WO2017142291A1 - Composition de revêtement photodurcissable pour former une couche à faible réfraction - Google Patents

Composition de revêtement photodurcissable pour former une couche à faible réfraction Download PDF

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Publication number
WO2017142291A1
WO2017142291A1 PCT/KR2017/001609 KR2017001609W WO2017142291A1 WO 2017142291 A1 WO2017142291 A1 WO 2017142291A1 KR 2017001609 W KR2017001609 W KR 2017001609W WO 2017142291 A1 WO2017142291 A1 WO 2017142291A1
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WIPO (PCT)
Prior art keywords
low refractive
inorganic nanoparticles
layer
coating composition
refractive index
Prior art date
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PCT/KR2017/001609
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English (en)
Korean (ko)
Inventor
변진석
김재영
김부경
장석훈
장영래
Original Assignee
주식회사 엘지화학
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Publication date
Priority claimed from KR1020170019349A external-priority patent/KR102077797B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780003681.9A priority Critical patent/CN108139668B/zh
Priority to EP17753452.6A priority patent/EP3336604B1/fr
Priority to US15/762,383 priority patent/US11680172B2/en
Priority to JP2018515203A priority patent/JP6812630B2/ja
Publication of WO2017142291A1 publication Critical patent/WO2017142291A1/fr

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    • 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
    • C08J7/043—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
    • 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
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

Definitions

  • the present invention relates to a photocurable coating composition for forming a low refractive index, a method for producing an antireflective film using the photocurable coating composition, and an antireflective film prepared using the photocurable coating composition.
  • 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 a filler such as inorganic fine particles in a resin and coating on a base film and imparting irregularities (ant i-glare: AG coating); There are a method of forming a plurality of layers having different refractive indices on a base film to use interference of light (ant i-ref lect ion: AR coating), or a method of using them in common.
  • 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, many studies on AR coatings have been made recently.
  • the film using the AR coating a multilayer structure in which a hard coating layer (high refractive layer), a low refractive layer, and the like are laminated on a base film is commercially available.
  • the method of forming a plurality of layers as described above has a disadvantage in that scratch resistance is inferior due to weak adhesion between the layers (interface ' adhesive force) as a separate process of forming each layer.
  • a method of adding various particles having a nanometer size for example, particles of silica, alumina, zeolite, etc.
  • the present invention provides a photocurable coating composition for forming a low refractive layer.
  • the present invention also provides a method for producing an antireflective film using the photocurable coating composition.
  • the present invention also provides an antireflection film prepared using the photocurable coating composition.
  • the present inventors have conducted research on the antireflection film, so that the hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles are surface-treated in a binder resin in which the low refractive layer of the anti-reflection film can be combined with the hard coating layer.
  • the present invention was completed by confirming that having a structure distributed so as to distinguish from each other can realize high scratch resistance and antifouling property while showing very low reflectance and high light transmittance.
  • a photocurable coating composition for forming a low refractive layer according to a specific embodiment of the present invention, a method for producing an antireflection film for forming a low refractive layer using the photocurable coating composition and an antireflection film prepared by the method This will be described.
  • the invention comprises two or more photopolymerizable compounds, photoinitiators, surface-treated hollow inorganic nanoparticles and surface-treated solid inorganic nanoparticles, one or more of the two or more photopolymerizable compounds
  • the compound is provided with a photocurable coating composition for forming a low refractive index layer represented by the formula (1).
  • R 1 is 2 ⁇
  • X is hydrogen, a monovalent moiety derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxycarbonyl group having 1 to 4 carbon atoms,
  • Y is a single bond, -co- or -coo-
  • R 2 is a divalent moiety derived from an aliphatic hydrocarbon having 1 to 20 carbon atoms, or at least one hydrogen of the divalent moiety is a divalent moiety substituted with a hydroxy, carboxyl or epoxy group, or at least one of the divalent moieties. Divalent residues substituted with -0-, -C0-0-, -0-C0- or -0-C0-0- so that -C3 ⁇ 4-oxygen atoms are not directly linked,
  • A is any of monovalent residues derived from hydrogen and aliphatic hydrocarbons having 1 to 6 carbon atoms,
  • B is any one of monovalent residues derived from aliphatic hydrocarbons having 1 to 6 carbon atoms
  • n is an integer of 0-2.
  • the photopolymerizable compound which may be included in the photocurable coating composition according to the embodiment may include a monomer or oligomer including a (meth) acryloyl group or a vinyl group.
  • a 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) acryloyl [(meth) acryloyl] is acryloyl (acryloyl) And methacryloyl.
  • the photocurable coating composition according to the embodiment comprises two or more such photopolymerizable compounds, and one or more photopolymerizable compounds (hereinafter referred to as ' ⁇ photopolymerizable compound 1 ') of two or more photopolymerizable compounds. It includes a compound represented by the formula (1).
  • the monovalent moiety derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms may be a straight chain, branched chain or cyclic alkyl group or an alkenyl group.
