WO2018043839A1 - 반사방지 필름용 조성물, 이로부터 형성된 반사방지 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치 - Google Patents

반사방지 필름용 조성물, 이로부터 형성된 반사방지 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치 Download PDF

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WO2018043839A1
WO2018043839A1 PCT/KR2016/015315 KR2016015315W WO2018043839A1 WO 2018043839 A1 WO2018043839 A1 WO 2018043839A1 KR 2016015315 W KR2016015315 W KR 2016015315W WO 2018043839 A1 WO2018043839 A1 WO 2018043839A1
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antireflection film
composition
formula
layer
refractive index
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PCT/KR2016/015315
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English (en)
French (fr)
Korean (ko)
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박세현
임형태
조성흔
민경준
오부근
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삼성에스디아이 주식회사
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Priority to CN201680090468.1A priority Critical patent/CN109923165B/zh
Publication of WO2018043839A1 publication Critical patent/WO2018043839A1/ko

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5398—Phosphorus bound to sulfur
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • 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
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • 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 technology for manufacturing an antireflection film by including a hard coating layer having a hard coating function and an inorganic particle on a substrate layer and sequentially laminating a high refractive layer having a high refractive index and an antistatic function and a low refractive layer has been developed. However, this consisted of three coating layers, resulting in the complexity of antireflective film production.
  • the problem to be solved by the present invention is to provide a composition for an antireflective film, which is excellent in the hard coat function and 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.
  • Another problem to be solved by the present invention is to provide an anti-reflection film that can implement an antistatic function, a mechanical property and an anti-reflection function in two layers, which was conventionally implemented in three layers.
  • the antireflective film composition of the present invention may include a compound of Formula 1, a UV curable compound, an antistatic agent and an initiator:
  • R 1 , R 2 , Ar 1 , X 1 , X 2 , Y 1 , Y 2 , n 1 , and n 2 are as defined in the following detailed description of the invention).
  • a substrate layer, a high refractive layer, and a low refractive layer are sequentially stacked, the high refractive layer has a higher refractive index than the low refractive layer, and the antireflective film has a minimum reflectance of about 0.6% or less,
  • the surface resistance of the low refractive layer may be about 9 x 10 10 Pa / ⁇ or less.
  • 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.
  • the present invention provides an anti-reflection film that can implement the antistatic function, mechanical properties and anti-reflection functions in two layers, which were implemented in the existing three layers.
  • 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" of the antireflective film herein is prepared by laminating a CL-885 black acrylic sheet of Nitto resin with a pressure sensitive 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 measured specimens were measured at a wavelength of 320 nm to 800 nm in a reflection mode with a reflectometer, and mean the lowest values of reflectance measured at wavelengths of 440 nm to 550 nm.
  • the "average reflectance" of the laminate of the high refractive index layer and the base layer is a laminate of CL-885 black acrylic sheet of Nitto resin with a pressure-sensitive adhesive having a refractive index of 1.46 to 1.50 on the base layer side of the laminate of the high refractive layer and the base layer. (The adhesive and the substrate layer are laminated) measured in the reflection mode with a wavelength range of 320nm to 800nm in the reflection mode, 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 antireflection film may include a compound of Formula 1, a UV curable compound, an antistatic agent and an initiator.
  • 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 this embodiment may include a compound of Formula 1 and a UV curable compound together, thereby increasing the refractive index of the high refractive layer to significantly lower the minimum reflectance of the antireflection film.
  • the refractive index of the high refractive index layer can be increased and chargeability can be ensured.
  • the composition for an antireflective film may have a refractive index of about 1.570 to about 1.680, specifically about 1.575 to about 1.645. Within this range, the refractive index of the high refractive layer can be increased.
  • the composition for antireflection films can raise the average reflectance of the laminated body of the hardened
  • the laminate of the cured product of the composition for antireflection film and the base layer may have an average reflectance of 6.0% or more, for example, 6.0% or more and 8.0% or less.
  • the minimum reflectance may be 0.6% or less, preferably 0.5% or less, more preferably 0.4% or less.
  • 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 antireflection film and the base layer may have a pencil hardness of about 2H or more, for example, about 2H or more and about 3H or less. In the above range, the hardness of the antireflection film can be increased.
  • 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 1.65 or more, specifically about 1.65 to about 1.80, more specifically about 1.65 to about 1.75. Can be. Within this range, the refractive index of the cured product can be increased to lower the lowest reflectance of the antireflective film:
