WO2018062631A1 - Antireflective film composition, antireflective film formed therefrom, polarizing plate including same, and optical display device including same - Google Patents

Abstract

Provided are an antireflective film composition, an antireflective film formed therefrom, a polarizing plate including the same, and an optical display device including the same, the composition comprising: a compound of chemical formula 1; a compound of chemical formula 2; a UV curable compound; an antistatic agent; an initiator; and zirconia.

Description

Composition for antireflection film, antireflection film formed therefrom, polarizing plate comprising same and optical display device comprising same

The present invention relates to an antireflection film composition, an antireflection film formed therefrom, 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.

On the other hand, since the antireflection 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 technique for manufacturing an antireflection film by stacking a high refractive index layer and a low refractive index layer having a hard coat function and an antistatic function on a base material layer has been developed. However, even with a hard coat function and an antistatic function, there was a limit in lowering the reflectance of the antireflective film. There is a method of lowering the reflectance by increasing the refractive index of the high refractive layer by including inorganic particles in the high refractive layer. However, there is a limit in lowering the reflectance of the antireflection film, and when the refractive index is lowered by using the inorganic hollow particles in the low refractive index layer, the refractive index may be sufficiently lowered, but there may be problems in surface property degradation and material cost increase.

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 a composition for an antireflective film, which is excellent in hard coat function, antistatic function and high refractive index can significantly lower the lowest reflectance of the antireflective film.

Another problem to be solved by the present invention is to provide an antireflection film composition, which can realize an antireflection film having excellent optical properties and excellent scratch resistance.

Another problem to be solved by the present invention is to provide an antireflective film having excellent low antireflection and excellent antireflection function, and excellent hardness and antistatic function.

The composition for an antireflective film of the present invention may include a compound of Formula 1, a compound of Formula 2, a UV curable compound, an antistatic agent, an initiator, and zirconia:

<Formula 1>

(In Formula 1, m, n, R are as defined in the detailed description of the invention)

<Formula 2>

(In Formula 2, n, R are as defined in the detailed description of the invention below).

In the antireflection film of the present invention, a substrate layer, a high refractive layer, and a low refractive layer are sequentially stacked, and the high refractive layer has a higher refractive index than the low refractive layer, and the antireflective film has a minimum reflectance of about 0.5% or less. The refractive index difference between the high refractive layer and the low refractive layer may be about 0.26 or more.

The polarizing plate of the present invention may include a polarizer and an antireflection film of the present invention formed on at least one surface of the polarizer.

The optical display device of the present invention may include an antireflection film or a polarizing plate of the present invention.

The present invention provides a composition for an antireflection film, which is excellent in a hard coat function, an antistatic function, and has a high refractive index, which can significantly lower the minimum reflectance of the antireflection film.

The present invention provides an antireflective film composition, which can realize an antireflection film having excellent optical properties and excellent scratch resistance.

The present invention provides an antireflective film having a low minimum reflectance and excellent antireflection function, and excellent hardness and antistatic function.

1 is a cross-sectional view of an antireflective film according to an embodiment of the present invention.

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.

As used herein, the "lowest reflectance" refers to a specimen prepared by laminating a CL-885 black acrylic sheet of Nitto resin with an adhesive having a refractive index of 1.46 to 1.50 on the substrate layer side of the antireflective film (the adhesive and the substrate layer are laminated). The reflectance meter is measured in the wavelength 320nm to 800nm in the reflection mode, it means the lowest value of the reflectance measured at the wavelength of 440nm to 550nm.

In the present specification, "average reflectance" refers to a CL-885 black acrylic sheet of Nitto resin with a pressure-sensitive adhesive having a refractive index of 1.46 to 1.50, laminated on the substrate layer side of the laminate of the high refractive index layer and the substrate layer (the adhesive and the substrate layer are laminated). For the specimen prepared by using a reflectance measuring device in the reflection mode in the wavelength range of 320nm to 800nm, the average value of the reflectance at the wavelength of 380nm to 780nm.

In the present specification, "composition for antireflection film" may mean "composition for high refractive layer".

Hereinafter, the composition for an antireflective film according to an embodiment of the present invention may include a compound of Formula 1, a compound of Formula 2, a UV curable compound, an antistatic agent, an initiator, and zirconia.

