WO2017150938A1 - Film antireflet - Google Patents

Film antireflet Download PDF

Info

Publication number
WO2017150938A1
WO2017150938A1 PCT/KR2017/002332 KR2017002332W WO2017150938A1 WO 2017150938 A1 WO2017150938 A1 WO 2017150938A1 KR 2017002332 W KR2017002332 W KR 2017002332W WO 2017150938 A1 WO2017150938 A1 WO 2017150938A1
Authority
WO
WIPO (PCT)
Prior art keywords
substituted
clause
group
film
compound
Prior art date
Application number
PCT/KR2017/002332
Other languages
English (en)
Korean (ko)
Inventor
김부경
변진석
송인영
장영래
장석훈
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170027321A external-priority patent/KR101959510B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/067,857 priority Critical patent/US10768342B2/en
Priority to EP17760342.0A priority patent/EP3378902B1/fr
Priority to CN201780005502.5A priority patent/CN108473791B/zh
Priority to JP2018548637A priority patent/JP2019501425A/ja
Publication of WO2017150938A1 publication Critical patent/WO2017150938A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the present invention relates to an antireflective film, and more particularly, to an antireflective film having high reflectivity and scratch resistance at the same time with low reflectance and high light transmittance, and which can increase the sharpness of a screen of a display device. will be.
  • a flat panel display device such as a PDP or LCD is equipped with an antireflection film for minimizing reflection of light incident from the outside.
  • a method for minimizing the reflection of light a method of dispersing a filler such as inorganic fine particles in a resin, coating on a base film and imparting irregularities (ant i-gl are: 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.
  • a multilayer structure in which a hard coating layer (high refractive index layer), a low reflection coating layer, and the like are laminated on a base film is commercially available.
  • a method of forming a plurality of worms is As the process of forming the layer is performed separately, the adhesion between the layers (interface adhesion) is weak, and thus scratch resistance is inferior.
  • the present invention is to provide an anti-reflection film that can have high alkali resistance and scratch resistance at the same time with a low reflectance and a high light transmittance and can increase the sharpness of the screen of the display device.
  • a binder resin comprising a crosslinked polymer between a photopolymerizable compound and a polysilsesquioxane (po lys l sesqui oxane) in which at least one semi-functional group is substituted; And an inorganic fine particle dispersed in the binder resin; and a low refractive index layer and a hard coating layer, wherein the ratio of the internal haze (Hi) to the total haze (Ha) is 97% or less and before and after the alkali treatment.
  • b *) is provided with an antireflection film having a variation of 0.7 or less.
  • 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.
  • (meth) acryl [(Meth) acryl] is meant to include both acryl and Methacryl.
  • a (co) polymer is meant to include both a copolymer and a homopolymer.
  • hollow silica particles silica particles derived from a silicon compound or an organosilicon compound, and particles having a form having an empty space on the surface and / or inside of the silica particles. it means.
  • a binder resin comprising a cross-linked polymer between a photopolymerizable compound and a polysilsesquioxane (polysyl sesquioxane) substituted with at least one semi-active functional group; And an inorganic fine particle dispersed in the binder resin; and a low refractive index layer and a hard coating layer, wherein the ratio of the internal haze (Hi) to the total haze (Ha) is 97% or less, and before and after the alkali treatment.
  • An antireflection film having a variation of (b *) of 0.7 or less can be provided.
  • the ratio of the internal haze (Hi) to the total haze (Ha) described above including the low refractive index layer and the hard coating layer described above and the reflection satisfying the variation of the color coordinate value (b *) before and after the alkali treatment The anti-reflective film can realize lower reflectance and high light transmittance, improve alkali resistance and secure excellent abrasion resistance or scratch resistance, and the anti-reflective film can increase the sharpness of the screen of the display device while providing excellent mechanical properties. It was confirmed through the experiment that can represent and completed the invention.
  • the antireflection film may have a ratio of internal haze (Hi) to total haze (Ha) of 97% or less, or 95% or less, or 30% to 90%, or 52% to 89%.
  • the total haze (Ha) is defined as the sum of the surface haze (Hs) and the internal haze (Hi), the total haze can be obtained by measuring the haze on the anti-reflection film itself, the internal haze is subjected to alkali treatment
  • a planarization layer may be coated and measured on the surface of one antireflective film, and the surface haze value may be defined as the overall haze and internal haze values are defined.
  • the effect is further increased, and the surface haze must be secured to some extent so as to ensure a smooth visibility in the display device.
