WO2017155336A1 - Film antireflet - Google Patents

Film antireflet Download PDF

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Publication number
WO2017155336A1
WO2017155336A1 PCT/KR2017/002581 KR2017002581W WO2017155336A1 WO 2017155336 A1 WO2017155336 A1 WO 2017155336A1 KR 2017002581 W KR2017002581 W KR 2017002581W WO 2017155336 A1 WO2017155336 A1 WO 2017155336A1
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WO
WIPO (PCT)
Prior art keywords
substituted
functional group
film
group
fluorine
Prior art date
Application number
PCT/KR2017/002581
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English (en)
Korean (ko)
Inventor
김부경
장영래
심재훈
박진영
구재필
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2018533614A priority Critical patent/JP6789593B2/ja
Priority to US16/064,039 priority patent/US11312874B2/en
Priority to EP17763597.6A priority patent/EP3415959B1/fr
Priority to CN201780005868.2A priority patent/CN108431639B/zh
Priority claimed from KR1020170029955A external-priority patent/KR101889956B1/ko
Publication of WO2017155336A1 publication Critical patent/WO2017155336A1/fr

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Classifications

    • 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

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 using scattering of light through unevenness.
  • the AG coating has poor screen clarity due to surface irregularities, many studies on AR coatings have recently been made.
  • the film using the AR coating As the film using the AR coating, 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 commercialized.
  • the interlayer adhesion force interface adhesion force
  • the interlayer adhesion force is increased by separately performing the process of forming each layer. It is weak and has a disadvantage of poor scratch resistance.
  • 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 binder resin comprising a crosslinked polymer between a photopolymerizable compound and a polysilsesquioxane substituted with at least one semi-functional 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 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer is 0.0 an to 0.2.
  • Rz 10-point average roughness
  • the photopolymerizable compound is collectively referred to as a compound that causes polymerization reaction when irradiated with light, for example, visible light or ultraviolet light.
  • (meth) acryl [(Meth) acryl] is meant to include both acryl and Methacryl.
  • (co) polymers are co-polymers and homopolymers (homo— polymer) means to include both.
  • hollow silica particles are silica particles derived from a silicon compound or an organosilicon compound, and particles having a form in which empty space exists on the surface and / or inside of the silica particles. it means.
  • a binder resin comprising a cross-linked polymer between the photopolymerizable compound and polysilsesquioxane (polysi 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 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer is 0.05 ffli to 0.2 m.
  • Prevention films may be provided.
  • the present inventors have conducted research on the low refractive index layer and the antireflection film, and include the aforementioned low refractive index layer and the hard coating layer, and the above-described numerical values relating to the 10-point average roughness Rz of the uneven shape of the surface of the low refractive index layer.
  • a satisfactory anti-reflective film can realize lower reflectance and high light transmittance, improve alkali resistance, secure excellent wear resistance or scratch resistance, and increase the sharpness of the screen of the display device while showing excellent mechanical properties.
  • the 10-point average roughness Rz of the uneven shape of the surface of the low refractive index layer is 0.05 // m to 0.2, or 0.10 / -0.180 ⁇ , or 0.127 / m-0.141 kPa Can be.
  • the anti-reflection film derives an optimal surface concave-convex structure that can realize antireflection effect and visibility simultaneously.
  • the surface roughness of the antireflection film is represented by the ten-point average roughness Rz of the surface irregularities.
  • the ten-point average roughness refers to the sum of the average values of the absolute values of the five highest height peaks and the five lowest valleys, based on the average line, within the measurement length in the surface unevenness curve.
  • Rz which is the height of 10-point unevenness
  • Rz is 0.05 to 0.2 / ⁇ , or 0. 10 / ⁇ To 0.180, or 0.127 / ⁇ to 0.141
  • the antireflection effect and visibility may be simultaneously implemented.
  • the 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive index layer is less than 0.03 ⁇ 4, the antireflection effect and the poor hiding power of the panel are reduced, and the 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer is reduced.
