WO2017043948A1 - Film anti-reflet et dispositif d'affichage - Google Patents

Film anti-reflet et dispositif d'affichage Download PDF

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Publication number
WO2017043948A1
WO2017043948A1 PCT/KR2016/010272 KR2016010272W WO2017043948A1 WO 2017043948 A1 WO2017043948 A1 WO 2017043948A1 KR 2016010272 W KR2016010272 W KR 2016010272W WO 2017043948 A1 WO2017043948 A1 WO 2017043948A1
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WO
WIPO (PCT)
Prior art keywords
film
compound
substituted
fine particles
fluorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2016/010272
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English (en)
Korean (ko)
Inventor
장영래
심재훈
서정현
박진영
이수경
구재필
김태순
김민수
홍경기
문주종
이혜민
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LG Chem Ltd
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LG Chem Ltd
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Filing date
Publication date
Priority claimed from KR1020160116740A external-priority patent/KR102018287B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP16844764.7A priority Critical patent/EP3299851B1/fr
Priority to CN201680041085.5A priority patent/CN107850692B/zh
Priority to JP2018521166A priority patent/JP6683374B2/ja
Priority to US15/739,586 priority patent/US10690810B2/en
Publication of WO2017043948A1 publication Critical patent/WO2017043948A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/16—Halogens
    • C08F12/20—Fluorine
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
    • 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
    • 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

Definitions

  • the present invention relates to an antireflection film and a display device. More particularly, the present invention relates to an antireflection film having excellent sparkability, high visibility, and excellent workability when manufacturing a display, and excellent external black vision and contrast ratio. A display device that provides characteristics and high screen sharpness.
  • a flat panel display device such as a PDP or LCD is equipped with an antireflection film for minimizing reflection of light incident from the outside.
  • a method for minimizing the reflection of light a method of dispersing a filler such as inorganic fine particles in a resin and coating on a base film and imparting irregularities (ant i-gl are: AG coating);
  • the absolute amount of reflected light is equivalent to that of a general hard coating, but a low reflection effect can be obtained by reducing the amount of light entering the eye by using light scattering through unevenness.
  • the AG coating is inferior in the clarity of the screen due to the surface irregularities, a lot of research has been made recently in the AR coating.
  • the film using the AR coating is a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, etc. are laminated on a base film. It is commercialized. However, in the case of a clear coating having no irregularities on the surface, the effect of preventing glare is not sufficient and defects in the display are easily seen, and thus the yield is low.
  • the reflectance inside the panel is increased by the metal included in the electrode, and the optical characteristics of the display such as the external black luminous contrast and the contrast ratio are deteriorated.
  • the present invention is to provide an anti-reflection film is less sparkling phenomenon when applied to a high-resolution display, excellent visibility and excellent workability when manufacturing the display.
  • an object of the present invention is to provide a display device that provides excellent external characteristics, such as black vision and contrast ratio, and high screen sharpness.
  • the 10-point average roughness (Rz) of the concave-convex shape of the surface is 0.0 an to 0.2 / kPa and the internal haze of 0.5% to 53 ⁇ 4 hard coating layer; And a low refractive layer formed on the hard coating layer is provided.
  • the ten-point average roughness (Rz) of the concave-convex shape on the surface of the hard coating layer is a result measured using a non-contact surface shape measuring instrument (3D Opt i Cal Prof ler).
  • the average value of the ratios of the respective luminous values at angles of +1 degrees and -1 degrees from the specular reflection relative to the specular luminous intensity value is 0.005 to 0. 100, or 0.010 to 0.080.
  • the result of the diffusion distribution of the reflective light source for the antireflective film applies an angle of incidence of 45 ° .
  • the specular reflectance value is the reflected diffuse intensity value at 45 degrees corresponding to the specular reflection of the incident angle.
  • the antireflection film may have a reflectance of about 1.6% or less in a wavelength range of 380 nm to 780 nm.
  • the hard coating layer may include a binder resin including a (co) polymer of a photopolymerizable compound and organic or inorganic fine particles dispersed in the binder resin.
  • the organic or inorganic fine particles may be spherical particles having a particle diameter of 0.5 to 10 mm 3, or 0.5 to 5, preferably 1 to 5 urn, more preferably 1 to 3 /.
  • the hard coating layer may include two or more organic or inorganic fine particles, and the refractive index difference between at least two of the two or more organic or inorganic fine particles may be 0.01 to 0.08.
  • the hard coating layer may include 1 to 20 parts by weight of the organic or inorganic fine particles with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
  • the binder resin of the hard coating layer may further include a high molecular weight (co) polymer having a weight average molecular weight of 10,000 or more.
  • the hard coating layer may further include inorganic nanoparticles having a diameter of 1 nm to 150 nm, or 5 mm to 120 nm.
  • the low refractive index layer may include a binder resin including a fluorine-containing compound or a silicon-based compound including a (co) polymer of the photopolymerizable compound and a photoreactive functional group.
  • the photopolymerizable compound may include a monomer or oligomer including a (meth) acrylate or a vinyl group.
  • the photoreactive functional group included in the fluorine-containing compound or silicon-based compound may include at least one functional group selected from the group consisting of (meth) acrylate groups, epoxide groups, vinyl groups (Vinyl), and thiol groups (Thi ol). have.
  • the fluorine-containing compound comprising the photo-banung functional group is i) one or more Aliphatic compounds or aliphatic ring compounds in which a photoreactive functional group is substituted and at least one fluorine is substituted for at least one carbon; ii) a hetero aliphatic compound or a heteroaliphatic ring compound substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; iii) a polydialkylsiloxane polymer in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; And iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine;
  • the anti-reflection film may further include inorganic fine particles dispersed in the binder resin.
