WO2018062631A1 - Composition de film antireflet, film antireflet formé à partir de celle-ci, plaque polarisante le comprenant, et dispositif d'affichage optique le comprenant - Google Patents

Composition de film antireflet, film antireflet formé à partir de celle-ci, plaque polarisante le comprenant, et dispositif d'affichage optique le comprenant Download PDF

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WO2018062631A1
WO2018062631A1 PCT/KR2016/015363 KR2016015363W WO2018062631A1 WO 2018062631 A1 WO2018062631 A1 WO 2018062631A1 KR 2016015363 W KR2016015363 W KR 2016015363W WO 2018062631 A1 WO2018062631 A1 WO 2018062631A1
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composition
layer
refractive index
formula
compound
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Korean (ko)
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조성흔
박세현
오부근
임형태
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삼성에스디아이 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F20/68—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F20/70—Nitriles; Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/694—Polymers of conjugated dienes containing carboxylic ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent

Definitions

  • 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.
  • 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.
  • the refractive index may be sufficiently lowered, but there may be problems in surface property degradation and material cost increase.
  • 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.
  • 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:
  • n, R are as defined in the detailed description of the invention below.
  • 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.
  • FIG. 1 is a cross-sectional view of an antireflective film according to an embodiment of the present invention.
  • (meth) acryl refers to acrylic and / or methacryl.
  • 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.
  • 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).
  • the average value of the reflectance at the wavelength of 380nm to 780nm is the average value of the reflectance at the wavelength of 380nm to 780nm.
  • composition for antireflection film may mean “composition for high refractive layer”.
  • composition for an antireflective film 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.
  • 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.
  • the lowest reflectance when the low refractive layer is laminated on the laminate can be about 0.5% or less.
  • 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.
  • the hardness of the antireflection film can be increased.
  • 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.
  • 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:
  • n 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).
  • m + n may be four.
  • 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:
  • 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.
  • the refractive index of the high refractive layer can be sufficiently increased.
  • 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.
  • 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.
  • a UV curable compound can form the matrix of a high refractive layer, and can raise the hardness of a high refractive layer.
  • 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.
  • 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.
  • 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.
  • 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) acryl
  • 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
  • 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
  • the polyol may include one or more of an aromatic polyol, an aliphatic polyol, and an alicyclic polyol.
  • an aliphatic polyol and an alicyclic polyol may be used.
  • 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.
  • the hardness of the high refractive index layer can be increased.
  • 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.
  • 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.
  • 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.
  • 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.
  • composition for antireflection film may further include conventional additives known to those skilled in the art.
  • antifoaming agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents and the like may further include, but are not limited thereto.
  • 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.
  • FIG. 1 is a cross-sectional view of an antireflective film according to an embodiment of the present invention.
  • 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.
  • 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.
  • 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.
  • it may be a cellulose ester resin including triacetyl cellulose or the like.
  • the base layer 110 may have a thickness of about 10 ⁇ m to about 150 ⁇ m, specifically about 30 ⁇ m to about 100 ⁇ m, and more specifically about 40 ⁇ m to about 90 ⁇ m. 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 ⁇ m to about 50 ⁇ m, specifically about 1 ⁇ m to about 30 ⁇ m, and more specifically about 5 ⁇ m to about 10 ⁇ m. 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.
  • 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.
  • the KY-1200 series Shin-Yetsu Corporation
  • 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,
  • 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.
  • composition for the low refractive index layer may further include conventional additives known to those skilled in the art.
  • 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.
  • 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.
  • the optical display device 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.
  • THRULYA 5320 JGC Catalyst and chemicals LTD
  • a hollow silica-containing sol 2.75 g of M306 (TOAGOSEI)
  • TOAGOSEI TOAGOSEI
  • a fluorine-free monomer was completely dissolved to obtain a mixture.
  • 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.
  • 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.
  • 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 °C, 100mJ / cm 2 in a nitrogen atmosphere It hardened
  • 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 °C, 100mJ / cm 2 in a nitrogen atmosphere It hardened
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the antireflection film composition of the present invention was able to implement an antireflection film having excellent optical properties and good scratch resistance.
  • 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.

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Abstract

L'invention concerne une composition de film antireflet, un film antireflet formé à partir de celle-ci, une plaque polarisante le comprenant, et un dispositif d'affichage optique le comprenant, la composition comprenant: un composé de formule chimique 1; un composé de formule chimique 2; un composé durcissable aux UV; un agent antistatique; un initiateur; et de la zircone.
PCT/KR2016/015363 2016-09-28 2016-12-28 Composition de film antireflet, film antireflet formé à partir de celle-ci, plaque polarisante le comprenant, et dispositif d'affichage optique le comprenant WO2018062631A1 (fr)

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KR1020160125152A KR101955766B1 (ko) 2016-09-28 2016-09-28 반사방지 필름용 조성물, 이로부터 형성된 반사방지 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치
KR10-2016-0125152 2016-09-28

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WO2020091552A1 (fr) * 2018-11-02 2020-05-07 주식회사 엘지화학 Plaque de polarisation circulaire
KR102337211B1 (ko) 2019-03-12 2021-12-09 주식회사 엘지화학 반사 방지 필름, 편광판 및 디스플레이 장치

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JP2005257786A (ja) * 2004-03-09 2005-09-22 Fuji Photo Film Co Ltd 反射防止フィルムおよびその製造方法
KR20080050335A (ko) * 2006-12-01 2008-06-05 제이에스알 가부시끼가이샤 경화성 수지 조성물 및 반사 방지막
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