  • the monovalent moiety derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms may be a straight chain alkyl group having 1 to 6 carbon atoms; Straight chain alkyl groups having 1 to 3 carbon atoms; Branched or cyclic alkyl groups having 3 to 6 carbon atoms; Straight chain alkenyl group having 2 to 6 carbon atoms; Or a branched or cyclic alkenyl group having 3 to 6 carbon atoms.
  • the monovalent residue derived from an aliphatic hydrocarbon having 1 to 6 carbon atoms is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n_ It may be a pentyl group, i so _ pentyl group, neo- pentyl group, n_ nucleosil group, tert- nucleosil group, is is nuclear group, ne hexyl group or cyclonuclear group.
  • the alkoxy group having 1 to 6 carbon atoms may be a straight chain, branched chain or cyclic alkoxy group.
  • the alkoxy group having 1 to 6 carbon atoms is a straight alkoxy group having 1 to 6 carbon atoms; Linear alkoxy groups having 1 to 3 carbon atoms; Or a C3-C6 branched-chain or cyclic alkoxy group.
  • the alkoxy group having 1 to 6 carbon atoms has a hydroxy group, an hydroxy group, n-propoxy group, i so-propoxy group, n-subgroup, i so-subgroup, tert-subgroup, n_pentoxy group , i so-pentoxy group, neo_phenoxy group, n_ nucleooxy group, i so-nucleooxy group, tert-nucleooxy group, neo-nucleooxy group or cyclonucleooxy group.
  • the alkoxycarbonyl group having 1 to 4 carbon atoms has a structure of —C 0 -R a and R a may be an alkoxy group having 1 to 4 carbon atoms.
  • the alkoxycarbonyl group having 1 to 4 carbon atoms may be -C0-0C3 ⁇ 4, -C0-0CH 2 CH 3 or -C0-0C3 ⁇ 4CH 2 C3 ⁇ 4 and the like.
  • a single bond means a case where no separate atom is present in the portion represented by Y.
  • the divalent residue derived from an aliphatic hydrocarbon having 1 to 20 carbon atoms is straight or branched chain. Or a cyclic alkylene group or an alkenylene group.
  • the divalent residue derived from an aliphatic hydrocarbon having 1 to 20 carbon atoms may be a straight alkylene group having 1 to 20 carbon atoms; Straight chain alkylene groups having 1 to 10 carbon atoms; Linear alkylene groups having 1 to 5 carbon atoms; Branched or cyclic alkylene groups having 3 to 20 carbon atoms; Branched or cyclic alkylene groups having 3 to 15 carbon atoms; Branched or cyclic alkylene groups having 3 to 10 carbon atoms; Linear alkenylene groups having 2 to 20 carbon atoms; Or a branched or cyclic alkenylene group having 3 to 20 carbon atoms.
  • the divalent residue derived from an aliphatic hydrocarbon having 1 to 20 carbon atoms is methylene group, ethylene group, n-propylene group, 1, 2-propylene group, n-butylene group, 1, 2-butylene group or isobutylene group And the like.
  • Non-limiting examples of the divalent residue in which at least one hydrogen of the divalent residue is substituted with a hydroxy group, a carboxyl group or an epoxy group include a 1-hydroxypropylene group and a propylene group where one hydrogen of the propylene group is substituted with a hydroxyl group.
  • the first photopolymerizable compound is a -R 1 group and a hard coating layer which may be polymerized with another photopolymerizable compound other than Chemical Formula 1 (hereinafter, referred to as ' first second photopolymerizable compound') to form a binder resin of a low refractive layer. It contains-Si (B) n (0-A) 3- thoughtsgroup that can be combined with. Accordingly, by using the first photopolymerizable compound, a low refractive index layer bonded to the hard coating layer may be formed.
  • the -Si (B) n (0-A) 3 - n group of the first photopolymerizable compound is combined with the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles and the black-black interaction
  • the hollow inorganic nanoparticles surface-treated and the solid inorganic nanoparticles surface-treated may be more strongly fixed to the binder resin of the low refractive layer.
  • the first photopolymerizable compound does not include an aromatic ring in the -R 2 group can form a low refractive index layer of low refractive index.
  • a compound represented by the following Chemical Formula 2 may be used as the first photopolymerizable compound.
  • X a is hydrogen or a methyl group
  • R 3 is any one of monovalent residues derived from hydrogen and aliphatic hydrocarbons having 1 to 6 carbon atoms
  • R 4 is any one of monovalent residues derived from aliphatic hydrocarbons having 1 to 6 carbon atoms
  • n is an integer of 0-2.
  • the first photopolymerizable compound is 3-
  • the second photopolymerizable compound which is a photopolymerizable compound other than Chemical Formula 1, may include a monomer or oligomer including one or more, two or more, or three or more (meth) acryloyl groups or vinyl groups.