  • the inorganic fine particles included in the low refractive layer are selected from the group consisting of hollow inorganic fine particles having a number average particle diameter of 10 to 200 nm and solid inorganic fine particles having a number average particle diameter of 0.5 to 10 nm. It may include more than one species.
  • the low refractive layer may include 10 to 400 parts by weight of the inorganic fine particles and 20 to 300 parts by weight of the silicon-based compound including the photoreactive functional group with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
  • the binder resin of the low refractive index layer may further include a polysilsesquioxane substituted with at least one semi-functional functional group.
  • the low refractive index layer may include 0.5 to 40 parts by weight of polysilsesquioxane substituted with at least one semi-aromatic functional group relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
  • a display device including the anti-reflection film may be provided.
  • the display device includes a pair of polarizing plates facing each other; A thin film transistor, a curly filter, and a liquid crystal cell sequentially stacked between the pair of polarizing plates; And a liquid crystal display device including a backlight unit.
  • the anti-reflection film may be formed between the other surface of the polarizer in contact with the liquid crystal cell or between the polarizer and the backlight unit.
  • a high-resolution display display device that provides a high screen sharpness, such as an anti-reflection film with excellent visibility and excellent workability when manufacturing a display, excellent external bluishness and contrast ratio, and high screen clarity May be provided.
  • the anti-reflective film may be applied to a high resolution display to provide high panel hiding power and excellent antireflection performance and visibility.
  • the antireflection performance can be exhibited by applying to a COT panel having a high internal reflectance of the panel.
  • FIG. 1 schematically shows a cross section of a liquid crystal display device provided with an antireflection film of Example 1.
  • the photopolymerizable compound is collectively referred to as a compound that causes polymerization reaction when irradiated with light, for example, visible light or ultraviolet light.
  • a fluorine-containing compound means the compound containing at least 1 or more fluorine elements among the compounds.
  • (meth) acryl [(Meth) acryl] is meant to include both acryl and Methacryl.
  • (co) polymer is meant to include both co-polymers and homo-polymers.
  • hollow silica particles are silica particles derived from a silicon compound or an organosilicon compound, and mean particles having a void space on the surface and / or inside of the silica particles. do.
  • the ten-point average roughness (Rz) of the concave-convex shape of the surface is 0.05 Pa to 0.2 and the internal haze of 0.5% to 5% hard coating layer; And a low refractive layer formed on the hard coating layer may be provided.
  • the coating layer having fine concavo-convex is commonly referred to as an AG coating layer and has a concave-convex structure of several hundred nm to several heights.
  • the film having the uneven structure is excellent in the antireflection effect because it can induce diffuse reflection when light enters from the outside, but the image from the inside is also distorted at the surface, causing the problem of deterioration of the sharpness or resolution of the image.
  • the image distortion is severe in a high resolution display of ultra high def initon (UHD) or higher, it is necessary to control the uneven structure.
  • the present inventors have derived an optimal surface uneven structure that can simultaneously implement the anti-reflection effect and visibility.
  • the surface roughness of the antireflection film is represented by the ten-point average roughness Rz of the surface irregularities.
  • the 10-point average roughness refers to the difference between the average values of the five highest height peaks and the five lowest valleys within the measurement length in the surface unevenness curve.
  • the Rz which is the height of the 10-point unevenness
  • the 10-point average roughness of the concave-convex shape of the surface of the hard coating layer is less than 0.05 ⁇ , the anti-reflective effect and the poor hiding power of the panel are lowered. If the 10-point average roughness of the concave-convex shape of the surface of the hard coating layer is more than 0.2, the resolution decreases like sparking. The phenomenon and sharpness may be degraded.
  • Rz 10-point average roughness
  • the internal haze of the hard coating layer is 0.5% to 53 ⁇ 4, it was possible to improve the hiding power of panel defects while maintaining clarity. Hard If the internal haze of the coating layer is less than 0.5%, the panel hiding power may be lowered. If the internal haze of the hard coating layer is more than 5%, the visibility may be reduced, such as a decrease in contrast ratio.
  • the ratio of the respective luminous values at angles of +1 degree and -1 degree from the specular reflection to the specular luminous intensity value as a result of the diffuse distribution of the reflecting light source for the antireflective film is at least 0.005, or 0.005 to 0. 100, or 0.010 To 0.080.
  • the diffused light distribution of the reflected light source may be measured.
  • the hiding power of the display device panel is good when the ratio of each luminous value at an angle of +1 degree and -1 degree from the specular reflection to the specular luminous intensity value as a result of the diffusion distribution of the reflecting light source to the antireflective film is 0.005 or more. On the contrary, when the ratio is less than 0.005, the rate at which light is diffused may be greatly reduced, and the hiding power of the display apparatus panel may also be poor.
  • the diffusion distribution of the reflective light source represented by the anti-reflection film is incident when the incident light is introduced at a predetermined angle with respect to the normal direction of the film, for example, 30 degrees to 60 degrees, or 45 degrees, and is diffusely reflected.
  • the light can be obtained by measuring in a predetermined range, for example, in a range of -85 degrees to 85 degrees based on the normal direction of the surface of the anti-reflection film.
  • the diffused light distribution may be measured using a photo-goniometer, and the specific measuring device is not limited, but for example, the reflected diffuse intensity may be measured using r GP-200j manufactured by Murakami Color Industry Co., Ltd. It can be measured.
  • the specular reflectance value is the reflected diffuse intensity value at 45 degrees corresponding to the specular reflection of the incident angle.
