WO2017155337A1 - Film antireflet - Google Patents

Film antireflet Download PDF

Info

Publication number
WO2017155337A1
WO2017155337A1 PCT/KR2017/002582 KR2017002582W WO2017155337A1 WO 2017155337 A1 WO2017155337 A1 WO 2017155337A1 KR 2017002582 W KR2017002582 W KR 2017002582W WO 2017155337 A1 WO2017155337 A1 WO 2017155337A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
inorganic nanoparticles
low refractive
refractive index
binder resin
Prior art date
Application number
PCT/KR2017/002582
Other languages
English (en)
Korean (ko)
Inventor
송인영
변진석
김부경
장석훈
장영래
오성준
Original Assignee
주식회사 엘지화학
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/554,966 priority Critical patent/US10222510B2/en
Priority to EP17733956.1A priority patent/EP3251832B1/fr
Priority to CN201780000863.0A priority patent/CN107635765B/zh
Priority claimed from KR1020170029953A external-priority patent/KR101790240B1/ko
Publication of WO2017155337A1 publication Critical patent/WO2017155337A1/fr
Priority to US16/239,376 priority patent/US10802178B2/en
Priority to US16/239,371 priority patent/US10983252B2/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings

Definitions

  • the present invention relates to an antireflection film, and more particularly, to a high anti-reflective and antifouling property while having a low reflectance and a high light transmittance. will be.
  • a flat panel display device such as a PDP or LCD is equipped with an anti-reflection film for minimizing reflection of light incident from the outside.
  • a method for minimizing the reflection of light a method of dispersing fillers such as inorganic fine particles in resin and coating on a base film and imparting irregularities (ant i ⁇ glare: AG coating); The method of using the interference of light by forming a plurality of layers having different refractive indices on the base film (AR coating), or a common method thereof.
  • 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 has poor screen clarity due to surface irregularities, much research has recently been conducted on AR coatings.
  • the AR coating film may be a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film. It is commercialized.
  • the method of forming a plurality of layers as described above has a disadvantage in that scratch resistance is inferior due to weak interlayer adhesion (interface adhesion) as a separate process of forming each layer.
  • the present invention is to provide an anti-reflection film having a low reflectance and a high light transmittance and at the same time can implement a high scratch resistance and antifouling resistance and can increase the sharpness of the screen of the display device.
  • the hard coating layer In the present specification, the hard coating layer; And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
  • the low refractive layer includes a first layer containing at least 70 volume 3 ⁇ 4 of the total solid inorganic nanoparticles and a second layer containing at least 70 volume% of the total hollow inorganic nanoparticles,
  • ⁇ ( ⁇ ) is a refractive index at ⁇ wavelength
  • ⁇ is in the range of 300 nm to 1800 ⁇
  • A, B and C are Kosh parameters.
  • the hard coating layer; and a low refractive index layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin;
  • the low refractive layer includes a first layer containing at least 70 volume 3 ⁇ 4 of the total solid inorganic nanoparticles and a second layer containing at least 70 volume% of the total hollow inorganic nanoparticles,
  • An antireflection film which is 1.65, is provided.
  • the hard coating layer and a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
  • the low refractive layer includes a first layer containing at least 70% by volume of the total solid inorganic nanoparticles and a second layer containing at least 70% by volume of the entire hollow inorganic nanoparticles,
  • the photopolymerizable compound is collectively referred to as a compound that causes a polymerization reaction when light is irradiated, 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.
  • silica hollow 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 hard coating layer And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, wherein the low refractive layer is 70% by volume or more of the total solid inorganic nanoparticles.
  • an excessive amount of inorganic particles was added to increase scratch resistance of the antireflection film, but there was a limit in improving scratch resistance of the antireflection film, but there was a problem in that reflectance and antifouling property were lowered.
  • the present inventors proceed with a study on the antireflection film, When the hollow inorganic nanoparticles and the solid inorganic nanoparticles are distributed so as to be distinguished from each other in the low refractive layer included in the antireflection film, high scratch resistance and antifouling property can be simultaneously realized while having low reflectance and high light transmittance. It was confirmed through the experiment to complete the invention.
  • the anti-reflection film may include a hard coating layer; and a low refractive index layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin; It may include a first layer containing at least 70% by volume of the total solid inorganic nanoparticles and a second layer containing at least 70 volume 3 ⁇ 4> of the entire hollow inorganic nanoparticles.
  • Ellipsometry is a low refraction layer comprising a first layer containing at least 70 vol% of the solid inorganic nanoparticles and a second layer containing at least 70 vol% of the entire hollow inorganic nanoparticles.
  • the ellipticity of the polarization measured by ellipsometry of the second layer included in the low refractive layer is optimized by the Cauchy model of the following general formula (1), the following A is 1.0 to 1.50 and B is from 0 to 0.007, and C may satisfy the condition of 0 to 1 x 10-3.
  • the following A is 1.10 to 1.40, or 1.20 to 1.35, or 1.211 to 1.349
  • the following B is 0 to 0.007, or 0 to 0.00550, or 0 to 0.00513
  • C may satisfy a condition of 0 to 1 * 1 ( ⁇ 3 , or 0 to 5.0 * 10 ⁇ 4 , or 0 to 4.8685 * 1 ( ⁇ 4 ).
  • ⁇ ( ⁇ ) is the refractive index at the ⁇ wavelength
  • ⁇ is in the range of 300 nm to 1800 nm
  • A, B and C is Kosh Parameter.
  • the ellipticity of the polarization measured by ellipsometry with respect to the first layer included in the low refractive layer is optimized by the Cauchy model of the following general formula (1), the following A is 1.0 to 1.65 and B is 0.0010 to 0.0350, and C may satisfy the condition of 0 to 1 x 10-3.
  • the following A is 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511
  • the following B is 0 to 0.005, or 0 to 0.00580, or 0 to 0.00573 , to C it may satisfy the 0-1 * 10-3, or from 0 to 5.0 * 10-4, or from 0 to 4.1352 ⁇ 10-4 conditions.
  • the ellipticity of the polarization and related data (Ellipsometry data ( i P, A)) measured by the ellipsometry can be measured using conventionally known methods and devices. For example, for the first layer and the second layer included in the low refractive layer, JA Woo 11 am Co. Using the device of the M-2000, it is possible to apply an angle of incidence of 70 ° and measure linearly polarized light in the wavelength range of 380 nm to 1000 ran. The measured linear light measurement data (Ellipsometry (1 ⁇ 3 ( ⁇ , ⁇ )) is divided into the first layer and the second layer by a Cauchy model of Formula 1 using the Complete EASE software. Can be optimized so that the MSE is 3 or less.
  • the Kosh parameters A, B, and C in each of the first and second layers included in the low refractive index layer described above relate to changes in refractive index and extinction coefficient according to wavelengths, respectively,
  • the layer satisfies the Kosh parameters A, B, and C ranges as a result of the fitting to the above-described Cauchy model of Formula 1, it is possible to maintain an optimized electron density and refractive index distribution therein. As a result, a lower reflectance may be realized and a relatively stable structure may be prevented from scratches or external contaminants.