  • a pentaerythri is tri (meth) acrylate, a pentaerythri (tetra) (meth) acrylate, dipentaerythroxy penta (meth) acrylic acid Latent, dipentaerythride, nucleated (meth) acrylate, tripentaerythrite, hepta (meth) acrylate, triylene diisocyanate, xylene diisocyanate, Nucleated methylene diisocyanate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2—ethylnuclear (meth) acrylate,
  • the monomer or oligomer containing the vinyl group include divinylbenzene, styrene, paramethyl styrene or oligomers obtained by polymerizing one or more of these.
  • the molecular weight of the oligomer may be adjusted to 1,000 to 10,000 g / lM) l.
  • the content of the photopolymerizable compound in the photocurable coating composition is not particularly limited, the content of the photopolymerizable compound in the solid content of the photocurable coating composition in consideration of the mechanical properties of the low refractive index layer or the anti-reflection film to be produced finally Silver can be adjusted to 5% to 80% by weight.
  • the content of the photopolymerizable compound means the sum of the contents of the first and second photopolymerizable compounds.
  • the solid content of the photocurable coating composition means only a solid component excluding a liquid component, for example, an organic solvent or the like, which may be selectively included as described below, in the photocurable coating composition.
  • first photopolymerizable compound and the second photopolymerizable compound may have a weight ratio of 0.001: 1 to 4: 1, 0.01: 1 to 3: 1, 0.1: 1 to 2: 1, or 0.5: 1 to 1.5: 1. Can be used.
  • the photocurable coating composition may further include a fluorine-containing compound including a photo-banung functional group.
  • the fluorine-containing compound including the photo-cyclic functional group has a weight average molecular weight of 2,000 g / mol or more and is represented by fluorine. Substituted compounds, which are defined as not included in the definition of the photopolymerizable compound described above.
  • At least one photoreactive functional group is introduced into the fluorine-containing compound, and the photoreactive functional group means 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) acryloyl groups, epoxy groups, vinyl (vinyl) groups, or mercaptos. And the like can be mentioned.
  • the at least one photoreactive functional group may be any one of the listed functional groups or may be composed of two or more selected from the listed functional groups.
  • the fluorine-containing compound including the photo-banung functional group is silicon; Or the side chain black derived from a silicon compound may further contain a repeating unit.
  • the content of silicon may be 0.01 wt% to 20 wt% based on the total weight of the fluorine-containing compound.
  • Silicon contained in the fluorine-containing compound including the photo-banung functional group may increase compatibility with other components included in the photocurable coating composition of the embodiment, and thus haze occurs in the low refractive layer to be finally manufactured. It can play a role of increasing transparency by preventing it.
  • the content of silicon in the fluorine-containing compound including the photoreactive functional group is too high, the compatibility between the other components included in the photocurable coating composition and the fluorine-containing compound may be rather deteriorated, thus the final manufacturing
  • the low refractive index layer or the antireflection film does not exhibit a sufficient light transmittance or antireflection performance, and the antifouling property of the surface may also be reduced.
  • the fluorine-containing compound including the photo-banung functional group may have a weight average molecular weight of 2,000 to 200, 000 g / mol or 5,000 to 100, 000 g / nl. If the weight average molecular weight of the fluorine-containing compound including the photoreactive functional group is too small, the fluorine-containing compound is not uniformly arranged on the surface of the low refractive layer obtained from the photocurable coating composition, and thus is placed therein so that the antifouling property of the low refractive layer This decreases, and the crosslinking density of the low refractive index layer is lowered, and thus mechanical properties such as overall strength and scratch resistance of the antireflection film may be lowered.
  • the photobanungseong When the weight average molecular weight of the fluorine-containing compound including the functional group is too large, compatibility with other components included in the photocurable coating composition may be low, thereby increasing the haze of the low refractive layer to be manufactured and light transmittance. In addition, the strength of the low refractive layer may also be lowered.
  • the weight average molecular weight means a conversion value with respect to standard polystyrene measured by gel permeat ion chromatograph (GPC).
  • the fluorine-containing compound including the photoreactive functional group is i) an aliphatic compound or aliphatic ring compound substituted with at least one photoreactive functional group, at least one hydrogen is substituted with fluorine; ii) silicon-based compounds in which at least one carbon of the aliphatic compound or aliphatic ring compound is substituted with silicon; iii) a siloxane compound in which at least one carbon of the aliphatic compound or aliphatic ring compound is substituted with silicon and at least one -CH 2 -is substituted with oxygen; iv) fluoropolyethers substituted with one or more -C 3 -oxygens of the aliphatic compound or aliphatic ring compound; Or two or more kinds thereof, or a polymer.
  • the photocurable coating composition may include a fluorine-containing compound including 20 to 300 parts by weight of the photoreactive functional group based on 100 parts by weight of the photopolymerizable compound.