  • the specular reflectance value may be 75 to 95, or 80 to 90. If the anti-reflection film has a specular reflectance value of 75 to 95, the color may be clearly realized, and a clear image without distortion of the hard surface may be realized. On the contrary, if the luminance value is too small, light scattering may increase, resulting in low image and color clarity. In addition, if the brightness value is too large, hiding power, such as the transparent electrode of the panel is visible can be greatly reduced.
  • the surface roughness includes a hard coating layer having a ten-point average roughness Rz of 0.05 to 0 ffli and an internal haze of 0.53 ⁇ 4> to 5) and a low refractive layer formed on the hard coating layer.
  • the antireflection film may exhibit an average reflectance of 1.6% or less in the wavelength range of 380 nm to 780 nm. Accordingly, the anti-reflection film can maximize the anti-reflection function, and can suppress a decrease in visibility due to external light in a COT panel.
  • the ten-point average roughness (Rz) and the internal haze of the concave-convex shape of the surface of the hard coating layer can be adjusted by the composition of the composition forming the hard coating layer and the hard coating layer forming method.
  • the hard coating layer may be formed from a hard coating composition including a photo-synthesizing compound, a photoinitiator and organic fine particles or inorganic fine particles.
  • the hard coating layer may include a binder resin including a (co) polymer of a photopolymerizable compound and organic or inorganic fine particles dispersed in the binder resin.
  • the photopolymerizable compound included in the hard coating composition forming the hard coating layer may be a photopolymerization type / photocurable compound that may cause polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art.
  • the (co) polymers include urethane acrylate oligomers, epoxide acrylate oligomers, polyester acrylates, and polyether acrylates. Reactive acrylate oligomer group; And dipentaerythri nucleoacrylate, dipentaerythri hydroxy pentaacrylate, pentaerythri tetraacrylate, pentaerythri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol tree Multifunctional acrylate consisting of acrylate, trimethylpropane specific triacrylate, 1, 6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may be a (co) polymer formed from one or more selected from the group of monomers.
  • the hard coating layer includes organic or inorganic fine particles together with the (co) polymer of the photopolymerizable compound to impart surface irregularities and internal haze.
  • the organic or inorganic fine particles have a particle diameter of 0.5 to 10 / m, or 0. It may be a spherical particle of 5 to 5, preferably 1 to 5 urn, more preferably 1 to 3 m.
  • the particle diameter of the organic or inorganic fine particles may be 0.5 p or more to express surface irregularities and internal haze, and may be 10 mi or less in terms of haze or coating thickness.
  • the coating thickness must be increased to match the fine surface irregularities, which may cause a problem that the crack resistance of the film is lowered.
  • the organic or inorganic fine particles are not limited.
  • the organic or inorganic fine particles may be organic fine particles made of acrylic resin, styrene resin, epoxide resin and nylon resin, or may be silicon oxide, titanium dioxide, indium oxide, or oxide.
  • Inorganic fine particles consisting of tin, zirconium oxide, and zinc oxide.
  • the hard coating layer may include 1 to 20 parts by weight of the organic or inorganic fine particles, or 5 to 15 parts by weight, preferably 6 to 10 parts by weight, relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
  • the organic or inorganic fine particles When the organic or inorganic fine particles are contained in less than 1 part by weight with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound, by internal scattering Haze values may not be implemented sufficiently. In addition, when the organic or inorganic fine particles exceed 20 parts by weight with respect to 100 parts by weight of the (co) polymer of the photopolymerizable compound, the viscosity of the coating composition becomes high, resulting in a problem of poor coating properties.
  • the refractive index of the organic or inorganic fine particles has a difference from the refractive index of the photocurable resin forming the matrix.
  • the difference in the proper refractive index is determined according to the content of the particles, and it is preferable that the refractive index difference is 0.01 to 0.08. If the difference in refractive index between the fine particles and the photocurable resin is less than 0.01, it may be difficult to obtain an appropriate haze value. In addition, when the difference in refractive index between the fine particles and the photocurable resin is more than 0.08, a very small amount of particle content should be used to obtain a desired level of surface irregularities.
  • the organic or inorganic fine particles may be an organic fine particle group consisting of an acrylic resin, a styrene resin, an epoxy resin, a nylon resin, and a copolymer resin thereof; And inorganic fine particles selected from the group consisting of silicon oxide, titanium dioxide, indium oxide, tin oxide, zirconium oxide, and zinc oxide.
  • the organic fine particles are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth).
  • the organic fine particles are polystyrene, polymethylmethacrylate polymethylacrylate, polyacrylate, polyacrylate -co-styrene polymethylacrylate -co-styrene, polymethylmethacrylate -co-styrene polycarbonate, Polyvinyl chloride, polybutylene terephthalate polyethylene terephthalate, polyamide, polyimide, polysulfone polyphenylene oxide, polyacetal, epoxy resin, phenol resin, silicone resin melamine resin, benzoguamine, polydivinylbenzene , A single substance selected from polydivinylbenzene-co-styrene polydivinylbenzene-CO-acrylate, polydiallylphthalate and triallyl isocyanurate polymer or a combination thereof
  • Two or more copolymers may be used, but the present invention is not limited thereto.
  • the hard coating layer may further comprise inorganic nanoparticles having a diameter of 1 nm to 150 nm, or 5 nm to 120 nm. Certain functional groups or compounds may be bonded to the surface of the inorganic nanoparticles.
  • the shape of the surface irregularities of the hard coating layer may be smoothly adjusted and the mechanical properties of the coating layer may be improved.
  • the content of the inorganic nanoparticles may be used 10 parts by weight or less per 100 parts by weight of the (co) polymer of the photopolymerizable compound.
  • silicon oxide, alumina, titania, or the like may be used as specific types of the inorganic nanoparticles.
