflection film of the present invention has good adhesion between the first layer and the second layer and low reflectance.

The hollow particles may be included in an amount of 40 wt% to 60 wt%, for example 45 wt% to 55 wt%, and 50 wt% to 60 wt% in the second layer. In the above range, the reflectance of the antireflection film can be lowered and the hardness can be ensured.

The curable compound is cured to form a matrix of the second layer, allows the air hole to be stably formed, and blocks the air hole from collapsing by catching hollow particles or the like. In addition, the curable compound may fix the hollow particles and the non-hollow particles by wetting the hollow particles and the non-hollow particles.

The curable compound may include one or more of a thermosetting compound and a photocurable compound. Preferably, the curable compound may be a photocurable compound so that the second layer is formed quickly and the air holes are well formed. The curable compound may include a (meth) acrylate group which is a UV curable functional group as the curable functional group. Preferably the curable compound may comprise a hydroxyl group.

The curable compound may include at least one of a non-fluorine-based curable monomer or oligomer thereof that does not contain fluorine, a fluorine-based curable monomer or oligomer thereof containing fluorine. Preferably, by using a non-fluorine type and a fluorine type simultaneously, the refractive index of a 2nd layer is reduced, and there exists an effect of improving the intensity | strength of a 2nd layer.

In one embodiment, the non-fluorine curable monomer may comprise a bifunctional or more than, for example, bifunctional to 10 functional polyfunctional (meth) acrylate-based monomers. The non-fluorine curable monomer may be a polyfunctional (meth) acrylate such as an ester of a polyhydric alcohol and (meth) acrylic acid (non-urethane polyfunctional (meth) acrylate without containing a urethane bond), or a polyhydric alcohol, an isocyanate compound, One or more of the polyfunctional urethane (meth) acrylates synthesized from the hydroxy esters of (meth) acrylic acid.

The bifunctional (meth) acrylate is, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, Nonanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) Di (meth) acrylates, such as an acrylate and hydroxy pivalate neopentyl glycol di (meth) acrylate, etc. are mentioned. As a trifunctional or more than (meth) acrylate compound, For example, trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, Tri (meth) acrylates such as tris2-hydroxyethylisocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylic Trifunctional (meth) acrylate compounds such as acrylate and ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra ( Meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate And trifunctional or higher polyfunctional (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate and ditrimethylolpropane hexa (meth) acrylate, and some of these (meth) acrylates may be alkyl groups or? -Capro The polyfunctional (meth) acrylate compound etc. which were substituted by lactone are mentioned.

Polyfunctional urethane (meth) acrylate is synthesize | combined from the hydroxy ester of a polyol, an isocyanate type compound, and (meth) acrylic acid. The polyol may include one or more of an aromatic polyol, an aliphatic polyol, and an alicyclic polyol. Preferably, at least one of an aliphatic polyol and an alicyclic polyol may be used. In this case, yellowing of the antireflection film may be less. The polyol may include, but is not limited to, one or more of polyester diols, polycarbonate diols, polyolefin diols, polyether diols, polythioether diols, polysiloxane diols, polyacetal diols, polyesteramide diols. The isocyanate compound can be any aliphatic, cycloaliphatic or aromatic polyfunctional isocyanate compound.

In one embodiment, the fluorine-based curable monomer may include a compound in which at least one hydrogen atom of the above-described multifunctional (meth) acrylate and polyfunctional urethane (meth) acrylate is substituted with fluorine.

In another embodiment, the fluorine-based curable monomer is a fluorine monomer having a pentaerythritol skeleton, a fluorine monomer having a dipentaerythritol skeleton, a fluorine monomer having a trimethylolpropane skeleton, a fluorine monomer having a ditrimethylolpropane skeleton, a cyclohexyl skeleton It may be a fluorine-based monomer having a linear, a fluorine-based monomer having a linear skeleton or a mixture thereof, but is not limited thereto. In this case, the fluorine monomer may be a (meth) acrylate monomer.

The cured product of the curable compound may be included in an amount of 30 wt% to 50 wt%, preferably 40 wt% to 50 wt% in the second layer. In the above range, there can be excellent hardness and scratch prevention effect.