The antireflection film composition of the present embodiment may form a high refractive layer in the antireflection film in which the base layer, the high refractive layer, and the low refractive layer are sequentially stacked. The high refractive layer has a higher refractive index than the low refractive layer. The composition of the present embodiment includes a compound of Formula 1, a compound of Formula 2, zirconia and a UV curable compound together, thereby increasing the refractive index of the high refractive layer and securing a difference in refractive index between the high refractive layer and the low refractive layer to about 0.26 or more. The lowest reflectance of the antireflective film can be significantly lowered.

The composition for an antireflective film may have a refractive index of about 1.530 to about 1.700, specifically about 1.550 to about 1.650. Within this range, the refractive index of the high refractive layer can be increased.

The laminate of the cured product (high refractive layer) of the composition for antireflection film and the substrate layer may have an average reflectance of about 5% or more, for example, about 5.3% or more and about 10% or less. In the above range, the lowest reflectance when the low refractive layer is laminated on the laminate can be about 0.5% or less. In particular, when the low refractive layer formed of a composition containing hollow particles and a fluorine-containing monomer is laminated on the cured product, the lowest reflectance may be particularly low.

The laminate of the cured product of the composition for antireflective film and the substrate layer may have a pencil hardness of about 2H or more, for example, about 2H to about 3H in the cured product. In the above range, the hardness of the antireflection film can be increased. In particular, the composition of the present invention can be such that there is no decrease in hardness even if the low refractive layer is further laminated on the high refractive layer.

Hereinafter, the composition for antireflection films is explained in full detail.

The compound of Formula 1 has a higher refractive index than the UV curable compound. Accordingly, the refractive index of the cured product (high refractive layer) formed of the composition for an antireflective film may be increased: The compound of Formula 1 may have a refractive index of about 1.6 or more, specifically about 1.615 to about 1.635, and more specifically about 1.62 to about 1.63. Can be. Within this range, the refractive index of the cured product can be increased to lower the lowest 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. In this case, when used in combination with a UV curable compound, in particular the urethane (meth) acrylate described below, the refractive index and hardness of the cured product can be increased, and the lowest reflectance when the low refractive index layer described below will be reduced to about 0.5% or less. Can be.

The compound of Formula 2 has a higher refractive index than the UV curable compound. Accordingly, the refractive index of the cured product (high refractive layer) formed of the composition for an antireflective film may be increased: The compound of Formula 2 may have a refractive index of about 1.55 or more specifically about 1.56 to about 1.59 and more specifically about 1.57 to about 1.58. Can be. Within this range, the refractive index of the cured product can be increased to lower the lowest 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 compound of Formula 1 and the entire compound of Formula 2 are about 5% by weight to about 60% by weight, for example, about 5, 6, 7, 8, 9, 10, 11, 12 based on solids in the composition for antireflection film , 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 , 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60% by weight Can be. Within this range, the refractive index of the high refractive layer can be sufficiently increased. Preferably from about 10% to about 45% by weight. Within this range, the minimum reflectance at the time of lamination with the low refractive layer can be sufficiently lowered, and the hardness of the antireflection film can be sufficiently increased.

As used herein, the term "solid content" means the entirety of the composition except for the solvent, and is not limited to the shape of a liquid phase, a solid phase, and the like.

The UV curable compound has a lower refractive index than the compound of Formula 1 and the compound of Formula 2. However, a UV curable compound can form the matrix of a high refractive layer, and can raise the hardness of a high refractive layer. When only the compound of Formula 1 and the compound of Formula 2 are included, the minimum refractive index can be lowered by increasing the refractive index of the high refractive layer, but the hardness of the antireflection film is lowered and thus cannot be used in an optical display device.

The UV curable compound may be preferably a compound having a UV curable group such as a (meth) acrylate group or an epoxy group. The UV curable compound may comprise at least one of a bifunctional or higher polyfunctional (meth) acrylate-based monomer, an oligomer formed therefrom, or a resin formed therefrom. For example, the UV curable compound may be a bifunctional to 10 functional (meth) acrylate-based compound.

The UV curable compound is a polyfunctional urethane (meth) synthesized from a polyfunctional (meth) acrylate such as an ester of a polyhydric alcohol and (meth) acrylic acid, or a hydroxy ester of a polyhydric alcohol, an isocyanate compound or a (meth) acrylic acid. It may comprise one or more of acrylates. Preferably, by using a polyfunctional urethane (meth) acrylate in combination with the compound of the formula (1), the compound of the formula (2) to increase the refractive index and hardness, it is possible to lower the minimum reflectance when laminating the low refractive layer.

As a bifunctional (meth) acrylate compound, 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) acrylic Rate, 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 And di (meth) acrylates such as hydroxypivaline neopentylglycol di (meth) acrylate.