  • the hard coating composition forming the hard coating layer may include a photoinitiator, and the photoinitiator may be a photoinitiator that is commonly known without any significant limitation.
  • the photoinitiator are selected from 1-hydroxycyclonucleophenylphenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether.
  • One single or two or more combinations may be used, but the invention is not limited to the examples described above.
  • the photoinitiator is 0.1 to 100 parts by weight of the photopolymerizable compound. To 10 parts by weight may be added.
  • the photoinitiator is contained in an amount of less than 0.01 part by weight based on 100 parts by weight of the photopolymerizable compound, layered photocuring may not occur due to ultraviolet irradiation, and more than 10 parts by weight based on 100 parts by weight of the photopolymerizable compound.
  • the film strength of the anti-glare film may be reduced.
  • the hard coating composition forming the hard coating layer may further include an organic solvent.
  • an organic solvent is added, the configuration thereof is not limited, but in consideration of securing the proper viscosity of the coating composition and the film strength of the film to be finally formed, it is preferably 50 to about 100 parts by weight of the photocurable resin. 500 parts by weight, more preferably 100 to 400 parts by weight, most preferably 150 to 350 parts by weight may be used.
  • the type of organic solvent that can be used is not limited in its constitution, but lower alcohols of 1 to 6 carbon atoms, acetates, ketones, cellosolves, dimethylformamide, tetrahydrofuran, propylene glycol monomethyl ether, One or more mixtures selected from the group consisting of luene and xylene can be used.
  • the lower alcohols may include methanol, ethanol isopropyl alcohol, butyl alcohol, isobutyl alcohol, diacetone alcohol and the like, but the present invention is not limited to the above examples.
  • the acetate may be methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, or cellosolve acetate
  • the ketones may be methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, or acetone.
  • the hard coating composition for forming the hard coating layer may further comprise at least one additive selected from the group consisting of additives, leveling agents, wetting agents, antifoaming agent.
  • the additive may be added in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the photopolymerizable compound, respectively.
  • the leveling agent serves to make the surface of the coated coating film uniform by using an anti-glare coating composition.
  • the wetting agent serves to lower the surface energy of the anti-glare coating composition, When the anti-glare coating composition is coated on the transparent substrate layer, it helps to achieve a uniform application.
  • the antifoaming agent may be added to remove the bubbles in the anti-glare coating composition.
  • the hard coating layer may have a thickness of 0.5 m to 100.
  • the low refractive index layer may be prepared using a photocurable coating composition comprising a photopolymerizable compound, a fluorine-containing compound or a photo-based compound containing a photoreactive functional group and a photoinitiator.
  • the antireflection film including the low refractive index layer can improve the wear resistance or scratch resistance while lowering the reflectance and increasing the light transmittance, and at the same time, it can secure excellent antifouling property against external contaminants.
  • the low refractive layer may include a binder resin containing a fluorine-containing compound or a silicon-based compound containing a (co) polymer of the photopolymerizable compound and a photobanung functional group.
  • the photopolymerizable compound may include a monomer or oligomer including a (meth) acrylate or a vinyl group.
  • the photopolymerizable compound may include a monomer or oligomer containing at least one, or at least two, or at least three (meth) acrylate or vinyl groups.
  • the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythrione nucleated (meth) acrylate, Tripentaerythrione hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethyl propane tri (meth) acrylate, trimethyl All propane polyethoxy tri (meth) acrylate, trimethyl to propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more combinations thereof Or urethane modified acrylate oligomer Hitting the side-acrylate Murray
  • the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyrene.
  • the photopolymerizable compound may further include a fluorine-based (meth) acrylate-based compound in addition to the above-described monomer or oligomer.
  • a fluorine-based (meth) acrylate-based compound in addition to the above-described monomer or oligomer.
  • the weight ratio of the fluorine-based (meth) acrylate compound to the monomer or oligomer containing the (meth) acrylate or vinyl group is from 0.13 ⁇ 4> to 10% Can be.
  • fluorine-based (meth) acrylate-based compound may include at least one compound selected from the group consisting of the following Chemical Formulas 1 to 5.
  • R 1 is a hydrogen group or an alkyl group having 1 to 6 carbon atoms, a is an integer of 0 to 7, b is an integer of 1 to 3.
  • the integer is 1 to 10.
  • d is an integer of 1 to 11.
  • e is an integer of 1 to 5.
  • f is an integer of 4 to 10.
  • the fluorine-containing compound or silicon-based compound containing the photo-reflective functional group may include or replace one or more photo-reflective functional groups, the photo-reflective functional group by irradiation of light, for example by irradiation of visible light or ultraviolet It means a functional group capable of participating in the polymerization reaction.
  • the photo-reflective functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include (meth) acrylate groups, epoxide groups, vinyl groups, or cyclo groups ( Thiol) is mentioned.
  • Each of the fluorine-containing compound or the silicon-based compound including the photo-banung functional group has a weight average molecular weight of 2, 000 to 200,000, preferably 5,000 to 100, 000 (weight average molecular weight in terms of polystyrene measured by GPC method).
  • the weight average molecular weight of the fluorine-containing compound or the silicon-based compound including the photo-reflective functional group is too high, the compatibility with other components in the photocurable coating composition may be lowered, thereby resulting in low refractive haze
  • the light transmittance may be increased or the light transmittance may be decreased, and the strength of the low refractive index layer may also be reduced.
