WO2017155338A1 - Film antireflet - Google Patents

Film antireflet Download PDF

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Publication number
WO2017155338A1
WO2017155338A1 PCT/KR2017/002583 KR2017002583W WO2017155338A1 WO 2017155338 A1 WO2017155338 A1 WO 2017155338A1 KR 2017002583 W KR2017002583 W KR 2017002583W WO 2017155338 A1 WO2017155338 A1 WO 2017155338A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
low refractive
inorganic nanoparticles
refractive index
scattering
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/KR2017/002583
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English (en)
Korean (ko)
Inventor
변진석
이정규
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 EP17763598.4A priority Critical patent/EP3318903B1/fr
Priority to CN201780003073.8A priority patent/CN108027452B/zh
Priority to CN202010379588.1A priority patent/CN111580192B/zh
Priority to JP2018518713A priority patent/JP6476347B2/ja
Priority to US15/750,330 priority patent/US10627547B2/en
Priority claimed from KR1020170029959A external-priority patent/KR101906492B1/ko
Publication of WO2017155338A1 publication Critical patent/WO2017155338A1/fr
Anticipated expiration legal-status Critical
Priority to US16/815,227 priority patent/US11262481B2/en
Priority to US16/815,256 priority patent/US11275199B2/en
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 multilayer 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 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.
  • a 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 habble compound means the compound in which at least 1 or more fluorine element is contained among compounds.
  • (meth) acryl [(Meth) acryl] is meant to include both acryl and Methacryl.
  • the (co) polymer is meant to include both co-polymers and homo-polymers.
  • 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.
  • at least one in the scattering vector ( ax ) of 0.0758-0. 1256 ⁇ ⁇ 1 An antireflection film may be provided that exhibits a peak.
  • the present inventors have conducted a study on the antireflection film, and in the graph of the log value of the scattering intensity with respect to the scattering vector defined in the incineration scattering by X-ray irradiation, the scattering vector of 0.0758-0. 1256 nm- 1 ( Experiments confirmed that the antireflection film satisfying the condition showing one or more peaks in 3 ⁇ ) can simultaneously realize high scratch resistance and antifouling property while having low reflectance and high light transmission, and completed the invention.
  • the antireflection film is the graph of the log value of scattering intensity of the scattering vector, defined in the small angle scattering of X-ray irradiation, 0.0758 to 0. 1256 ⁇ first scattering of the vector from one or more (3 ⁇ ) scattering intensity Whether a log value peak can be exhibited may be related to the internal structure of the antireflection film, for example, the average distance between organic or inorganic particles included in the antireflection film. .
  • the antireflection film satisfying the condition showing one or more peaks in the scattering vector of 0.0758 to 0.125 ⁇ 1 was optimized.
  • the refractive index value can be maintained, and thus the antireflection film can realize a low reflectance.
  • the organic or included in the antireflection film may be increased due to the distance between the inorganic particles being too far, and thus the reflectance may be greatly increased.
  • the peak is an extreme value in which the log value of the scattering intensity is convex upward in the graph of the log value of the scattering intensity for the scattering vector defined in the incineration scattering by X-ray irradiation.
  • This peak or the inflection point may be the "point at which scattering is maximized by the arrangement of the organic or inorganic particles contained in the antireflection film.
  • the anti-reflection film of the embodiment is one or more peaks in the scattering vector () of 0.0758 to 0.1256 nnf 1 in the graph of the log value of the scattering intensity for the scattering vector defined in the incineration scattering by X-ray irradiation. Can be represented. More specifically, in the graph of the log value of the scattering intensity for the scattering vector defined in the incineration scattering by X-ray irradiation to the anti-reflection film of the embodiment of the scattering vector of 0.0758 to 0.1256 nnf 1 (c range is It may be the point where the peak of the log value of the scattering intensity for the vector first appears.
  • the scattering vector defined in incineration scattering by X-ray irradiation is defined by the following general formula (1).
  • q 4 ⁇ sinG I ⁇
  • q is a scattering vector
  • ⁇ is a half value of the scattering angle
  • ⁇ is a wavelength of irradiated X-ray.