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 tris 2-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?-. And polyfunctional (meth) acrylate compounds substituted with caprolactone.

Among the UV-curable compounds, polyfunctional urethane (meth) acrylates, for example, bifunctional or the like, can be designed so that the desired molecular weight and molecular structure can be designed and the balance of physical properties of the high refractive layer formed can be easily taken. Ten-functional urethane (meth) acrylate can be used preferably. 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.

The UV curable compound is about 20% to about 60% by weight based on solids in the composition for antireflective film, for example about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56 , 57, 58, 59, and 60% by weight. In the above range, the hardness of the high refractive index layer can be increased. Preferably from about 35% to about 50% by weight. Within this range, the minimum reflectance at the time of lamination with the low refractive layer can be sufficiently lowered, and the hardness of the antireflection film can be sufficiently increased.

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.

The antistatic agent is about 2% to about 10% by weight based on solids in the composition for antireflective film, for example about 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight, preferably about 3 Weight percent to about 7 weight percent. In the above range, the antistatic effect may come out and may not affect the hardness of the antireflection film and the like, prevent the degradation of physical properties such as hardness, and prevent the migration of the antistatic agent.

An initiator may form a high refractive layer by curing the compound of Formula 1, the compound of Formula 2, and a UV curable compound. The initiator may comprise one or more of conventional photo radical initiators, photo cationic initiators known to those skilled in the art. Although not particularly limited, the initiator may enable the production of a high refractive index layer only by photocuring upon curing of the compound of Formula 1 and the UV curable compound by using an initiator having an absorption wavelength of 400 nm or less.

The radical radical initiator generates a radical by light irradiation to catalyze curing, and includes at least one of phosphorus, triazine, acetophenone, benzophenone, thioxanthone, benzoin, oxime, and phenyl ketone. can do. 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, bis [4- such as diaryl iodonium, triphenylsulfonium, 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 initiator may be included in about 2% to about 5% by weight, for example about 2, 3, 4, 5% by weight based on solids in the composition for the antireflective film. In the above range, the composition can be sufficiently cured and the light transmittance of the antireflective film can be prevented from being lowered due to the remaining amount of initiator. Preferably 2 wt% to 4 wt% may be included. In the above range, it may be possible to manufacture the high refractive index layer only by photocuring.

Zirconia can add a refractive index increase and a hardness increase of a coating film to a high refractive layer. Zirconia may or may not be surface treated, 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 about 5% to about 50% of the total surface area of zirconia. In the above range, through the UV curable compound, the compound of Formula 1, the compound of Formula 2 may be effective in increasing the hardness. Zirconia has an average particle diameter (D50) of about 1 nm to about 50 nm, specifically about 5 nm to about 20 nm, for example about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 nm. In the above range, there may be a hardness increase effect without deterioration of the optical properties of the antireflection film.

Zirconia is about 2% to about 35% by weight based on solids in the composition for antireflective film, for example about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 , 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35% by weight. In the above range, there may be a hardness increase effect without deteriorating the optical properties of the antireflection film. Preferably from about 5% to about 30% by weight. In the above range, there may be an effect of increasing the hardness without deterioration of the optical properties.

The composition for antireflection film may further include conventional additives known to those skilled in the art. For example, antifoaming agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents and the like may further include, but are not limited thereto.

The composition for antireflection film may further include a solvent to improve the coating property of the composition for antireflection film. The solvent may comprise one or more of propylene glycol monomethyl ether, methylethylketone.

Hereinafter, an antireflection film according to an embodiment of the present invention will be described with reference to FIG. 1. 1 is a cross-sectional view of an antireflective film according to an embodiment of the present invention.

Referring to FIG. 1, in the antireflection film 100 according to the present exemplary embodiment, the base layer 110, the high refractive layer 120, and the low refractive layer 130 may be sequentially stacked. The low refractive index layer 130 has a lower refractive index than the high refractive layer 120, and the high refractive layer 120 may be formed of an antireflective film composition according to an embodiment of the present invention. Therefore, the antireflection film 100 of the present embodiment has a minimum reflectance of about 0.5% or less, for example, about 0% or more and about 0.5% or less, and the pencil hardness of the low refractive layer is about 2H or more, for example, about 2H or more 3H or less, the surface resistance in the low refractive layer may be about 9 × 10 ¹⁰ Pa / □ or less, for example, about 1 × 10 ¹⁰ Pa / □ or less.