The fluorine-based curable monomer or oligomer thereof in the curable compound may be included in an amount of 15 wt% to 45 wt%, preferably 25 wt% to 42 wt%, and 28 wt% to 42 wt% in the second layer. In the above range, there may be a stable reflectance reduction effect. The non-fluorine curable monomer or oligomer thereof in the curable compound may be included in an amount of 5 wt% to 20 wt%, preferably 7 wt% to 15 wt% in the second layer. In the above range, there may be an effect of improving the crosslinking density.

The initiator cures the curable compound and optionally the curable compound and the hollow particles. The initiator may comprise one or more of conventional photo radical initiators, photo cationic initiators known to those skilled in the art. The radical radical initiator generates a radical by light irradiation and catalyzes curing, and includes a phosphorus, triazine, acetophenone, benzophenone, thioxanthone, benzoin, oxime, phenylketone and hydroxyketone It may include one or more of. Photo cationic initiators may include salts of cations and anions. As a specific example of a cation, diphenyl iodonium, 4-methoxy diphenyl iodonium, bis (4-methylphenyl) iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium, bis (4-tert) -Triarylsulfonium, such as diaryl iodonium, triphenylsulfonium, and diphenyl-4-thiophenoxyphenylsulfonium, such as -butylphenyl) iodonium and bis (dodecylphenyl) iodonium; (Diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, (η5-2,4-cyclopenta Dien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] iron (1+), etc. are mentioned. Specific examples of the anionic examples include borate (BF ₄ ^-) tetrafluoroborate, phosphate (PF ₆ ^-) hexafluoropropane, antimonate hexafluorophosphate (SbF ₆ ^-), are Senate hexafluorophosphate (AsF ₆ ^-), hexamethylene Chloro antimonate (SbCl ₆ ⁻ ) and the like.

The composition for the second layer may further include a solvent to increase the coating property of the composition. The solvent may include methyl isobutyl ketone, methyl ethyl ketone, ethylene glycol dimethyl ether, and the like, but is not limited thereto.

The solvent may be included in the remaining amount in the composition for the second layer.

In one embodiment, the composition for the second layer may include 40 wt% to 60 wt% of the hollow particles, 30 wt% to 50 wt% of the curable compound, and 0.5 wt% to 10 wt% of the initiator. In the above range, there can be an excellent anti-reflective effect and excellent scratch resistance effect. Preferably, the composition for the second layer may include 50 wt% to 60 wt% of the hollow particles, 37 wt% to 49.5 wt% of the curable compound, and 0.5 wt% to 3 wt% of the initiator. More preferably, the composition for the second layer is 50% by weight to 60% by weight of the hollow particles, 7% to 15% by weight of the non-fluorine monomer, 28% to 42% by weight of the fluorinated monomer, and 1% to 3% by weight of the initiator. May contain%. Within this range, there can be an excellent antireflection effect.

The second layer may further comprise non-hollow particles.

Non-hollow particles may be included in the second layer to improve the mechanical strength of the second layer.

Non-hollow particles may include one or more of inorganic particles and organic particles. Preferably, non-hollow particles may use silica. The non-hollow particles may use untreated particles that have not been surface treated, but by using non-hollow particles surface-treated with a curable functional group (such as a UV curable functional group), the hardness of the second layer may be further increased through a curing reaction with the curable compound. It can increase. Non-hollow particles may include particles such as spherical and amorphous. The average particle diameter (D50) of the non-hollow particles may be 30 nm to 150 nm, for example, 50 nm to 100 nm. In the above range, it can be included in the second layer, and can improve optical characteristics such as haze and transmittance.

Non-hollow particles may be included in an amount of 1% to 5% by weight, for example 2% to 5% by weight of the second layer. In the above range, there may be a scratch prevention effect.

In one embodiment, the composition for the second layer is based on solids, 40% to 60% by weight hollow particles, 35% to 50% by weight curable compound, 0.5% to 10% by weight initiator, 1% to 5% non-hollow particles It may include weight percent. In the above range, there may be an effect to improve scratch prevention. Preferably, the composition for the second layer is based on solids, 40% to 60% by weight hollow particles, 5% to 15% by weight non-fluorine monomer, 22% to 42% by weight fluorinated monomer, 1% to 3% initiator %, Non-hollow particles may contain 1% to 5% by weight. In the above range, there may be an effect to improve scratch prevention.