  • the incineration scattering by the X-ray irradiation means a transmission mode or grazing angle X-ray incineration scattering, for example, 0.63 A to 1.54 A for an antireflection film having a size of lcm * lcm (horizontal * vertical). It can be measured by irradiating X-ray of the wavelength at a distance of 1 ⁇ 2.
  • SAXS X-ray small angle scattering analysis
  • Scattering can be achieved by measuring the scattering intensity according to the scattering vector (q) by transmitting the X-ray through the sample in the Pohang accelerator 4C beamline. More specifically, the incineration scattering measurement can be measured by injecting X-ray with a sample placed about 4m away from the detector, using X-ray having a vertical size of 0.023 ⁇ and a horizontal size of 0.3 ⁇ , 2D mar CCD can be used as a detector. In addition, the scattered 2D diffraction pattern is obtained as an image, and cal ibrat ion is obtained using the sample-to-detector distance obtained through the standard sample, and the scattering intensity according to the scattering vector (q) can be converted through the ci rcular average. have.
  • the condition indicating can be achieved by adjusting components, optical properties, surface properties, internal properties, and the like contained in the antireflection film, which are properties of the anti-reflection film.
  • the antireflection film may include a hard coating layer; And a low refractive layer including a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles dispersed in the binder resin.
  • 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 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 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 At least 70% by volume of the total particles may be present within 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.
  • 'More than 70% by volume of the entire solid inorganic nanoparticles are present in a specific region 1 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 volume 3 ⁇ 4 or more of the whole solid inorganic nanoparticles can 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 hard coating layer and the low refractive index layer Hollow inorganic nanoparticles may be mainly distributed toward the opposite side of the interface between the low refractive layers. Specifically, at least 30% by volume, at least 50% by volume, or at least 70% by volume of the hollow inorganic nanoparticles is The solid 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 index layer than the whole.
  • 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.
  • 70% by volume or more of the entire hollow inorganic nanoparticles may be present in an area of more than 30% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.
  • the solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive index layer, and the hollow inorganic nanoparticles are mainly distributed toward the surface opposite to the interface. 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 solid inorganic nanoparticles may have a density higher than or equal to 0.50 g / cirf than the hollow inorganic nanoparticles, and the difference in density between the solid inorganic nanoparticles and the hollow inorganic nanoparticles is 0.50. g / ciD 3 to 1.50 g / cirf, or 0.60 g / cm 3 to 1.00 g / cin ! Can be. 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. However, as can be seen in the manufacturing methods and examples described below, despite the difference in density between the two particles, a predetermined drying temperature and time must be applied to the particles in the above-described low refractive layer. Distribution patterns can be implemented.
  • the reflective ring film may exhibit an average reflectance of 0.7% or less, or 0.50 to 0.7%, or 0.60% to 0.70%, or 0.62% to 0.67% in the visible light wavelength range of 380 nm to 780 nm.
  • the low refractive index layer is a first layer containing 70% by volume or more of the total solid inorganic nanoparticles and 70% by volume or more of the entire increase of the hollow inorganic nanoparticles It may include two layers, 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.
  • an area in which the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed may form an independent layer visible in the low refractive layer.
  • the first layer including 70 volume 3 ⁇ 4> or more of the entire 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, the first layer including 70% by volume or more of the total 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 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.
  • a volume% or more, or 50 volume 3 ⁇ 4> or more, or 70 volume 3 ⁇ 4 or more is between the hard coating layer and the low refractive layer than the entire solid inorganic nanoparticles. It may be present at a greater distance from the interface in the thickness direction of the low refractive index layer. Accordingly, as described above, 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 second layer which is a region where the solid inorganic nanoparticles and the hollow inorganic nanoparticles are mainly distributed, is present in the low refractive layer.
  • the transmission and electron microscope [Transmission Electron Microscope] or the scanning electron microscope [Scanning Electron Microscope] can be used to visually confirm that each of the first layer and the second layer in the low refractive layer, and also low refractive index
  • the proportion of solid inorganic nanoparticles and hollow inorganic nanoparticles distributed in each of the first and second layers in the layer can also be ascertained.
  • 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 each share a common optical property in one layer. It may 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 thickness of the first layer and the second layer can also be derived.
  • the first layer and the second layer can be defined in the low refractive layer.