The base layer 110 may support the antireflection film 100 and increase the mechanical strength of the antireflection film 100.

The base layer 110 may have a refractive index of about 1.40 to about 1.80, for example, about 1.45 to about 1.70. In the above range, when the high refractive index layer and the low refractive layer are laminated sequentially, the lowest reflectance can be lowered. The base layer 110 may be formed of an optically transparent resin. Specifically, the resin may be a cellulose ester resin including triacetyl cellulose or the like, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyester resin including polybutylene naphthalate or the like, polycarbonate resin, polymethylmethacryl And one or more of poly (meth) acrylate resins, polystyrene resins, polyamide resins, polyimide resins, including rates and the like. Preferably, it may be a cellulose ester resin including triacetyl cellulose or the like. The base layer 110 may have a thickness of about 10 μm to about 150 μm, specifically about 30 μm to about 100 μm, and more specifically about 40 μm to about 90 μm. It can be used in the antireflection film in the above range.

The high refractive layer 120 may be formed on the base layer 110 to increase the hardness of the antireflection film, lower the minimum reflectance, and lower the surface resistance. The high refractive layer 120 is formed directly on the base layer 110. The "directly formed" means that no other adhesive layer or optical layer is formed between the high refractive layer 120 and the base layer 110.

The high refractive index layer 120 has a refractive index of about 1.53 to about 1.70, for example, about 1.56 to about 1.65, for example about 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, It can be 1.65, 1.66, 1.67, 1.68, 1.69, 1.70. Within this range, the lowest reflectance can be lowered when the low refractive layers are laminated. The high refractive index layer 120 may have an average reflectance of about 5% or more, for example, about 5.3% or more and about 10% or less. Within this range, the lowest reflectance can be lowered when the low refractive layers are laminated.

The high refractive layer 120 has a higher refractive index than the base layer 110. The refractive index difference between the high refractive index layer and the base layer is about 0.03 or more and about 0.15 or less, for example, about 0.05 or more and about 0.15 or less, for example, about 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15. Within this range, there can be the lowest reflectance reduction effect in the final product.

The high refractive layer 120 may have a thickness of about 1 μm to about 50 μm, specifically about 1 μm to about 30 μm, and more specifically about 5 μm to about 10 μm. It can be used in the antireflection film in the above range, it can ensure the hardness.

The low refractive layer 130 may be formed on the high refractive layer 120 to lower the minimum reflectance of the antireflection film. The low refractive layer 130 is formed directly on the high refractive layer 120. The "directly formed" means that no other adhesive layer or optical layer is formed between the low refractive layer 130 and the high refractive layer 120.

The low refractive index layer 130 may have a lower refractive index than the high refractive index layer 120 to lower the minimum reflectance of the antireflection film. The refractive index difference between the high refractive index layer 130 and the low refractive index layer 120 may be about 0.26 or more, for example, about 0.26 or more and about 0.30 or less. Within this range, the refractive index of the antireflection film can be lowered and optical properties such as haze can be improved. The low refractive index layer 130 may have a refractive index of about 1.35 or less, for example, about 1.25 or more and about 1.32 or less.

The low refractive layer 130 may have a thickness of about 50 nm to about 300 nm, specifically about 80 nm to about 200 nm, and more specifically about 80 nm to about 150 nm. It can be used in the antireflection film in the above range.

The low refractive layer 130 may be formed of a composition for low refractive layers. The composition for low refractive layers may include inorganic particles, fluorine-containing monomers or oligomers thereof, fluorine-free monomers or oligomers thereof, initiators and fluorine-containing additives.

The inorganic particles may have a hollow structure and have a low refractive index, thereby lowering the refractive index of the low refractive layer. The refractive index of the inorganic particles may be about 1.4 or less, for example about 1.2 to about 1.38. Hollow silica may be used for the inorganic particles. The inorganic particles may be untreated hollow particles that have not been surface treated, or may be surface treated with a UV curable functional group. The average particle diameter (D50) of the inorganic particles is equal to or less than the thickness of the low refractive layer, and may be about 30 nm to about 150 nm, for example, about 50 nm to about 100 nm. In the above range, it can be included in the low refractive layer, it is possible to improve the optical properties such as haze and transmittance.

The fluorine-containing monomer or oligomer thereof lowers the refractive index of the low refractive layer with the inorganic particles and forms a matrix of the low refractive layer with the fluorine-free monomer or the oligomer thereof. The fluorine-containing monomer may include a fluorine-containing (meth) acrylate compound. Fluorine-containing monomers may include conventional compounds known to those skilled in the art.