  • the fluorine-containing compound including the photo-cyclic functional group is i) an aliphatic compound or aliphatic ring compound in which at least one photo-cyclic functional group is substituted, at least one fluorine is substituted in at least one carbon; i i) a heteroaliphatic compound or a heteroaliphatic ring compound substituted with one or more photocyclic functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; i i i) polydialkylsiloxane polymers (eg, polydimethylsiloxane polymers) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine, or a mixture of two or more of the above i) to iv) or a copolymer thereof.
  • the photocurable coating composition may include 20 to 300 parts by weight of the fluorine-containing compound or silicon-based compound based on 100 parts by weight of the photopolymerizable compound.
  • the fluorine-containing compound including the photobanung functional group may further include silicon or a silicon compound. That is, the fluorine-containing compound including the photo-cyclic functional group may optionally contain a silicon or a silicon compound therein, specifically, of the silicon-containing fluorine-containing compound including the photo-cyclic functional group
  • the content may be from 0.1 wt% to 20 wt%.
  • the anti-reflection film may further include inorganic fine particles dispersed in the binder resin.
  • the inorganic fine particles included in the low refractive index layer in the group consisting of hollow inorganic fine particles having a number average particle diameter of 10 to 200 nm and solid inorganic fine particles having a number average particle diameter of 0.5 to 10 nm may include one or more selected.
  • the solid inorganic fine particles refer to particles having a maximum diameter of microns or nano units and having no empty space therein. Specific examples of the solid inorganic fine particles include nano silica particles.
  • the hollow inorganic fine particles refers to particles having a maximum diameter of microns or nano units and having a void space on the surface and / or inside thereof.
  • Specific examples of the hollow inorganic fine particles include hollow silica particles.
  • the hollow silica particles are silica particles derived from a silicon compound or an organosilicon compound, and mean particles having a void space on the surface and / or inside of the silica particles. .
  • the hollow silica particles, the inorganic fine particles have a number average particle diameter of 10 to 100 nm.
  • the hollow silica particles refer to silica particles having an empty space on the surface and / or inside of the particles.
  • the hollow silica particles may have a low refractive index compared to the hollow particles, thereby exhibiting excellent antireflection properties.
  • the hollow silica particles may have a number average particle diameter of 10 to 100 nm, preferably 20 to 70 nm, more preferably 30 to 70 nm;
  • the shape of the particles is preferably spherical, but may be irregular.
  • those whose surfaces are coated with a fluorine compound may be used alone, or may be used in combination with the hollow silica particles whose surface is not coated with a fluorine compound.
  • the surface of the hollow silica particles Coating with a fluorine-based compound can lower the surface energy, and thus the hollow silica particles can be more uniformly distributed in the photocurable coating composition of the embodiment, and the durability or scratch resistance of the film obtained from the photocurable coating composition You can improve your sex.
  • a particle coating method or a polymerization method commonly known as a method of coating a fluorine compound on the surface of the hollow silica particles can be used without any significant limitation.
  • the hollow silica particles and the fluorine compound may be solized in the presence of water and a catalyst. It is possible to bind the fluorine-based compound to the surface of the hollow silica particles by hydrolysis and condensation reaction by the gel reaction.
  • the hollow silica particles may be included in the composition in the form of a colloid dispersed in a predetermined dispersion medium.
  • the colloidal phase including the hollow silica particles may include an organic solvent as a dispersion medium.
  • the hollow silica may include a structure having a predetermined functional group on the surface in order to be more easily dispersed in the organic solvent.
  • organic functional groups that can be substituted on the surface of the hollow silica particles are not particularly limited, and examples thereof include (meth) acrylate groups, vinyl groups, hydroxy groups, amine groups, allyl groups, epoxy groups, hydroxy groups, isocyanate groups, An amine group or fluorine may be substituted on the hollow silica surface.
  • the solid content of the hollow silica particles in the colloidal phase of the hollow silica particles may be determined in consideration of the content range of the hollow silica or the viscosity of the photocurable coating composition in the photocurable coating composition of the embodiment, for example the colloidal phase Solid content of the hollow silica particles
  • alcohols such as methanol, isopropyl alcohol, ethylene glycol and butanol
  • Ketones such as methyl ethyl ketone and methyl isobutyl ketone
  • Aromatic hydrocarbons such as toluene and xylene
  • Dimethylformamide Amides such as dimethylacetamide N-methylpyridone; Esters such as ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or combinations thereof.
  • the low refractive layer is compared with 100 parts by weight of the (co) polymer of the photopolymerizable compound It may comprise 10 to 400 parts by weight, or 50 to 300 parts by weight of the inorganic fine particles.
  • the binder resin of the low refractive index layer may further include a polysilsesquioxane substituted with at least one semi-functional functional group.
  • the polysilsesquioxane in which one or more semi-functional functional groups are substituted may have a semi-functional functional group on the surface thereof, thereby improving mechanical properties of the low refractive layer, for example, scratch resistance.
  • the low refractive index layer may include 0.5 to 40 parts by weight of polysilsesquioxane, or 1.5 to 30 parts by weight, of at least one semi-aromatic functional group, relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
  • the coating film formed during photocuring of the photocurable coating composition when the content of the polysilsesquioxane substituted with at least one of the semi-aromatic functional groups is greater than that of the (co) polymer of the photopolymerizable compound in the photocurable coating composition.
  • the content of the polysilsesquioxane substituted with at least one reactive functional group in the photocurable coating composition compared to the photopolymerizable compound, the transparency of the low refractive index layer or the antireflection film prepared from the photocurable coating composition May be lowered, and scratchability may be lowered.