  • ⁇ ( ⁇ ) is the refractive index at the ⁇ wavelength (refractive index)
  • lambda is in the range of 300 nm to 1800 nm
  • A, B, and (: 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 is within a layer. Accordingly, when an interface exists between the first layer and the second layer, there may exist a region where the Kosh parameters A, B, and C of the first layer and the crab layer overlap. However, even in such a case, the thickness and position of the first and second layers may be specified according to the area satisfying the average values of the Kosh parameters A, B and C of the first and second layers, respectively. have.
  • the ellipticity of the polarization measured by ellipsometry of 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, B is 0.0010 to 0.0350, C may satisfy a condition of 0 to 1 * 10 3 , and A is 1.30 to 1.55, or 1.40 to 1 for the system 1 layer included in the low refractive layer.
  • 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, or from 0 to 5.0 * 10-4, or from 0 to 4.1352 * 10-4 may satisfy the conditions.
  • A is 1.0. 1 to 1.50
  • B is 0 to 0.007
  • C may satisfy the condition of 0 to 1 * ⁇ 3
  • A is 1.10 to 1.40, or 1.20 to 1.35, Or 1.211 to 1.349, wherein B is 0 to 0.007, or 0 to 0.00550, or 0 to 0.00513, wherein C is 0 to 1 * 10 _3 , or 0 to 5.0 * 10— 4 , or 0 to 4.8685 * 10—
  • the condition of 4 can be satisfied.
  • the low refractive index layer The first layer and the second layer included may have different refractive indices.
  • 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 two layers 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.
  • 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 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 nm 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 30 nm.
  • 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 thiol 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 is a photopolymerizable compound, a photobanung functional group It can be prepared from a photocurable coating composition comprising a fluorine-containing compound, hollow inorganic nanoparticles, solid inorganic nanoparticles 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.
  • a pentaerythri is tri (meth) acrylate, a pentaerythri tetra (meth) acrylate, a dipentaerythrene penta (meth) acrylic acid Latent, dipentaerythrione nucleated (meth) acrylate, tripentaerythrione hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethylolpropane tri (meth) acrylate , Trimethylolpropane polyethoxy tri (meth) acrylate, trimethyl propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more thereof Complexes, or urethane
  • the monomer or oligomer containing the vinyl group include divinylbenzene and styrene S as paramethylstyrene.
  • the content of the photopolymerizable compound in the photocurable coating composition is not particularly limited, but in consideration of the mechanical properties of the low refractive index layer or the anti-reflection film to be produced in the solid content of the photocurable coating composition
  • the content of the photopolymerizable compound may be 5% by weight to 80% by weight.
  • Solid content of the photocurable coating composition means only the components of the solid excluding components of the photocurable coating composition thickening liquid, for example components such as organic solvent which may be optionally included as described below.
  • the photopolymerizable compound may further include a fluorine-based (meth) acrylate monomer or oligomer other than the above-described monomer or oligomer.
  • a fluorine-based (meth) acrylate monomer or oligomer other than 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. From 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 1 to 6 carbon atoms, a is an integer of 0 to 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.
  • the fluorine-containing compound including the photoreactive functional group may include or replace one or more photoreactive functional groups, 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 groups are various functional groups known to be able to participate in the polymerization reaction by the irradiation of light. A specific example thereof may include a (meth) acrylate group, an epoxide group, a vinyl group (Vinyl), or a thiol group (Thiol).
  • Each of the fluorine-containing compounds 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. It is located inside the low refractive layer to be manufactured, thereby reducing the antifouling property of the surface of the low refractive layer and lowering the crosslinking density of the low refractive layer can reduce the mechanical properties such as overall strength and scratch resistance have.
  • the weight average molecular weight of the fluorine-containing compound including 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-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 photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; i i i) polydialkylsiloxane polymers (eg, polydimethylsiloxane polymers) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; iv) a polyether compound substituted with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine, or a mixture of two or more of the above i) to iv) or a copolymer thereof.
  • the photocurable coating composition may include 20 to 300 parts by weight of the fluorine-containing compound including the photobanung functional group based on 100 parts by weight of the photopolymerizable compound.
  • the fluorine-containing compound containing the photoreactive functional group is added in excess of the photopolymerizable compound, the coating property of the photocurable coating composition of the embodiment is lowered or the low refractive layer obtained from the photocurable coating composition is more durable or scratch resistant. You may not have a last name.