The fluorine-free monomer or the oligomer thereof forms a matrix of the low refractive layer and may include a UV curable compound. The fluorine-free monomer or the oligomer thereof may be a bifunctional or more than, for example, a (meth) acrylate-based compound of bifunctional to 10 functional. Specifically, the fluorine-free monomer may include a polyfunctional (meth) acrylate such as the ester of the polyhydric alcohol and (meth) acrylic acid described above.

The initiator may be the same or different from those described above in the composition for the high refractive index layer.

The additive adds antifouling function and slimness to the low refractive layer, and conventional additives known to those skilled in the art can be used. The additive may include one or more of fluorine-containing additives and silicone-based additives. The fluorine-containing additive may be a UV curable fluorinated acrylic compound. For example, the KY-1200 series (Shin-Yetsu Corporation) containing KY-1203 can be used.

The composition for the low refractive index layer is about 20% to about 70% by weight of the inorganic particles based on solids, for example, about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70% by weight, about 10% to about 50% by weight fluorine-containing monomer or oligomer thereof, for example about 10, 11, 12 , 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 , 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50% by weight, about 5% to about 25% by weight fluorine-free monomer or oligomer thereof for example about 5 , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25% by weight, about 2% by weight to initiator 5% by weight such as about 2, 3, 4, 5% by weight, and about 1% to about 10% by weight of additives such as about 1, 2, 3, 4, 5, 6, 7, 8, 9, It may comprise 10% by weight. In the above range, the pencil hardness of about 2H or more, the anti-fingerprint effect can be obtained. Preferably, the composition for the low refractive index layer is about 40% to about 60% by weight of the inorganic particles based on solids, about 20% to about 40% by weight of the fluorine-containing monomer or oligomer thereof, and about 5% by weight of the fluorine-free monomer or oligomer thereof To about 15 wt%, about 2 wt% to about 4 wt% initiator, and about 2 wt% to about 7 wt% additive.

The composition for the low refractive index layer may further include conventional additives known to those skilled in the art. For example, antifoaming agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents and the like may further include, but are not limited thereto.

The composition for the low refractive index layer may further include a solvent to improve the coating property. The solvent may comprise one or more of methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol dimethyl ether.

Hereinafter, a polarizing plate according to an embodiment of the present invention will be described.

The polarizing plate according to the present embodiment may include an antireflection film according to an embodiment of the present invention. The polarizing plate may include a polarizer and 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.

Production Example  One: For low refractive index  Composition preparation

To 61.3 g of THRULYA 5320 (JGC Catalyst and chemicals LTD), a hollow silica-containing sol, 2.75 g of M306 (TOAGOSEI), a fluorine-free monomer, was completely dissolved to obtain a mixture. 5.17 g of AR-110 (DAIKIN), a fluorine-containing monomer, was added to the mixture, followed by stirring for 5 minutes. 3.75 g of KY-1203 (Shinetsu), a fluorine-containing additive, was added to the mixture, followed by stirring for 5 minutes. 0.75 g of Irgacure 127 (BASF), an initiator, was added to the mixture, followed by complete dissolution. 585 g of methyl ethyl ketone (Samjeon Chemical), 197 g of methyl isobutyl ketone (Samjeon Chemical), and 97.5 g of ethylene glycol dimethyl ether (Samjeon Chemical) were added to the mixture, followed by stirring for 30 minutes to prepare a composition for a low refractive layer.

The composition for the low refractive index layer comprises 50% by weight of hollow silica, 32% by weight of fluorine-containing monomer, 10% by weight of fluorine-free monomer, 3% by weight of initiator and 5% by weight of additive.

Example  One

13 g of a UV-curable compound UP111 (Entis, polyfunctional urethane acrylate), 14 g of BPS022S (concentrate), a solution containing a mixture of the compound of Formula 1 and the compound of Formula 2, and a surface-treated zirconia-containing sol (Lancos) 10 g, propylene glycol monomethyl ether (Samjeon Chemical) 30g, methyl ethyl ketone (Samjeon Chemical) 25g was added and completely dissolved. 1.25 g of Irgacure 184 (BASF), an initiator, was added thereto, followed by stirring for 5 minutes. 9.4 g of antistatic agent-containing solution TBAS-2 (ARAKAWA) was added thereto, followed by stirring for 20 minutes to prepare a composition for a high refractive layer.

The composition for the high refractive index layer 45% by weight of the total of the compound of formula 1 and formula 2, 41% by weight of the UV curable compound, 5% by weight of the antistatic agent, 4% by weight of the initiator, 5% by weight of zirconia.