The second layer may further comprise conventional additives included in the antireflective film. Additives may include, but are not limited to, for example, surfactants, antistatic agents, antifoams, antioxidants, and the like. The additive may be included in up to 5% by weight, for example up to 3% by weight of the second layer.

The second layer may have a thickness of 150 nm or less, for example, 50 nm to 150 nm, 95 nm to 120 nm. In the above range, it can be used for the antireflection film.

First floor

The first layer supports the second layer, and facilitates the formation of air holes in the second layer, thereby significantly lowering the reflectance of the antireflective film and increasing adhesion between the first layer and the second layer. In addition, the second layer may be in close contact with the base layer through the first layer.

The first layer may include a layer having a surface energy of 20 dyne / cm to 23 dyne / cm at 25 ° C. As a result, the air layer may be formed in the second layer to decrease the reflectance of the antireflection film, and the adhesion between the first layer and the second layer may be enhanced. In addition, even when the first layer is curved, the surface roughness of the second layer can be lowered.

The layer having a surface energy of 20 dyne / cm to 23 dyne / cm at 25 ° C. may have a surface energy modifier of 0.001% to 0.7% by weight, for example, 0.002% to 0.5% by weight, for example, 0.002% to 0.1% by weight. It may include. In the above range, the reflectance of the antireflection film can be lowered by having the surface energy.

The surface energy modifier may use a silicon-based surface energy modifier. For example, the silicone-based surface energy may be, but is not limited to, a polyester modified acryl functional polydimethylsiloxane having a polyester-modified acrylic functional group, for example, UV 3500 (BYK Chem).

In one embodiment, the first layer may be a hard coat layer formed of a composition comprising the surface energy modifier, the non-fluorine-based curable compound, and the initiator. In this case, the first layer may increase the hardness of the antireflection film by increasing the hardness of the first layer while providing the surface energy.

The surface energy modifier may be included in an amount of 0.001 parts by weight or more and less than 0.3 parts by weight, for example, 0.001 parts by weight to 0.2 parts by weight based on 100 parts by weight of the total amount of the non-fluorine-based curable compound, the initiator and the solvent. Within this range, the surface energy of the first layer can be secured.

The total amount of the non-fluorine-based curable compound and the initiator may be 70 parts by weight to 95 parts by weight, and the initiator may be included in an amount of 5 parts by weight to 30 parts by weight. It is preferable that a non-urethane-type polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate mixture are included as said non-fluorine-type curable compound. In this case, 10 parts by weight to 50 parts by weight of the non-urethane-based polyfunctional (meth) acrylate in a total of 100 parts by weight of the non-urethane-based polyfunctional (meth) acrylate, the polyfunctional urethane (meth) acrylate and the initiator, and a polyfunctional urethane ( 40 to 80 parts by weight of meth) acrylate and 5 to 30 parts by weight of initiator may be included. Within this range, it is possible to easily reach the surface energy of the present invention when the surface energy modifier is included and to facilitate the formation of air holes in the second layer.

The composition may further include conventional additives such as antistatic agents. The antistatic agent lowers the surface resistance of the antireflective film, and may include a material having a quaternary ammonium cation and an anion. Anion include a halogen ion, HSO ₄ ^- and the like can ^{_{be, PO 4 3- -, SO 4}} 2-, NO 3. The antistatic agent may include a quaternary ammonium cation, but may include an acrylic material containing a quaternary ammonium cation as a functional group in the molecule. In this case, the antireflection film may have a surface resistance of 9 × 10 ¹⁰ Pa / □ or less, for example, 7 × 10 ⁹ Pa / □ or less in the second layer.

In addition to the antistatic agent, the composition may further include conventional additives such as an antifoaming agent, an antioxidant, an ultraviolet absorber, and a light stabilizer.

In another embodiment, the first layer may be a high refractive index layer formed of the composition including the non-fluorine-based curable compound, the high refractive index curable compound, and the initiator on the surface energy modifier. The high refractive index curable compound has a higher refractive index than the non-fluorine curable compound. Therefore, by increasing the refractive index of the first layer it is possible to further lower the reflectance of the antireflection film. The refractive index of the first layer is higher than that of the second layer. Specifically, the refractive index of the first layer may be 1.50 or more, for example 1.51 to 1.57. In the above range, it is possible to lower the reflectance of the antireflection film together with the second layer.