  • 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. That is, 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 containing the photo-banung functional group is from 0.01% by weight to 20% by weight May be%.
  • Silicon contained in the fluorine-containing compound including the photoreactive functional group can increase the compatibility with other components included in the photocurable coating composition of the embodiment, and accordingly, 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.
  • 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 solid-type inorganic nanoparticles in the low refractive index layer is too small, Many of the solid inorganic nanoparticles may be difficult to locate in an area close to an interface between the hard coating layer and the low refractive layer, and the reflectance of the low refractive layer may be significantly increased.
  • the low refractive index layer may have a thickness of Iran to 300 nm, or 50 nm to 200 ⁇ .
  • the hard coating layer a conventionally known hard coating layer can be used without great limitation.
  • the photocurable resin included in the hard coat 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 resin is a semi-aromatic acrylate oligomer group consisting of a 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, and the inorganic particles may have a particle size of 1 ran to 500 ran 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.
  • specific examples of 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 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.
  • distributed to the said binder resin is mentioned.
  • the photocurable resin included in the hard coat 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 it is 2 to 7, it is advantageous in terms of securing physical properties of the hard coating layer.
  • the photocurable compound is nucleated pentaerythritol tri (meth) acrylate, pentaerythriri tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythride Hepta (meth) acrylate, tripentaerythr (hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethyl) (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; Sulfonic acid base, sulfate ester base, phosphoric acid Anionic compounds such as ester bases and phosphonic acid bases; 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 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 can be used without limitation low molecular type or polymer type.
  • a conductive polymer and metal oxide fine particles can also be used as said 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.
  • 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, 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 is a metal alkoxide-based compound And it can be prepared through the sol-gel reaction of the composition comprising 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 is O. It may have a thickness of l / zm 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.
  • a resin composition for forming a low refractive index layer including a fluorine-containing compound, a photoinitiator, hollow inorganic nanoparticles, and solid inorganic nanoparticles, including a (co) polymer photoreactive functional group is coated on a hard coating layer, and then applied at 35 ° C to 100 ° C, Or drying at a temperature of 40 ° C. to 80 0 C; And photocuring the dried material of the resin composition.
  • the anti-reflection film provided by the method for 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 and thus low With high reflectivity and high light transmittance, high scratch resistance and antifouling property can be realized simultaneously.
  • 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.
  • 70% by volume or more of the total 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 low refractive index layer of the first layer and at least 70% by weight of the entire solid inorganic nanoparticles and the entire hollow inorganic nanoparticles may include a second layer containing more than 70% by weight, 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 photoreactive functional groups, a photoinitiator, hollow inorganic nanoparticles, and a resin composition for forming a low refractive 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 ° C.
  • a resin composition for forming a low refractive index layer coated on the hard coating layer If the drying temperature is less than 35 ° C., the antifouling property of the formed low refractive index layer may be greatly reduced. In addition, if 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 may have a density of 2.00 g / cin 3 to 4.00 g / cirf
  • the hollow inorganic nanoparticles may have a density of 1.50 g / cm 3 to 3.50 g / cirf. .
  • 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 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 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, and the like can be used.
  • the low refractive layer may have a thickness of lnm to 300 nm, or 50nm to 200 nm. Accordingly, the thickness of the photocurable coating composition applied on the predetermined substrate may be about lnm to 300 nm, 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 100 to 4,000 mJ / cin 2 when irradiated.
  • 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 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 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.
  • the content of the colloidal phase of each particle may be determined.
  • 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.
  • alcohols such as methanol, isopropyl alcohol, ethylene glycol and butane; 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.
  • the photopolymerization initiator may be used without limitation as long as it is a compound known to be used in the photocurable resin composition. Specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or the like may be used. Two or more kinds thereof can be used. With respect to 100 parts by weight of the photopolymerizable compound, the photopolymerization initiator may be used in an amount of 1 to 100 parts by weight. If the amount of the photopolymerization initiator is too small, an uncured material remaining in the photocuring step of the photocurable coating composition may be issued. If the amount of the photopolymerization initiator is too large, the 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 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 is each included in the photocurable coating composition
  • the ingredients may be added at the time of mixing or may be included in the photocurable coating composition as each ingredient is added in a dispersed or mixed state in an organic solvent.