The prepared high refractive index composition was coated on a triacetyl cellulose film (FUJI, TG60UL,), which is a base layer, using No. 14 Mayer bar. After drying for 2 minutes at 80 ℃, 100mJ / cm ² in a nitrogen atmosphere It hardened | cured by the above-mentioned light quantity. After coating the obtained composition for the low refractive index layer of Preparation Example 1 using a No. 4 Mayer bar, and dried for 2 minutes at 80 ℃, 250mJ / cm ² in a nitrogen atmosphere Cured to the above-described light amount, on the substrate layer (thickness: 60㎛, refractive index: 1.485), high refractive index layer (thickness: 7㎛, refractive index is in Table 1), low refractive layer (thickness: 130nm, refractive index: 1.30) An antireflection film having a three-layer structure laminated in this order was prepared.

Example  2

17 g of a UV-curable compound UP111 (Entis, polyfunctional urethane acrylate), 5 g of BPS022S (concentrated), a solution containing a mixture of the compound of Formula 1 and the compound of Formula 2, and a surface-treated zirconia-containing sol (Lancos) 30 g, propylene glycol monomethyl ether (three electrochemical) 15 g, and methyl ethyl ketone (three electrochemical) 20 g were added and completely dissolved. 1.25 g of Irgacure 184 (BASF), an initiator, was added thereto, followed by stirring for 5 minutes. 9.4 g of antistatic agent-containing solution TBAS-2 (ARAKAWA) was added thereto, followed by stirring for 20 minutes to prepare a composition for a high refractive layer.

The composition for the high refractive index layer comprises a total of 15% by weight of the compound of Formula 1 and Formula 2, 50% by weight of the UV curable compound, 5% by weight of the antistatic agent, 4% by weight of the initiator, 26% by weight of zirconia on a solids basis.

The prepared high refractive index composition was coated on a triacetyl cellulose film (FUJI, TG60UL) as a base layer using No. 14 Mayer bar. After drying for 2 minutes at 80 ℃, 100mJ / cm ² in a nitrogen atmosphere It hardened | cured by the above-mentioned light quantity. After coating the composition for the low refractive index layer of Preparation Example 1 using a No. 4 Mayer bar, and dried for 2 minutes at 80 ℃, 250mJ / cm ² in a nitrogen atmosphere Cured to the above-described light amount, on the substrate layer (thickness: 60㎛, refractive index: 1.485), high refractive index layer (thickness: 7㎛, refractive index is in Table 1), low refractive layer (thickness: 130nm, refractive index: 1.30) An antireflection film having a three-layer structure laminated in this order was prepared.

Comparative example  One

31 g of UP111 (Entis), a UV curable compound, 30 g of propylene glycol monomethyl ether (three electrochemical), and 30 g of methyl ethyl ketone (three electrochemical) were added and completely dissolved. 1.25 g of Irgacure 184 (BASF) as an initiator was added thereto, followed by stirring for 5 minutes. After adding 9.4 g of antistatic agent-containing solution TBAS-2 (ARAKAWA), the mixture was stirred for 20 minutes to prepare a composition for a high refractive layer. An antireflective film was prepared in the same manner as in Example 1 using the prepared composition.

Comparative example  2

31 g of CN120C80 (Sartomer), a mixture of bisphenol A epoxy acrylate (refractive index: 1.541) and trimethyl propane triacrylate, 30 g of propylene glycol monomethyl ether (three electrochemical), and 30 g of methyl ethyl ketone (three electrochemical) were completely dissolved. . 1.25 g of Irgacure 184 (BASF), an initiator, was added thereto, followed by stirring for 5 minutes. After adding 9.4 g of antistatic agent-containing solution TBAS-2 (ARAKAWA), the mixture was stirred for 20 minutes to prepare a composition for a high refractive layer. An antireflective film was prepared in the same manner as in Example 1 using the prepared composition.

Comparative example  3

23 g of UP111 (Entis, polyfunctional urethane acrylate), a UV curable compound, 5 g of BPS022S (concentrated), a solution containing a mixture of the compound of Formula 1 and the compound of Formula 2, and surface-treated TiO ₂ nanoparticles (fuji Titan) G) 8 g, propylene glycol monomethyl ether (Samjeon Chemical) 30g, and methyl ethyl ketone (Samjeon Chemical) 30g were added and completely dissolved. 1.25 g of Irgacure 184 (BASF), an initiator, was added thereto, followed by stirring for 5 minutes. 9.4 g of antistatic agent-containing solution TBAS-2 (ARAKAWA) was added thereto, followed by stirring for 20 minutes to prepare a composition for a high refractive layer.