  • a fluorine-containing compound including 20 to 300 parts by weight of the photoreactive functional group based on 100 parts by weight of the photopolymerizable compound When the fluorine-containing compound containing the photoreactive functional group is added to the photopolymerizable compound in an excessive amount, the coating property of the photocurable coating composition is reduced or the low refractive layer obtained from the photocurable coating composition has excellent durability or scratch resistance. May not have.
  • the amount of the fluorine-containing compound containing the photo-banung functional group relative to the photopolymerizable compound is too small, the low refractive index layer obtained from the photocurable coating composition may not have sufficient antifouling resistance or scratch resistance.
  • the photocurable coating composition according to the embodiment includes the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles.
  • the inorganic nanoparticles refer to inorganic nanoparticles having a size of several nm to several hundred nm derived from (organic) metal compound or (organic) metalloid compound
  • hollow inorganic nanoparticles refer to inorganic nanoparticles.
  • solid inorganic nano Particle means a particle having a form in which no empty space exists.
  • the surface-treated solid inorganic nanoparticles are distributed close to the interface between the low refractive layer and the hard coating layer, and the surface-treated hollow inorganic nanoparticles are the low refractive index. It is distributed close to the surface, which is the back side of the surface in contact with the hard coating layer of the layer. Due to the specific distribution of such surface-treated hollow inorganic nanoparticles and surface-treated solid inorganic nanoparticles, it is possible to provide an antireflection film having lower reflectance and improved scratch resistance and antifouling property.
  • a hollow inorganic surface-treated with a solid inorganic nanoparticles surface-treated for the specific distribution of the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles may be used. Due to this density difference, when the low refractive layer is formed of the photocurable coating composition, solid inorganic nanoparticles surface-treated on the surface close to the hard coating layer are mainly distributed, and hollow inorganic nanoparticles surface-treated on the surface far from the hard coating layer Mainly distributed.
  • the surface-treated hollow inorganic nanoparticles may be used as a surface-treated inorganic nanoparticles having a density of 1.50 to 3.50 g / cm 3
  • the surface-treated solid inorganic nanoparticles may be used from 2.00 to Surface treated inorganic nanoparticles having a density of 4.00 g / cm 3 can be used.
  • the surface-treated hollow inorganic nanoparticles are not particularly limited, but surface-treated inorganic nanoparticles having a maximum diameter of about 200 nm or less may be used. Specifically, the surface-treated hollow inorganic nanoparticles may be used surface-treated inorganic nanoparticles having a diameter of about 1 to 200 nm or 10 to 100 nm.
  • the surface-treated solid inorganic nanoparticles are not particularly limited, but surface-treated inorganic nanoparticles having a maximum diameter of about 100 nm or less may be used. Specifically, the surface-treated solid inorganic nanoparticles may be used surface-treated inorganic nanoparticles having a diameter of about 0.5 to 100 nm or 1 to 30 nm.
  • the surface-treated hollow inorganic nanoparticles may be used in an amount of 10 to 400 parts by weight, 100 to 300 parts by weight, and black of 150 to 250 parts by weight, based on 100 parts by weight of the photopolymerizable compound.
  • the surface-treated solid inorganic nanoparticles may be used in an amount of 10 to 400 parts by weight, 10 to 200 parts by weight, 10 to 100 parts by weight, or 10 to 50 parts by weight based on 100 parts by weight of the photopolymerizable compound.
  • the content of the surface-treated hollow inorganic nanoparticles and surface-treated solid inorganic nanoparticles is excessive, between the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles when forming a low refractive index layer Phase separation may not occur sufficiently and may be common. As a result, the reflectance of the low refractive layer may be increased, and surface irregularities may be excessively generated, thereby degrading antifouling properties.
  • the surface-treated solid inorganic nanoparticles are mainly distributed in the area close to the interface between the hard coating layer and the low refractive layer.
  • the reflectance of the low refractive layer may increase.
  • particles containing the same type of metal or metalloid may be used or different. Particles containing any kind of metal or metalloid may be used.
  • hollow silica particles may be used as the hollow inorganic nanoparticles
  • solid silica particles may be used as the solid inorganic nanoparticles.
  • the hollow and solid inorganic nanoparticles may be surface treated to be included in the photocurable coating composition to form a low refractive index layer having a higher crosslinking degree, thereby further improving scratch resistance and antifouling resistance.
  • the hollow and solid inorganic nanoparticles may be surface treated by reacting with an organosilicon compound including a photoreactive functional group.
  • the photo-reflective functional group examples include a (meth) acryloyl group epoxy group, a vinyl (vinyl) group, a mercapto group, and the like.
  • the light reflection Specific examples of the organosilicon compound containing a functional group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxy-specific) silane, 2- (3,4-epoxycyclonuclear chamber) ethyltrimethic Cysilane, Y-glycidoxy methyltrimethic silane, ⁇ -glycidoxy methyl trie specific silane, ⁇ - glycidoxy ethyl trimethoxysilane, glycidoxy ethyl trioxy silane, glycidoxy propyl Trimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - ( ⁇ -glycidoxyoxy) propyltrimethoxysilane,
  • (Meth) acryloyloxypropyl methyl dimethoxysilane,-(meth) acryloyloxypropyl triethoxysilane,-mercaptopropyl trimethoxysilane, etc. are mentioned.