  • R 1 and R 2 are each independently an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylarylene group having 7 to 20 carbon atoms, and Ar 1 is an alkyl group having 6 to 10 carbon atoms.
  • An aryl group, X 1 and X 2 are each independently —O— or —S—, and Y 1 and Y 2 are each independently a hydrogen atom, —OH, —SH, —NH 2 , or
  • R 3 is a hydrogen atom or a methyl group
  • X 3 is —O— or —N (R) —
  • R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • * represents a bonding site
  • n 1 and n 2 are each independently 1 to 4).
  • X 3 may be —O— or —N (R) — (R: a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
  • R a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the lowest reflectance can be lowered to about 0.6% or less upon lamination of the UV curable compound, in particular the urethane (meth) acrylate described below and the low refractive layer described below.
  • the compound of Formula 1 may be represented by any one of the following Formula 1-1 to 1-6.
  • the compound of Formula 1 may include any one of the following Formulas 1a to 1e:
  • Me is a methyl group
  • the compound of Formula 1 may be included in about 30% by weight to about 70% by weight based on solids in the composition for antireflection film.
  • the refractive index of the high refractive layer can be increased to about 1.58 or more, for example, 1.60 or more.
  • the compound of Formula 1 may be about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42,43, 44, based on solids in the composition for antireflective film.
  • the reflectance is high, the minimum reflectance at the time of lamination with the low refractive layer can be sufficiently lowered, and the hardness of the anti-reflection film can ensure a pencil hardness level of 2H.
  • 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 compound of Formula 1 may be synthesized using conventional synthetic methods known to those skilled in the art.
  • the UV curable compound has a lower refractive index than the compound of Formula 1.
  • a UV curable compound can form the matrix of a high refractive layer, and can raise the hardness of a high refractive layer.
  • 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 for example, bifunctional to 10 functional urethane (meth) acrylate to increase the refractive index and hardness when combined with the compound of the formula (1), but the low refractive layer laminated The minimum reflectance can be lowered.
  • 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 tris2-hydroxyethylisocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylic Trifunctional (meth) acrylate compounds such as acrylate and ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra ( Meth) acrylate, dipentaerythritol
  • a polyfunctional urethane (meth) acrylate can be preferably used even in the reason that the desired molecular weight and molecular structure can be designed and the balance of the physical properties of the high refractive layer formed can be easily taken.
  • Polyfunctional urethane (meth) acrylate is synthesize
  • 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.
  • 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 may be included in about 20% by weight to about 60% by weight based on solids in the antireflective film composition.
  • the minimum reflectance at the time of lamination with the low refractive layer can be sufficiently lowered, and the pencil hardness of the antireflection film can be secured to 2H or more.
  • 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 may be included in about 2% by weight to about 10% by weight based on solids in the antireflective film composition. In the above range, the antistatic effect may come out and may not significantly affect the hardness of the antireflection film. Preferably about 3% to about 7% by weight, for example about 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight. In the above range, there may be no deterioration in physical properties such as hardness of the antireflection film and no migration.
  • the initiator may form a high refractive layer by curing the compound of Formula 1 and the 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 by only curing the compound of Formula 1 and the UV curable compound by using an initiator having an absorption wavelength of about 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% by weight to about 5% by weight based on solids in the composition for 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.
  • composition for antireflection film may further include conventional additives known to those skilled in the art.
  • antifoaming agents antioxidants, ultraviolet absorbers, light stabilizers and the like may be further included, 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 0.6% or less, preferably about 0.5% or less, about 0.4% or less, for example, about 0% or more and about 0.5% or less, the pencil hardness of the surface resistance in all of 2H or higher, for example at least about 2H about 3H or less, the low refractive layer, for about 9 x 10 10 ⁇ / ⁇ or less for example, may be about 7 x 10 9 ⁇ / ⁇ 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.
  • 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 may have a refractive index of about 1.580 or more and about 1.680 or less, for example, about 1.580 to about 1.635 and 1.600 to about 1.635. 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 6.0% or more, for example, about 6.0% or more and about 8.0% 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 0.2 or less, preferably about 0.1 or more and about 0.2 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, 0.16, 0.17, 0.18, 0.19, 0.2. Within this range, the rainbow can be made invisible.
  • 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, more specifically about 3 ⁇ m to about 10 ⁇ m, and 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 difference in refractive index between the high refractive index layer 130 and the low refractive index layer 120 may be about 0.2 or more, for example, about 0.2 or more and about 0.4 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 1.32 or less, for example, about 1.27 or more and about 1.31 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, more specifically about 80 nm to about 150 nm, about 100 nm to about 130 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 1.20 to about 1.38.
  • Hollow silica may be used for the inorganic particles.
  • the inorganic particles may be untreated hollow particles that are not surface treated, or may be surface treated with a UV curable functional group.
  • the average particle diameter (D50) of the inorganic particles 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 index 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 slip or antifouling function 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 a silicone-based additive and a fluorine-based additive. UV curable fluorinated acrylic compounds.
  • 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, fluorine-free monomer or oligomer thereof about 5% to about 25% by weight for example about 5 , 6, 7,
  • the pencil hardness of about 2H or more level, anti-fingerprint effect can be obtained.
  • 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 and the like may be further included, 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 include 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.
  • EtOAC ethyl acetate
  • reaction solution was filtered to remove the amine salt, cooled to 0 ° C., 21.3 g (210 mmol) of triethylamine was added, and 18.6 g (205 mmol) of acryloyl chloride was diluted with 100 mL of THF. The solution was slowly added and reacted by stirring at 0 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered to remove the amine salt and distilled under reduced pressure to remove excess solvent.
  • a compound represented by the following Chemical Formula 1d was prepared in the same manner as in Preparation Example 3, except that 25.23 g (200 mmol) of 4-hydroxybenzenethiol was used instead of 4-aminobenzenethiol.
  • 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 added and completely dissolved to obtain a mixture.
  • 51.7 g of AR-110 (DAIKIN) a fluorine-containing monomer
  • 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.
  • 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 at 80 ° C. for 2 minutes, the mixture was cured at a light quantity of 150 mJ / cm 2 in a nitrogen atmosphere.
  • the low refractive index layer of Preparation Example 6 was coated on the obtained coating layer using No. 4 Mayer bar, dried at 80 ° C.
  • a base layer (thickness: 60 On the micrometer, refractive index: 1.485), an antireflection film having a three-layer structure in which a high refractive index layer (thickness: 8 ⁇ m, a refractive index is in Table 1 below) and a low refractive layer (thickness: 130 nm) were sequentially stacked.
  • a composition for a high refractive index layer was prepared in the same manner as in Example 1, except that 16 g of the compound of Formula 1b of Preparation Example 2 was used instead of 16 g of the compound of Formula 1a of Preparation Example 1.
  • An antireflection film was prepared in the same manner as in Example 1 using the prepared high refractive index composition.
  • a composition for a high refractive index layer was prepared in the same manner as in Example 1, except that 16 g of the compound of Formula 1c of Preparation Example 3 was used instead of 16 g of the compound of Formula 1a of Preparation Example 1.
  • An antireflection film was prepared in the same manner as in Example 1 using the prepared high refractive index composition.
  • a composition for a high refractive index layer was prepared in the same manner as in Example 1, except that 16 g of the compound of Formula 1d of Preparation Example 4 was used instead of 16 g of the compound of Formula 1a of Preparation Example 1.
  • An antireflection film was prepared in the same manner as in Example 1 using the prepared high refractive index composition.
  • a composition for a high refractive layer was prepared in the same manner as in Example 1, except that 16 g of the compound of Formula 1e of Preparation Example 5 was used instead of 16 g of the compound of Formula 1a of Preparation Example 1.
  • An antireflection film was prepared in the same manner as in Example 1 using the prepared high refractive index composition.
  • Refractive index of the composition for a high refractive index layer and the refractive index of a high refractive layer In the case of the high refractive layer composition of an Example and a comparative example, after drying a solvent, it measured by the Abbe refractive index meter.
  • the refractive index of the high refractive layer formed from the composition for high refractive layers of Examples and Comparative Examples was measured by a general Abbe refractive index meter.
  • the substrate layer of the specimen was laminated on a CL-885 black acrylic sheet of Nitto resin having an adhesive having a refractive index of 1.46 to 1.50 on one side thereof, and measured by Perkin Elmer's UV / 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.
  • the antireflection film composition of the present invention can significantly lower the lowest reflectance of the antireflection film compared to the high refractive index compound having a similar refractive index by the compound of formula (1).

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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PCT/KR2016/015315 2016-08-31 2016-12-27 반사방지 필름용 조성물, 이로부터 형성된 반사방지 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치 WO2018043839A1 (ko)

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KR20160000102A (ko) * 2014-06-23 2016-01-04 제일모직주식회사 광학시트, 이를 위한 광학패턴 형성용 조성물, 이를 포함하는 복합광학시트 및 이를 포함하는 광학표시장치
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