  • the reactive functional groups substituted in the polysilsesquioxane are alcohols, amines, carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, olepins [al ly, cycloalkenyl ( cyc loalkenyl) or vinyldimethylsilyl, etc.], polyethyleneglycol, cyclic and vinyl groups, and may include one or more functional groups, preferably epoxide or
  • the semi-functional group include (meth) acrylate, alkyl (meth) acrylate having 1 to 20 carbon atoms, cycloalkyl epoxide having 3 to 20 carbon atoms, and alkyl cycloalkane having 1 to 10 carbon atoms ( cycloalkane) epoxides.
  • the alkyl (meth) acrylate means that the other part of the 'alkyl' which is not bonded to the (meth) acrylate is a bonding position
  • the cycloalkyl Epoxide means that the other part of 1 cycloalkyl 'that is not bonded to the epoxide is a bonding position
  • alkyl cycloalkane epoxide is an' alkyl 'which is not bonded to a cyclo locane epoxide. This means that the other part of is the binding position.
  • the polysilsesquioxane substituted with one or more of the semi-active functional group is a linear or branched alkyl group of 1 to 20 carbon atoms, a cyclonuclear group of 6 to 20 carbon atoms and 6 to 20 carbon atoms in addition to the above-mentioned semi-functional functional group
  • At least one unreactive functional group selected from the group consisting of aryl groups may further include at least one.
  • the semi-functional and un- semi-functional functional groups are substituted on the surface of the polysilsesquioxane, so that the siloxane bond (-Si-0-) is in the molecule of the polysilsesquioxane in which the semi-functional functional group is substituted at least one. It can be located at and not exposed to the outside, so that it can be more compatible with other organic materials, and as the siloxane bond is firmly bonded between the semi-functional group or other organic materials, it is not separated by external pressure. It may serve as a solid support in the coating film or binder resin formed during photocuring of the photocurable coating composition, thereby greatly increasing the strength or scratch resistance of the low refractive layer or the antireflection film to be finally manufactured. .
  • the polysilsesquioxane may be expressed as (! ⁇ ⁇ ⁇ ⁇ (Where n is 4 to 30 or 8 to 20), and have a variety of structures, such as random, ladder, cage and partial cage Can be.
  • the semi-functional functional group is substituted with at least one semi-functional functional group and the cage ( Polyhedral oligomeric silsesquioxanes having a structure
  • the polyhedral oligomeric silsesquioxane having at least one functional group substituted and having a cage structure is a silicon in a molecule.
  • a polyhedral oligomer having the cage structure At least one or more of the silicon of the silsesquioxane may be substituted with a semi-male functional group, and the non-single-functional functional group may be substituted with the silicones in which the semi-male functional group is not substituted.
  • the mechanical properties of the coating film or the binder resin formed during photocuring of the photocurable coating composition may be improved.
  • the substitution of non-banung functional groups in the remaining silicon causes molecular structural steric hinderance, which significantly reduces the frequency or probability of exposing the siloxane bond (-Si-0-) to other organic materials.
  • the siloxane bond is firmly bonded between the semi-ungseong functional groups or other organic materials, so as not to be separated by the external pressure, which is formed during photocuring of the photocurable coating composition It can serve as a solid support inside the coating film or binder resin, La can greatly improve the final strength of the scratch resistance of the low refractive index layer or anti-reflection film and to be produced.
  • polyhedral oligomeric silsesquioxanes having one or more such semi-functional functional groups and having a cage structure
  • POSSs polyhedral oligomeric silsesquioxanes
  • TMP Diollsobutyl POSS Cyclohexanediol Isobutyl POSS, 1 and 2-Propanedi o.
  • POSS substituted with one or more alcohols such as 11 sobuty 1 POSS, Oct a (3 ⁇ hydroxy ⁇ 3 methylbutyldimethylsioxy) POSS; Aminopropyl Isobutyl POSS, Aminopropyl Isooctyl POSS,
  • POSS in which at least one amine is substituted such as AminophenylCyclohexyl POSS and Aminophenyl Isobutyl POSS; Maleamic Acid-Cyclohexyl POSS, Maleamic Ac id- Isobutyl
  • POSS in which at least one carboxylic acid is substituted such as POSS and Oct a Maleamic Acid POSS;
  • POSS substituted with at least one epoxide such as GlycidylEthyl POSS, Glycidyl Isobutyl POSS, Glycidyl Isooctyl POSS; POSS Maleimide Cy c 1 ohexy 1, POSS Maleimide Isobutyl, and the like.
  • POSS substituted with one or more (meth) acrylates POSS in which at least one nitrile group such as Cyanopropyl Isobutyl POSS is substituted; POSS in which at least one norbornene group is substituted, such as Norbornenyl ethyl Ethyl POSS, Norbornenyl ethyl Isobutyl POSS, Norbornenyl ethyl DiSi lanolsobutyl POSS, and Tr isnorbornenyl Isobutyl POSS; POSS substituted with at least one vinyl group such as Allyl Isobutyl POSS, MonoVinyl Isobutyl POSS, Oct aCy c 1 ohexeny 1 di me t hy 1 si 1 y 1 POSS, OctaVinyldimethylsiyl POSS, OctaVinyl POSS; POSS substituted with at least one olefin such as Al
  • the photopolymerization initiator may be used without limitation as long as it is a compound known to be used in the photocurable resin composition. Specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or the like may be used. Two or more kinds thereof can be used. With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight. If the amount of the photopolymerization initiator is too small, an uncured material remaining in the photocuring step of the photocurable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the non-aqueous initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or reflectance of the film.
  • the photocurable coating composition may further include an organic solvent.
  • organic solvents include ketones, alcohols, acetates and ethers, or combinations of two or more thereof. Specific examples of such organic solvents include methyl ethyl kenone, Ketones such as methyl isobutyl ketone, acetylacetone or isobutyl ketone; Methanol, ethanol ,.