  • the surface of the hollow or solid inorganic nanoparticles is surface-modified with one type of organosilicon compound to introduce one type of photoreactive functional group, or black or surface type is modified with two or more types of organosilicon compounds to produce two or more type of photoreactive functional groups. Can be introduced.
  • the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles may be used as a colloidal phase dispersed in a dispersion medium.
  • the dispersion medium may be alcohol such as methanol, isopropyl alcohol, ethylene glycol, butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Dimethylformamide.
  • Amides such as dimethylacetamide and N-methylpyridone; Esters such as ethyl acetate, butyl acetate and gamma butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; Or organic solvents such as mixtures thereof.
  • the content of the surface-treated hollow inorganic nanoparticles or the surface-treated solid inorganic nanoparticles in the colloidal phase may be appropriately determined in consideration of the content of each inorganic nanoparticle to be used and the viscosity of the photocurable coating composition.
  • the solids content of the surface-treated hollow inorganic nanoparticles or surface-treated solid inorganic nanoparticles in the colloidal phase may be about 5% to 60% by weight.
  • various initiators known in the art to which the present invention pertains may be used.
  • a photoinitiator a benzophenone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, an oxime type compound, or 2 or more types of these mixtures can be used.
  • the photoinitiator may be used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the photopolymerizable compound. If the amount of the photoinitiator is too small, uncured monomer or oligomer may remain in the photocuring step of the photocurable coating composition. On the other hand, if the amount of the photoinitiator is too large, the mechanical properties of the antireflection film manufactured by the unreacted initiator remains as impurities or the crosslinking density is low, or the reflectance may be greatly increased.
  • the photocurable coating composition according to the embodiment may further comprise an organic solvent.
  • the organic solvent include ketones, alcohols, acetates, ethers or two or more kinds thereof.
  • Specific examples of such organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone acetylacetone or isobutyl ketone; Alcohols such as methanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol, i-butanol, or t-butanol; Acetates such as ethyl acetate, i-propyl acetate, or polyethylene glycol monomethyl ether acetate; Ethers such as tetrahydrofuran or propylene glycol monomethyl ether; Or two or more kinds thereof.
  • the organic solvent may be included in the photocurable coating composition while being added at the time of mixing each component included in the photocurable coating composition or in the state in which each component is dispersed or mixed in the organic solvent.
  • the organic solvent may be included such that the concentration of the total solids of the components is from 1% to 50% by weight or from 2 to 20% by weight.
  • the step of applying and drying the photocurable coating composition on a hard coating layer provides a method for producing an anti-reflection film comprising the step of photocuring the dried material obtained in the above step.
  • the method of manufacturing the antireflection film of another embodiment may provide an antireflection film according to a method known in the art, in addition to forming a low refractive layer using the photocurable coating composition described above.
  • the above-mentioned photocurable coating composition may be applied to the hard coating layer.
  • the hard coating layer various types of hard coating layers known in the art may be used.
  • the hard coating layer may include a hard coating layer including a photocurable resin and an antistatic agent dispersed in the photocurable resin.
  • the photocurable resin is a polymer in which the photopolymerizable compound is polymerized by light such as ultraviolet rays, and may be a conventional resin known in the art.
  • the photocurable resin may be a polymer of 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, it is advantageous in terms of securing physical properties of the hard coating layer.
  • the photocurable resin is pentaerythri tri (meth) acrylate, pentaerythri tetra (meth) acrylate, dipentaerythri penta (meth) acrylate, dipentaeryeri nucleus (meth Acrylates, tripentaerythrates, hepta (meth) acrylates, triylene diisocyanates, xylene diisocyanates, nuxamethylene diisocyanates, trimethyl to propane tri (meth) acrylates and trimethylolpropane polyespecial tree ( It may be a polymer of one or more polyfunctional (meth) acrylate monomers selected from the group consisting of meth) acrylates.
  • the antistatic agent is a quaternary ammonium salt compound; Pyridinium salts; Cationic compounds having from 1 to 3 amino groups; Sulfonic acid base, sulfate ester base, phosphoric acid Anionic compounds such as ester base and phosphonic acid base; Positive compounds, such as an amino acid type or amino sulfate ester type compound; Nonionic compounds such as imino alcohol compounds, glycerin compounds, and polyethylene glycol compounds; Organometallic compounds such as metal alkoxide compounds including tin or titanium; Metal chelate compounds such as acetylacetonate salts of the organometallic compounds; Two or more semi-ungmuls or polymerized compounds of these compounds; It may be a combination of two or more of these compounds.
  • the quaternary ammonium salt compound may be a compound having one or more quaternary ammonium salt groups in the molecule, it can be used without limitation low molecular type or polymer type.
  • a conductive polymer and metal oxide fine particles may also be used as the antistatic agent.
  • the conductive polymer include aromatic conjugated poly (paraphenylene), polycyclic heterocyclic conjugated system, polythiophene, aliphatic conjugated polyacetylene, and heteroatom-containing polyaniline conjugated conjugated system.
  • the metal oxide fine particles include zinc oxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indium oxide, aluminium oxide, antimony doped tin oxide, aluminum doped zinc oxide, and the like.
  • the photocurable resin; And an antistatic agent dispersed in the photocurable 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, glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane.
  • 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 may be carried out by a method similar to the method for preparing an alkoxy silane oligomer described above. Can be.
  • the sol-gel reaction may be performed by diluting the metal alkoxide-based compound in an organic solvent and slowly dropping water.
  • the molar ratio of the metal alkoxide compound to water is preferably adjusted within the range of 3 to 170.
  • the metal alkoxide-based compound may be at least one compound selected from the group consisting of titanium tetra-isopropoxide, zirconium isopropoxide and aluminum isopropoxide.
  • the hard coating layer may have a thickness of 0.1 to 100.
  • the hard coating layer may be formed on one surface of the substrate.
  • 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 may be used without particular limitation.
  • the photocurable coating composition may be applied to the hard coating layer using methods and apparatus known in the art.
  • the photocurable coating composition may be applied through a bar coating method such as Meyer bar, gravure coating method, 2 roll reverse coating method, vacuum slot die coating method or 2 roll coating method.
  • the photocurable coating composition may be applied so that the thickness of the low refractive layer formed after photocuring is 1 ran to 300 nm or 50 nm to 200 nm.
  • the photocurable coating composition may be dried at 35 ° C to 100 ° C after applying the photocurable coating composition. If the drying temperature is out of the above range, the phase-separated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles do not sufficiently undergo phase separation between the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles. It is common to not only reduce scratch resistance and antifouling property of the low refractive layer, but also significantly increase the reflectance. The layered phase of the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles. The drying temperature may be adjusted to about 40 ° C to 80 ° C for separation.
  • the coating film obtained by applying a photocurable coating composition comprising the same
  • the surface-treated solid inorganic nanoparticles may be mainly distributed on the surface close to the hard coating layer due to the difference in density, and the surface-treated hollow inorganic nanoparticles may be mainly distributed on the surface far from the hard coating layer. .
  • This specific distribution can provide a low refractive index layer having lower reflectance and more improved scratch resistance and stain resistance.
  • the coating film obtained by applying the photocurable coating composition may be dried for about 10 seconds to 5 minutes or 30 seconds to 4 minutes in the above-described temperature range.
  • the drying time is too short, phase separation between the surface-treated solid inorganic nanoparticles and the surface-treated hollow inorganic nanoparticles may not occur sufficiently, and when the drying time is too long, the formed The low refractive layer can be eroded into the hard coat layer.
  • the dried material of the photocurable coating composition may be photocured by irradiating ultraviolet light or visible light in the wavelength range of 200 to 400 nm.
  • the exposure amount of the irradiated light can be adjusted in the range of 100 to 4,000 mJ / cm 2 , the exposure time can be appropriately adjusted according to the exposure apparatus, the wavelength of the irradiation light or the exposure amount used.
  • Photocuring the dried material may be performed under a nitrogen atmosphere. Accordingly, black before the photocuring step may be further purged with nitrogen during the photocuring step.
  • the low refractive index layer prepared from the photocurable coating composition as described above is used in the binder resin and the binder resin formed by cross-polymerization of the first and second photopolymerizable compounds and a fluorine-containing compound including a photoreactive functional group that can be used as necessary.
  • Binding blacks include dispersed surface treated hollow inorganic nanoparticles and surface treated solid inorganic nanoparticles.
  • the binder resin is hard Can be combined with the coating layer further improves the adhesion of the low refractive layer to the hard coating layer, and serves to more strongly fix the surface-treated hollow inorganic nanoparticles and surface-treated solid inorganic nanoparticles.
  • the surface-treated hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles are distributed so as to be distinguished from each other:
  • the low refractive index layer exhibits a lower reflectivity and a high light transmittance and simultaneously realizes high scratch resistance and antifouling resistance. Can be.
  • the hard coating layer On the other hand, according to another embodiment of the invention, the hard coating layer; And a low refractive layer formed on one surface of the hard coating layer, and including a photocurable material of the photocurable coating composition, and having a surface within 50% of the total thickness of the low refractive layer from an interface between the hard coating layer and the low refractive layer.
  • An antireflective film is provided in which at least 70% by volume of all of the treated solid inorganic nanoparticles are present.