  • the ten-point average roughness Rz of the uneven shape of the surface of the low refractive layer can be measured using a non-contact surface profiler (3D Optical Profiler).
  • the total haze and the internal haze of the anti-reflection film may be less than, respectively, specifically, the total haze of the anti-reflection film may be 3% or less, or 2% to 3%, or 2.5% to 2/75%.
  • the internal haze of the antireflection film may be 2.7% or less, or 2% to 2.7%, or 2.30% to 2.65%.
  • 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 anti-reflection film has a ratio of the internal haze (Hi) to the total haze (Ha) of 97% or less, or 96% or less, or 30% to 96%, or 90% to 96%, or 92.0% to 95.90 3 ⁇ 4).
  • the ratio of the internal haze to the total haze (Ha) in the anti-reflection film exceeds 97%, the surface haze (Hs) ratio of the total haze (Ha) becomes less, substantially the Not only is the antireflective film not easy to ensure a sufficiently low reflectance, but also the interference fringes of the antireflective film are easily exposed, so that the sharpness or visibility may be degraded in the finally applied display device.
  • the anti-reflection film may implement a low reflectance and a high light transmittance, and specifically, surface properties and optical properties may not change significantly before and after exposure to alkali.
  • the antireflection 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, 0.2 to 0.45, or 0.3 to 0.42. have.
  • the anti-reflection film was measured before and after the predetermined alkali treatment, and the measurement of the variation of the color coordinate value (b *) was carried out for 1 second to 100 seconds in an alkaline aqueous solution (sodium hydroxide, etc.) diluted with 5 to 5 OT in distilled water after optical pretreatment. It can be measured using.
  • an alkaline aqueous solution sodium hydroxide, etc.
  • the antireflection film may have an average reflectance of 2.5% or less, or 2.0% or less, 1.6% or less, or 1.10% to 2.25% in the visible light wavelength range of 380 nm to 780 nm.
  • the low refractive layer has a thickness of Iran to 200nm
  • the hard coating layer may have a thickness of 0.1 to 1 or 10.
  • 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 semi-ungular functional group on its surface to increase mechanical properties of the low refractive index layer, for example, scratch resistance, and may include silica, alumina, Unlike the case of using fine particles such as zeolite, the alkali resistance of the low refractive index layer While improving, external appearance characteristics such as average reflectance and color can be improved.
  • the low refractive index layer is a binder resin containing a cross-linked polymer between a photopolymerizable compound and a polysilsesquioxane (po lys i I sesqui oxane) substituted with at least one semi-functional group and inorganic fine particles dispersed in the binder resin It may include.
  • the polysilsesquioxane may be represented as (! ⁇ ⁇ ⁇ (Where n is 4 to 30 or 8 to 20), and may have a variety of structures, such as random, ladder, cage and partial cage have.
  • the semi-functional functional group is substituted with one or more polysilsesquioxanes having one or more reactive functional groups substituted therein.
  • Polyhedral oligomeric silsesquioxane Polyhedral Oligomeric Si I sesquioxane
  • 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-acyclic functional groups may be substituted with silicones not having a semi-active functional group substituted therein.
  • a reactive functional group such as a methyl methacrylate, a methyl methacrylate, a methyl methacrylate, and the above-mentioned non-acyclic functional groups may be substituted with silicones not having a semi-active functional group substituted therein.
  • silicones of the polyhedral oligomeric silsesquioxane having a cage structure may be substituted with a reactive functional group, and the above-mentioned non-acyclic functional groups may be substituted with silicones not having a semi-active functional group substituted therein.
  • the mechanical properties of the coating film or the binder resin formed during photopolymerization of the photopolymerizable coating composition may be improved.
  • the non-acyclic functional group is substituted in the remaining silicon, the molecular structural steric hindrance appears, thereby greatly reducing the frequency or probability of exposing the siloxane bond (-Si-0-) to the outside and thus the photopolymerizable property.
  • the alkali resistance of the coating film and binder resin formed at the time of photopolymerization of a coating composition can be improved.
  • the semi-functional group substituted in the polysilsesquioxane is alcohol, amine, Carboxylic acids, epoxides, imides, (meth) acrylates, nitriles, norbornenes, olefins [ally, cycloalkenyl or vinyldimethylsilyl], polyethylene glycol, thiol and vinyl groups It may include one or more functional groups selected from the group consisting of, preferably epoxide or (meth) acrylate.
  • the semi-functional group include (meth) acrylate, alkyl (meth) acrylate having 1 to 20 carbon atoms, cycloalkyl epoxide having 3 to 20 carbon atoms, and alkyl cycloalkane having 1 to 10 carbon atoms ( cyc loalkane) epoxide.
  • 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 bond site alkyl cycloalkane (epoxy) epoxide means that the other portion of the 'alkyl' that does not bond with the cycloalkane (cyc loalkane) epoxide is the binding site.
  • 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.
  • a siloxane bond (-Si-0-) is formed in the molecule in the polysilsesquioxane in which the reactive functional group is substituted at least. While being positioned so as not to be exposed to the outside, the alkali resistance and scratch resistance of the low refractive index layer and the antireflection film may be further improved.
  • P0SSs polyhedral oligomeric silsesquioxanes
  • TMP Diol lsobutyl P0SS Cyclohexanediol Isobutyl P0SS, 1, 2 ⁇ Propanediol P0SS wherein Is is substituted with at least one alcohol such as Duty 1 P0SS, 0c ta (3-hydroxy-3 methylbutyldimethyl sioxy) P0SS; Aminopropyl Isobutyl P0SS, Aminopropyl Isooctyl P0SS, Aminoethylaminopropyl Isobutyl POSS, N-Pheny 1 am i nop r opy 1 POSS, N ⁇ Me t hy 1 am i no r opy 1 Isobutyl POSS, OctaAmmonium POSS,
  • POSS substituted with at least one amine such as Am i nopheny 1 Cy c 1 ohexy 1 POSS and Aminophenyl Isobutyl POSS; POSS in which at least one carboxylic acid is substituted, such as Maleamic Ac-Cycl ohexy 1 POSS, Maleamic Acid-Isobutyl POSS, Oct a Maleamic Acid POSS; POSS substituted with at least one epoxide such as EpoxyCyc 1 ohexy 1 Isobutyl POSS, Epoxycycl ohexy 1 POSS, Glycidyl POSS, GlycidylEthyl POSS, Glycidyl Isobutyl POSS, Glycidyl Isooctyl POSS; POSS maleimide Cyc 1 ohexy 1, POSS Maleimide Isobutyl, and the like; Acrylolsobutyl POSS, (Meth) acryl Is
  • POSS in which one or more (meth) acrylates are substituted, such as (Meth) acryl Isooctyl POSS, (Meth) acrylPhenyl POSS, (Meth) acryl POSS, and Acrylo POSS; POSS in which at least one nitrile group such as Cyanopropyl Isobutyl POSS is substituted; POSS in which at least one norbornene group is substituted, such as NorbornenylEthyl POSS, Norbornenyl ethyl Isobutyl POSS, Nor bornenyl ethyl DiSi lanolsobutyl POSS, and Tr isnorbornenyl Isobutyl POSS; POSS substituted with at least one vinyl group such as Allyllsobutyl POSS, MonoVinyllsobutyl POSS, OctaCyclohexenyldimethylsilyl POSS, OctaVinyldimethyl
  • the weight ratio of a portion derived from the binder resin compared to a part derived from a photopolymerizable compound from the male half functional group is one or more substituted polysilsesquioxane (p 0 ly S il sesqu oxane i) the
  • a monomer or oligomer containing a (meth) acrylate or a vinyl group may be included.
  • 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.