  • alcohols such as n-propane, i-propanol, n-butanol, i-butanol, or t-butane; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or two or more kinds thereof.
  • the organic solvent may be included in the photocurable coating composition while being added at the time of mixing each component included in the photocurable coating composition or in the state in which each component is dispersed or mixed in the organic solvent. If the content of the organic solvent in the photocurable coating composition is too small, defects may occur, such as streaks in the resulting film due to the flowability of the photocurable coating composition is reduced. In addition, when the excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation is not enough, the physical properties and surface properties of the film may be lowered, and defects may occur during the drying and curing process. have. Accordingly, the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1% by weight to 50% by weight, or 2 to 20% by weight.
  • the anti-reflection film may be obtained by applying the hard coating composition on one surface of the substrate, and after drying and photocuring, applying a coating composition for forming the low refractive index layer on the formed hard coating layer and photocuring the applied resultant have.
  • the hard coating layer may be semi-cured, and the method of final curing at the time of photocuring the low refractive index is most preferred.
  • the specific kind or thickness of the substrate is not particularly limited, and a substrate known to be used in the manufacture of a low refractive index layer or an antireflection film can be used without great limitation.
  • the method and apparatus conventionally used to apply the photo-chemical coating composition may be used without particular limitation, for example, a bar coating method such as Meyer bar, gravure coating method, 2 roll l reverse coating method, vacuum slot die coating, 2 roll coating, and the like can be used.
  • a bar coating method such as Meyer bar, gravure coating method, 2 roll l reverse coating method, vacuum slot die coating, 2 roll coating, and the like can be used.
  • the hard coat layer is preferably a final dry thickness of 1 kPa to 10 / M, If less than the lim mechanical strength of the coating layer is lowered and it is difficult to implement fine irregularities on the surface. In addition, at 10 or more, the coating layer is thick, and thus there is a disadvantage in that cracks are easily generated when the coating film is handled.
  • the low refractive layer may have a thickness of 1 nm to 300 nm, or 50 nm to 200 ⁇ .
  • the photocurable coating composition may be irradiated with ultraviolet light or visible light having a wavelength of 200 to 400nm, the exposure dose is preferably 100 to 4,000 mJ / cin 2 when irradiated. Exposure time is not specifically limited, either, The exposure apparatus used can be changed suitably according to the wavelength or exposure amount of irradiation light.
  • the photocurable coating composition may be nitrogen purging to apply nitrogen atmospheric conditions.
  • the antireflective film produced by the above-described method has an average reflectance of 1.6% or less.
  • a display device including the anti-reflection film may be provided.
  • the display device includes a pair of polarizing plates facing each other; A thin film transistor, a curly filter, and a liquid crystal cell sequentially stacked between the pair of polarizing plates; And a liquid crystal display device including a backlight unit.
  • a schematic structure of the display device includes a liquid crystal panel having a structure in which a thin film transistor, a color filter, and a liquid crystal cell are sequentially stacked, and polarizing plates provided on both sides thereof.
  • the anti-reflection film may be formed between the other surface of the polarizer in contact with the liquid crystal cell or between the polarizer and the backlight unit.
  • Specific embodiments of the invention are described in more detail in the following examples. However, the following examples are merely to illustrate specific embodiments of the invention, the content of the specific embodiments of the invention is not limited by the following examples. Preparation Examples 1 to 5: Preparation of Hard Coating Liquid
  • BEAMSET 371 Arakawa, epoxy acrylate polymer, molecular weight 40,000
  • PETA Pentaerythritol triacrylate (multifunctional monomer, molecular weight 298)
  • Irgacure 184 Photoinitiator (Ciba)
  • -103BQ spherical acrylic-styrene copolymer resin particles (average particle size about 2 ⁇ , refractive index about 1.515, XX-103BQ, manufactured by Sekisui Plastic)
  • 113BQ spherical acryl-styrene copolymer resin particles (average particle size about 2, refractive index about 1.555, XX-113BQ, manufactured by Sekisui Plastic)
  • -Spherical organic fine particles 1 Acryl-styrene copolymer resin (XX-68BQ, manufactured by Sekisui Plastic Co., Ltd.), which is a spherical organic fine particle having an average particle diameter of 3.5 / penetration and a refractive index of 1.555.
  • X24-9600A Silica particles having a volume average particle diameter of 100 nm (Shinetsu)
  • Leveling agent BY 300 0.5 0.5 0.5 0.5 0.5 0.5 0.5
  • Fine Particles 1 Fine Particles 1
  • the anti-glare hard coating composition was prepared in the same manner as in Preparation Example 1, except that the components shown in Table 2 were used.
  • the transmittance is measured according to JIS K 7361 standard
  • the haze is measured according to JIS K 7105 standard
  • the average value is calculated by measuring three times with a haze meter (HM-150, A light source, Murakamisa).
  • the 10-point average roughness of the surface irregularities is measured using a 3D optical profiler (Model: NewView 7300, Zygo). Measurement conditions are as follows
  • Average reflectance was measured using a SolidSpec 3700 manufactured by SHIMADZU. Specifically, a black tape (3M) is attached to the surface where the hard coating layer of the base film is not formed to transmit light, and the instant conditions are fixed at a sampling interval of 1 nm, time constant 0.1 sec, slit width 20 nm, and medium scanning speed. Thereafter, 100T mode was applied to the antireflection film at room temperature, and then irradiated with light in a wavelength range of 380 nm to 780 nm. 4. Sharpness Measurement
  • the sharpness value was measured using the ICM-1T of Sugar Test Instrument Co., Ltd .. Specifically, the base film was mounted on the sample holder, and the image sharpness was measured when the slits were 0.125 mm and 0.25 mm in all transmissions.