  • the Kosh parameter A is related to the refractive index at the maximum wavelength
  • B and C are related to the degree of decrease in the refractive index with increasing wavelength. Accordingly, each of the first layer and the second layer included in the low refractive layer is described above.
  • the Kosher parameters A, B, and C ranges obtained by the fitting of the Cauchy model of Formula 1 are satisfied, the above-described effects may be further improved and maximized.
  • the low refractive layer includes a first layer containing at least 70% by volume of the total solid inorganic nanoparticles and a second layer containing at least 70% by volume of the entire hollow inorganic nanoparticles,
  • the following A is 1.0 to An antireflection film, which is 1.65, may be provided.
  • ⁇ ( ⁇ ) is the refractive index at the ⁇ wavelength
  • ⁇ is in the range of 300 ran to 1800 ran
  • A, B and C are Kosh parameters.
  • the Kosh parameter A relates to the refractive index at the maximum wavelength, as the Kosh parameter A for the first layer is 1.0 to 1.65, or 1.30 to 1.55, or 1.40 to 1.52, or 1.480 to 1.515, or 1.491 to 1.511.
  • the anti-reflection film of the embodiment may maintain an optimized refractive index distribution therein, and thus may implement a lower reflectance in a required wavelength range.
  • the ellipticity of the polarization and related data (Ellipsometry data (, A)) measured by the ellipsometry may be measured and confirmed by the method described above with respect to the antireflection film according to one embodiment. More specifically, the ellipticity of the polarization measured by the ellipsometry can be determined by applying an incident angle of 70 ⁇ and measuring linearly polarized light in the wavelength range of 380 nm to 1000 nm.
  • the hard coating layer And a low refractive layer comprising a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
  • the low refractive index layer includes a first layer containing at least 70 vol% of the total solid inorganic nanoparticles and a second layer containing at least 70 vol% of the entire hollow inorganic nanoparticles,
  • the ellipticity of the polarization measured by ellipsometry for each of the first and second layers included in the low refractive index layer was optimized by a Cauchy model of the following general formula (1).
  • An antireflection film may be provided in which the difference between the A value for the first layer and the A value for the second layer is 0.100 to 0.200.
  • ⁇ ( ⁇ ) is the refractive index at the wavelength ⁇ ( ⁇ )
  • ⁇ is in the range of 300 nm to 1800 ran
  • A, B and C are Kosh parameters.
  • the Kosh parameter A relates to the refractive index at the maximum wavelength, wherein the difference between the A value for the first layer and the A value for the second layer is 0.100 to 0.200, or 0.120 to 0.190, or 0.140 to 0.180, or 0.145.
  • the anti-reflection film of the embodiment can greatly improve the mechanical properties of the outer surface while maintaining an optimized refractive index distribution, thereby realizing a lower reflectivity, and relative to scratches or external contaminants It may have a stable structure.
  • A is A for the first layer included in the low refractive layer. 1.0 to 1.65, or 1.30 to 1.55, or 1.40 to 1.52, or 1.491 to 1.511.
  • A May be 1.0 to 1.50, or 1.10 to 1.40, or 1.20 to 1.35, or 1.211 to 1.349.
  • the ellipticity of the polarization and related data (Ellipsometry data ( i P, Z)) measured by the ellipsometry may be measured and confirmed by the method described above with respect to the antireflection film according to one embodiment.
  • the ellipticity of the polarization measured by the ellipsometry may be determined by applying an incident angle of 70 ° and measuring linearly polarized light in the wavelength range of 380 nm to 1000 ran.
  • the low refractive layer has a volume of at least 70 vol% of the first layer and at least 70 vol% of the entire hollow inorganic nanoparticles. It may include a second layer included, the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the second layer.
  • solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer, and hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface.
  • a region in which the inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed may form an independent layer that is visible in the low refractive layer.
  • the hard coating layer of the low refractive layer of the anti-reflection film And in the case of mainly distributing solid inorganic nanoparticles near the interface between the low refractive layers and mainly distributing hollow inorganic nanoparticles toward the opposite side of the interface, to the actual reflectivity previously obtainable using the inorganic particles. Compared with this, a lower reflectance can be achieved, and the low refractive index layer can realize both scratch resistance and antifouling resistance.
  • the first layer including more than 70 volume 3 ⁇ 4> of the total solid inorganic nanoparticles may be located within the total thickness of the low refractive index layer 5 from the interface between the hard coating layer and the low refractive index layer. More specifically, there may be a first layer including 70 volume 3 ⁇ 4 or more of the entire solid inorganic nanoparticles within 30% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer.
  • hollow inorganic nanoparticles may be mainly distributed toward the opposite surface of the interface between the hard coating layer and the low refractive layer in the low refractive layer.
  • the volume% or more or 50 volume% or more, or 70 volume or more may be present at a distance farther in the thickness direction of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer than the entire solid inorganic nanoparticles.
  • the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the second layer.
  • '70% by volume or more of the entire solid inorganic nanoparticles are present in a specific region 'is defined as meaning that the solid inorganic nanoparticles are mostly present in the specific region in the cross-section of the low refractive index layer. 70% by volume or more of the total solid inorganic nanoparticles may be confirmed by measuring the volume of the whole solid inorganic nanoparticles.
  • each of the first layer and the second layer which is a region in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, is present in the low refractive layer.
  • the ratio of the solid inorganic nanoparticles and the hollow inorganic nanoparticles distributed in the first layer and the second layer in the low refractive layer can also be confirmed.
  • each of the first layer including 70% by volume or more of the solid inorganic nanoparticles and the second layer including 70% or more by volume of the hollow inorganic nanoparticles all share common optical properties in one layer. It can be defined as a single layer accordingly.
  • each of the first layer and the second layer has a specific Kosh parameter A when the ellipticity of the polarity measured by ellipsometry is optimized by the Cauchy model of Equation 1.
  • B and C and thus, the first layer and the second layer may be distinguished from each other.
  • the thicknesses of the first and second layers can also be derived.
  • the first layer and the second layer can be defined in the low refractive layer.
  • the Kosh parameters A, B, and C derived when the ellipticity of the polarization measured by the ellipsometry is optimized by the Cauchy model of Equation 1 are in one layer. It may be an average value of. Accordingly, in the case where an interface exists between the first and second crab layers, there may be a region where the Kosh parameters A, B, and C of the first and second crab layers overlap. However, even in this case, the thickness and position of the first layer and the second layer may be specified according to an area satisfying the average values of the Cosch parameters A, B, and C of the first layer and the second layer, respectively. .
  • whether the hollow inorganic nanoparticles and solid inorganic nanoparticles are present in the specified region is determined by whether each of the hollow inorganic nanoparticles or solid inorganic nanoparticles are present in the specified region, Particles that exist across the interface of the particular region are determined to be excluded.