  • the monomer or oligomer containing the (meth) acrylate include tri (meth) acrylate for pentaerythrite, tetra (meth) acrylate for pentaerythri, penta (meth) acrylate for dipentaerythr, Dipentaerythri nucleus (meth) acrylate, tripentaerythrib hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, nucleamethylene diisocyanate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane polyespecial tri (meth) acrylate, trimethyl propane trimethacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, nuxaethyl methacrylate, butyl methacrylate or two or more thereof Compounds, or urethane modified acrylate oligomers, epox
  • the monomer or oligomer containing the vinyl group include divinylbenzene, styrene or paramethylstyrene.
  • the content of the portion derived from the photopolymerizable compound in the binder resin is not limited to a large amount, the content of the photopolymerizable compound is 20% by weight to 80 in consideration of mechanical properties of the low refractive index layer or the antireflection film to be manufactured. Weight%.
  • the low refractive index 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 further increase 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 one or more semi-active functional groups are 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 photoreactive functional group may include various functional groups known to be able to participate in the polymerization reaction by irradiation of light, and specific examples thereof include (meth) acrylate groups, epoxide groups, vinyl groups, or thiol groups ( Thiol) is mentioned.
  • fluorine-based compounds including photoreactive functional groups, may have a fluorine content of 1 to 60 weight 3 ⁇ 4>. If the content of fluorine is too small in the fluorine-based compound including the photoreactive functional group, it may be difficult to sufficiently secure physical properties such as alkali resistance because the fluorine component may not be sufficiently arranged on the surface of the low refractive index layer. In addition, if the content of the fluorine 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 anti-reflection film is subjected to a peeling voltage during a post-process to produce a product (for example, a TV or a monitor) to which the antireflection film is finally applied.
  • a product for example, a TV or a monitor
  • the fluorine content of the 1% to 25% by weight A fluorine-based compound including a photobanung functional group having can be used.
  • the fluorine-based compound including the photoreactive functional group may further include silicon or a silicon compound. That is, the fluorine-based compound including the photoreactive functional group may optionally contain a silicon or silicon compound therein, specifically, the content of silicon in the fluorine-based compound including the photoreactive functional group is from 0.01% to 20% by weight> day. Can 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 bloso-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 may have a weight average molecular weight (weight average molecular weight in terms of polystyrene measured by the GPC method) of 2,000 to 200, 000. If the weight average molecular weight of the fluorine-based compound including the photoreactive functional group is too small, the low refractive index layer may not have sufficient 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 photo-reflective 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 at least one photo-reflective functional group is substituted, and at least one fluorine is substituted for at least one carbon; ii) 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; 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 with at least one photoreactive functional group and at least one hydrogen is substituted with fluorine Polyether compounds, or a mixture of two or more of the above i) to iv) or a copolymer thereof.
  • the low refractive layer may include 1 to 75 parts by weight of the fluorine 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 amount of the fluorine-based compound including the photoreactive functional group relative to the photopolymerizable compound is too small, the low refractive index layer may not have sufficient alkali resistance.
  • the binder resin is fluorine-based 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 is from 0.01% to 0.1%. May be 10%.
  • 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 carbon number 1
  • a is an integer of 0-7
  • b is an integer of 1-3.
  • 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 nanoparticle refers to a particle having a maximum diameter of 100 nm or less and having no empty space therein.
  • the hollow inorganic nanoparticles mean a particle having a maximum diameter of 200 ran or less and a hollow space present on the surface and / or inside thereof.
  • the solid inorganic nanoparticles may have a diameter of 0.5 to ⁇ ⁇ ⁇ ⁇ , or from 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 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 improving scratch and antifouling properties. It can be secured.
  • 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 bloso-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 compound on the surface of the hollow inorganic nanoparticles can be used without great limitation.
  • the hollow inorganic nanoparticles and the fluorine compound can be used as a catalyst for water and a catalyst. Hydrolysis and condensation by sol-gel reaction in the presence of Through the reaction, the fluorine-based compound may be bonded to the surface of the hollow inorganic nanoparticle.
  • 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 groups that can be substituted on the surface of the hollow silica particles are not particularly limited, and examples thereof include (meth) acrylate groups, vinyl groups, hydroxy groups, amine groups, and allyl groups; An epoxy group, a hydroxyl group, an 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 300 parts by weight based on the loo parts by weight of the photopolymerizable compound.
  • the low refractive layer is a photopolymerizable coating composition comprising a photopolymerizable compound, inorganic fine particles and polysilyl sesquioxane substituted with one or more semi-functional functional groups on a predetermined substrate and applied It can be obtained by photopolymerizing the result.
  • the specific kind or thickness of the substrate is not particularly limited, and a substrate known to be used in the manufacture of a low refractive index layer or an antireflection film can be used without great limitation.
  • the 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 is greatly limited as long as it is a compound known to be used in the photopolymerizable resin composition. It may be used without, and specifically, a benzophenone compound, acetophenone compound, biimidazole compound, triazine compound, oxime compound, or a combination of two or more thereof may 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.
  • the photopolymerizable coating composition may further include an organic solvent.
  • the organic solvents include ketones, alcohols, acetates and ethers, or combinations of two or more thereof.
  • 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-butane, 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.
  • 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-butane, or
  • 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. If the content of the organic solvent in the photopolymerizable coating composition is too small, defects may occur such that the flowability of the photopolymerizable coating composition is lowered, resulting in streaks in the final film. In addition, when 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. Accordingly, the photopolymerizable 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 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.
  • the exposure amount is preferably 100 to 4,000 mJ / cin 2 when irradiated.
  • Exposure time is also special It is not limited, It can change suitably according to the exposure apparatus used, the wavelength of irradiation light, or an exposure amount.
  • the hard coating layer can be used without a large limitation to the conventional known hard coating layer.
  • 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 resin is a semi-ungsung acrylate oligomer group consisting of urethane acrylate oligomer, epoxide acrylate oligomer, polyester acrylate, and polyether acrylate; And dipentaerythritol nucleoacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythroli tetraacrylate, pentaerythroli triacrylate, trimethylene propyl triacrylate, propoxylated glycerol Triacrylate Trimethylpropane polyfunctional acrylate consisting of triacrylate, 1, 6-nucleic acid diol diacrylate, propoxylated glycerol triacrylate, tripropylene glycol
  • 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 nm, or 1 nm to 300 nm. .
  • the organic or inorganic fine particles included in the hard coating film are not limited.
  • the organic or inorganic fine particles may be acrylic resin, styrene resin, epoxide resin, and nylon. It may be organic fine particles made of a resin or inorganic fine particles made of silicon oxide, titanium dioxide, indium oxide, tin oxide, zirconium oxide and zinc oxide.
  • the binder resin of the hard coating film 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 at least one selected from the group consisting of a cellulose polymer, an acrylic polymer, a styrene polymer, an epoxide polymer, a nylon polymer, a urethane polymer, and a polyolefin polymer.
  • 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.
  • a binder resin of a photopolymerizable resin As another example of 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 the (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 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, trimethyl propane It may be at least one member selected from the group consisting of meth) acrylate, and trimethylolpropane polyethoxy tri (meth) acrylate.
  • the antistatic agent may be a quaternary ammonium salt compound, a conductive polymer or a combination thereof.
  • the quaternary ammonium salt compound is in the molecule It may be a compound having one or more quaternary ammonium bases, and low molecular or polymer types may be used without limitation.
  • 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, methacryloxypropyl It may be at least one compound selected from the group consisting of trimethoxysilane, glycidoxypropyl trimethoxysilane, and glycidoxypropyl trioxysilane.
  • the metal alkoxide-based oligomer may be prepared through the sol-gel reaction of the composition comprising a metal alkoxide-based compound and water.
  • the sol-gel reaction can be carried out by a method similar to the method for producing an alkoxy silane oligomer described above.
  • the sol-gel reaction may be performed by diluting the metal alkoxide compound in an organic solvent and slowly dropping water.
  • the molar ratio of the metal alkoxide compound to water is preferably adjusted within the range of 3 to 170.
  • the metal alkoxide-based compound may be at least one compound selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide, and aluminum isopropoxide.
  • the 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.
  • a photopolymerizable coating composition capable of providing a low refractive index layer having both low reflectance and high light transmittance and simultaneously providing high alkali resistance and scratch resistance, and a low refractive layer obtained from such a photopolymerizable coating composition.
  • Anti-reflection film may be provided that can increase the sharpness of the screen of the display device and yet exhibit excellent mechanical properties.
  • the low refractive index layer does not significantly reduce the appearance properties such as reflectance or light transmittance and the mechanical properties such as abrasion resistance or scratch resistance even when exposed to alkali, so that the application of an additional protective film for external surface protection can be omitted. To simplify and reduce production costs.
  • 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. 150 mJ / cirf was irradiated to the dried material to prepare a hard coat film having a thickness of 6.
  • Preparation Example 2 Preparation of Hard Coating Film 2 (HD2)
  • the hard coating solution composition thus obtained was applied 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 / cuf to prepare a hard coating film having a thickness of 6 kPa.
  • Preparation Example 4 Preparation of Hard Coating Film 4 (HD4)
  • Pentaerythritol triacrylate 30 g high molecular weight co-polymer (BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000) 2.5 g, methyl ethyl ketone 20 g, photoinitiator (Irgacure 184, ciba) 2 g and leveling agent (Tego wet 270) )
  • BEAMSET 371, Arakawa, Epoxy Acrylate, molecular weight 40,000 2.5 g
  • methyl ethyl ketone 20 g photoinitiator (Irgacure 184, ciba) 2 g and leveling agent (Tego wet 270)
  • acrylic-styrene copolymer resin fine particles (Techpolymer, average particle diameter: 2 ⁇ m, manufacturer: Sekisui Plastic) having a refractive index of 1.544 were added to prepare a hard coating composition.
  • 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. 150 mJ / ciif was irradiated to the dried material to prepare a hard coat film having a thickness of 6 kPa.
  • Preparation Example 5 Preparation of Hard Coating Film 5 (HD5)
  • the hard coating solution composition thus obtained was applied to a triacetyl cellulose film.
  • photoinitiator Irgacure 184, ciba
  • leveling agent Tiego wet 270
  • the hard coating solution composition thus obtained was applied to a triacetyl cellulose film.
  • THRULYA 4320 catalyzed product: hollow silica dispersion (solids 20 weight D 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%, refraction 1.39) (2) Preparation of low refractive index layer and antireflection film
  • 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 180 mJ / citf of ultraviolet rays 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. aqueous NaOH solution diluted with 10% of distilled water, washed with water, and then wiped dry.
  • the steel wool (# 0000) 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 ten-point average roughness of the surface irregularities of the antireflection film obtained in each of the above Examples and Comparative Examples was measured using a white light three-dimensional optical interference profile (3D opt i cal prof iler, model name: NewView 7300, Zygo). .
  • the lens magnification used measured the area
  • the antireflection film to be measured is placed on the sample stage in a flat state, and then proceeded after obtaining an opt i cal prof i ler image. At this time, the measurement was performed by setting the horizontal length to 3mm, and 10-point average roughness was calculated by obtaining two to three line prof iles from the image obtained here. 5. Haze measurement
  • Pentaerythride is mixed with triacrylate and Ebecryl 220 (oligomer of SK cytec) in a weight ratio of 6: 1, and solid content 60 in a 2: 1 weight ratio mixed solvent of methyl ethyl ketone and toluene. Diluted to a weight%, and applied to the dry film thickness mi using wi re bar, and then the surface irregularities were flattened after drying and curing. 6. Sharpness Measurement
  • the image sharpness was measured using an ICM-1T of Sugar Test Instrument.