The composition for the high refractive index layer comprises a total of 13% by weight of the compound of Formula 1 and Formula 2, 59% by weight of the UV curable compound, 5% by weight of the antistatic agent, 3% by weight of the initiator, 20% by weight of TiO ₂ on a solids basis.

The following physical properties were evaluated for the compositions for high refractive layers of the examples and the comparative examples, and the results are shown in Table 1 below.

(1) Refractive index of the composition for the high refractive index layer and the refractive index of the high refractive layer: For the composition of the Examples and Comparative Examples and the high refractive layer of the cured product thereof, the liquid refractive index was measured with an Abbe refractive index meter for the composition, and for the high refractive layer, The pressure-sensitive adhesive having a refractive index of 1.46 to 1.50 is laminated to a coating layer composed of 100% of the composition, and then, a CL-885 black acrylic sheet of Nitto resin is placed on one side, and the reflectance is measured by a UV-spectrometer. Measured by the method.

(2) Average reflectance: The composition for high refractive layers of Examples and Comparative Examples was coated on the triacetyl cellulose film (FUJI, TG60UL, thickness: 60㎛) as a base layer using No. 14 Mayer bar, and dried at 80 ° C. for 2 minutes. , And cured at a light quantity of 150 mJ / cm ² in a nitrogen atmosphere to prepare a specimen (high refractive layer thickness: 7 μm).

The specimen was prepared by laminating a CL-885 black acrylic sheet of Nitto resin with an adhesive having a refractive index of 1.46 to 1.50 at 70 ° C. (adhesive and substrate layer laminated) on the substrate layer side of the specimen and measuring the UV / reflectometer of Perkin Elmer. It was measured with a VIS spectrometer Lambda 1050. In the reflection mode, measurements were made in the range of 320 nm to 800 nm, and the average value of the reflectance at 380 nm to 780 nm is the average reflectance.

(3) Pencil hardness: Measured using a HEIDON instrument, using a Mitsubishi pencil with a corresponding hardness of 0.5mm / sec, weight of 500g, 1, 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, 5/5 if not all scratches, 0/5 if all 5 scratches.

	Refractive Index of the Composition for High Refractive Layer	Refractive Index of High Refractive Layer	Average reflectance (%)	Pencil Hardness (2H)
Example 1	1.562	1.583	5.542	4/5
Example 2	1.575	1.592	5.840	5/5
Comparative Example 1	1.510	1.530	4.820	5/5
Comparative Example 2	1.530	1.550	4.832	5/5
Comparative Example 3	1.602	-	-	-

* In case of Comparative Example 3, the haze was increased due to the TiO ₂ dispersion degree, and the low refractive index layer was not coated.

The following physical properties were evaluated for the antireflection films of Examples and Comparative Examples and the results are shown in Table 2 below.

(1) Haze and transmittance: The antireflection films of the Examples and Comparative Examples were measured in the visible light region having a wavelength of 400 nm to 700 nm with NDH 2000 (NIPPON DENSHOKU), which is a haze meter.

(2) Lowest reflectance: Laminates CL-885 black acrylic sheet of Nitto resin with an adhesive having a refractive index of 1.46 to 1.50 at 70 DEG C on the base layer side of the antireflection films of Examples and Comparative Examples (adhesive and base layer are laminated). The prepared specimens were measured with a reflectance meter Perkin Elmer's UV / VIS spectrometer Lambda 1050. In the reflection mode, the measurement was performed in the range of 320 nm to 800 nm, and the lowest value of the reflectance at the wavelength of 440 nm to 550 nm was obtained.

(3) Surface resistance: In the antireflection film surface of the antireflection film of the Example and the comparative example, it measured using the surface resistance measuring instrument MCP-HT450 (MITSUBICHI Co., Ltd.) at 100 V of press voltage and 10 micrometers of measurement thickness.

(4) Pencil hardness: Measured using a HEIDON instrument, using a Mitsubishi pencil with a corresponding hardness of 0.5mm / sec, weight of 500g, 1, 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, 5/5 if not all scratches, 0/5 if all 5 scratches.

