WO2017155335A1 - Film antireflet - Google Patents

Film antireflet Download PDF

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Publication number
WO2017155335A1
WO2017155335A1 PCT/KR2017/002580 KR2017002580W WO2017155335A1 WO 2017155335 A1 WO2017155335 A1 WO 2017155335A1 KR 2017002580 W KR2017002580 W KR 2017002580W WO 2017155335 A1 WO2017155335 A1 WO 2017155335A1
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WO
WIPO (PCT)
Prior art keywords
layer
low refractive
inorganic nanoparticles
refractive index
hard coating
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/KR2017/002580
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English (en)
Korean (ko)
Inventor
변진석
구자필
김부경
장석훈
장영래
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
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 LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP17763596.8A priority Critical patent/EP3376266B1/fr
Priority to US16/068,249 priority patent/US10895667B2/en
Priority to JP2018518611A priority patent/JP2018533068A/ja
Priority to CN202010756995.XA priority patent/CN111929751B/zh
Priority to CN201780005924.2A priority patent/CN108474870A/zh
Priority claimed from KR1020170029954A external-priority patent/KR101907653B1/ko
Publication of WO2017155335A1 publication Critical patent/WO2017155335A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C08C19/40—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings

Definitions

  • the present invention relates to an anti-reflection film, and more particularly, to an anti-reflection film that 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 a screen of a display device.
  • 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 multi-layered structure in which a hard coating layer (high refractive index layer) and a low reflection coating layer 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 adhesion between the layers (interface adhesion force) 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 photopolymerizable compound is collectively referred to as a compound that causes 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 copolymers and homopolymers.
  • the hollow silica particles is a silica particle derived from a silicon compound or an organosilicon compound, means a particle in the form of an empty space on the surface and / or inside of the silica particles. do .
  • the thickness of 35 ran to 55 nm from the surface of the Cu-K c (Four ier transform analysis results of X-ray reflectance measurement results by rays)
  • An antireflection film can be provided that exhibits one extreme at and one extreme at a thickness of 85 nm to 105 ran from the surface.
  • the present inventors have conducted research on the antireflection film, and from the results of Fourier transform analysi s on the X-ray reflectance measurement result by Cu-K ⁇ -ray, 35 nm to 55 from the surface.
  • An antireflection film exhibiting one extreme value in the thickness of the ran and one extreme value in the thickness of 85 nm to 105 ran from the surface has high scratch resistance and antifouling property with low reflectance and high light transmittance. Experiments confirmed that it can be implemented at the same time and completed the invention.
  • the Fourier transform analysis results of the X-ray reflectance measurement results by Cu— ⁇ ⁇ for the anti-reflection film are graphs of the Y axis versus the thickness of the film on the X axis. Fourier transform magni tude.
  • the extreme value of the Fourier transform intensity is related to the change of the electron density in the thickness direction, and from 35 ran to 55 ran from the surface described above. If the extremes of one Fourier transform intensity in thickness and the extremes of one Fourier transform intensity in thickness between 85 ⁇ and 105 nm from the surface, two layers with different electron densities in the film thickness direction While present, it is possible to realize a lower reflectance and to improve scratch resistance and antifouling properties.
  • the anti-reflection film is one in the thickness of 35 nm to 55 nm from the surface in the Fourier transform analysis (Fourier transform analysis) results graph for the X-ray reflectance measurement results by Cu-K ⁇ -rays
  • Fourier transform analysis Frier transform analysis
  • the extreme value is convex in the direction of the Fourier transform analysis intensity of the reflectance corresponding to the y-axis in the Fourier transform analysis result graph of the X-ray reflectance measurement result by the Cu-K ⁇ ray for the antireflection film. It means the point that appears.
  • the extremal value is the thickness of the X-axis that appears in the graph of the Fourier transform analysis of the Cu-K c (X-ray reflectance measurement result by the ray for the antireflection film ( Fourier transform magnitude on the Y axis for the thickness) is the largest or smallest value compared to the surrounding function, for example, the Fourier transform strength on the Y axis for the thickness of the X axis.
  • (Fourier transform magnitude) means a point at which the value differentiating the function of 1 is 0.
  • the extreme value may mean a local maximum.