  • the low refractive index layer comprises a photo-set product of the photocurable resin composition according to the embodiment. That is, the low refractive layer is a binder resin and the binder resin formed by crosslinking polymerization of the compound represented by Formula 1 (first photopolymerizable compound) and another photopolymerizable compound (second photopolymerizable compound) other than the compound of Formula 1 It includes the surface-treated hollow inorganic nanoparticles and surface-treated solid inorganic nanoparticles bonded or dispersed in. And, 70% by volume or more of the entire surface-treated solid inorganic nanoparticles included in the low refractive layer is present within 50% of the total thickness of the low refractive layer from the interface between the hard coating layer and the low refractive layer.
  • '70% by volume or more of the entire surface-treated solid inorganic nanoparticles are present in a specific region 1 , where the surface-treated solid inorganic nanoparticles are mostly present in the specific region in the cross-section of the low refractive index layer. It is defined as meaning. Specifically, 70% by volume or more of the total surface-treated solid inorganic nanoparticles may be confirmed by measuring the total volume of the surface-treated solid inorganic nanoparticles.
  • the content of the surface-treated inorganic nanoparticles present in a specific region except for the content of the surface-treated inorganic nanoparticles that exist over the interface of different regions, the surface-treated inorganic nanoparticles present in a specific region Determined by the content of.
  • the surface is the back surface of the surface in contact with the hard coating layer in the low refractive index layer
  • the treated hollow inorganic nanoparticles may be mainly distributed. Specifically, at least 30% by volume of the entire surface-treated hollow inorganic nanoparticles is greater than that of the solid inorganic nanoparticles having the total surface treatment. It may be present at a greater distance in the thickness direction of the low refractive index layer from the interface between. That is, only the surface-treated hollow inorganic nanoparticles are present in the region having a predetermined thickness from the surface of the low refractive layer, which is the rear surface of the surface in contact with the hard coating layer, and the content of the surface-treated hollow inorganic nanoparticles present in this region. More than 30 volumes 3 ⁇ 4> of this total.
  • At least 70% by volume of the total surface-treated solid inorganic nanoparticles may be present within 30% of the total thickness of the low refractive index from the interface between the hard coating layer and the low refractive index layer.
  • at least 70% by volume of the entire surface-treated hollow inorganic nanoparticles may be present in an area of more than 30% of the total thickness of the low refractive index layer from an interface between the hard coating layer and the low refractive index layer.
  • the surface-treated solid inorganic nanoparticles are mainly distributed near the interface between the hard coating layer and the low refractive index, and the hollow inorganic nanoparticles surface-treated to the opposite side of the interface are mainly distributed. Accordingly, two or more portions or two or more layers having different refractive indices may be formed in the low refractive layer, and thus the reflectance of the antireflection film may be lowered.
  • the low refractive layer is a first layer containing at least 70% by volume of the total surface-treated solid inorganic nanoparticles and a second containing at least 70% by volume of the total surface-treated hollow inorganic nanoparticles Layer, and the crab first layer may be located closer to the interface between the hard coating layer and the ' low refractive index layer ' than the second layer.
  • solid inorganic nanoparticles surface-treated near the interface between the hard coating layer and the low refractive layer are mainly distributed, and the hollow surface surface-treated toward the opposite side of the interface. Inorganic nanoparticles are predominantly distributed, and the areas where the surface-treated solid inorganic nanoparticles and the surface-treated hollow inorganic nanoparticles are mainly distributed are independently identified in the low refractive layer.
  • a layer can be formed.
  • Such an antireflection film can achieve a reflectance lower than the reflectance previously obtained using inorganic nanoparticles.
  • the reflective ring film may exhibit an average reflectance of 0.7% or less, 0.6% or less, or 0.55% or less in the visible light wavelength range of 380 nm to 780 nm.
  • the low refractive index layer in the anti-reflection film may have a thickness of 1 nm to 300 nm or 50 nm to 200 nm.
  • the anti-reflection film is a binder resin included in the low refractive index layer can be combined with the hard coating layer is very good adhesion between the low refractive index layer and the hard coating layer, the solid inorganic nanoparticles surface-treated in the low refractive layer Is mainly distributed near the interface between the hard coating layer and the low refractive layer, and the surface-treated hollow inorganic nanoparticles are mainly distributed near the opposite side of the interface, compared to the actual reflectivity previously obtained using the inorganic nanoparticles. Low reflectance can be achieved, and can also exhibit greatly improved scratch and stain resistance.
  • an anti-reflection film which can simultaneously realize high scratch resistance and antifouling property while exhibiting low reflectance and high light transmittance.
  • KY0EISHA salt type antistatic hard coating solution 50 wt% solids, product name: LJD-1000 was coated on a triacetylcell film with # 10 mayer bar and dried at 90 ° C for 1 minute. Thereafter, the obtained coating film was irradiated with ultraviolet light of 150 mJ / cm 2 to form a hard coating layer having a thickness of about 5 to 6 /, thereby preparing a hard coating film.