(5) Scratch resistance: For HEIDON 14F machine, steel wool uses LIBERON's 0000 product. Stick the antireflection film on a flat glass plate with tape. The contact area with the film is circular and the diameter should be 10 ± 2mm. The speed is 4000mm / min, the movement distance is 50mm, the number of movements is 10 times and the load is given by using 1kg weight. After 10 iterations, visually check for scratches. If no scratch occurs, it is evaluated as good, less than 10 is good and 10 is NG.

	Haze (%)	Permeability (%)	Average reflectance (%)	Reflectance (%)	Surface resistance (Ω / □)	Pencil hardness	Scratch resistance	Difference in Refractive Index between High Refractive Layer and Substrate Layer	Difference in Refractive Index between High and Low Refractive Layers
Example 1	0.42	95.53	5.542	0.493	5.78 x 10 9	4/5	Good	0.098	0.283
Example 2	0.39	95.41	5.840	0.431	5.5 x 10 9	5/5	Good	0.107	0.292
Comparative Example 1	0.34	95.82	4.820	0.964	1.81 x 10 9	5/5	Great	0.045	0.230
Comparative Example 2	0.44	95.66	4.832	0.911	over	5/5	Good	0.065	0.250
Comparative Example 3	63.12	80.27	-	-	Over	-	NG	-	-

As shown in Table 1, Table 2, the antireflection film composition of the present invention was excellent in the hard coat function, antistatic function and high refractive index was able to significantly lower the lowest reflectance of the antireflection film. In addition, the antireflection film composition of the present invention was able to implement an antireflection film having excellent optical properties and good scratch resistance.

On the other hand, Comparative Examples 1 and 2, which deviate from the composition of the present invention, have a higher average reflectance and the lowest reflectance than the present invention, and thus the lowest reflectance of the present invention cannot be obtained.

Comparative Example 3 containing titania particles in the scope of the present invention instead of zirconia particles is not good TiO ₂ dispersion degree is high haze can not be used as an antireflection film.

Simple modifications or changes of the present invention can be easily carried out 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 (14)

1. To include a compound of formula 1, a compound of formula 2, a UV curable compound, an antistatic agent, an initiator and zirconia, a composition for an antireflective film:

   <Formula 1>

   

   (In Formula 1, m, n are each an integer of 1 or more, m + n is an integer of 2 to 8, R is hydrogen or a methyl group)

   <Formula 2>

   

   (In Formula 2, n is an integer of 1 to 4, R is hydrogen or a methyl group).
2. The composition for antireflection film according to claim 1, wherein the cured product of the composition for antireflection film and the first laminate of the substrate layer have an average reflectance of about 5% or more.
3. The composition for antireflection film according to claim 2, wherein the second laminate having a low refractive index layer including hollow particles and a fluorine-containing monomer on the cured product has a minimum reflectance of about 0.5% or less.
4. The antireflection film composition of claim 1, wherein the UV curable compound has a lower refractive index than the compound of Formula 1 and the compound of Formula 2.
5. The composition for antireflection film according to claim 1, wherein the UV curable compound contains a polyfunctional urethane (meth) acrylate.
6. The composition of claim 1, wherein the zirconia is surface treated.
7. The composition of claim 1, wherein the zirconia has an average particle diameter (D50) of about 5 nm to about 20 nm.
8. According to claim 1, wherein the composition for the anti-reflection film is about 5% to about 60% by weight of the total of the compound of Formula 1 and the compound of Formula 2 based on solids, about 20% to about 60% by weight of the UV curable compound %, About 2% to about 10% by weight of the antistatic agent, about 2% to about 5% by weight of the initiator and about 2% to about 35% by weight of the zirconia.
9. The base layer, the high refractive layer, and the low refractive layer are sequentially stacked,

   The high refractive layer has a higher refractive index than the low refractive layer,

   The lowest reflectance is about 0.5% or less,

   The refractive index difference between the high refractive index layer and the low refractive index layer is about 0.26 or more.
10. The antireflection film according to claim 9, wherein the high refractive index layer comprises a high refractive index layer formed of the composition for antireflection film of any one of claims 1 to 8.
11. The antireflection film according to claim 9, wherein the low refractive layer is formed of a composition comprising inorganic particles, a fluorine-containing monomer or oligomer thereof, a fluorine-free monomer or oligomer thereof, an initiator and a fluorine-containing additive.
12. 10. The antireflective film of claim 9, wherein the antireflective film has a pencil hardness of at least about 2H and a surface resistance of at most about 9 x 10 &lt; ¹⁰ &gt;
13. A polarizing plate comprising the antireflection film of claim 9.
14. An optical display device comprising the antireflective film of claim 9.

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