The high refractive index curable compound may have a refractive index of 1.65 or more, for example, 1.70 to 1.75. In the above range, there may be an effect of increasing the refractive index of the first layer. Specifically, the high refractive index curable compound is one of a fluorene curable compound, a biphenyl curable compound, a bisphenol curable compound, a thiophenyl curable compound, a thiobenzyl curable compound, a phenyl sulfide curable compound, a thionaphthalene curable compound It may contain the above.

In one embodiment, the high refractive index curable compound may include a compound of Formula 1 and a compound of Formula 2.

The compound of Formula 1 may have a refractive index of 1.6 or more, specifically 1.615 to 1.635, and more specifically 1.62 to 1.63. Within this range, the refractive index of the cured product can be increased to lower the reflectance of the antireflective film:

<Formula 1>

(In Chemical Formula 1, m and n are each an integer of 1 or more, m + n is an integer of 2 to 8, and R is hydrogen or a methyl group). Preferably, m + n may be four.

The compound of Formula 2 may have a refractive index of 1.55 or more specifically 1.56 to 1.59 and more specifically 1.57 to 1.58. Within this range, the refractive index of the cured product can be increased to lower the reflectance of the antireflective film:

<Formula 2>

(In Formula 2, n is an integer of 1 to 4, R is hydrogen or a methyl group).

The compounds of Formula 1 and Formula 2 may be synthesized by a conventional method, or may use a commercially available product.

The surface energy modifier may be included in an amount of 0.001 parts by weight or more and less than 0.3 parts by weight based on 100 parts by weight of the total amount of the non-fluorine-based curable compound, the high refractive index curable compound, the initiator, and the solvent. Within this range, the surface energy of the first layer can be secured.

The total amount of the non-fluorine-based curable compound, the high refractive index curable compound and the initiator is 40 parts by weight to 70 parts by weight, 25 parts by weight to 59 parts by weight of the high refractive index curable compound, the initiator It may be included in 1 part by weight to 5 parts by weight. In the case where the non-fluorine-based curable compound includes a non-urethane-based polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate mixture, a non-urethane-based polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate mixture, 20 to 40 parts by weight of the non-urethane polyfunctional (meth) acrylate, 60 to 80 parts by weight of the polyfunctional urethane (meth) acrylate, 100 parts by weight of the high refractive index curable compound and the initiator, 25 It may be included in parts by weight to 59 parts by weight and 1 part by weight to 5 parts by weight of the initiator. In the above range, there can be a high refractive index and excellent hardness effect.

The composition may further include additives such as the antistatic agent described above.

In another embodiment, the first layer may be a high refractive layer formed of a composition including the non-fluorine-based curable compound, the high refractive index curable compound, the initiator, and zirconia in the surface energy modifier. The zirconia may add a refractive index increase and a hardness increase of the coating film to the first layer. The zirconia may be untreated but may be surface treated (eg, a (meth) acrylate group) to improve compatibility with other components in the composition and further increase the hardness of the high refractive layer. Surface treatment may be from 5% to 50% of the total surface area of zirconia. In the above range may be the effect of increasing the hardness through bonding with the curable compound, high refractive index curable compound. Zirconia may have an average particle diameter (D50) of 1 nm to 50 nm, specifically 5 nm to 20 nm. In the above range, there may be a hardness increase effect without deterioration of the optical properties of the antireflection film. Instead of zirconia may comprise alumina (Al ₂ O ₃ ) particles.

The surface energy modifier may be included in an amount of 0.001 parts by weight or more and less than 0.3 parts by weight with respect to a total of 100 parts by weight of the non-fluorine-based curable compound, the high refractive index curable compound, the initiator, the zirconia and the solvent. Within this range, the surface energy of the first layer can be secured.

50 parts by weight to 70 parts by weight of the non-fluorine curable compound, 100 parts by weight of the high refractive index curable compound, the initiator and the zirconia, and 0 parts by weight to 45 parts by weight of the high refractive index curable compound, The initiator may include 1 part by weight to 5 parts by weight, and 5 parts by weight to 25 parts by weight of the zirconia. When the non-fluorine-based curable compound includes a non-urethane-based polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate mixture, a non-urethane-based polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate mixture, 20 to 40 parts by weight of the non-urethane polyfunctional (meth) acrylate, 60 to 80 parts by weight of the polyfunctional urethane (meth) acrylate, 100 parts by weight of the high refractive index curable compound and the initiator, high refractive index curable compound 0 5 parts by weight to 45 parts by weight, 1 part by weight to 5 parts by weight of initiator, 5 parts by weight to 25 parts by weight of the zirconia may be included. In the above range, there may be an effect of increasing the refractive index and improving the reliability for UV light.