  • the sharpness values of the slits of 1.125 s and the values of the sharpness of 0,125 s, 0.5 s, 1.0 s and 2.0 mm slit were added to compare the image sharpness.
  • 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. It was confirmed that it has more excellent scratch resistance compared with.
  • the 10-point average roughness (Rz) of the concave-convex shape of the surface of the low refractive layer included in the anti-reflection film of the embodiment is 0.0 zm to 0. an
  • the anti-reflection film has a color coordinate value (b) after alkali pretreatment. It was confirmed that the variation of *) was in the range of 0.25 to 0.45. It was also confirmed that the total haze of the antireflection film was 3% or less and the internal haze was 2.7 3 ⁇ 4> or less, and the ratio of the internal haze (Hi) to the total haze (Ha) of the antireflection film was 97% or less.
  • the value in the narrow slit may be high and the image is clear, and the image sharpness measurement result for the antireflection film is 0.125. It is applicable to the high resolution display when the image sharpness in the mm slit is 80% or more and the sum of the image sharpness values excluding the 0.25 mm slit is 350% or more. It was confirmed that the numerical values of the image sharpness and the image sharpness of the 125 mm slit satisfy all of the above-mentioned ranges.
  • the antireflection film of the comparative example had a relatively large variation in color coordinate values or low scratch resistance after alkali treatment.
  • the antireflective film of the comparative example exhibits relatively high total haze (Ha) and internal haze (Hi) values, and also has a relatively low image sharpness in the 0.125 ⁇ slit, thus having a relatively low light transmittance and a thermal optical It is confirmed that the characteristics are shown.

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Abstract

La présente invention concerne un film antireflet comprenant une couche de revêtement dur et une couche à faible indice de réfraction, qui comprend : une résine de liant comprenant un polymère réticulé entre un composé photopolymérisable et un polysilsesquioxane substitué par un ou plusieurs groupes fonctionnels réactifs ; et des microparticules inorganiques dispersées dans la résine de liant, la rugosité moyenne de dix points (Rz) de la forme des irrégularités sur la surface de la couche à faible indice de réfraction étant comprise entre 0,05 et 0,2 µm.
PCT/KR2017/002581 2016-03-09 2017-03-09 Film antireflet WO2017155336A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2018533614A JP6789593B2 (ja) 2016-03-09 2017-03-09 反射防止フィルム
US16/064,039 US11312874B2 (en) 2016-03-09 2017-03-09 Antireflection film
EP17763597.6A EP3415959B1 (fr) 2016-03-09 2017-03-09 Film antireflet
CN201780005868.2A CN108431639B (zh) 2016-03-09 2017-03-09 抗反射膜

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KR20160028464 2016-03-09
KR10-2016-0028464 2016-03-09
KR10-2017-0029955 2017-03-09
KR1020170029955A KR101889956B1 (ko) 2016-03-09 2017-03-09 반사 방지 필름

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JPWO2019187746A1 (ja) * 2018-03-26 2021-02-12 株式会社ダイセル ニュートンリング防止フィルム並びにその製造方法及び用途
JP2021509973A (ja) * 2018-10-17 2021-04-08 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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KR20080040927A (ko) * 2006-11-06 2008-05-09 제일모직주식회사 반사방지 필름 코팅용 조성물, 이를 이용한 반사 방지 필름및 반사 방지 필름을 포함하는 화상 표시 장치
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KR20080040927A (ko) * 2006-11-06 2008-05-09 제일모직주식회사 반사방지 필름 코팅용 조성물, 이를 이용한 반사 방지 필름및 반사 방지 필름을 포함하는 화상 표시 장치
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2019187746A1 (ja) * 2018-03-26 2021-02-12 株式会社ダイセル ニュートンリング防止フィルム並びにその製造方法及び用途
JP7008127B2 (ja) 2018-03-26 2022-01-25 株式会社ダイセル ニュートンリング防止フィルム並びにその製造方法及び用途
JP2021509973A (ja) * 2018-10-17 2021-04-08 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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