  • the ratio of the internal haze (Hi) to the total haze (Ha) of the anti-reflection film exceeds 973 ⁇ 4
  • the ratio of the surface haze (Hs) of the total haze (Ha) is substantially reduced, Not only is the antireflection film not easy to ensure a low reflectance, but also the interference fringes of the antireflection film are easily exposed, so that the sharpness or visibility may be degraded in the final applied display device.
  • the total haze (Ha) of the anti-reflection film for example 5
  • aha or 0.05 — to 4%, or iii). It may be 100 to 3.2%.
  • the internal haze of the anti-reflection film is also not limited, but may be, for example, 4% or less, or 0.1 to 3%, or 0.300 to 2.800.
  • the anti-reflection film may realize a low reflectance and a high light transmittance, and in particular, surface properties and optical properties may not change significantly before and after exposure to alkali.
  • the reflective anti-magnetic film may have a variation in color coordinate values (b *) before and after a predetermined alkali treatment of 0.7 or less, or 0.05 to 0.7, or 0.5 or less, or 0.1 to 0.5, or 0.28 to 0.4.
  • the measurement of the variation of the color coordinate value (b *) of the anti-reflection film before and after the predetermined alkali treatment was performed before and after the alkaline pretreatment by soaking for 1 second to 100 seconds in an alkaline aqueous solution (sodium hydroxide, etc.) which was distilled with 5 to 50% with distilled water. Can be measured using an optical device.
  • the antireflection film is characterized by the properties of the low refractive layer including the polysilsesquioxane substituted with at least one semi-functional functional group.
  • the polysilsesquioxane substituted with at least one reactive functional group has a reactive functional group present on the surface thereof to increase mechanical properties of the low refractive index layer, for example, scratch resistance, and may include silica, alumina, and the like.
  • the alkali resistance of the low refractive index layer can be improved, and the appearance characteristics such as average reflectance and color can be improved.
  • the following A is 1.20 to 1.65
  • B Is 0 to 0.05 and the following C can satisfy the conditions of 0 to 0.05
  • the following A is 1.35 to 1.40
  • the following B is 0.00200 to 0.00800 and the following C can satisfy the conditions of 0 to 0.005.
  • ⁇ ( ⁇ ) is the refractive index at the wavelength ⁇ ( ⁇ )
  • ⁇ is in the range of 300 ran to 1800 nm
  • A, B and C are Kosh parameters.
  • A is 1.30 to 1.75
  • B is 0 to 0.05 and the following C may satisfy the conditions of 0 to 0.005
  • the A is 1.500 to 1.520
  • the following B is 0.00100 to 0.00600
  • the following C may satisfy the conditions of 0.00001 to 0.0.
  • the ellipticity of the polarization and related data (Ellipsometry (1 ⁇ 3 ( ⁇ , ⁇ )) measured by the ellipsometry can be measured using a commonly known method and apparatus. With respect to the low refractive index layer and the hard coating layer of the film, by using the apparatus of JA Woo 11 am Co. M-2000, an angle of incidence of 70 ° may be applied and linearly polarized light may be measured in the wavelength range of 380 nm to 1000 ran.
  • the linear light measurement data (Ellipsometry (1 ⁇ 3 ( ⁇ , ⁇ )) can be optimized so that the MSE is 3 or less with the Cauchy model of the above formula 1 using the Complete EASE software.
  • Coke parameters A, B and C in the low refractive index layer and the hard coating layer are respectively related to the change of the refractive index and the extinction coefficient according to the wavelength, and each of the low refractive index layer and the hard coating layer described above Model (Cauchy In case of satisfying Kosh parameter A, B and C range by the result of optimizing with model), internally optimized electron density and refractive index distribution can be maintained, which results in lower reflectance and scratch. Alternatively, it may have a relatively stable structure against external pollutants.
  • the Kosh parameter A is related to the lowest refractive index for each wavelength, and B and C are related to the degree of decrease of the refractive index with increasing wavelength.
  • the low refractive index layer may have a thickness of about Iran to 200 nm, and the hard coating layer may have a thickness of about 100 1, or about 1 / im to about 10 nm.
  • the thickness of each of the low refractive index layer and the hard coating layer may be confirmed by optimizing the ellipticity of the polarization measured by ellipsometry (Cauchy model) of Formula 1 below (f i tt ing).
  • the low refractive index layer includes a binder resin containing a cross-linked polymer between the photopolymerizable compound and a polysilsesquioxane (polys i I sesquioxane) substituted with at least one semi-functional group and inorganic fine particles dispersed in the binder resin can do.
  • a binder resin containing a cross-linked polymer between the photopolymerizable compound and a polysilsesquioxane (polys i I sesquioxane) substituted with at least one semi-functional group and inorganic fine particles dispersed in the binder resin can do.
  • the polysilsesquioxane is ( ⁇ ;? ⁇ Can be expressed as and (wherein, n will have a variety of structures, such as 4 to 30 or 8 to 20), a random, ladder-type, cage and partial cage. Can be.