  • the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer, and the hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface. Therefore, two or more portions or two or more layers having different refractive indices may be formed in the low refractive layer, and thus the reflectance of the antireflection film may be lowered.
  • the photocurable resin composition for forming a low refractive index layer containing two kinds of nanoparticles can be obtained by adjusting the dry silver.
  • the solid inorganic nanoparticles may have a density of 0.50 g / cin 3 or more higher than the hollow inorganic nanoparticles, and the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles may be 0.50 g / orf to 1.50 g / cin 3 , or 0.60 g / cin 3 to 1.00 g / cin 3 .
  • the solid inorganic nanoparticles may be located closer to the hard coating layer in the low refractive layer formed on the hard coating layer.
  • a predetermined drying temperature and time should be applied to implement the distribution pattern of the particles in the above-described low refractive layer. Can be.
  • the reflective ring film has an average reflectance of 1.5% or less, or 1.0% or less, or 0.50 to 1.0%, or 0.60% to 0.70%, or 0.62% to 0.67% in the visible light wavelength range of 380 nm to 780 nm. Can be represented.
  • the first layer is 1 nm to 50 nm, or 2 nm to 40 nm, or
  • the second layer is 5 nm to 300 ran, or 10 nm to 200 nm, or 20 nm to 150 nm, or 25 nm to 120 nm, 30 nm It may have a thickness of 100 ran.
  • the thickness of the first layer and the second layer can also be confirmed by optimizing the ellipticity of the polarity measured by ellipsometry (F i tt ting) with a Cauchy model of the following general formula (1).
  • the solid inorganic nanoparticles refer to particles having a maximum diameter of 100 ran or less and no hollow space therein.
  • the hollow inorganic nanoparticles mean a particle having a maximum diameter of 200 ran or less and having a void space on the surface and / or inside thereof.
  • the solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, or 1 to 50 ran or 5 to 30 ran, or 10 to 20 nm.
  • the hollow inorganic nanoparticles may have a diameter of 1 to 200 ran, or 10 to 100 ran, or 20 to 80 ran, or 40 to 70 nm.
  • the diameter of each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may refer to the longest diameter of the nanoparticles identified in the cross section.
  • each of the solid inorganic nanoparticles and the hollow inorganic nanoparticles are at least one half selected from the group consisting of (meth) acrylate group, epoxide group, vinyl group (Vinyl) and thio group (Thiol) on the surface It may contain male functional groups.
  • the solid inorganic nanoparticles and the hollow inorganic nanoparticles each contain the semi-functional functional groups described above on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby improving scratch and antifouling properties. It can be secured.
  • the first layer and the second layer included in the low refractive layer may have a different refractive index.
  • the first layer included in the low refractive layer may have a refractive index of 1.420 to 1.600, or 1.450 to 1.550, or 1.480 to 1.520, or 1.491 to 1.511 at 550 nm.
  • the second layer included in the low refractive layer may have a refractive index of 1.200 to 1.410, or 1.210 to 1.400, or 1.211 to 1.375 at 550 ran. have.
  • Measurement of the above-mentioned refractive index may use a conventionally known method, for example, the elliptical polarization measured at a wavelength of 380 nm to 1,000 nm for each of the first layer and the second layer included in the low refractive layer;
  • the Cauchy model can be used to calculate and determine the refractive index at 550 nm.
  • the above-described low refractive layer may be prepared from a photocurable coating composition including a photopolymerizable compound, a fluorine-containing compound including a photoreactive functional group, a hollow inorganic nanoparticle, a solid inorganic nanoparticle, and a photoinitiator.
  • the binder resin included in the low refractive index layer may include a cross-linked (co) polymer between the (co) polymer of the photopolymerizable compound and the fluorine-containing compound including the photoreactive functional group.
  • the photopolymerizable compound included in the photocurable coating composition of the embodiment may form a base material of the binder resin of the low refractive index layer to be prepared.
  • the photopolymerizable compound may include a monomer or oligomer including a (meth) acrylate or a vinyl group. More specifically, the photopolymerizable compound may include a monomer or oligomer containing (meth) acrylate or vinyl group of one or more, or two or more, or three or more.
  • the monomer or oligomer containing the (meth) acrylate include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythri nuclei "(meth) acrylate, tripentaerythrib hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane polyethoxy tri (meth) acrylate, trimethyl to propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more thereof Compounds or urethane modified acrylate oligo
  • the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyreneol.
  • the content of the photopolymerizable compound in the photocurable coating composition is not particularly limited, the content of the photopolymerizable compound in the solid content of the photocurable coating composition in consideration of the mechanical properties of the low refractive index layer or the anti-reflection film to be produced finally May be from 5% to 80% by weight.
  • Solid content of the photocurable coating composition means only the components of the solid except the components of the liquid, for example, an organic solvent that may be optionally included as described below in the photocurable coating composition.
  • the photopolymerizable compound may further include a fluorine-based (meth) acrylate monomer or oligomer in addition to the above-described monomer or oligomer.
  • a fluorine-based (meth) acrylate monomer or oligomer in addition to the above-described monomer or oligomer.
  • the weight ratio of the fluorine-based (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group is 0.1% to May be 10%.
  • fluorine-based (meth) acrylate-based monomer or oligomer include at least one compound after selection from the group consisting of the following formulas (11) to (15).
  • 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.
  • 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 low refractive index layer containing fluorine-containing functional groups Portions derived from the compound may be included.
  • One or more photoreactive functional groups may be included in or substituted with the photolysogenic functional group including a photoreactive functional group, and the photoreactive functional group may participate in a polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light.
  • the photoreactive 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 (Vinyl), or thiol groups ( Thiol) is mentioned.
  • Each of the ambles compound including the photo-banung functional group may have a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by GPC method) of 2, 000 to 200, 000, preferably 5, 000 to 100, 000. have.
  • the fluorine-containing compounds in the photocurable coating composition may not be uniformly and effectively arranged on the surface, but are positioned inside the low refractive layer to be finally manufactured. Accordingly, the antifouling property of the surface of the low refractive index layer is lowered, and the crosslinking density of the low refractive index layer is lowered, so that mechanical properties such as overall strength and scratch resistance may be reduced.
  • the weight average molecular weight of the fluorine-containing compound containing the photo-reflective functional group is too high, the compatibility with other components in the photocurable coating composition may be lowered, thereby increasing the haze of the low refractive layer to be produced Light transmittance may be lowered, and the strength of the low refractive index layer may also be lowered.