  • Example 1 Preparation of Anti-Reflection Film
  • the photocurable coating composition obtained above was coated with # 4 mayer bar on the hard coat layer of the hard coat film prepared in Preparation Example 1, and dried at 60 ° C. for 1 minute. Thereafter, the obtained coating film was irradiated with ultraviolet light of 180 mJ / cm 2 under nitrogen purge to form a low refractive layer having a thickness of 110 to 120 nm to prepare an antireflection film.
  • Example 2 Preparation of Anti-Reflection Film
  • An anti-reflection film was prepared in the same manner as in Example 1, except that 3-methacryloxypropyltrimethoxysilane was used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1.
  • Example 3 Preparation of Anti-Reflection Film
  • Example 1 except that 3-methacryloxypropyltriethoxysilane is used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1
  • An antireflection film was prepared in the same manner.
  • Example 4 Preparation of Anti-Reflection Film
  • An anti-reflection film was prepared in the same manner as in Example 1, except that 3-acryloxypropyltrimethoxysilane was used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1.
  • Example 5 Preparation of Anti-Reflection Film
  • An anti-reflection film was prepared in the same manner as in Example 1, except that 3-acryloxypropylmethyldieoxysilane was used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1. Comparative Example 1: Preparation of Anti-Reflection Film
  • An anti-reflection film was prepared in the same manner as in Example 1, except that 3-glycidoxypropylmethyldieoxysilane was used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1. Comparative Example 2: Preparation of Anti-Reflection Film
  • An anti-reflection film was prepared in the same manner as in Example 1, except that N-phenyl-3-aminopropyltrimethoxysilane was used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1. Comparative Example 3: Preparation of Anti-Reflection Film
  • An anti-reflection film was prepared in the same manner as in Example 1, except that P-styryltrimethoxysilane was used instead of 3-methacryloxypropylmethyldimethoxysilane in Example 1. Comparative Example 4: Preparation of Anti-Reflection Film
  • An anti-reflection film was prepared in the same manner as in Example 1, except that 3-methacryloxypropylmethyldimethoxysilane was not used in Example 1.
  • the average reflectance of the antireflective films obtained in Examples and Comparative Examples in the visible light region was measured using a Sol idspec 3700 (SHIMADZU) instrument.
  • the steel wool of grade # 0000 was subjected to a specific load and reciprocated 10 times at a speed of 27 rpm to rub the surface of the antireflective film obtained in the examples and the comparative examples.
  • the maximum load at which no scratches were observed visually under the LED 50W ceiling light was measured.
  • the load is defined as the weight in grams per square centimeter (2 cm 2 ) by 2 cm by 2 cm.
  • a 5 cm long straight line was drawn with a black name pen on the surface of the antireflective film obtained in Examples and Comparative Examples, and the straight line was rubbed with a dust-free cloth. At this time, the antifouling property was evaluated by counting the number of times rubbing with zero vacuum until the straight line was erased.
  • the hollow inorganic nanoparticles and the surface-treated solid inorganic nanoparticles surface-treated in the binder resin prepared from the compound represented by the formula (1) photopolymerizable compound as shown in Example 1 When distributed so as to be distinguishable, it is confirmed that the reflectance is lower than that of the phase-separated structure of the comparative example and further improved scratch resistance.
  • the first photopolymerizable compound is confirmed to further lower the reflectance and more scratch resistance of the antireflection film by providing a binder resin that can be bonded to the hard coating layer, and other reactivity such as epoxy group, amino group, styryl It is confirmed that this effect cannot be realized with a compound having a functional group.

Abstract

La présente invention concerne une composition de revêtement photodurcissable pour former une couche à faible réfraction, un procédé de préparation d'un film antireflet utilisant la composition de revêtement photodurcissable, et un film antireflet préparé en utilisant la composition de revêtement photodurcissable. Selon la présente invention, une couche à faible réfraction est formée d'une composition de revêtement photodurcissable contenant deux types de composés photopolymérisables ou plus, un photo-initiateur, des nanoparticules inorganiques creuses traitées en surface, et des nanoparticules inorganiques pleines traitées en surface.
PCT/KR2017/001609 2016-02-19 2017-02-14 Composition de revêtement photodurcissable pour former une couche à faible réfraction WO2017142291A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780003681.9A CN108139668B (zh) 2016-02-19 2017-02-14 用于形成低折射率层的可光固化的涂层组合物
EP17753452.6A EP3336604B1 (fr) 2016-02-19 2017-02-14 Composition de revêtement photodurcissable pour former une couche à faible réfraction
US15/762,383 US11680172B2 (en) 2016-02-19 2017-02-14 Photocurable coating composition for forming low refractive layer
JP2018515203A JP6812630B2 (ja) 2016-02-19 2017-02-14 低屈折層形成用光硬化性コーティング組成物

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KR20160019945 2016-02-19
KR10-2016-0019945 2016-02-19
KR10-2017-0019349 2017-02-13
KR1020170019349A KR102077797B1 (ko) 2016-02-19 2017-02-13 저굴절층 형성용 광경화성 코팅 조성물

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