  • the semi-functional functional group is at least one of polysilsesquioxane substituted with at least one semi-functional functional group.
  • Substituted polyhedral oligomeric silsesquioxanes having a cage structure can be used.
  • the polyhedral oligomeric silsesquioxane having one or more functional groups and having a cage structure may include 8 to 20 silicon in the molecule.
  • At least one or more of the silicones of the polyhedral oligomeric silsesquioxane having a cage structure may be substituted with a reactive functional group, and the above-mentioned non-reactive functional groups may be substituted with silicones not having a substituted functional group.
  • the reactive functional group is substituted in at least one of the polysilicon polysaccharide oligomeric silsesquioxane silicones having a cage structure, the mechanical properties of the coating film or the binder resin formed during photopolymerization of the photopolymerizable coating composition may be improved.
  • the semi-functional groups substituted in the polysilsesquioxanes are alcohols, amines, carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, olefins [al ly, cycloalkenyl ( cycloalkenyl) or vinyldimethylsilyl and the like], polyethylene glycol, thiol and vinyl groups, and may include one or more functional groups selected from the group consisting of epoxides or
  • the semi-functional group include (meth) acrylate, alkyl (meth) acrylate having 1 to 20 carbon atoms, cycloalkyl (cyc loalkyl) epoxide having 3 to 20 carbon atoms, and alkyl cycloalkane having 1 to 10 carbon atoms. (cyc loalkane) epoxides.
  • the alkyl (meth) acrylate means that the other part of the 'alkyl' which is not bonded with the (meth) acrylate is a bonding position
  • the cycloalkyl epoxide is the other part of the 'cycloalkyl' which is not bonded with the epoxide
  • the bonding position alkyl cycloalkane epoxide means that the other portion of the 'alkyl' that is not bonded to the cycloalkane (epoxy) epoxide is the binding position.
  • the polysilsesquioxane substituted with at least one semi-active functional group is a linear or branched alkyl group of 1 to 20 carbon atoms, a cyclonuclear group of 6 to 20 carbon atoms and 6 to 20 carbon atoms in addition to the above-mentioned semi-functional functional group
  • At least one non-banung functional group selected from the group consisting of aryl groups may further include at least one.
  • the semi-functional male group and the un-functional male group are substituted on the surface of the polysilsesquioxane, so that the reactive functional group is at least one.
  • the siloxane bond (-Si-0-) is located inside the molecule and is not exposed to the outside, thereby improving alkali resistance and scratch resistance of the low refractive index layer and the antireflection film.
  • polyhedral oligomeric silsesquioxane having one or more such reactive functional groups and having a cage structure
  • TMP Diol Isobutyl POSS Cyclohexanediol Isobutyl POSS, 1,2-Propanediol Isobutyl POSS, POSS substituted with one or more alcohols such as 0c ta (3-hydroxy-3 methylbutyldimethylsiloxy) POSS; Aminopropyl Isobutyl POSS, Aminopropyl Isooctyl POSS, Am i noe t fiy 1 am i nopr opy 1 Isobutyl POSS, N-Pheny 1 am i nopr dpy 1 POSS, N ⁇ Met hy 1 am i nopr opy 1 Isobutyl POSS, OctaAmmonium POSS,
  • POSS substituted with at least one amine such as AminophenylCyclohexyl POSS and Am inophenyl Isobutyl POSS; POSS in which at least one carboxylic acid is substituted, such as Maleamic Acid-Cyclohexyl POSS, Maleamic Acid-Isobutyl POSS, Oct a Maleamic Acid POSS; POSS substituted with at least one epoxide such as EpoxyCyclohexyl Isobutyl POSS, Epoxycyclohexyl POSS, Glycidyl POSS, GlycidylEthyl POSS, Glycidyl Isobutyl POSS, Glycidyl Isooctyl POSS; POSS in which at least one imide is substituted, such as POSS Maleimide Cyclohexyl and POSS Maleimide Isobutyl; Acrylolsobutyl POSS, (Meth) acryl Isobut
  • P0SS substituted with one or more (meth) acrylates such as (Meth) acryl Isooctyl POSS, (Meth) acrylPhenyl POSS, (Meth) acryl POSS, and Acrylo POSS; P0SS in which at least one nitrile group such as Cyanopropyl Isobutyl POSS is substituted; POSS in which at least one norbornene group is substituted, such as NorbornenylEthyl POSS, Norbornenyl ethyl Isobutyl POSS, Norbornenyl ethyl DiSi lanolsobutyl POSS, and Tr isnorbornenyl Isobutyl POSS; POSS substituted with at least one vinyl group such as Allyllsobutyl POSS, MonoVinyl Isobutyl POSS, OctaCyclohexenyldimethylsiyl POSS, OctaVinyldi
  • the weight ratio of the portion derived from polysilsesquioxane in which at least one semi-amen functional group is substituted with the portion derived from the photopolymerizable compound in the binder resin is 0.005 to 0.50, or 0.005 to 0.25, or 0.015. To 0. 19.
  • the alkali resistance of the low refractive index layer is too small when the content of the portion derived from polysilsesquioxane in which the semi-ungsung group is one or more substituted with the portion derived from the photopolymerizable compound in the binder resin is too small. However, it may be difficult to sufficiently secure scratch resistance.
  • the content of the portion derived from polysilsesquioxane in which the reactive functional group is substituted at least one of the portion derived from the photopolymerizable compound of the binder resin in the photopolymerizable coating composition is too large, Transparency of the low refractive index layer or the antireflection film may be lowered, and scratchability may be lowered.
  • the photopolymerizable compound forming the binder resin may include a monomer or oligomer containing (meth) acrylate or vinyl group.
  • the photopolymerizable compound may include a monomer or oligomer containing (meth) acrylate or vinyl group of one or more, two or more, or three or more.
  • a pentaerythri is tri (meth) acrylate, a pentaerythri (tetra) (meth) acrylate, dipentaerythritol (penta) acrylate , Dipentaerythrione nucleated (meth) acrylate , Tripentaerythrione hepta (meth) acrylate , Tylene diisocyanate , Xylene diisocyanate , Hexamethylene diisocyanate , Trimethylolpropane tri (meth) acrylate , Trimethylolpropane polyethoxy Tri (meth) acrylate ⁇ trimethyl to propanetrimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more kinds thereof, or
  • the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyrene.
  • the content of the portion derived from -the—photopolymerizable compound is not particularly limited, but the content of the photopolymerizable compound is 20 wt% in consideration of mechanical properties of the low refractive index layer or the antireflection film to be manufactured. 3 ⁇ 4> -80% by weight.
  • the low refractive layer may further include a portion derived from a fluorine-based compound including a photoreactive functional group.
  • the fluorine-based compound including the photo-reflective functional group is included, the low refractive index layer and the antireflection film may have a lower reflectance and an improved light transmittance, and may further improve alkali resistance and scratch resistance.
  • the binder resin may further include a crosslinked polymer between a photopolymerizable compound, a fluorine-based compound including a photoreactive functional group, and a polysilsesquioxane in which at least one semi-reactive functional group is substituted.
  • the fluorine-based compound may include or replace one or more photo-reflective functional groups
  • the photo-reflective functional group refers to a functional group capable of participating in the polymerization reaction by irradiation of light, for example, by irradiation of visible light or ultraviolet light.
  • the photo-reflective functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include (meth) acrylate groups, epoxide groups, vinyl groups, or cyclo groups ( Thiol) is mentioned.
  • the fluorine-based compound including the photoreactive functional group may have a fluorine content of 1 to 60 weight 3 ⁇ 4>. Fluorine-based including the photo-banung functional group If the content of fluorine in the compound is too small, it may be difficult to sufficiently secure the physical properties such as alkali resistance because the fluorine component is not arranged to the surface of the low refractive index layer. In addition, if the fluorine content in the fluorine-based compound including the photo-reflective functional group is too large, the surface properties of the low refractive index layer may be lowered or the incidence of defective products during the post-stage process to obtain the final result.
  • the low refractive layer when the low refractive layer is formed on one surface of the hard coating layer having an anti-reflection function, in order to minimize the problems caused by peeling electrification voltage that may occur in the manufacturing process or the actual application of the anti-reflection film, the low The refractive layer may include a fluorine-based compound including a photoreactive functional group having a fluorine content of 1 wt% to 25 wt%.
  • the fluorine-based compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the bloso-based compound including the photoreactive functional group may optionally contain a silicon or silicon compound therein, and specifically, the content of silicon in the fluorine-based compound including the photoreactive functional group is 0.1 weight 3 ⁇ 4> to 20 weight May be).
  • Silicon included in the fluorine-based compound including the photoreactive functional group may serve to increase transparency by preventing haze from occurring in the low refractive layer.
  • the content of silicon in the fluorine-based compound including the photo-reflective functional group is too large, the alkali resistance of the low refractive index layer may be lowered.
  • the fluorine-based compound including the photoreactive functional group is from 2,000 to
  • the low refractive layer may not have a layered alkali resistance.
  • the low refractive index layer may not have sufficient durability or scratch resistance, and also the compatibility between the fluorine-based compound and the other components including the photoreactive functional group Since the property is lowered, there is no uniform dispersion during the production of the low refractive index layer, thereby lowering the internal structure or surface properties of the final product. .
  • the fluorine-based compound including the photo-reflective functional group includes: i) an aliphatic compound or an aliphatic ring compound in which one or more photo-reflective functional groups are substituted, and at least one fluorine is substituted for at least one carbon; ii) heteroaliphatic compounds or heteroaliphatic ring compounds substituted with one or more photoreactive functional groups, at least one hydrogen substituted with fluorine, and one or more carbons substituted with silicon; iii) polydialkylsiloxane polymers (eg, polydimethylsiloxane polymers) in which at least one photoreactive functional group is substituted and at least one fluorine is substituted in at least one silicon; iv) substituted by one or more photoreactive functional groups there may be mentioned a polyether compound, or the ⁇ to iv) at least two of the common u compound or a copolymer thereof is substituted by at least one of the hydrogen fluoride.
  • a polyether compound or the
  • the low refractive layer may include 1 to 75 parts by weight of the fluorine-based compound including the photoreactive functional group based on 100 parts by weight of the photopolymerizable compound.
  • the low refractive layer may not have sufficient durability or scratch resistance.
  • the low refractive index layer may not have a layered alkali resistance.
  • the binder resin may further include a portion derived from the fluorine-based (meth) acrylate compound in addition to the photopolymerizable compound described above.
  • the fluorine-based (meth) acrylate compound may also be in a state crosslinked with any one or more of the other components included in the binder resin.
  • the weight ratio of the fluorine-based (meth) acrylate compound to the monomer or oligomer containing the (meth) acrylate or vinyl group may be 0.1% to 103 ⁇ 4 » have.
  • fluorine-based (meth) acrylate-based compound may include at least one compound selected from the group consisting of the following formulas (11) to (15).
  • R 1 is a hydrogen group or a C 1 alkyl group, a is an integer of 0 to 7, b is an integer of 1 to 3.
  • 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 inorganic fine particles refers to inorganic particles having a diameter of nanometer or micrometer unit.
  • the inorganic fine particles may include solid inorganic nanoparticles and / or hollow inorganic nanoparticles.
  • 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 50 nm. ,
  • the hollow inorganic nanoparticles may have a diameter of 1 to 200 nm, or 10 to 100 nm.
  • 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 solid inorganic nanoparticles and the hollow inorganic nanoparticles As the particles each contain the above-mentioned semi-functional functional groups on the surface, the low refractive index layer may have a higher degree of crosslinking, thereby ensuring improved scratch resistance and antifouling resistance.
  • the surface of the hollow inorganic nanoparticles may be used alone or in combination with the hollow inorganic nanoparticles whose surface is not coated with the fluorine-based compound. Coating the surface of the hollow inorganic nanoparticles with a fluorine-based compound may lower the surface energy, thereby increasing the durability and scratch resistance of the low refractive layer.
  • a particle coating method or a polymerization method commonly known as a method of coating a fluorine-based compound on the surface of the hollow inorganic nanoparticles may be used without any significant limitation.
  • the hollow inorganic nanoparticles and the bloso-based compound may be mixed with water. By sol-gel reaction in the presence of a catalyst, the fluorine-based compound may be bonded to the surface of the hollow inorganic nanoparticle through hydrolysis and condensation reaction.
  • hollow inorganic nanoparticles include hollow silica particles.
  • the hollow silica may include predetermined functional groups that are most ringed on the surface in order to be more easily dispersed in an organic solvent.
  • organic functional group that can be substituted on the surface of the hollow silica particles are not particularly limited. For example, (meth) acrylate group, vinyl group, hydroxy group, amine group, allyl group, allyl group, epoxy group, hydroxy group, isocyanate group, An amine group or fluorine may be substituted on the hollow silica surface.
  • the binder resin of the low refractive index layer may include 10 to 350 parts by weight of the inorganic fine particles, or 50 to 280 parts by weight based on 100 parts by weight of the photopolymerizable compound.
  • the hollow particles are added in an excessive amount, scratch resistance or abrasion resistance of the coating film may decrease due to a decrease in the content of the binder.
  • the low refractive layer is applied to a predetermined substrate by applying a photopolymerizable coating composition comprising a polysilsesquioxane (polysi l sesquioxane) substituted with at least one photopolymerizable compound, inorganic fine particles and semi-aromatic functional groups It can be obtained by photopolymerizing the result.
  • a photopolymerizable coating composition comprising a polysilsesquioxane (polysi l sesquioxane) substituted with at least one photopolymerizable compound, inorganic fine particles and semi-aromatic functional groups It can be obtained by photopolymerizing the result.
  • the specific kind or thickness of the substrate is not particularly limited, and is used in the manufacture of a low refractive index layer or an antireflection film. Known substrates can be used without great limitation.