  • the fluorine-containing compound including the photo-reflective functional group is i) an aliphatic compound or aliphatic ring compound in which at least one photo-reflective functional group is substituted, at least one fluorine is substituted in at least one carbon; ii) hetero aliphatic compounds or heteroaliphatic ring compounds substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; iii) 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) 1 And polyether compounds substituted with the above photo-banung functional groups 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.
  • polydialkylsiloxane polymers e
  • the photocurable coating composition may include 20 to 300 parts by weight of the fluorine-containing compound including the photobanung functional group based on 100 parts by weight of the photopolymerizable compound.
  • the fluorine-containing compound containing the photoreactive functional group When the fluorine-containing compound containing the photoreactive functional group is added to the photopolymerizable compound in an excessive amount, the coating property of the photocurable coating composition of the embodiment is reduced or the low refractive layer obtained from the photocurable coating composition has excellent durability or scratch resistance. You may not have a last name. In addition, when the amount of the ambleo compound including the photoreactive functional group relative to the photopolymerizable compound is too small, the low refractive index layer obtained from the photocurable coating composition may not have sufficient mechanical properties such as antifouling or scratch resistance.
  • 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-banung functional group may optionally contain a silicon or silicon compound, specifically, the content of silicon in the fluorine-containing compound containing the photo-banung functional group may be 0.1 to 20% by weight> have.
  • Silicon contained in the fluorine-containing compound including the photo-banung functional group can increase the compatibility with other components included in the photocurable coating composition of the embodiment, and thus it is observed that haze is generated in the final refractive layer. It can play a role of increasing transparency by preventing.
  • the content of silicon in the fluorine-containing compound containing the photoreactive functional group is too large, the compatibility between the other components included in the photocurable coating composition and the fluorine-containing compound may be rather lowered, thereby resulting in low Since the refractive layer or the antireflection film does not have sufficient light transmittance or antireflection performance, the antifouling property of the surface may also be reduced.
  • the low refractive layer may include 10 to 400 parts by weight of the hollow inorganic nanoparticles and 10 to 400 parts by weight of the solid inorganic nanoparticles relative to 100 parts by weight of the (co) polymer of the photopolymerizable compound.
  • the content of the hollow inorganic nanoparticles and solid inorganic nanoparticles in the low refractive index layer is excessive, phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not occur sufficiently in the manufacturing process of the low refractive index layer As a result, the reflectance may be increased, and surface irregularities may occur excessively, thereby degrading antifouling properties.
  • the content of the hollow inorganic nanoparticles and the solid inorganic nanoparticles of the low refractive index layer is too small, many of the solid inorganic nanoparticles are located in an area close to an interface between the hard coating layer and the low refractive layer. It may be difficult to, and the reflectance of the low refractive index layer may be significantly increased.
  • the low refractive layer may have a thickness of l nm to 300 nm, or 50 nm to 200 ran.
  • the hard coating layer a conventionally known hard coating layer may be used without great limitation.
  • the photocurable resin included in the hard coat layer is a polymer of a photocurable compound that may cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be conventional in the art.
  • the photocurable resin is a reactive acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythrite nucliacrylate, dipentaerythroxy hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythriri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylic Laterate, trimethylpropane ethoxy triacrylate, 1, 6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol It may include one or more selected from the group of polyfunctional
  • the organic or inorganic fine particles are not particularly limited in particle size, for example, the organic fine particles may have a particle size of 1 to 10, and the inorganic particles may have a particle size of 1 nm to 500 nm, or lnm to 300 nm. .
  • the particle size of the organic or inorganic fine particles may be defined as a volume average particle diameter.
  • the organic or inorganic fine particles included in the hard coating layer 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 silicon oxide, It may be an inorganic fine particle consisting of titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide.
  • 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 high molecular weight (co) polymer may be one or more selected from the group consisting of cellulose polymers, acrylic polymers, styrene polymers, epoxide polymers, nylon polymers, urethane polymers, and polyolefin polymers.
  • a binder resin of a photocurable resin As another example of the hard coating layer, a binder resin of a photocurable resin; And an antistatic agent dispersed in the binder resin.
  • the photocurable resin included in the hard coating layer is a polymer of a photocurable compound that may cause polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art.
  • the photocurable compound may be a polyfunctional (meth) acrylate monomer or oligomer, wherein the number of (meth) acrylate functional groups is 2 to 10, preferably 2 to 8, more preferably Preferably 2 to 7, in terms of securing physical properties of the hard coating layer It is advantageous .
  • the photocurable compound is pentaerythroxy tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythride nucleus (Meth) acrylate, dipentaerythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri ( Meth) acrylate, and trimethyl may be one or more selected from the group consisting of propane polyethoxy tri (meth) acrylate.
  • the antistatic agent is a quaternary ammonium salt compound; Pyridinium salts; Cationic compounds having from 1 to 3 amino groups; Anionic compounds such as sulfonic acid base, sulfate ester base, phosphate ester base and phosphonic acid base; Positive compounds, such as an amino acid type or amino sulfate ester type compound; Non-different compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Two or more semi-ungmuls or polymerized compounds of these compounds; It may be a combination of two or more of these compounds.
  • the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium salt groups in the molecule, it may be used without limitation low molecular or polymer type.
  • a conductive polymer and metal oxide fine particles may also be used as the antistatic agent.
  • the conductive polymer include an aromatic conjugated poly (paraphenylene), a polycyclic ring having a heterocyclic conjugate, polythiophene, a polyacetylene having an aliphatic conjugate, and a polyaniline conjugated with a hetero atom.
  • the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminium oxide, antimony doped tin oxide, aluminum doped zinc oxide, and the like.
  • the hard coating layer including the antistatic agent may further include at least one compound selected from the group consisting of an alkoxy silane oligomer and a metal alkoxide oligomer.