  • 20760 ° gloss was measured using BYK Gardner's micro-TRI-gloss. Specifically, a black tape (3M) is attached to the surface where the hard coating layer of the base film is not formed so that light does not transmit, and the incident angles of light are 20 ° and 60 °. It was defined as the data average value measured 5 times or more for each.
  • VS3 Light-receiving part aperture
  • a black tape (3M) was attached to the opposite side of the coated surface of the film so as not to transmit light, and it was mounted at the sample position, and then the reflection diffusion luminous intensity was measured. At this time, if the specular intensity value is greater than 100, adjust the sensitivity control dial so that the specular intensity value is 100. It reflected diffusion light intensity at 85 ° to 85 ° - since, to prevent light transmitted through the surface hard coat layer is not formed in the sample film hanneu to measure denoted by the black tape (3M), after attaching the sample to the sample position measurement range was measured.
  • the specular luminous intensity is the reflected diffuse luminous intensity value at 45 degrees corresponding to the specular reflection of the incident angle.
  • the hiding power value was calculated by dividing each of the luminosities by the specular luminous intensity from the specular reflection at + 1 ° to -1 ° and calculating the average value.
  • the hard coating layer of the anti-reflection film of the embodiment has a 10-point average roughness (Rz) of the surface irregularities from 0.0 ⁇ to
  • the average value of the ratios of the respective luminous values at angles of +1 degree and -1 degree from the specular reflection with respect to the specular luminous intensity value is 0.005 to 0. It was also confirmed that it could be maintained in the range of 100, thereby improving the antireflection effect and the poor hiding power of the panel.
  • the 10-point average roughness of the uneven shape of the surface of the hard coat layer of the antireflective films of Comparative Examples 1 and 2 is in excess of, so that not only the image sharpness and gloss are relatively low, but also the resolution is reduced such as sparkling.
  • the panel hiding power exceeded 100. The image was distorted and the sharpness of colors including black was reduced.
  • the internal haze of the hard coat layer of the anti-reflection film of Comparative Examples 3 and 4 is less than 0.5%, the image sharpness and glossiness can be secured to some degree, but the angle of +1 degree and -1 degree from the specular reflection with respect to the specular luminous intensity value The average value of the ratio of each luminous intensity was found to be quite low, and it was found that it was difficult to secure sufficient panel hiding power.

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Abstract

La présente invention concerne un film anti-reflet et un dispositif d'affichage comprenant le film anti-reflet, le film anti-reflet comprenant : une couche de revêtement dur ayant une rugosité moyenne (Rz), de 10 points de la surface irrégulière de cette dernière, de 0,05 µm à 0,2 µm et un flou interne de 0,5 % à 5 % ; et une couche à réfraction faible formée sur la couche de revêtement dur.
PCT/KR2016/010272 2015-09-11 2016-09-12 Film anti-reflet et dispositif d'affichage Ceased WO2017043948A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP16844764.7A EP3299851B1 (fr) 2015-09-11 2016-09-12 Film anti-reflet et dispositif d'affichage
CN201680041085.5A CN107850692B (zh) 2015-09-11 2016-09-12 防反射膜和显示设备
JP2018521166A JP6683374B2 (ja) 2015-09-11 2016-09-12 反射防止フィルムおよびディスプレイ装置
US15/739,586 US10690810B2 (en) 2015-09-11 2016-09-12 Antireflection film and display device having hard coating layer with specified surface roughness and internal haze

Applications Claiming Priority (4)

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KR20150129309 2015-09-11
KR10-2015-0129309 2015-09-11
KR1020160116740A KR102018287B1 (ko) 2015-09-11 2016-09-09 반사 방지 필름 및 디스플레이 장치
KR10-2016-0116740 2016-09-09

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US20200301195A1 (en) * 2017-11-28 2020-09-24 Lg Chem, Ltd. Visibility improving film for display panel and display device comprising same
JP2020535462A (ja) * 2018-01-24 2020-12-03 エルジー・ケム・リミテッド 反射防止フィルム、偏光板およびディスプレイ装置
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US11428848B2 (en) 2018-01-24 2022-08-30 Lg Chem, Ltd. Anti-reflective film, polarizing plate, and display apparatus
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US20200301195A1 (en) * 2017-11-28 2020-09-24 Lg Chem, Ltd. Visibility improving film for display panel and display device comprising same
US11833804B2 (en) * 2017-11-28 2023-12-05 Lg Chem, Ltd. Visibility improving film for display panel and display device comprising same
JP2020535462A (ja) * 2018-01-24 2020-12-03 エルジー・ケム・リミテッド 反射防止フィルム、偏光板およびディスプレイ装置
US11428848B2 (en) 2018-01-24 2022-08-30 Lg Chem, Ltd. Anti-reflective film, polarizing plate, and display apparatus
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CN110018532A (zh) * 2018-02-13 2019-07-16 日本板硝子株式会社 膜、液态组合物、光学元件、以及摄像装置
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JP2021515273A (ja) * 2018-05-18 2021-06-17 エルジー・ケム・リミテッド 反射防止フィルム、偏光板、およびディスプレイ装置
JP7205815B2 (ja) 2018-05-18 2023-01-17 エルジー・ケム・リミテッド 反射防止フィルム、偏光板、およびディスプレイ装置
US11732142B2 (en) 2018-05-18 2023-08-22 Lg Chem, Ltd. Anti-reflective film, polarizing plate, and display apparatus
US12245468B2 (en) 2020-05-06 2025-03-04 Samsung Display Co., Ltd Optical film, display device including optical film and manufacturing method of optical film

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