  • the content of the organic solvent in the photocurable coating composition is too small, defects may occur such that the flowability of the photocurable coating composition is lowered, resulting in a flaky pattern on the final film.
  • the excessive amount of the organic solvent is added, the solid content is lowered, coating and film formation are not divided, the physical properties and surface properties of the film may be lowered, and defects may occur in 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% 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 components used to form the hard coat layer are the same as described above with respect to the antireflection film of the embodiment.
  • 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 rol l reverse coating method, vacuum s lot die coating, 2 roll coating, etc. may be used.
  • the exposure dose is preferably 100 to 4, 000 mJ / cirf.
  • Exposure time is not specifically limited, either, It can change suitably according to the exposure apparatus used, the wavelength of irradiation light, or an exposure amount.
  • 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.
  • Figure 10 shows a graph of Example 1 i 0 g value of scattering intensity of the scattering vector, defined in the small angle scattering obtained by projecting the X-ray with respect to the antireflection film of the.
  • FIG. 11 shows a graph of log values of scattering intensity with respect to scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 2.
  • FIG. 12 shows the graph of the log value of scattering intensity with respect to the scattering vector defined by the small angle scattering obtained by irradiating X-ray to the antireflection film of Example 3.
  • Example 13 is a graph of log values of scattering intensity for scattering vectors defined in small angle scattering obtained by irradiating X-rays to the antireflection film of Example 4; It is shown.
  • Figure 14 shows a plot of i 0 g value of scattering intensity of the scattering vector, defined in the small angle scattering obtained by projecting the X-ray with respect to the fifth embodiment of the anti-reflection film.
  • Figure 15 shows a graph of Example 6 i 0 g value of scattering intensity of the scattering vector, defined in the small angle scattering obtained by projecting the X-ray with respect to the antireflection film of the.
  • FIG. 16 shows the graph of the log value of the scattering intensity with respect to the scattering vector defined by the small angle scattering obtained by irradiating X-ray to the antireflection film of the comparative example 1.
  • FIG. 17 shows the graph of the log value of the scattering intensity with respect to the scattering vector defined by the small angle scattering obtained by irradiating X-ray to the antireflection film of the comparative example 2.
  • Figure 18 shows a plot of i 0 g value of scattering intensity of the scattering vector, defined in the small angle scattering obtained by projecting the X-ray with respect to 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.
  • UV light 150 mJ / cin 2 to about 5 to
  • a hard coat film having a thickness of 6 mm 3 was prepared.
  • Example 1 to 5 Preparation of an antireflection film> Example l-4
  • 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 / cu under nitrogen purge.
  • Example 5
  • 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. Table 1
  • HD2 hard coating layer
  • BEAMSET high molecular weight copolymer
  • Coated with # 10 mayer bar and dried at 90 ° C for 1 minute.
  • 150 mJ / cin 2 was irradiated to the dried material to prepare a hard coating layer having a thickness of 5 / im.
  • 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 irradiated with ultraviolet light of 252 mJ / cuf under nitrogen purge.
  • 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 for applying the photocurable coating composition for preparing the low refractive index layer and drying at 140 ° C.
  • the antireflective films obtained in the examples and the comparative examples show visible light region 380.
  • 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 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 layers obtained in the above examples. Specifically, for the low refractive layer obtained in each of the above examples, JA Wool lam 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 ran.
  • ⁇ ( ⁇ ) is the refractive index at the ⁇ wavelength
  • ⁇ is in the range of 300 nm to 1800 nm
  • A, B and (: are Kosh parameters.
  • Scattering vector and scattering intensity can be measured by irradiating X-rays with a wavelength of 1.54 A at a distance of 4 m with respect to the (lateral * vertical) specimen.
  • the scattering angle was measured by scattering intensity according to the scattering vector (q) by transmitting the X-ray through the sample in the Pohang accelerator 4C bump line. More specifically, the incineration scattering measurement was performed by placing the sample at a position about 4m away from the detector and measuring the incident X-rays, using an X-ray having a vertical size of 0.023 mm and a horizontal size of 0.3 mm. 2D mar CCD was used. Then, the scattered 2D diffraction pattern is obtained as an image, cal ibrat i on using the sample-to-detector distance obtained through the standard sample, and the scattering intensity according to the scattering vector (q) is obtained through the ci rcul ar average. In conversion.