  • the alkoxy silane compound may be conventional in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methacryloxypropyl It may be at least one compound selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.
  • the metal alkoxide-based oligomer may be prepared through the sol-gel reaction of the composition comprising a metal alkoxide-based compound and water.
  • the sol-gel reaction can be carried out by a method similar to the method for producing an alkoxy silane-based oligomer described above.
  • the sol-gel reaction may be performed by diluting the metal alkoxide compound in an organic solvent and slowly dropping water.
  • the molar ratio of the metal alkoxide compound to water is preferably adjusted within the range of 3 to 170.
  • the metal alkoxide-based compound may be at least one compound selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.
  • the hard coating layer may have a thickness of 0.1 to 100.
  • 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 anti-reflection film of the embodiment a photocurable compound or a (co) polymer thereof, a fluorine-containing compound including a photobanung functional group, photoinitiator, hollow Applying a resin composition for forming a low refractive index layer including inorganic nanoparticles and solid inorganic nanoparticles on a hard coating layer and drying at a temperature of 35 ° C. to 100 ° C .; And photocuring the dried material of the resin composition.
  • the anti-reflection film provided by the method of manufacturing the anti-reflection film is distributed in the low refractive layer so that the hollow inorganic nanoparticles and the solid inorganic nanoparticles can be distinguished from each other, thereby providing a low reflectance and a high light transmittance. It can have high scratch resistance and antifouling at the same time.
  • the low refractive layer is the first layer and 70% by weight of the total solid inorganic nanoparticles and the hollow inorganic nano
  • the second layer may include a second layer including 70% by weight or more of the whole particles, and the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the second layer.
  • the low refractive index layer comprises a photocurable compound or a (co) polymer thereof, a fluorine-containing compound including a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and a resin composition for forming a low refractive index layer including solid inorganic nanoparticles on a hard coating layer. It can be formed by applying to and drying at a temperature of 35 ° C to 100 V, or 40 ° C to 80 ° C.
  • the temperature of drying the resin composition for forming the low refractive index layer applied on the hard coating layer is less than 35 ° C.
  • the antifouling property of the formed low refractive layer may be greatly reduced.
  • the temperature of drying the low refractive index layer-forming resin composition applied on the hard coating layer is more than 100 ° C, phase separation between the hollow inorganic nanoparticles and solid-type inorganic nanoparticles during the low refractive layer manufacturing process is sufficient. It does not occur and is common, and not only the scratch resistance and antifouling property of the low refractive index layer is lowered, but also the reflectance can be greatly increased.
  • the solid inorganic nanoparticles together with the drying temperature in the process of drying the resin composition for forming a low refractive index layer applied on the hard coating layer And by adjusting the density difference between the hollow inorganic nanoparticles can form a low refractive layer having the above characteristics.
  • the solid inorganic nanoparticles may have a density of 0.50 g / cin 3 or more higher than that of the hollow inorganic nanoparticles, and due to the density difference, the solid inorganic nanoparticles in the low refractive layer formed on the hard coating layer. May be located closer to the hard coating layer.
  • the solid inorganic nanoparticles may have a density of 2.00 g / cirf to 4.00 g / cuf
  • the hollow inorganic nanoparticles may have a density of 1.50 g / cin 3 to 3.50 g / cirf.
  • Drying at a temperature of 35 ° C to 100 ° C may be performed for 10 seconds to 5 minutes, or 30 seconds to 4 minutes.
  • the low refractive layer is a photocurable compound or a (co) polymer thereof, photoreactive. It can be prepared from a photocurable coating composition comprising a fluorine-containing compound containing a functional group, hollow inorganic nanoparticles, solid inorganic nanoparticles and a photoinitiator.
  • the low refractive layer can be obtained by applying the photocurable coating composition on a predetermined substrate and photocuring the applied resultant.
  • 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.
  • Methods and apparatuses conventionally used to apply the photocurable coating composition may be used without particular limitation, for example, bar coating method such as Meyer bar, gravure coating method, 2 rol l reverse coating method, vacuum s lot die coating, 2 roll coating, etc. may be used.
  • the low refractive layer has a thickness of l nm to 300 nm, or 50 nm to 200 nm.
  • the thickness of the photocurable coating composition applied on the predetermined substrate may be about 1 nm to 300 ran, or 50 nm to 200 nm.
  • the photocurable coating composition may be irradiated with ultraviolet light or visible light of a wavelength of 200 ⁇ 400nm, the exposure dose is preferably from 100 to 4,000 mJ / cu '. 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.
  • fluorine-containing compound including the photocurable compound hollow inorganic nanoparticles, solid inorganic nanoparticles, and photoreactive functional groups include the above-described contents with respect to the anti-reflection film of the embodiment.
  • Each of the vaporized inorganic nanoparticles and the solid inorganic nanoparticles may be included in the composition in the form of a colloid dispersed in a predetermined dispersion medium.
  • Each colloidal phase including the hollow inorganic nanoparticles and the solid inorganic nanoparticles may include an organic solvent as a dispersion medium.
  • the colloidal phase of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in consideration of the content range of the hollow inorganic nanoparticles and the solid inorganic nanoparticles or the viscosity of the photocurable coating composition in the photocurable coating composition Heavy content may be determined, for example, the solid content of each of the hollow inorganic nanoparticles and the solid inorganic nanoparticles in the colloidal phase may be 5% by weight to 60% by weight.
  • examples of the organic solvent in the dispersion medium include 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 and N-methylpyridone; Esters of ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or mixtures thereof.
  • 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 and N-
  • the photopolymerization initiator may be used in the photocurable resin composition As long as it is a known compound, it can be used without a restriction
  • 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 unreacted initiator may remain as an impurity or have a low crosslinking density, thereby lowering mechanical properties or significantly increasing 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 ketones such as methyl ethyl kenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methane, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butane, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethylyl 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, the solid content is lowered when the excess amount of the organic solvent is added, the 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.
  • the photocurable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1 wt% to 50 wt%, or 2 to 20 wt%.
  • the hard coating layer may be used without any limitation as long as it is a material known to be used for the antireflection film.
  • the method for producing the anti-reflection film may further include applying a photocurable compound or a (co) polymer thereof, a polymer resin composition for forming a hard coating layer including a photoinitiator and an antistatic agent on a substrate and photocuring the same. , Through the above steps can form a hard coating layer.