  • X-ray reflectance measurement by the Cu-K ⁇ -rays was measured using a Cu-K ⁇ -ray having a wavelength of 1.5418 A for the antireflection film having a size of 1 cm * l cm (horizontal * vertical). It can be measured. Specifically, after adjusting the sample stage so that the value of 2theta (29) becomes 0, checking the hal f-cut of the sample, and then performing reflectance measurement with the incident angle and the reflecting angle satisfying the specular condition, thereby performing the X-ray reflectance pattern Measure
  • Fourier transform analysis of the X-ray reflectance measurement result by the Cu-K ⁇ -rays can be performed using the X 'pert reflective avi ty program of PANalytical.
  • Fourier transform input values include start angle, end angle, and cr iti cal angle.For example, start angle is set to 0.01 °, end angle is set to 1.2 °, and cr it ical angle is set. You can enter 0. 163 0 or 0. 18 °. .
  • the Fourier transform analysis result of the X-ray reflectance measurement by Cu-K ⁇ -ray shows one extreme value at a thickness of 35 ran to 55 nm in the graph of the results of Fourier transform analysis.
  • the antireflection film exhibiting one extreme value in the thickness of the ran may be achieved by adjusting components, optical properties, surface properties, internal properties, and the like included in the antireflection film.
  • the antireflection film of the embodiment may comprise a conventionally known detailed configuration, for example the antireflection film may comprise a hard coating layer; And a low refractive layer formed on the hard coating layer, and may further include one or more layers having other characteristics as necessary.
  • a thickness of 35 nm to 55 ran and a thickness of 85 nm to 105 nm, respectively, from the surface are defined or measured from the surface of the antireflective film, and as described above, the antireflective film may include a hard coating layer; And a low refractive layer formed on the hard coating layer, each of the thickness of 35 nm to 55 ⁇ and the thickness of 85 ran to 105 nm may be the thickness from the surface of the low refractive layer.
  • the anti-reflection film is a hard coating layer; And hollow inorganic nanoparticles and solid particles dispersed in the binder resin and the binder resin. It may include; low refractive index layer containing inorganic nanoparticles.
  • the solid inorganic nanoparticles may be distributed more than the hollow inorganic nanoparticles near the interface between the hard coating layer and the low refractive layer.
  • the hollow inorganic nanoparticles and the solid inorganic nanoparticles so as to be distinguished from each other in the low refractive layer included in the antireflection film, they have high scratch resistance and antifouling resistance while having low reflectance and high light transmittance. Can be implemented at the same time.
  • the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive layer among the low refractive layers of the antireflection film, and the hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface. It is possible to achieve a lower reflectance compared to the actual reflectivity previously obtained using inorganic particles, and the low refractive index layer can realize a significantly improved scratch resistance and antifouling resistance.
  • the Fourier transform analysis result of the X-ray reflectance measurement by Cu-K ⁇ -ray shows one extreme value at a thickness of 35 ran to 55 nm in the graph of the results of Fourier transform analysis.
  • the anti-radiation film exhibiting one extreme value in the thickness of nm may be due to the surface or internal characteristics of the low refractive layer.
  • the anti-reflection film has a thickness of 35 ran to 55 ran in a Fourier transform analysis (F 0ur i er transform analysi s) result graph for X-ray reflectance measurement results by Cu-K ⁇ -rays.
  • F 0ur i er transform analysi s Fourier transform analysis
  • the low refractive layer includes a binder resin, hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin, and may be formed on one surface of the hard coating layer, the solid inorganic nano More than 70 volume 3 ⁇ 4 »of the total particles may be present within 50% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer.
  • At least 70% by volume of the total solid inorganic nanoparticles is 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. At least 70% by volume of the total solid inorganic nanoparticles may be confirmed by measuring the volume of the whole solid inorganic nanoparticles.
  • Whether the hollow inorganic nanoparticles and the solid inorganic nanoparticles are present in the specified region is determined by whether each of the hollow inorganic nanoparticles or the solid inorganic nanoparticles is present in the specified region, and wherein the specific It is determined by excluding particles that exist across the interface of the region.
  • the 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 index layer.
  • the volume% or more, 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.
  • 70% by volume or more of the entire solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.
  • at least 70% by volume 3 ⁇ 4> of the entire hollow inorganic nanoparticle may be present in an area of more than 30% of the total thickness of the low refractive index layer from an interface between the hard coating layer and the low refractive index layer.