The composition may further include additives such as the antistatic agent described above.

The first layer may be a single layer formed of the first layer composition.

Alternatively, the first layer may be a multilayer, and the multilayer may be formed directly on the second layer, and the uppermost layer may have a surface energy of 20 dyne / cm to 23 dyne / cm at 25 ° C. The uppermost layer may be formed of the composition for the first layer. In one embodiment, the first layer may be two layers in which the uppermost layer and the hard coating layer are sequentially formed. In another embodiment, the first layer may be two layers in which the uppermost layer and the normal hard coating layer are sequentially formed.

The first layer may have a thickness of 20 μm or less, for example 5 μm to 15 μm. In the above range, it can be used for the antireflection film.

Substrate layer

The base layer may support the antireflection film and increase the mechanical strength of the antireflection film.

The base layer may include a film formed of an optically transparent resin. Specifically, the resin may be a cellulose ester resin including triacetyl cellulose, a polyethylene terephthalate, a polyethylene naphthalate, a polybutylene terephthalate, a polyester resin including a polybutylene naphthalate, and the like, a polycarbonate resin, a polymethylmethacryl And one or more of poly (meth) acrylate resins, polystyrene resins, polyamide resins, polyimide resins, including rates and the like.

The base layer may have a refractive index of 1.40 to 1.80, for example, 1.45 to 1.70. In the above range, when the first layer and the second layer are sequentially stacked, the reflectance can be lowered.

The base layer may have a thickness of 10 μm to 150 μm, specifically 30 μm to 100 μm, and more specifically 40 μm to 90 μm. It can be used in the antireflection film in the above range.

Hereinafter, an optical member according to an embodiment of the present invention will be described.

The optical member may include the antireflective film of the present invention. The optical member may include a polarizer, a polarizing plate, a retardation film, a protective film, a conductive film, a window film, a panel, and the like. For example, the polarizing plate may include a polarizer, an antireflection film formed on at least one surface of the polarizer, and the antireflection film may include an antireflection film according to the present embodiment. The polarizing plate may further include a conventional optical compensation film, a protective film, etc. in addition to the antireflection film.

Hereinafter, an optical display device according to an embodiment of the present invention will be described.

The optical display device according to the present embodiment may include an antireflection film or a polarizing plate according to the present embodiment. The optical display device may include a liquid crystal display device, an organic light emitting display device, and the like, but is not limited thereto.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Example  One

For first floor  Composition preparation

25 weight% of curable compound UP111 (Entis, polyfunctional urethane acrylate), 10 weight% of curable compound HDDA (Entis, hexanediol diacrylate), 5 weight% of initiator Irgacure 184 (Ciba specialty chemical), methyl isobutyl ketone 60% by weight was mixed. As shown in Table 1, 0.005 parts by weight of the surface energy regulator UV 3500 (BYK chem) was added to 100 parts by weight of the solution to prepare a composition for the first layer. The surface energy modifier in the first layer composition was included as 0.0125% by weight based on solids.

For the second floor  Composition preparation

1% by weight of THRULYA 5320 (JGC Catalyst and chemicals LTD), a hollow silica-containing sol, 0.6% by weight of AR-110 (DAIKIN), a fluorine-based curable compound, 0.36% by weight of PETA (Entis), a non-fluorine-based curable compound, initiator Irgacure 127 (Ciba specialty chemical) 0.04% by weight and 98% by weight of solvent methyl isobutyl ketone were mixed to prepare a composition for a second layer.

Anti-reflective film manufacturing

The first layer composition prepared above was applied to a TAC film (Fujifilm, TG60UL, thickness: 60 μm) as a base layer using a wire bar coater # 14, dried at 80 ° C. for 2 minutes, and then light quantity of 300 mJ / cm ² in a nitrogen atmosphere. It hardened | cured and formed the 1st layer (thickness: 10micrometer). The contact angle was measured with a contact angle meter Phoenix 2000 at 25 ° C. for the first layer and converted into surfaces to obtain surface energy. The surface energy of the first layer is shown in Table 1 below. The second layer composition prepared above was applied to the first layer using a wire bar coater # 14, dried at 80 ° C. for 1 minute, and cured at a light amount of 300 mJ / cm ² in a nitrogen atmosphere to prepare a second layer (thickness: 100 nm). The antireflection film having a three-layer structure in which the base layer, the first layer, and the second layer were sequentially formed was prepared by forming.

Example  2

For first floor  Composition preparation

25 weight% of curable compound UP111 (Entis, polyfunctional urethane acrylate), 10 weight% of curable compound HDDA (Entis, hexanediol diacrylate), 5 weight% of initiator Irgacure 184 (Ciba specialty chemical), methyl isobutyl ketone 60% by weight was mixed. 0.001 parts by weight of a surface energy modifier UV 3500 (BYK chem) was added to 100 parts by weight of the resulting solution to prepare a composition for a first layer. The surface energy modifier in the composition for the first layer was included at 0.0025% by weight based on solids. An antireflection film was prepared in the same manner as in Example 1 using the prepared first layer composition.

Example  3

For the second floor  Composition preparation

1% by weight of THRULYA 5320 (JGC Catalyst and chemicals LTD), a hollow silica-containing sol, 0.6% by weight of AR-110 (DAIKIN), a fluorine-based curable compound, 0.36% by weight of PETA (Entis), a non-fluorine-based curable compound, initiator Irgacure 127 (Ciba specialty chemical) 0.04% by weight, and 98% by weight of solvent methyl isobutyl ketone. 0.0002 parts by weight of SST250U (Ranco), a spherical (non-hollow) silica-containing sol, was added to 100 parts by weight of the obtained liquid mixture to prepare a composition for a second layer. An antireflection film was prepared in the same manner as in Example 1 using the prepared second layer composition.

Comparative example  One

In Example 1, the composition for a first layer was prepared without adding 0.001 parts by weight of a surface energy modifier UV 3500 (BYK chem). An antireflection film was prepared in the same manner as in Example 1 using the prepared first layer composition.

Comparative example  2

In Example 1, the composition for the first layer was prepared in the same manner except that 0.0001 parts by weight of the surface energy modifier UV 3500 (BYK chem) was added instead of 0.005 parts by weight of the surface energy modifier UV 3500 (BYK chem). . An antireflection film was prepared in the same manner as in Example 1 using the prepared first layer composition.

Comparative example  3

In Example 1, the composition for the first layer was prepared in the same manner except that 0.35 part by weight of the surface energy modifier UV 3500 (BYK chem) was added instead of 0.005 part by weight of the surface energy modifier UV 3500 (BYK chem). . An antireflection film was prepared in the same manner as in Example 1 using the prepared first layer composition.

The following physical properties were evaluated about the composition for 2nd layers of an Example and a comparative example, and an antireflection film, and the result is shown in following Table 1, FIG.

(1) Wetting property of the composition for the second layer: The composition for the second layer was evaluated visually after coating and drying the composition for the second layer on the cured product of the first layer. It is evaluated by the ratio of the area of the entire coating surface where no wetting occurs. ○ If the area ratio of the non-wetting is less than 10%, ○ is over 10% and less than 30%, △, if more than 30% is evaluated as X.

(2) Whether or not air holes were generated in the second layer: SEM measurement was performed on the antireflection films of Examples and Comparative Examples to evaluate whether or not air holes were generated. When it is confirmed by 25.0K magnification by SEM analysis, it evaluates as (circle) when there are three or more air holes (air column), (triangle | delta) when less than three one or less, and X when no air hole is formed.

(3) Reflectance: Spectrophotometer (Konica Minolta, CM-3600A) on a specimen prepared by laminating a black acrylic sheet (Nitto Jushi Kogyo, CLAREX) on the lower surface of the base layer of the antireflection films of Examples and Comparative Examples The Y value represents the reflectance measured at a wavelength of 360 nm to a wavelength of 740 nm in the SCI reflection mode (light source: D65 light source, light source aperture: φ 8 mm).

(4) Pencil hardness: Measured using a HEIDON instrument, using a Mitsubishi pencil with a hardness of 0.5mm / sec, weight of 500g, corresponding hardness such as 1H, 2H, etc. If the surface of the film is not scratched after inspecting with a 2H Mitsubishi pencil, it is considered to have a hardness of 2H. Measure 5 times each. Pencil hardness is measured with respect to the surface of the second layer in the antireflective film.