  • q 4 ⁇ s in9 I ⁇
  • q is a scattering vector
  • ⁇ 1/2 of the scattering angle
  • ⁇ is the wavelength of the irradiated X-ray.
  • the first peak in the graph of the log value of the scattering intensity for the scattering vector is The value of the scattering vector coming out ( ax ) was obtained.
  • the antireflection films of Examples 1 to 6 exhibited 0.0758 to 0 in a graph of log values of scattering intensity for scattering vectors defined in incineration scattering by X-ray irradiation. It was confirmed that at least one peak in a scattering vector of 1256 nm _1 and high scratch resistance and antifouling property can be simultaneously realized while exhibiting a low reflectance of 0.70% or less in the visible light region as shown in Table 2 above.
  • 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 reflect It is confirmed that most are present and clustered toward the interface between the hard coat layer and the low refractive layer of the prevention film, and the hollow inorganic nanoparticles are mostly present and crowded away from the hard coating layer.
  • the first and second regions 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 where the inorganic inorganic nanoparticles were mainly distributed showed a refractive index of 1.420 or more, and the second region where the hollow inorganic nanoparticles were mainly distributed showed a refractive index of 1.400 or less.

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Abstract

La présente invention concerne un film antireflet qui présente au moins une crête apparaissant avec un vecteur de diffusion de 0,0758 à 0,1256 nm-1 (qmax) sur un graphique représentant la valeur log de l'intensité de diffusion pour le vecteur de diffusion défini par rapport à la diffusion aux petits angles du rayonnement X.
PCT/KR2017/002583 2016-03-09 2017-03-09 Film antireflet Ceased WO2017155338A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP17763598.4A EP3318903B1 (fr) 2016-03-09 2017-03-09 Film antireflet
CN201780003073.8A CN108027452B (zh) 2016-03-09 2017-03-09 减反射膜
CN202010379588.1A CN111580192B (zh) 2016-03-09 2017-03-09 减反射膜
JP2018518713A JP6476347B2 (ja) 2016-03-09 2017-03-09 反射防止フィルム
US15/750,330 US10627547B2 (en) 2016-03-09 2017-03-09 Anti-reflective film
US16/815,227 US11262481B2 (en) 2016-03-09 2020-03-11 Anti-reflective film
US16/815,256 US11275199B2 (en) 2016-03-09 2020-03-11 Anti-reflective film

Applications Claiming Priority (8)

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KR20160028468 2016-03-09
KR10-2016-0028468 2016-03-09
KR20160029336 2016-03-11
KR10-2016-0029336 2016-03-11
KR20160030395 2016-03-14
KR10-2016-0030395 2016-03-14
KR10-2017-0029959 2017-03-09
KR1020170029959A KR101906492B1 (ko) 2016-03-14 2017-03-09 반사 방지 필름

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US16/815,256 Continuation US11275199B2 (en) 2016-03-09 2020-03-11 Anti-reflective film
US16/815,227 Continuation US11262481B2 (en) 2016-03-09 2020-03-11 Anti-reflective film

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JP2020535462A (ja) * 2018-01-24 2020-12-03 エルジー・ケム・リミテッド 反射防止フィルム、偏光板およびディスプレイ装置
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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
US11506820B2 (en) 2018-01-24 2022-11-22 Lg Chem, Ltd. Anti-reflective film, polarizing plate, and display apparatus
JP2020532765A (ja) * 2018-06-26 2020-11-12 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
US11624857B2 (en) 2018-06-26 2023-04-11 Lg Chem, Ltd. Anti-reflective film, polarizing plate, and display apparatus
US20220155507A1 (en) * 2019-03-29 2022-05-19 Lg Chem, Ltd. Reddening-resistant layer
JP2022527897A (ja) * 2019-03-29 2022-06-07 エルジー・ケム・リミテッド 耐赤化層
JP7399536B2 (ja) 2019-03-29 2023-12-18 エルジー・ケム・リミテッド 耐赤化層
US12124068B2 (en) * 2019-03-29 2024-10-22 Lg Chem, Ltd. Reddening-resistant layer

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