  • the photopolymerizable coating composition may further include a fluorine-based compound including the photoreactive functional group.
  • the photopolymerizable coating composition may further include a photoinitiator.
  • the photopolymerization initiator may be used without any limitation as long as it is a compound known to be used in the photopolymerizable resin composition. Specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound or 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, a material that remains uncured in the photopolymerization step of the photopolymerizable 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 photopolymerizable 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, 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 photopolymerizable coating composition while being added at the time of mixing the respective components included in the photopolymerizable coating composition or in the state in which each component is dispersed or mixed in the organic solvent.
  • the photopolymerizable coating composition may include an organic solvent such that the concentration of the total solids of the components included is 1 weight 3 ⁇ 4) to 50 weight 3 ⁇ 4>, or 2 to 20 weight%.
  • the method and apparatus conventionally used to apply the photopolymerizable coating composition can be used without particular limitation, for example, bar coating method such as Meyer bar, gravure coating method, 2 roll l reverse coating method, vacuum s lot die coating, 2 roll coating, etc. can be used.
  • Ultraviolet light or visible light having a wavelength of 200 to 400 nm can be irradiated, and the exposure dose during irradiation is preferably 100 to 4, 000 mJ / cuf.
  • 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.
  • nitrogen purging may be performed to apply nitrogen atmospheric conditions.
  • the antireflection film may have an average reflectance of 2.2% or less, 1.5% or less, or 1.20% or less.
  • the hard coating layer can be used without a large limitation to the conventional known hard coating layer.
  • the hard coat film examples include a binder resin including a photopolymerizable resin and a high molecular weight (co) polymer having a weight average molecular weight of 10, 000 or more, and a hard coat film including organic or inorganic fine particles dispersed in the binder resin. Can be mentioned.
  • 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.
  • the photopolymerizable resin included in the hard coating layer is a polymer of a photopolymerizable compound which may cause a polymerization reaction when light such as ultraviolet rays is irradiated, and may be conventional in the art.
  • the photopolymerizable resin is A semi-active acrylate oligomer group consisting of urethane acrylate oligomers, epoxide acrylate oligomers, polyester acrylates, and polyether acrylates; And dipentaerythritol nucleoacrylate, dipentaerythroxy hydroxy pentaacrylate, pentaerythriri tetraacrylate, pentaerythriri triacrylate, trimethylene propyl triacrylate, propoxylated glycerol Multifunctional acrylic 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 rate monomer group.
  • the organic or inorganic fine particles are not particularly limited in particle size, but 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 lnm to 300 nm. have.
  • 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 hard coat film may be formed from an anti-glare coating composition comprising organic or inorganic fine particles, a photopolymerizable resin, a photoinitiator, and a high molecular weight (co) polymer having a weight average molecular weight of 10, 000 or more.
  • the hard coating film a binder resin of a photopolymerizable resin; And the hard coat film containing the antistatic agent disperse
  • the photopolymerizable resin included in the hard coating layer is a polymer of a photopolymerizable compound that may cause polymerization reaction when irradiated with light such as ultraviolet rays, and may be conventional in the art.
  • the photopolymerizable 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 2 to 7 is advantageous in terms of securing physical properties of the hard coat layer.
  • the photopolymerizable compound is pentaerythroxy tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythride (Meth) acrylate, dipentaerythritol hepta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nusamethylene diisocyanate, trimethylolpropane tri ( It may be at least one selected from the group consisting of meth) acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate.
  • the "cheoncheon-cho” inhibitor may be a quaternary ammonium salt compound-,-a conducting polymer or a combination thereof.
  • 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.
  • the conductive polymer may be used as a low molecular type or a polymer type without limitation, the kind may be conventional in the art to which the present invention belongs, and is not particularly limited.
  • Binder resin of the photopolymerizable 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, methacryl It may be at least one compound selected from the group consisting of oxypropyltrimethoxysilane, 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 (based on metal ions) 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 anti-reflection film may further include a substrate bonded to the other surface of the hard coating layer.