(5) Adhesion: In the antireflection films of Examples and Comparative Examples, 11 horizontal lines and 11 vertical lines were scraped with a cutter knife in 1 cm each. The thickness of the cutter knife should be 0.6 mm or less. 100 squares will be created in total area of 1cm ² . This part is completely attached with 3M 801 scotch tape and then torn off to obtain the number of flakes remaining on the antireflective film out of a total of 100 flakes. The greater the number of flakes remaining, the better the adhesion between the first layer and the second layer.

(6) Scratch resistance: For HEIDON 14F machine, steel wool uses LIBERON's 0000 product. The antireflection film of Example and Comparative Example is stuck on a flat glass plate so that the low refractive index layer faces upward using a tape. In the scratch resistance, the weight contact area with the film should be circular and the diameter should be 10 ± 2mm. The speed is 4000mm / min, the travel distance is 50mm and the number of movements is 10 times. Evaluate while increasing the weight of the weight. The greater the weight mass, the greater the scratch resistance.

Example Comparative example One 2 3 One 2 3 Surface energy regulator content used in the first layer
(Parts by weight) 0.005 0.001 0.005 0 0.0001 0.3 Surface energy regulator content in the first layer
(weight%) 0.0125 0.0025 0.0125 0 0.00025 0.75 Surface energy of the first layer
(dyne / cm) 23 20     23 30 25 15 Wetting of the second layer ○ ○ ○ ○ ○ x Air hole occurrence in the second layer ○ ○ ○ x △ x reflectivity
(%) 0.29 0.28 0.28 0.36 0.32 0.35 Pencil hardness 2H 2H 2H 2H 2H 2H Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 Scratch resistance 250 g 250 g 250 g 250 g 250 g 250 g

As shown in Table 1, the antireflection film of the present invention was excellent in the adhesion between the second layer and the first layer including the air hole and significantly low reflectance. In addition, as shown in Figure 3, the anti-reflection film of the present invention can be confirmed that the air hole (air pillar) is well formed.

On the other hand, Comparative Examples 1 to 3, which deviate from the surface energy range of the present invention, are similar to those of Examples, but have a significantly high reflectance. Particularly, Comparative Examples 2 to 3 deviate from the surface energy of the present invention, in which case no air holes are formed or slightly formed, whereas the embodiment of the present invention can lower the reflectance by forming air holes well.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (17)

The base layer, the first layer and the second layer is an antireflection film sequentially laminated,
The second layer includes an air hole and is directly formed in the first layer,
The first layer has a surface energy of 20 dyne / cm to 23 dyne / cm at 25 ℃,
The antireflection film has a reflectance of 0.3% or less,
The second layer comprises a hollow particle, the second layer is the anti-reflection film, which comprises 40% to 60% by weight of the hollow particles.
The antireflection film of claim 1, wherein the antireflection film has a pencil hardness of 2H or more measured at the second layer.
The antireflective film of claim 1, wherein the antireflective film has a surface roughness of 50 nm or less measured in the second layer.
The antireflective film of claim 1, wherein the air hole comprises an air pillar.
delete The antireflection film of claim 1, wherein the air hole is formed surrounded by the hollow particles.
delete The antireflective film of claim 1, wherein the hollow particles comprise hollow silica.
The antireflective film of claim 1, wherein the second layer further comprises non-hollow particles.
The antireflection film of claim 9, wherein the second layer comprises 1 wt% to 5 wt% of the non-hollow particles.
The antireflection film according to claim 1, wherein the first layer is formed of a composition containing a fluorine-based curable monomer.
The antireflection film of claim 1, wherein the second layer has a refractive index of 1.30 or less.
The antireflective film of claim 1, wherein the first layer comprises a silicon-based surface energy modifier.
The antireflection film of claim 1, wherein the refractive index of the first layer is higher than the refractive index of the second layer.
The antireflection film according to claim 1, wherein an average particle diameter of the air hole is larger than an average particle diameter of the hollow particles.
The polarizing plate containing the antireflection film of any one of Claims 1-4, 6, 8-15.
An optical display device comprising the antireflection film of any one of claims 1 to 4, 6, and 8 to 15.

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