  • the components used to form the hard coat layer are the same as described above with respect to the antireflection film of the embodiment.
  • the polymer resin composition for forming the hard coat layer may further include at least one compound selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers.
  • the method and apparatus conventionally used to apply the polymer coating composition for forming the hard coating layer can be used without particular limitation, for example, bar coating method such as Meyer bar, gravure coating method, 2 rol l reverse coating method , Vacuum s lot die coating, 2 roll coating etc. can be used.
  • the exposure amount is preferably 100 to 4, 000 mJ / cin 2 when irradiation.
  • 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 polymer resin composition for forming a hard coating layer may be purged with nitrogen in order to apply nitrogen atmospheric conditions.
  • an anti-reflection film and a method of manufacturing the anti-reflection film which can simultaneously realize high scratch resistance and antifouling property while having a low reflectance and a high light transmittance and can increase the sharpness of the screen of the display device.
  • FIG. 1 shows a cross-sectional TEM photograph of the antireflective film of Example 1.
  • FIG. Figure 2 shows a cross-sectional TEM photograph of the anti-reflection film of Example 2.
  • FIG. 3 shows a cross-sectional TEM photograph of the antireflective film of Example 3.
  • FIG. 4 shows a cross-sectional TEM photograph of the antireflective film of Example 4.
  • Figure 5 shows a cross-sectional TEM photograph of the anti-reflection film of Example 5.
  • FIG. 6 shows a cross-sectional TEM photograph of the antireflective film of Example 6.
  • FIG. 7 shows a cross-sectional TEM photograph of the antireflective film of Comparative Example 1.
  • FIG. 8 shows a cross-sectional TEM photograph of the antireflective film of Comparative Example 2.
  • Antistatic hard coating solution of KYOEISHA salt type 50 wt% solids, product name: LJD-1000 was coated on a triacetyl cellulose film with # 10 mayer bar and dried at 90 ° C for 1 minute, and then 150 mJ / cin 2 Ultraviolet rays were irradiated to prepare a hard coating layer having a thickness of about 5.
  • MIBK diacetone alcohol
  • MIBK
  • the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 120 ran, and dried and cured at the temperatures and times shown in Table 1 below. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge.
  • Example 5
  • silica nanoparticles 268 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 ran, density: 1.96 g / cirf, manufactured by JSC catalyst and chemicals) based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA) Silica nanoparticles (diameter: about 12 nm, density: 2.65 g / cu) 55 parts by weight, 1 fluorine-containing compound (X-71-1203M, ShinEtsu) 144 parts by weight, second fluorine-containing compound (RS-537, 21 parts by weight of DIC) and 31 parts by weight of an initiator (Irgacure 127, Ciba) were diluted in a solvent of methyl isobutyl ketone (MIBK) to a solid content of 3% by weight.
  • MIBK methyl isobutyl ketone
  • the photocurable coating composition obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 nm, and dried and cured at the temperatures and times shown in Table 1 below. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cin 2 under nitrogen purge.
  • Example 5 60 ° C 3 minutes
  • Example 6
  • HD2 Hard Coating Layer
  • the hard coating composition thus obtained was coated on a triacetylsalose film with # 10 mayer bar and dried at 90 ° C. for 1 minute. 150 mJ / cui 2 was irradiated to the dried material to prepare a hard coating layer having a thickness of 5.
  • the photocurable coating composition for producing a low refractive index layer obtained above is coated with a # 4 mayer bar to a thickness of about 110 to 120 nm, and dried at a temperature of 60 ° C for 1 minute. And cured. At the time of curing, the dried coating was subjected to 252 mJ / cuf under nitrogen purge. Ultraviolet rays were irradiated.
  • the antireflection film was prepared in the same manner as in Example 1 except that the photocurable coating composition for preparing the low refractive index layer was dried and dried at room temperature (25 ° C.). Comparative Example 2
  • the average reflectance of the antireflective films obtained in Examples and Comparative Examples in the visible light region was measured using a Sol idspec 3700 (SHIMADZU) instrument.
  • a 5 cm long straight line was drawn with a black name pen on the surface of the antireflective film obtained in Examples and Comparative Examples, and the antifouling properties were measured by checking the number of times erased when rubbed using a dust-free cloth.
  • the steel was loaded on and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in the Examples and Comparative Examples.
  • the maximum load at which 1 scratch or less of 1 cm or less observed with the naked eye was observed was measured. 4.
  • the ellipticity of the polarization was measured by ellipsometry on the low refractive index layer obtained in each of the above Examples and Comparative Examples.
  • the low refractive index layer obtained in each of the above Examples and Comparative Examples JA Wool lam Co.
  • an angle of incidence of 70 ° was applied and linearly polarized light was measured in the wavelength range of 380 ran to 1000 ran.
  • the measured Coplanar Measurement data (Ellipsometry data (3 ⁇ 4 f , Z) is used for the first and second layers (Layer 1, Layer 2) of the low refractive index layer using the Complete EASE software. Cauchy model) to fit the MSE to 3 or less (fitting).
  • ⁇ ( ⁇ ) is a refractive index at ⁇ wavelength
  • ⁇ is in the range of 300 nm to 1800 ntn
  • A, B and C are Kosh Parameter.
  • the refractive index at 550 nm was calculated using a Cauchy model measured at a wavelength of 380 nm to 1,000 nm for each of the first included in the low refractive index layer obtained in the above examples.
  • the low refractive index layer is 70% of the first layer and the entire hollow inorganic nanoparticles, including 70% by volume or more of the total solid inorganic nanoparticles.
  • a second layer having a volume of at least 3 ⁇ 4> wherein the solid inorganic nanoparticles are mostly present and flocked toward the interface between the hard coating layer and the low refractive layer of the antireflection film, and the hollow inorganic nanoparticles are hard
  • the first layer containing at least 70% by volume of the total solid inorganic nanoparticles is within 50% of the total thickness of the low refractive index layer from the interface between the low refractive index layers. Will be located.
  • a 1.0 to 1.65 and B is 0.0010 to 0.0350, and C must satisfy the condition of 0 to 1 x 10-3.
  • the anti-reflection film of the embodiment can realize a high scratch resistance and antifouling at the same time while showing a low reflectance of 0.70% or less in the visible light region.
  • the first layer and the second layer included in the low refractive layer of the embodiment has a different refractive index range, specifically, the first layer of the low refractive layer has a refractive index of 1.420 or more It was confirmed that the second layer of the low refractive layer exhibits a refractive index of 1.400 or less.
  • Comparative Example 1 It is confirmed that hollow inorganic nanoparticles and solid inorganic nanoparticles are common without being separated in the low refractive layer of the antireflection film of the invention.
  • the antireflection films of Comparative Examples 1 and 2 were measured with an antireflection film of Example when the ellipticity of the polarization measured by elliptical polarization (eUipsometry) was optimized by the Cauchy model of Formula 1. In the results and the fitting results by the Cauchy model, it was confirmed that they exhibit different ranges and also have relatively high reflectance and low scratch resistance and antifouling resistance.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