  • 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.
  • Two or more parts or two having different refractive indices in the low refractive layer The above layer may be formed, and thus the reflectance of the anti-reflection film may be lowered.
  • the photocurable resin composition for forming a low refractive layer including the nanoparticles of a species can be obtained by controlling the drying temperature.
  • 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 / crf to 1.50 g / cin 3 , or 0.60 g / cirf to 1.00 g / cin 3 . Due to the density difference, the solid inorganic nanoparticles may be located closer to the hard coating layer in the low refractive layer formed on the hard coating layer.
  • the reflective ring film has an average of 1.5% or less, or 1.0% or less, or 0.50 to 1.0%, 0.7% or less, or 0.60% to 0.70%, or 0.62% to 0.67% in the visible light wavelength range of 380 nm to 780 ran. It can indicate reflectance.
  • the low refractive layer is a crab containing at least 70% by volume of the total solid inorganic nanoparticles and the crab containing at least 70% by volume of the entire hollow inorganic nanoparticles It may include two layers, wherein the first layer is the hard coating layer and the low refractive layer compared to the second layer It can be located closer to the interface of the liver.
  • the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive index, and the hollow inorganic nanoparticles are mainly distributed toward the opposite side of the interface.
  • a region in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed may form an independent layer that is visually identified in the low refractive layer.
  • the first layer containing 70% by volume or more of the total solid inorganic nanoparticles may be located within 50% of the total thickness of the low refractive index layer from the interface between the hard coating layer and the low refractive index layer. More specifically, there may be a first layer including 70 vol 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.
  • the 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 3 ⁇ 4> or more, or 70 volume% or more may be present at a distance farther in the thickness direction of the low refractive layer from the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticle.
  • the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the second layer.
  • each of the first layer and the crab 2 layer which are areas in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, is present in the low refractive layer.
  • the transmission electron microscope [Scanning Electron Mi croscope] or the scanning electron microscope [Scanning Electron Mi croscope], etc. can be visually confirmed that each of the first layer and the second layer in the low refractive layer.
  • the ratio of the solid inorganic nanoparticles and the hollow inorganic nanoparticles distributed in each of the crab 1 layer and the crab 2 layer in the low refractive layer can also be confirmed.
  • each of the first and second layers including at least 70% by volume of the entire hollow inorganic nanoparticles may share common optical properties in one layer, and thus may be defined as one layer.
  • 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 the general formula (1). , B and C, so that the first layer and the second layer can be distinguished from each other.
  • the thickness of the first layer and the second layer of the crab can be derived by fitting the ellipticity of the polarization measured by the ellipsometry to the Cauchy model of the following general formula (1), In the low refractive layer, definition of a crab layer and a crab layer is possible.
  • nO is a refractive index at lambda wavelength
  • lambda is in the range of 300 nm to 1800 nm
  • A, B and C are Kosh parameters.
  • the coarse parameters A, B, and (:) obtained when the ellipticity of the polarization measured by the ellipsometry is optimized by the Cauchy model of Equation 1 Accordingly, when 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 layers overlap. However, even in such a case, the thicknesses and positions of the first and second layers may be specified according to the regions satisfying the average values of the Cosch parameters A, B and () of the first and second layers, respectively. Can be.
  • the following A Is 1.0 to 1.65 and B is 0.0010 to 0.0350, and C is from 0 to 1 x may satisfy the condition of 10-3, but also with respect to the said first layer comprises a low refractive index layer, and A is 1.30 to 1.55, or from 1.40 to 1.52, or 1.491 to 1.511, yet, the B is from 0 to 0.005, or from 0 to 0.00580, or yet from 0 to 0.00573, the C is from 0 to 1 ⁇ 10 _3 eu or 0 to 5.0 * 10-4, or from 0 to 4.1352 * 10-4 can be satisfied with the conditions.
  • the ellipticity of the polarization measured by el lsosometry (el l ipsometry) for the two layers included in the low refractive index layer is optimized (Cauchy model) of Formula 1 (fi tt ing)
  • the A is 1.0 to 1.50
  • the B is 0 to 0.007
  • the C may satisfy the condition of 0 to 1 * 1 ( ⁇ 3 , and for the two layers included in the low refractive layer, the A is 1. 10.
  • the B is from 0 to 0.007, or from 0 to about 0.00550, or from 0 to 00 513 while flying
  • the C is from 0 to 1 * 10-3, or from 0 to 5.0 * 10 — 4 , or 0 to 4.8685 * 10 — 4 can be satisfied.
  • the first layer and the crab layer 2 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 ran.
  • 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 nm.
  • Measurement of the above-described 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 solid-type inorganic nanoparticles mean a particle having a maximum diameter of less than 100 ran and there is no empty space therein.
  • the hollow inorganic nanoparticles have a maximum diameter of less than 200 ran and the particles having a form having an empty space on the surface and / or inside thereof it means.
  • the solid inorganic nanoparticles may have a diameter of 0.5 to 100 nm, or 1 to 30 ran.
  • the hollow inorganic nanoparticles may have a diameter of 1 to 200 nm, or 10 to 100 nm.
  • the diameter of the solid inorganic nanoparticles and the hollow inorganic nanoparticles may refer to the longest diameter identified in the particle 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 low refractive index layer may have a higher degree of crosslinking, thereby improving scratch and antifouling properties. It can be secured.
  • 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 contained in the low refractive index layer may comprise a crosslinked (co) polymer between the authentication box containing (co) polymer and a functional group of the photopolymerizable compound male flare fluoride "compound.
  • 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, Dipenta erythri nucleus (meth) acrylate, tripentaerythri Hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, trimethyl propanetrimethacryl Ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more kinds thereof, or urethane modified acrylate oligomers,
  • the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyrene.
  • 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 fluorine (meth) acrylate monomer or oligomer further comprises, the weight ratio of the fluorine (meth) acrylate monomer or oligomer to the monomer or oligomer containing the (meth) acrylate or vinyl group is 0.1. % To 10%.
  • fluorine-based (meth) acrylate monomers or oligomers 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 6 to 6 carbon atoms and an integer of 7, b is an integer of 1 to 3.
  • Formula 2 c is an integer of 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 low refractive index layer may include a portion derived from the fluorine-containing compound including the photo-reflective functional group.
  • One or more photoreactive functional groups may be included or substituted in the fluorine-containing compound including the photoreactive functional group, and the photoreactive functional groups may participate in the 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, or thiol groups ( Thiol) is mentioned.
  • Each of the fluorine-containing compounds including the photo-cyclic functional groups 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 of the fluorine-containing compound, and thus are located inside the low refractive layer that is 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-banung functional group is too high, different from the photocurable coating composition
  • the compatibility with the components may be lowered, and thus the haze of the low refractive layer to be produced may be increased or the light transmittance may be lowered, and the strength of the low refractive layer may be lowered.
  • 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 300 parts by weight of the inside of the fluorine-containing compound 20 including the photobanung functional group based on 100 parts by weight of the photopolymerizable compound.
  • the excess amount of the habso compound containing the photo-banung functional group compared to the photopolymerizable compound is reduced in the coating property of the photocurable coating composition of the embodiment or the low refractive index layer obtained from the photocurable coating composition has a durable durability or scratch You may not have a last name.
  • the amount of the fluorine-containing compound containing the photo-reflective functional group relative to the photopolymerizable compound is too small, the low refractive index layer obtained from the photocurable coating composition may not have mechanical properties such as layered antifouling or scratch resistance.
  • the fluorine-containing compound including the photobanung functional group may further include silicon or a silicon compound.
  • the fluorine-containing compound including the photoreactive functional group may optionally contain a silicon or silicon compound therein, specifically, the content of silicon in the fluorine-containing compound including the additive photo-banung functional group is from 0.1 to 3 ⁇ 4 to 20 Weight%.
  • Silicon contained in the fluorine-containing compound containing the photo-banung functional group is It can increase the compatibility with other components included in the photocurable coating composition of the embodiment and thus may act to increase the transparency by preventing the generation of haze (haze) in the refractive layer to be finally produced.
  • 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.
  • phase separation between the hollow inorganic nanoparticles and the solid inorganic nanoparticles does not sufficiently occur in the low refractive layer manufacturing process.
  • 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 in the low refractive index layer is too small, many of the solid inorganic nanoparticles are located in a region close to the 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 greatly increased.
  • the low refractive index layer may have a thickness of Iran to 300 ran ⁇ or 50ran to 200 nm, or 85 nm to 300 nm.
  • the hard coating layer a conventionally known hard coating layer can be used without great limitation.
  • the photocurable resin included in the hard coating layer is a polymer of a photocurable compound that can cause polymerization reaction when irradiated with light such as ultraviolet rays, It may be conventional in the art.
  • the photocurable resin is a semi-aromatic acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol nucleoacrylate, dipentaerythroxy hydroxy pentaacrylate, pentaerythriri tetraacrylate, pentaerythriri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol Multifunctional acryl consisting of triacrylate, trimethylpropane ethoxy triacrylate, 1, 6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate It may include one or more selected from the group of the rate monomers.
  • 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 mm 3, and the inorganic particles may have a particle size of 1 ran to 500 nm or Iran to 300 ran. have.
  • 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 film are not limited.
  • the organic or inorganic fine particles may be organic fine particles or oxidized or composed of acrylic resin, styrene resin, epoxide resin and nylon resin. It may be an inorganic fine particle consisting of silicon, 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-based polymers, acrylic polymers, styrene-based polymers, epoxide-based polymers, nylon-based polymers, urethane-based polymers, and polyolefin-based polymers.
  • a binder resin of a photocurable resin As another example of the hard coating film, a binder resin of a photocurable resin; And the hard coat film containing the antistatic agent disperse
  • 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-based monomer or an oligomer, wherein the number of the (meth) acrylate-based functional groups is 2 to 10, preferably 2 to 8, Preferably 2 to 7, it is advantageous in terms of securing physical properties of the hard coating layer.
  • the photocurable compound is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythrite nucleus ( Meth) acrylate, dipentaerythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri (meth ) Acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate may be one or more selected from the group consisting of.
  • 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; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelating "compounds such as acetyl acetonate salt of the organic metal compound; 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 can be used without limitation low molecular type or polymer type.
  • a conductive polymer and metal oxide fine particles may also be used as the antistatic agent.
  • the conductive polymer include aromatic conjugated poly (paraphenylene), polycyclic heterocyclic conjugated polyolefin, polythiophene, aliphatic conjugated polyacetylene, and heteroanimal polyaniline conjugated conjugated system.
  • 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.
  • Binder resin of the photocurable resin; And an antistatic agent dispersed in the binder resin may further include one or more compounds selected from the group consisting of alkoxy silane oligomers and metal alkoxide oligomers.
  • the alkoxy silane compound may be conventional in the art, but preferably tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methoxy triethoxysilane, methacryloxy It may be at least one compound selected from the group consisting of propyltrimethoxysilane, 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 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 0.01 / 100. It may further include a substrate bonded to the other side of the hard coating layer.
  • 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 its
  • a resin composition for forming a low refractive index layer including a (co) polymer, a fluorine-containing compound including a photoreactive functional group, a photoinitiator, hollow inorganic nanoparticles, and solid inorganic nanoparticles is applied on a hard coating layer, and then 35 ° C to 100 ° C. Drying at a temperature of; And photocuring the dried product 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 anti-reflection film is a hard coating layer; And a low refractive index layer formed on one surface of the hard coating layer, the binder resin and hollow inorganic nanoparticles dispersed in the binder resin and solid inorganic nanoparticles; and between the hard coating layer and the low refractive layer.
  • 70 volume 3 ⁇ 4> or more of the entire solid inorganic nanoparticle may be present within 50% of the total thickness of the low refractive layer from an interface.
  • At least 30% by volume of the entire hollow inorganic nanoparticles may be present at a greater distance in the thickness direction of the low refractive layer than the interface between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles.
  • more than 70 vol 3> of the solid inorganic nanoparticles may be present 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.
  • the hollow type in an area of more than 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 At least 70% by volume of the total inorganic nanoparticles may be present.
  • the low refractive index layer is a crab layer and the entire hollow inorganic nanoparticles containing at least 70% by weight of the total solid inorganic nanoparticles.
  • the crab may include two layers of 70 wt% or more, and the first layer may be located closer to the interface between the hard coating layer and the low refractive layer than the two layers of crabs.
  • 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 ° C, or 40 ° C to 80 0 C.
  • the temperature for drying the low refractive index layer-forming resin composition applied on the hard coating layer is less than 35 0 C, antifouling property of the low refractive index layer may be greatly reduced.
  • the temperature of drying the resin composition for forming the low refractive index layer applied on the hard coating layer is more than 100 o C, phase separation between the hollow inorganic nanoparticles and solid inorganic nanoparticles in the low refractive layer manufacturing process layer It is not common to occur, so that the scratch resistance and antifouling property of the low refractive index layer may be lowered, and the reflectance may be greatly increased.
  • Low refractive index layer having the above-described characteristics by controlling the density difference between the solid inorganic nanoparticles and the hollow inorganic nanoparticles with the drying temperature in the process of drying the resin composition for forming the low refractive index layer applied on the hard coating layer Can be formed.
  • 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 are 2.00 g / cin 3 to 4.00 It has a density of g / crf, the hollow inorganic nanoparticles may have a density of 1.50 g / cirf to 3.50 g / orf.
  • the step of drying the resin composition for forming the low refractive index layer applied on the hard coating layer at a temperature of 35 ° C to 100 0 C may be performed for 10 seconds to 5 minutes, or 30 seconds to 4 minutes.
  • the low refractive layer may be prepared from a photocurable coating composition including a photocurable compound or a (co) polymer thereof, a fluorine-containing compound including a photoreactive functional group, a hollow inorganic nanoparticle, a solid inorganic nanoparticle, 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 care.
  • the method and apparatus 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, and the like can be used.
  • the low refractive layer may have a thickness of lnm to 300 ran, or 50 ⁇ to 200 rai. Accordingly, the thickness of the photocurable coating composition applied on the predetermined substrate may be about Iran to 300 ran, or 50nm to 200 nm.
  • the photocurable coating composition may be irradiated with ultraviolet light or visible light having a wavelength of 200 ⁇ 400nm, the exposure amount is preferably from 100 to 4,000 mJ / crf. Exposure time is also special It is not limited, It can change suitably according to the exposure apparatus used, the wavelength of irradiation light, or an exposure amount.
  • the photocurable coating composition may be nitrogen purging to apply nitrogen atmospheric conditions.
  • photocurable compound Details of the photocurable compound, the hollow inorganic nanoparticles, the solid inorganic nanoparticles, and the fluorine-containing compound including the photoreactive functional group include the above-described contents with respect to the anti-reflection film of the embodiment.
  • Each of the hollow 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 such as ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or combinations 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 without any limitation as long as it is a compound known to be used in the photocurable resin composition, and specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or the like. 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, it is uncured in the photocuring step of the photocurable coating composition Residual material 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 ketones such as methyl ethyl kenone, methyl isobutyl ketone, acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, 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 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, the solid content is lowered when the excessive amount of the organic solvent is added, the coating and film formation is not divided, the physical properties and surface properties of the film may be lowered, and a poor amount may occur during the drying and curing process. 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 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 polymer resin composition for forming a hard coating layer including a (co) polymer, a photoinitiator, and an antistatic agent on a substrate and photocuring the same.
  • a hard coating layer may be formed.
  • 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 coating layer may further include at least one compound selected from the group consisting of an alkoxy silane oligomer and a metal alkoxide oligomer.
  • Methods and apparatuses commonly used to apply the polymer resin composition for forming the hard coating layer 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 and 2 roll coating can be used.
  • the step of photocuring the polymer resin composition for forming the hard coating layer may be irradiated with ultraviolet light or visible light having a wavelength of 200 ⁇ 400nm, the amount of exposure during irradiation is preferably 100 to 4,000 mJ / cin 2 .
  • Exposure time is not specifically limited, either, According to the exposure apparatus used, wavelength of an irradiation light, or exposure amount, it can change suitably.
  • the step of photocuring the polymer resin composition for forming the 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 can be provided that 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. .
  • Figure 1 shows a cross-sectional TEM photograph of the anti-reflection film of Example 1.
  • Figure 2 shows a cross-sectional TEM photograph of the anti-reflection film of Example 2.
  • Figure 3 shows a cross-sectional TEM photograph of the anti-reflection film of Example 3.
  • Figure 4 shows a cross-sectional TEM photograph of the anti-reflection film of Example 4.
  • Figure 5 shows a cross-sectional TEM photograph of the anti-reflection film of Example 5.
  • Figure 6 shows a cross-sectional TEM photograph of the anti-reflection 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.
  • FIG. 9 shows a cross-sectional TEM photograph of the antireflective film of Comparative Example 3.
  • FIG. 10 shows a graph obtained by Fourier transform analysis of the results of measuring X-ray reflectance by Cu-K ⁇ -rays for the antireflection film of Example 1.
  • FIG. 11 shows a graph obtained by Fourier transform analysis of the result of measuring X-ray reflectance by Cu-K ⁇ -rays for the antireflection film of Example 2.
  • FIG. 12 shows a graph obtained by Fourier transform analysis of the results of measuring X-ray reflectance by Cu-K ⁇ -rays for the antireflection film of Example 3.
  • FIG. 12 shows a graph obtained by Fourier transform analysis of the results of measuring X-ray reflectance by Cu-K ⁇ -rays for the antireflection film of Example 3.
  • FIG. 13 shows the graph which carried out the Fourier transform analysis of the X-ray reflectance measurement result by Cu-K (alpha) ray about the antireflection film of Example 4.
  • FIG. 14 shows a graph obtained by Fourier transform analysis of the results of measuring X-ray reflectance by Cu-K ⁇ -rays for the antireflection film of Example 5.
  • FIG. 15 shows a graph obtained by Fourier transform analysis of X-ray reflectance measurement results using Cu-K ⁇ rays for the antireflection film of Example 6.
  • FIG. FIG. 16 shows the graph which carried out the Fourier transform analysis of the X-ray reflectance measurement result by Cu-K (alpha) ray about the antireflective film of the comparative example 1.
  • FIG. 17 shows a graph obtained by Fourier transform analysis of X-ray reflectance measurement results using Cu-K ⁇ -rays for the antireflection film of Comparative Example 2.
  • FIG. 18 shows a graph obtained by Fourier transform analysis of X-ray reflectance measurement results using Cu-K ⁇ rays for the antireflection film of Comparative Example 3.
  • KY0EISHA salt type antistatic hard coating solution 50 wt% solids, product name: LJD-1000 was coated on a triacetyl cellulose film with # 10 mayer bar.
  • the photocurable coating composition obtained above was coated with a # 4 mayer bar so as to have a thickness of about 110 to 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 / ciif under nitrogen purge.
  • Example 5
  • 268 parts by weight of hollow silica nanoparticles (diameter: about 50 to 60 ran, density: 1.96 g / cin 1 , manufactured by JSC catalyst and chemi cals) based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA), Solid silica nanoparticles (Diameter: about 12 ran, Density: 2.65 g / citf) 55 parts by weight, Crab 1 fluorine compound (X-71-1203M, ShinEtsu) 144 parts by weight, second fluorine-containing compound (RS- 537, DIC Corp.) 21 parts by weight, and 31 parts by weight of an initiator (Irgacure 127, Ciba) were diluted so as to have a solid concentration of 3% by weight in a MIBK (methyl i sobutyl ketone) solvent.
  • TMPTA trimethylolpropane triacrylate
  • Solid silica nanoparticles (Diameter: about 12 ran, Dens
  • 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 / cuf under nitrogen purge.
  • HD2 Pentaerythritol triacrylate 30 g, high molecular weight copolymer (BEAMSET 371, Era, Epoxy Acrylate, molecular weight 40,000) 2.5 g, methyl ethyl ketone 20 g and leveling agent (Tego wet 270) )
  • BEAMSET 371, Era, Epoxy Acrylate, molecular weight 40,000 2.5 g
  • methyl ethyl ketone 20 g and leveling agent Tego wet 270
  • 2 g of an acrylic-styrene copolymer volume average particle diameter: 2 ⁇ m, manufacturer: Sekisui Plastic
  • the hard coating composition thus obtained was coated on a triacetylcell film with # 10 mayer bar and dried at 90 ° C. for 1 minute.
  • 150 mJ / crf was irradiated to the dried material to prepare a hard coating layer having a thickness of 5.
  • the photocurable coating composition for preparing the low refractive index layer obtained above was coated with a # 4 mayer bar to have a thickness of about 110 to 120 ran, dried at a temperature of 60 X for 1 minute, and Cured. At the time of curing, the dried coating was irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge. Comparative Example: Preparation of Antireflection Film
  • 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 antireflection film was prepared in the same manner as in Example 5 except that the photocurable coating composition for preparing the low refractive layer was dried and dried at about 140 ° C.
  • the average reflectance which the antireflective film obtained by the Example and the comparative example shows in visible region (380-780 nm) was measured using the Sol idspec 3700 (SHIMADZU) apparatus.
  • the steel wool was loaded and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in Examples and Comparative Examples.
  • the maximum load at which one scratch or less of 1 cm or less observed with the naked eye was observed was measured.
  • the refractive index at 550 nm was calculated using the Cauchy model and the elliptical polarization measured at a wavelength of 380 nm to 1,000 nm for the phase-separated regions of the low refractive index layers obtained in the above examples. Specifically, for the low refractive index layer obtained in each of the above examples, J. A. Woo 11 am Co. Using the device of M-2000, an angle of incidence of 70 ° was applied and linearly polarized light was measured in the wavelength range of 380 nm to 1000 nm.
  • the measured linear light measurement data (Ellipsometry (1 ⁇ 3 ( ⁇ , ⁇ )) was applied to the first and second layers (Layer 1, Layer 2) of the low refractive index layer by using the Complete EASE software.
  • a Cauchy model was used to fit the MSE to 3 or less.
  • ⁇ ( ⁇ ) is a refractive index at ⁇ wavelength
  • ⁇ is in the range of 300 ran to 1800 ran
  • A, B and C are Kosh parameters.
  • X-ray reflectivity is about lcm * lcm (horizontal * vertical) sized antireflection film
  • the device used was a PANalytical X'Pert Pro MRD XRD, and applied a voltage of 45 kV and a current of 40 mA.
  • the optics used are as follows.
  • Diffracted beam optic Parallel plate col 1 imator (PPC) with silt (0.27)
  • the Fourier transform analysis on the X-ray reflectance measurement result by the Cu-K ⁇ -ray was performed using PANalytical's X'pert Reflectivity program, and the input angle during the Fourier transform was 0. ⁇ 5 as the start angle. Input was 1.2 ° for end angle and 0.163 ° for critical angle.
  • [PI] and [P2] are thicknesses in which the poles of the Fourier transform intensity of the Y-axis appear in the Fourier transform analysis result graph for the X-ray reflectance measurement results by Cu-K ⁇ rays, respectively.
  • hollow inorganic nanoparticles and solid inorganic nanoparticles are phase-separated in the low refractive layer of the antireflection film of Examples 1 to 6, and the solid inorganic nanoparticles are It is confirmed that most of the hollow inorganic nanoparticles are concentrated and existed toward the interface between the hard coating layer and the low refractive index layer of the anti-reflection film.
  • the hollow U nanoparticles and the second region in which the hollow inorganic nanoparticles and the solid inorganic nanoparticles are separated from each other by phases exhibit different refractive indices. It was confirmed that the first region in which the inorganic inorganic nanoparticles were mainly distributed showed a refractive index of 1.420 or more, and the second region in which the hollow inorganic nanoparticles were mainly distributed had a refractive index of 1.400 or less.
  • the low refractive layer of the antireflection films of Comparative Examples 1 to 3 may have a Fourier transform analysis (Four) on Cu-K c (X-ray reflectance measurement results by rays).

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Abstract

La présente invention concerne un film antireflet qui présente un extremum apparaissant à une épaisseur de 35 nm à 55 nm et un extremum apparaissant à une épaisseur de 85 nm à 105 nm sur un graphique montrant le résultat d'une analyse par transformée de Fourier pour un résultat de réflectivité des rayons X mesuré à l'aide d'un rayon Cu-Kα.
PCT/KR2017/002580 2016-03-09 2017-03-09 Film antireflet Ceased WO2017155335A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP17763596.8A EP3376266B1 (fr) 2016-03-09 2017-03-09 Film antireflet
US16/068,249 US10895667B2 (en) 2016-03-09 2017-03-09 Antireflection film
JP2018518611A JP2018533068A (ja) 2016-03-09 2017-03-09 反射防止フィルム
CN202010756995.XA CN111929751B (zh) 2016-03-09 2017-03-09 抗反射膜
CN201780005924.2A CN108474870A (zh) 2016-03-09 2017-03-09 抗反射膜

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KR20160028468 2016-03-09
KR10-2016-0028468 2016-03-09
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KR10-2016-0029336 2016-03-11
KR20160030395 2016-03-14
KR10-2016-0030395 2016-03-14
KR10-2017-0029954 2017-03-09
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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