  • the substrate may have a light transmittance of 90% or more and a haze of 1% or less.
  • the material of the substrate may be triacetyl cellulose, cycloolefin polymer, polyacrylate, polycarbonate, polyethylene terephthalate and the like.
  • the thickness of the base film may be 10 to 300 in consideration of productivity. However, the present invention is not limited thereto.
  • an anti-reflection film which can simultaneously have high alkali resistance and scratch resistance with low reflectance and high light transmittance and can increase the sharpness of the screen of the display device.
  • the anti-reflection film does not significantly reduce the appearance properties such as reflectance or light transmittance and the mechanical properties such as wear resistance or scratch resistance even when exposed to alkali, so that the application of an additional protective film for protecting the external surface can be omitted. To simplify and reduce production costs.
  • a hard coating solution composition obtained as described above was added to a triacetyl cellulose film.
  • the hard coating solution composition thus obtained was coated with a # 10 mayer bar on a triacetyl cellulose film and dried at 90 ° C. for 1 minute.
  • the dried material was irradiated with ultraviolet light of 150 mJ / ciif to prepare a hard coat film having a thickness of 4 m.
  • Preparation Example 3 Preparation of Hard Coating Film 3 (HD3)
  • a hard coating composition was prepared by adding 2 g of acrylic-styrene copolymer resin fine particles (volume average particle diameter: 2, manufacturer: Sekisui Plastic) having a refractive index of 1.544.
  • the hard coating solution composition thus obtained was coated with a # 10 mayer bar on a triacetyl cellulose film and dried at 90 ° C. for 1 minute.
  • the dried material was irradiated with ultraviolet light of 150 mJ / cin 2 to prepare a hard coat film having a thickness of 4.
  • Preparation Example 4 Preparation of Hard Coating Film 4 (HD4)
  • THRULYA 4320 (catalytic product): Hollow silica dispersion (20 wt 3 ⁇ 4 solid in MIBK solvent)
  • RS907 Fluorine compound containing photoreactive functional group and containing trace amount of silicon, diluted to 30% by weight of solids in MIBK solvent
  • AC-SQ-F manufactured by Dong-A Synthetic Co., Ltd. (silsesquioxane resin functional group concentration 678 g / mol, inorganic fraction 15%, refractive index 1.39) (2) Preparation of low refractive index layer and antireflection film (Examples and Comparative Examples)
  • the photopolymerizable coating composition obtained in Table 1 was coated with # 3 mayer bar, and dried at 60 ° C. for 1 minute.
  • an antireflection film was prepared by irradiating ultraviolet light of 180 mJ / cuf to the dried material under nitrogen purge to form a low refractive layer having a thickness of llOnm.
  • the antireflection films obtained in Examples and Comparative Examples were soaked for 30 seconds in a 55 ° C. NaOH aqueous solution diluted with 1OT with distilled water, washed with water, and then wiped dry.
  • the average reflectance and color coordinate values (b *) in the wavelength range of 380 nm to 780 ran were measured using the SolTspec 3700 (SHIMADZU) 100T mode.
  • the obtained average reflectance data was obtained by converting the UV-240 IPC program.
  • the steel wool (# 0000) was loaded and reciprocated 10 times at a speed of 24 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 was observed with the naked eye was measured.
  • the ellipticity of the polarization was measured by ellipsometry on the antireflection film obtained in each of Examples and Comparative Examples.
  • ⁇ ( ⁇ ) is the refractive index at the ⁇ wavelength
  • ⁇ is in the range of 300 nm to 1800 nm
  • A, B and C is a Kosh parameter.
  • the antireflection film of the example exhibits a relatively low average reflectance and does not have a large variation in color coordinates even after alkali treatment. Moreover, it was confirmed that it has more excellent scratch resistance compared with the comparative example.
  • the anti-radiation film of the embodiment has a ratio of the internal haze (Hi) to the total haze (Ha) of 97% or less, and the anti-reflective film of the anti-reflection film has a variation of the color coordinate value (b *) after alkali pretreatment of 0.28 It was confirmed that the range is from 0.40.
  • the low refractive index layer is A 1.20 to 1.65
  • the following B is 0 to 0.05 and the following C satisfies the Kosh parameter condition of 0 to 0.05
  • the hard coating layer A is 1.30 to 1.75
  • the following B is 0 to 0.05 and the following C is 0 to 0.005 Satisfies the Kosh parameter.
  • the antireflection films of Comparative Examples 1 to 3 had relatively high color coordinate values or low scratch resistance after alkali treatment.
  • the antireflective film of the comparative example has an internal haze ratio to the total haze (Ha) of more than 97% or alkali. It is confirmed that the variation in color coordinate values is relatively large after the treatment, indicating a relatively low light transmittance and poor alkali resistance and optical properties.

Landscapes

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

Abstract

La présente invention concerne un film antireflet comprenant une couche faiblement réfléchissante et une couche de revêtement dur, la couche faiblement réfléchissante comprenant : une résine liante comprenant un polymère réticulé entre un composé photopolymérisable et un polysilsesquioxane substitué par au moins un groupe fonctionnel réactif ; et des microparticules inorganiques dispersées dans la résine liante, le rapport du voile interne (Hi) au voile total (Ha) étant de 97 % ou moins et la variation d'une valeur de coordonnée de couleur (b*) avant et après un traitement alcalin étant de 0,7 ou moins.
PCT/KR2017/002332 2016-03-04 2017-03-03 Film antireflet WO2017150938A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/067,857 US10768342B2 (en) 2016-03-04 2017-03-03 Antireflection film comprising a low refractive index layer and a hard coating layer
EP17760342.0A EP3378902B1 (fr) 2016-03-04 2017-03-03 Film antireflet
CN201780005502.5A CN108473791B (zh) 2016-03-04 2017-03-03 抗反射膜
JP2018548637A JP2019501425A (ja) 2016-03-04 2017-03-03 反射防止フィルム

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160026376 2016-03-04
KR10-2016-0026376 2016-03-04
KR10-2017-0027321 2017-03-02
KR1020170027321A KR101959510B1 (ko) 2016-03-04 2017-03-02 반사 방지 필름

Publications (1)

Publication Number Publication Date
WO2017150938A1 true WO2017150938A1 (fr) 2017-09-08

Family

ID=59744242

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/002332 WO2017150938A1 (fr) 2016-03-04 2017-03-03 Film antireflet

Country Status (1)

Country Link
WO (1) WO2017150938A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019181165A1 (fr) * 2018-03-20 2019-09-26 株式会社ダイセル Film antireflet

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100249265A1 (en) * 2009-03-26 2010-09-30 Engardio Thomas J Scratch-resistant coatings with improved adhesion to inorganic thin film coatings
KR20130118069A (ko) * 2012-04-19 2013-10-29 제일모직주식회사 윈도우 시트 및 이를 포함하는 디스플레이 장치
WO2014092391A1 (fr) * 2012-12-13 2014-06-19 동우화인켐 주식회사 Film de revêtement dur pour substitution en tant que verre trempé
KR20140140139A (ko) * 2013-05-23 2014-12-09 에스케이이노베이션 주식회사 반사방지용 코팅조성물 및 이를 이용한 광학 필름
KR20160019367A (ko) * 2014-08-11 2016-02-19 주식회사 엘지화학 반사 방지 필름

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100249265A1 (en) * 2009-03-26 2010-09-30 Engardio Thomas J Scratch-resistant coatings with improved adhesion to inorganic thin film coatings
KR20130118069A (ko) * 2012-04-19 2013-10-29 제일모직주식회사 윈도우 시트 및 이를 포함하는 디스플레이 장치
WO2014092391A1 (fr) * 2012-12-13 2014-06-19 동우화인켐 주식회사 Film de revêtement dur pour substitution en tant que verre trempé
KR20140140139A (ko) * 2013-05-23 2014-12-09 에스케이이노베이션 주식회사 반사방지용 코팅조성물 및 이를 이용한 광학 필름
KR20160019367A (ko) * 2014-08-11 2016-02-19 주식회사 엘지화학 반사 방지 필름

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3378902A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019181165A1 (fr) * 2018-03-20 2019-09-26 株式会社ダイセル Film antireflet
JP2019164255A (ja) * 2018-03-20 2019-09-26 株式会社ダイセル 反射防止フィルム

Similar Documents

Publication Publication Date Title
KR101889956B1 (ko) 반사 방지 필름
EP3243884B1 (fr) Composition de revêtement durcissable par rayonnement, couche à faible indice de réfraction, et film antireflet
CN108473791B (zh) 抗反射膜
KR102093950B1 (ko) 반사 방지 필름 및 이의 제조 방법
JP6732015B2 (ja) 反射防止フィルム
WO2017119658A1 (fr) Film antireflet
KR102086054B1 (ko) 광경화성 코팅 조성물, 저굴절층 및 반사 방지 필름
KR20130120223A (ko) 내찰상성이 우수한 반사 방지 필름 및 이의 제조 방법
KR102055928B1 (ko) 광경화성 및 열경화성을 갖는 코팅 조성물, 저굴절층 및 반사 방지 필름
WO2017155336A1 (fr) Film antireflet
WO2017150938A1 (fr) Film antireflet
WO2017160027A1 (fr) Film antireflet
WO2017052186A1 (fr) Composition de revêtement photodurcissable, couche basse réfraction, et film antireflet
WO2017155358A1 (fr) Film antireflet et son procédé de production

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2018548637

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2017760342

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2017760342

Country of ref document: EP

Effective date: 20180620

NENP Non-entry into the national phase

Ref country code: DE