La présente invention concerne un film antireflet comprenant : une couche de revêtement dur ; et une couche à faible réfraction comprenant une résine de liant ainsi que des nanoparticules inorganiques creuses et des nanoparticules inorganiques pleines dispersées dans la résine de liant, la couche à faible réfraction comprenant une première couche comprenant au moins 70 % en volume du total des nanoparticules inorganiques pleines et une seconde couche comprenant au moins 70 % en volume du total des nanoparticules inorganiques creuses. Le film antireflet satisfait une condition prédéfinie lorsque l'ellipticité de la polarisation, mesurée par ellipsométrie par rapport à la première couche et/ou à la seconde couche intégrées dans la couche à faible réfraction, est ajustée par un modèle de Cauchy.
PCT/KR2017/002582 2016-03-09 2017-03-09 Film antireflet WO2017155337A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US15/554,966 US10222510B2 (en) 2016-03-09 2017-03-09 Anti-reflective film
EP17733956.1A EP3251832B1 (fr) 2016-03-09 2017-03-09 Film antireflet
CN201780000863.0A CN107635765B (zh) 2016-03-09 2017-03-09 抗反射膜
US16/239,376 US10802178B2 (en) 2016-03-09 2019-01-03 Anti-reflective film
US16/239,371 US10983252B2 (en) 2016-03-09 2019-01-03 Anti-reflective film

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
KR10-2016-0028468 2016-03-09
KR20160028468 2016-03-09
KR10-2016-0029336 2016-03-11
KR20160029336 2016-03-11
KR20160030395 2016-03-14
KR10-2016-0030395 2016-03-14
KR1020170029953A KR101790240B1 (ko) 2016-03-11 2017-03-09 반사 방지 필름
KR10-2017-0029953 2017-03-09

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US15/554,966 A-371-Of-International US10222510B2 (en) 2016-03-09 2017-03-09 Anti-reflective film
US16/239,371 Continuation US10983252B2 (en) 2016-03-09 2019-01-03 Anti-reflective film
US16/239,376 Continuation US10802178B2 (en) 2016-03-09 2019-01-03 Anti-reflective film

Publications (1)

Publication Number Publication Date
WO2017155337A1 true WO2017155337A1 (fr) 2017-09-14

Family

ID=59789628

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/002582 WO2017155337A1 (fr) 2016-03-09 2017-03-09 Film antireflet

Country Status (1)

Country Link
WO (1) WO2017155337A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110060810A (ko) * 2009-11-30 2011-06-08 제이에스알 가부시끼가이샤 반사 방지용 적층체 및 그 제조 방법, 그리고 경화성 조성물
KR20110121233A (ko) * 2010-04-30 2011-11-07 동국대학교 산학협력단 반사방지필름 및 그의 제조방법
KR20130120223A (ko) * 2012-04-25 2013-11-04 주식회사 엘지화학 내찰상성이 우수한 반사 방지 필름 및 이의 제조 방법
KR20140006876A (ko) * 2011-01-14 2014-01-16 다이니폰 인사츠 가부시키가이샤 반사 방지 필름, 반사 방지 필름의 제조 방법, 편광판 및 화상 표시 장치
KR20140006922A (ko) * 2011-04-26 2014-01-16 다이니폰 인사츠 가부시키가이샤 반사 방지 필름, 편광판 및 화상 표시 장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110060810A (ko) * 2009-11-30 2011-06-08 제이에스알 가부시끼가이샤 반사 방지용 적층체 및 그 제조 방법, 그리고 경화성 조성물
KR20110121233A (ko) * 2010-04-30 2011-11-07 동국대학교 산학협력단 반사방지필름 및 그의 제조방법
KR20140006876A (ko) * 2011-01-14 2014-01-16 다이니폰 인사츠 가부시키가이샤 반사 방지 필름, 반사 방지 필름의 제조 방법, 편광판 및 화상 표시 장치
KR20140006922A (ko) * 2011-04-26 2014-01-16 다이니폰 인사츠 가부시키가이샤 반사 방지 필름, 편광판 및 화상 표시 장치
KR20130120223A (ko) * 2012-04-25 2013-11-04 주식회사 엘지화학 내찰상성이 우수한 반사 방지 필름 및 이의 제조 방법

Similar Documents

Publication Publication Date Title
CN109298470B (zh) 抗反射膜
KR101936370B1 (ko) 반사 방지 필름
KR102093950B1 (ko) 반사 방지 필름 및 이의 제조 방법
KR101973196B1 (ko) 반사 방지 필름
TWI665273B (zh) 防反射膜
KR101973197B1 (ko) 반사 방지 필름
JP7138892B2 (ja) 反射防止フィルム
JP6690808B2 (ja) 反射防止フィルムおよびその製造方法
KR101977934B1 (ko) 반사 방지 필름
WO2017155338A1 (fr) Film antireflet
KR101977933B1 (ko) 반사 방지 필름 및 이의 제조 방법
WO2018062856A1 (fr) Film antiréflexion
WO2017155335A1 (fr) Film antireflet
WO2017155337A1 (fr) Film antireflet
KR101916944B1 (ko) 반사 방지 필름
KR20200020768A (ko) 반사 방지 필름 및 이의 제조 방법
WO2017155358A1 (fr) Film antireflet et son procédé de production

Legal Events

Date Code Title Description
REEP Request for entry into the european phase

Ref document number: 2017733956

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15554966

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2017547998

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE