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WO2013032120A1 - Film anti-éblouissement - Google Patents

Film anti-éblouissement Download PDF

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Publication number
WO2013032120A1
WO2013032120A1 PCT/KR2012/004764 KR2012004764W WO2013032120A1 WO 2013032120 A1 WO2013032120 A1 WO 2013032120A1 KR 2012004764 W KR2012004764 W KR 2012004764W WO 2013032120 A1 WO2013032120 A1 WO 2013032120A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
layer
compound
molecular weight
Prior art date
Application number
PCT/KR2012/004764
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English (en)
Korean (ko)
Inventor
김헌
장영래
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020120036337A external-priority patent/KR101226230B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2014527054A priority Critical patent/JP2014531608A/ja
Priority to CN201280041661.8A priority patent/CN103765250B/zh
Priority to EP12827399.2A priority patent/EP2749913B1/fr
Publication of WO2013032120A1 publication Critical patent/WO2013032120A1/fr
Priority to US13/842,758 priority patent/US20130222915A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B32B27/205—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents the fillers creating voids or cavities, e.g. by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/046—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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • G02B1/105—
    • 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • 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
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/18—Esters containing halogen
    • C08F222/185—Esters containing halogen the ester chains containing seven or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
    • C08F222/205—Esters containing oxygen in addition to the carboxy oxygen the ester chains containing seven or more carbon atoms

Definitions

  • the present invention relates to an antireflection film.
  • display devices such as PDPs, CRTs, and LCDs are equipped with anti-reflection films (or anti-glare films) for minimizing reflection of light incident on the screen from the outside.
  • anti-reflection films or anti-glare films
  • an antireflection layer is mainly formed on a light transmissive substrate.
  • the antireflection layer is most widely used in a three-layer structure in which a hard coat layer, a high refractive index layer and a low refractive index layer sequentially stacked from the light transmissive substrate side.
  • a two-layer structure in which the hard coat layer or the high refractive index layer is omitted from the antireflection layer is also commercialized.
  • an anti-reflection film provided with an anti-glare hard coat layer is also used.
  • the antireflection film is generally produced by a dry method or a wet method.
  • the dry method is a method of laminating a plurality of thin film layers by vapor deposition, sputtering, and the like, but the interfacial adhesion between layers is strong, but the manufacturing cost is high and it is not widely used commercially.
  • the wet method is a method of coating a composition including a binder, a solvent, and the like on a substrate, and drying and curing the wet method, which has a lower manufacturing cost than the dry method and is widely used commercially.
  • the wet method generally produces a composition required for forming each layer, such as a hard coat layer, a high refractive index layer, and a low refractive index layer, and uses the same to form each layer sequentially, thus making the manufacturing process complicated and interlayer interface.
  • Adhesion has a weak disadvantage.
  • the hard coat layer or the high refractive index layer is usually formed of a pure binder on the substrate, or formed of a separate layer including a binder and inorganic fine particles on the substrate, and a low refractive index layer in which hollow particles and the like are dispersed thereon.
  • the antireflection film of the structure as described above has a weak interfacial adhesion and poor durability.
  • the present invention provides an antireflection film that can be formed in a simplified process while exhibiting improved interlayer interfacial adhesion and scratch resistance.
  • a first layer comprising a first (meth) acrylate-based binder, inorganic fine particles in the first (meth) acrylate-based binder, eroded in the substrate; And a second layer comprising a second (meth) acrylate-based binder and hollow particles in the second (meth) acrylate-based binder and covering the first layer, wherein any cross section of the second layer is included.
  • An antireflection film is provided, wherein the ratio of the cross-sectional area of the hollow particles to the area is 70 to 95%.
  • the first (meth) acrylate-based binder may comprise a crosslinked polymer of a (meth) acrylate-based compound having a molecular weight of less than 600
  • the second (meth) acrylate-based binder may have a molecular weight of less than 600 It may include a crosslinked copolymer of a (meth) acrylate-based compound and a (meth) acrylate-based compound having a molecular weight of 600 to 100,000.
  • the first layer further includes a region in which a crosslinked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000 is located. It may include.
  • the region in which the crosslinked copolymer is positioned may be positioned to a depth of about 5 to 50% of the first charge based on the interface between the first layer and the second layer.
  • the crosslinked copolymer may be included to increase the distribution gradient in the direction of the second layer.
  • the second layer may further include inorganic fine particles.
  • the (meth) acrylate-based compound having a molecular weight of less than 600 may be tri (meth) acrylate for pentaerythri, tetra (meth) acrylate for pentaerythri, nucleus (meth) acrylate for dipentaerythr, tri Methylenepropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, 9,9-bis (4- (2-acryloxyephenyl) fluorene, bis (4-methacryloxythiophenyl) sulfide And at least one compound selected from the group consisting of bis (4-vinylthiophenyl) sulfide.
  • the second (meth) acrylate-based binder has a molecular weight of less than 600
  • a crosslinked copolymer in which a fluorine (meth) acrylate compound is further copolymerized may be included.
  • the (meth) acrylate-based compound having a molecular weight of 600 to 100,000 may include a compound having a structure in which two or more molecules of the (meth) acrylate-based compound having a molecular weight of less than 600 are connected by a linker, and the linker may include a urethane bond, Thioether bonds, ether bonds or ester bonds.
  • the (meth) acrylate-based compound having a molecular weight of 600 to 100,000 may have a substituent and at least one selected from the group consisting of an epoxy group, a hydroxyl group, a carboxyl group, a thil group, an aromatic or aliphatic hydrocarbon group having 6 or more carbon atoms, and an isocyanate group.
  • the inorganic fine particles may have a number average particle diameter of 5 to 50nm, for example, may be silica fine particles.
  • the hollow particles may be one having a number average particle diameter of 5 to 80 nm, for example, hollow silica particles.
  • the antireflective film according to the present invention can be formed by a single coating, so that it can be formed in a simpler process, while maintaining improved interfacial adhesion and scratch resistance between layers. Also, the above The antireflection film can exhibit an excellent antireflection effect and can be preferably applied to an antireflection film such as a display device.
  • FIG. 1 is a cross-sectional view schematically showing the structure of an anti-reflection film according to an embodiment of the present invention.
  • FIG. 2 is a flow chart schematically showing a method of manufacturing an anti-reflection film according to an embodiment of the present invention.
  • the term "inorganic fine particles” refers to particles derived from various inorganic materials, and may collectively refer to particles having a number average particle diameter on the nanometer scale, for example, a number average particle diameter of 100 nm or less. Such 'inorganic particulates' may be amorphous particles having substantially no empty space inside the particles.
  • the “silica fine particles” may be particles derived from a silicon compound or an organosilicon compound, and may refer to silicon compound or organosilicon compound particles having a number average particle diameter of 100 nm or less and no empty space inside the particles.
  • the term “hollow particles” may refer to particles in the form of empty spaces present on and / or inside the organic or inorganic particles.
  • the term “hollow silica particles” refers to silica particles derived from a silicon compound or an organosilicon compound, and may refer to particles having a void space on the surface and / or inside of the silica particles.
  • (meth) acrylate is defined as collectively referred to as acrylate (meth) or methacrylate (methacrylate).
  • such '(meth) acrylates' can be defined as having no bloso-containing substituents.
  • the compound having a fluorine-containing substituent may be referred to as a fluorine-based (meth) acrylate compound.
  • coating layer means a composition layer formed by applying (coating) a composition for antireflection coating described below on a predetermined base film.
  • phase separation means that a difference is formed in the distribution of specific components included in the composition due to differences in density, surface tension, or other physical properties of the components.
  • the coating layer when the coating layer is phase-separated, it may be divided into at least two layers based on whether a specific component is distributed, for example, the distribution of hollow particles.
  • 'eroding into the substrate' means that a component (for example, a (meth) acrylate-based compound and an inorganic fine particle, etc., for forming a binder of the layer) for forming a certain layer of the antireflection film It may be referred to as penetrating into the substrate to form the layer in question.
  • a component that has penetrated into the substrate can be dried and cured while penetrating into a region within the substrate to form a constant layer within the substrate of that region.
  • the formation of a layer 'on the substrate' means that the components for forming the layer are not substantially eroded within the substrate, and are dried and cured at an interface with the substrate, thereby ensuring that there is no overlapping area with the substrate. It may refer to forming a layer.
  • one layer e.g., the second layer of one embodiment described below
  • another layer e.g., the first layer of one embodiment, described below
  • no other layer is substantially present.
  • the second layer containing hollow particles' covers the first layer eroded in the substrate, and the first layer is an erosion layer in the substrate, and the hollow particles are contained. It may mean that there is no separate layer between the second layers, for example, no erosion into the substrate and no hollow particles.
  • a binder for example, a crosslinked polymer formed from a (meth) acrylate-based compound
  • inorganic fine particles is formed between the first layer, which is an erosion layer, and the second layer containing the hollow particles. It may mean that there is no separate layer that is included and not eroded into the substrate.
  • the inventors of the present invention in the course of repeated studies on the anti-reflection film, by using a predetermined composition described below to induce spontaneous phase separation to form an anti-reflection film, the interfacial adhesion between the layers and the scratch resistance is excellent It was confirmed that it was possible to provide an antireflection film showing an antireflection effect, and completed the invention.
  • the excellent characteristic of such an antireflection film is that the first layer serving as the hard coat layer is formed in the form of erosion in the substrate, and the second layer serving as the low refractive index layer is formed to cover the first layer. It seems to be due to structural characteristics.
  • a separate hard coat layer substantially free of hollow particles eg, substantially free of hollow particles, containing only a binder, or containing only a binder and inorganic fine particles.
  • a separate coating or curing process is required to form each layer, and the process is complicated or the interface adhesion between the layers is reduced. There is this.
  • the antireflection film of one embodiment in which the first layer (hard coat layer) eroded in the substrate covers the second charge (low refractive index layer) can be formed in a simplified manner through a unified coating and curing process, Excellent interfacial adhesion between layers can be exhibited.
  • One such embodiment includes the anti-reflection film has been eroded in the base material inorganic fine particles in the first (meth) acrylate-based binder and wherein the first (meth) acrylate-based binder Peer first layer; And a second layer including a second (meth) acrylate binder and hollow particles in the second (meth) acrylate binder and covering the first layer.
  • the ratio of the cross-sectional area of the hollow particles to any cross-sectional area of the second layer is about 70 to 95%, or about 75 to 93%, black about 80 to 90%, or about 85 to 92%.
  • the first layer eroded in the substrate may act as a high refractive index layer exhibiting a refractive index of about 1.5 or more, while acting as a hard coat layer of the antireflection film.
  • Such hard coat layer into the substrate An eroded first (meth) acrylate-based binder is included, and the first (meth) acrylate-based binder may include a crosslinked polymer of a (meth) acrylate-based compound having a molecular weight of less than 600.
  • the hard coat layer may include inorganic fine particles in the first (meth) acrylate-based binder.
  • the substrate I 1 2 charged in my eroded layer of the covering them in contact with the first layer is the whole of the hollow particles, or most (e.g., about 97 parts by weight 0/0 above, black is about 99 weight 0/0 above)
  • This may be substantially distributed to act as a low refractive index layer of the antireflection film.
  • Such a low refractive index layer may exhibit a low refractive index of about 1.45 or less, thereby exhibiting an appropriate antireflection effect.
  • the low refractive index includes a second (meth) acrylate-based binder, which is a (meth) acrylate-based compound having a molecular weight of less than 600 and a (meth) acrylate having a molecular weight of 600 to 100,000. It may include a crosslinked copolymer of the compound. In addition, the low refractive index layer may include vaporized particles in the second (meth) acrylate-based binder.
  • the 1 (meth) acrylate binder may further include a crosslinked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000.
  • the second layer serving as the low refractive index layer may further contain inorganic fine particles.
  • FIG. 1 A schematic schematic diagram of an example of such an antireflection film is shown in FIG. 1.
  • a first layer 2 serving as a hard coat layer is formed in a hardened state by erosion in the substrate 1, and a second layer 3 serving as a low refractive index layer.
  • the erosion layer can be formed on the substrate on which the erosion layer is formed while in contact with and covering the first layer 2 which is the erosion layer. At this time, no separate layer is distinguished between the first layer 2 eroded into the substrate and the second layer 3 over the substrate.
  • the absence of such a separate layer means that, for example, only the binder and / or the inorganic fine particles are included between the first layer, which is an erosion layer, and the second layer, in which the hollow particles are substantially distributed, and the hollow particles are substantially not. It may be referred to that it does not include a separate filling that does not include the erosion into the substrate.
  • the first layer 2 serving as the hard coat layer remains eroded into the substrate 1, and as the second layer 3 serving as the low refractive index layer is formed on the substrate to contact them.
  • Anti-reflection film of another embodiment is excellent in the interfacial adhesion of the substrate, the hard coat layer and the low refractive index layer can minimize the peeling phenomenon in the use process.
  • the ratio of the cross-sectional area of the hollow particles to any cross-sectional area of the second layer may be about 70 to 95%, black about 75 to 93%, or about 80 to 90%, or about 85 to 92%.
  • hollow particles may be densely distributed in the second layer serving as a low refractive index insect.
  • the antireflection film of one embodiment may exhibit excellent low refractive index characteristics and antireflection effects.
  • the antireflective film comprises a substrate.
  • the base material 1 is a normal transparent thin film, and if the 1st (meth) acrylate type binder and inorganic microparticles
  • a base material what originated in materials, such as polyester resin, polycarbonate resin, acrylic resin, and acetate cellulose resin, can be used.
  • a triacetate cell may be used as a base material of Rhodes (TAC) resin.
  • TAC Rhodes
  • the antireflection film contains the crosslinked polymer of the (meth) acrylate type compound of molecular weight less than 600 as a 1st (meth) acrylate type binder, and contains the inorganic fine particles in this 1st (meth) acrylate type binder.
  • the first layer 2 can be included as a hard coat layer. Such hardcoat worms can be layers eroded into the substrate.
  • the first layer 2 may be one in which the first (meth) acrylate-based binder and the inorganic fine particles are eroded into the substrate to be cured integrally with the substrate. Although the first pack 2 is shown as eroded to the entire surface of the substrate 1 in FIG.
  • the first layer 2 may be constructed by eroding a portion of the substrate 1.
  • the second layer 3 acting as a low refractive index layer may be formed to contact and cover the first erosion 2 eroded in the substrate 1 and be a layer comprising hollow particles. More specifically, between the first layer 2 and the second layer 3, there is no separate layer containing only binders and / or inorganic particulates and not eroding into the crawfish.
  • the anti-reflection film of one embodiment is a low refractive index layer
  • the acting second layer (3) is formed directly over and in contact with the substrate (1) and the first layer (2) acting as a hard coat layer, which can result in improved interlayer adhesion, scratch resistance and antireflection effect. .
  • the second (meth) acrylate binder of the second packing (3) may include a crosslinked copolymer of a (meth) acrylate compound having a molecular weight of less than 600 and a (meth) acrylate compound having a molecular weight of 600 to 100,000.
  • the second (meth) acrylate-based binder is a cross-linked air of a (meth) acrylate compound having a molecular weight of less than 600, a (meth) acrylate compound having a molecular weight of 600 to 100,000 and a fluorine (meth) acrylate compound It may also include coalescence.
  • the crosslinked copolymer further copolymerized with such a fluorine-based (meth) acrylate compound is included in the second (meth) acrylate-based binder, the lower refractive index of the second layer 3 serving as the low refractive index layer and excellent Anti-reflection effect can be realized. Moreover, the scratch resistance of the 2nd layer 3 can be improved more.
  • the crab second layer 3 may further include inorganic particulates in the second (meth) acrylate-based binder, through which the scratch resistance and the antireflection effect of the second layer 3 may be further improved.
  • the first (meth) acrylate-based binder of the first charge (2) is a (meth) acrylate-based compound and a molecular weight of less than 600 in addition to the crosslinked polymer of the (meth) acrylate-based compound having a molecular weight of less than 600 described above It may further comprise a crosslinking copolymer of 600 to 100,000 (meth) acrylate-based compound.
  • the crosslinked copolymer contained in the first (meth) acrylate-based binder of the first layer (2) is the first layer (2) and the first layer (based on the light interface of the second layer (3) 2) It may be included in a certain area, for example up to about 5-50% deep, or up to about 5-45% deep, or up to about 5-40% deep of the first layer 2. Then, the cross-linked copolymer contained in the binder of the first layer (2) may be included to increase the gradient distribution in the second layer (3) direction.
  • the (meth) acrylate-based compound having a molecular weight of 600 to 100,000 is crosslinked and copolymerized with the (meth) acrylate-based compound having a molecular weight of less than 600 with a distribution gradient to a certain depth of the first layer (2).
  • the interfacial adhesion between the first layer 2 and the second layer 3 can be further improved, and the hollow contained in the second layer 3 can be improved.
  • Particles can be densely distributed.
  • the first layer 2 is a layer having a higher refractive index than the second layer 3 serving as the low refractive index layer, and has a refractive index of about 1.5 to 1.58, black to about 1.5 to 1.57, Black may be about 1.51 to 1.56.
  • the second layer 3 may have a refractive index of about 1.1 to 1.45, or about 1.15 to 1.43, or about 1.2 to 1.42.
  • the anti-reflective film of another embodiment described above exhibits excellent anti-reflective properties such that the reflectance is about 0.5 to 4%, black is about 0.8 to 3%, or about 1 to 2%, and various PDP, CRT or LCD It can be suitably applied as an antireflection film in display devices.
  • Such antireflective coating compositions include (meth) acrylate compounds having a molecular weight of less than 600; (Meth) acrylate-based compounds having a molecular weight of 600 to 100,000; Inorganic particulates; And hollow particles. Each composition of such a composition is demonstrated as follows.
  • the antireflective coating composition may include a (meth) acrylate-based compound having a molecular weight of less than 600. Of these low molecular weights The (meth) acrylate-based compound may be at least partially eroded into the substrate when the composition is applied to any substrate.
  • the low molecular weight (meth) acrylate-based compound eroded into the substrate as described above is a first-layer binder copolymerized with homopolymerization or a high molecular weight (meth) acrylate-based compound having a molecular weight of 600 to 100,000, which will be described later. Can be formed.
  • the remainder of the low molecular weight (meth) acrylate compound may remain on the substrate without being eroded.
  • the remaining compound may be copolymerized with a high molecular weight (meth) acrylate compound to be described later to form a binder of a second layer covering the first layer of the erosion region.
  • the low molecular weight (meth) acrylate compound In order to enable the low molecular weight (meth) acrylate compound to be eroded into the substrate to form a binder and a first layer which acts as a hard coat layer of the antireflection film, the low molecular weight (meth) acrylate compound is For example, it may have a molecular weight of less than about 600, or less than about 500, or less than about 400, and in another example, may have a molecular weight of about 50 or more, or about 100 or more.
  • the low molecular weight (meth) acrylate-based compound is formed so that a first layer (eg, a hard coat layer and / or a high refractive index layer) exhibiting higher refractive index can be formed in the substrate.
  • a first layer eg, a hard coat layer and / or a high refractive index layer
  • Substituents and aromatic substituents such as sulfur, chlorine or metal may be used.
  • low molecular weight (meth) acrylate compounds include pentaerythroxy tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythroxy nucleated (meth) acrylate, trimethylenepropane tri ( Meth) acrylate, ethylene glycol di (meth) acrylate, 9,9-bis (4- (2-acryloxyephenyl) fluorene (refractories 1.62), bis (4-methacryloxythiophenyl) sulfide (Refractive index 1.689), and bis (4-vinylthiophenyl) sulfide (refractive index 1.695) may be included, and may include two or more kinds of combinations selected for these symptoms.
  • the antireflective coating composition may include a high molecular weight (meth) acrylate compound having a molecular weight of 600 to 100,000.
  • a high molecular weight (meth) acrylate compound having a molecular weight of 600 to 100,000 Such high molecular weight (meth) acrylate-based compounds, when the composition is applied to any substrate due to the large molecular weight and the bulky chemical structure thereof, and the like, compared with the above-described low molecular weight compound, the relatively small amount of the substrate May be eroded into, and the remaining substantial amount may remain on the substrate.
  • the high molecular weight (meth) acrylate compound is not eroded to the same depth as the low molecular weight (meth) acrylate compound described above.
  • the erosion region in the substrate can be divided into the following two regions. First, a region in which only the low molecular weight (meth) acrylate-based compound is eroded is a region at a depth that can be eroded, where a binder which is a crosslinked polymer of the low molecular weight (meth) acrylate-based compound may exist. have.
  • a binder in which a high molecular weight (meth) acrylate compound and a low molecular weight (meth) acrylate compound are crosslinked and copolymerized may be present.
  • the second layer (eg, a low refractive index layer of the antireflection film) which is copolymerized with the above-described low molecular weight compound to cover the erosion layer, with the remainder of the high molecular weight (meth) acrylate compound not eroded to the substrate.
  • the second (meth) acrylate binder can be formed. This improves the interfacial adhesion between the first layer that can act as a hard coat layer of the antireflection film and the second layer (low refractive index layer) covering the same, and at the same time improves the scratch resistance of the low refractive index layer,
  • the hollow particles included in the low refractive index layer can be more densely distributed.
  • Such a high molecular weight (meth) acrylate-based compound is a compound having a relatively large molecular weight and bulky structure compared to the low molecular weight compound described above, for example, about 400 or more, or about 500 or more, or about It may have a molecular weight of 600 or more, and as another example may have a molecular weight of about 100,000 or less, or about 80,000 or less, black is about 50,000 or less.
  • the high molecular weight (meth) acrylate-based compound may include a compound having a structure in which two or more molecules of the aforementioned low molecular weight (meth) acrylate-based compound are linked by a linker.
  • the linker may be a bivalent or more radical including an arbitrary chemical bond known to be capable of connecting a (meth) acrylate-based compound, for example, a urethane bond, a thioether bond, an ether bond or an ester bond.
  • the high molecular weight (meth) acrylate-based compound is preferably one or more substituents selected from the group consisting of an epoxy group, a hydroxyl group, a carboxy group, a thi group, an aromatic or aliphatic hydrocarbon group having 6 or more carbon atoms, and an isocyanate group for a bulkier structure. Can be.
  • a commercial article satisfying the above conditions may be used or may be directly synthesized.
  • examples of such commodities include UA-306T, UA-306I, UA-306H, UA-510T, UA-510I, UA-510H (above, manufactured by KYOEISHA); BPZA-66, BPZA-100 (above, manufactured by KYOEISHA Corporation); EB9260, EB9970 (above, manufactured by BAEYER); Examples include Miramer SP1107 and Miramer SP1114 (manufactured by MIWON).
  • High molecular weight (meth) acrylate type mentioned above The compound may be included in the antireflective coating composition at about 5 to 30 parts by weight, or about 5 to 25 parts by weight, and about 5 to 20 parts by weight of black, based on 100 parts by weight of the low molecular weight compound.
  • the content ratio of the high molecular weight (meth) acrylate compound is configured at the time of excessive addition while ensuring the minimum effect of the mixed use of the compound for forming a binder including a high molecular weight and a low molecular weight (meth) acrylate compound It may be set in consideration of optimization of physical properties of the layer or change in distribution tendency of hollow particles.
  • the above-described antireflective coating composition may further include a fluorine-based (meth) acrylate compound in which at least one fluorine is substituted as a compound for forming a binder.
  • a fluorine-based (meth) acrylate compound in which at least one fluorine is substituted as a compound for forming a binder.
  • fluorine-based (meth) acrylate compounds are not eroded into the substrate when the composition is applied to the substrate due to the presence of a fluorine-containing substituent.
  • the fluorine-based (meth) acrylate compound has a low molecular weight and Together with the high molecular weight (meth) acrylate compound, a second (meth) acrylate-based binder of the second layer serving as the low refractive index layer of the antireflection film can be formed.
  • the fluorine-based (meth) acrylate compound exhibits a lower refractive index, the refractive index of the low refractive index layer can be lowered.
  • the fluorine-based (meth) acrylate compound has excellent compatibility with the hollow particles to be described later as it contains a polar functional group. It can help improve scratch resistance.
  • the (meth) acrylate compound may have a structure in which one or more fluorine-containing substituents are bonded thereto.
  • fluorine-based (meth) acrylate compound examples include 1 selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 5 Species or more compounds may be mentioned:
  • R 1 is a hydrogen group or an alkyl group of 1 to 6 carbon atoms : a is an integer of 0 to 7 and b is an integer of 1 to 3;
  • c is an integer of 1 to 10;
  • d is an integer of 1 to 11;
  • e is an integer of 1 to 5;
  • f is an integer of 4 to 10.
  • the bloso-based (meth) acrylate compound is about 5 to 20 parts by weight, black is about 5 to 1 8 parts by weight, and black is about 10 to about 100 parts by weight of the low molecular weight (meth) acrylate compound described above. 16 parts by weight may be included in the antireflective coating composition.
  • fluorine-based (meth) acrylate compound a commercial article satisfying the above conditions may be used.
  • examples of such commercial articles include OPTOOL AR110 (manufacturer: DAI IN), LINC-3A, and LINC-102A (manufacturer: KYOEISHA). , PFOA (manufacturer: Exfluor), OP-38Z (manufacturer: DIC), and the like.
  • the anti-reflective coating composition may include inorganic fine particles.
  • the inorganic fine particles When the composition is applied to any substrate, the inorganic fine particles may be included in a state in which a portion thereof is eroded and dispersed in the substrate together with the above-described two or more compounds for forming a binder. In addition, the remainder not eroded into the substrate is included in the state dispersed in the second layer acting as the low refractive index layer, and may contribute to the improvement of scratch resistance and antireflection.
  • the inorganic fine particles are particles derived from various inorganic materials, and may have a number average particle diameter of nanometer scale.
  • Such inorganic particles may have a number average particle size, for example, about 100 nm or less, or about 5 to 50 nm, or about 5 to 20 nm.
  • the particle size of the inorganic fine particles may be adjusted to be in the above-described range.
  • silica particles derived from a silicon compound or an organosilicon compound may be used as the inorganic particles.
  • Inorganic fine particles are, for example, about 5 to 30 parts by weight, black to about 5 to 25 parts by weight, and black to about 5 to 20 parts by weight with respect to 100 parts by weight of the above-described low molecular weight (meth) acrylate-based compound. It may be included in the composition for anti-coat. Inorganic particles can be minimized by considering the amount of inorganic particles that can be eroded depending on the type of substrate, and the reduction of the anti-reflective effect due to the increase of reflectance when added in excess. The content of sweets can be adjusted in the above range.
  • the inorganic fine particles are dispersed in a predetermined dispersion medium, may be included in the form of a sol (solid) content of about 5 to 40 increase 0 /.
  • organic solvents that can be used as the dispersion medium include alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol, butanol (tmtanol); Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIBK); Aromatic carbon hydrogens such as toluene and xylene; Amides such as dimethyl formamide, dimethyl acetamide, and N-methyl pyrrolidone; esters such as ethyl acetate, butyl acetate, and ⁇ -butyrolactone; ); Ethers such as tetrahydroforan and 1,4-dioxane; Or combinations thereof.
  • alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol
  • silica sol may be used as the inorganic particles.
  • the anti-reflective coating composition may further include hollow particles.
  • hollow particles mean particles in the form of empty spaces on the surface and / or inside of the particles, and are components for achieving low low refractive index and antireflection effect.
  • hollow particles are not substantially distributed in the first layer, which acts as a hard coat layer of the antireflective film when the composition is applied to the substrate, and acts as a layer on the substrate covering this erosion layer, ie a low refractive index layer.
  • the hollow particles are not substantially distributed (included) in the first layer, meaning that the content ratio of the hollow particles present in the first layer, which is an eroding layer in the substrate, is less than about 5% by weight based on the total hollow particles, Or less than about 3% by weight, black may mean less than about 1% by weight.
  • the hollow particles may not be substantially distributed in the first layer, which is an erosion layer during phase separation, due to density differences or surface energy differences with other constituents, and may be densely distributed in the second layer serving as a low refractive index layer.
  • the second layer serving as a low refractive index layer.
  • the hollow particles are not particularly limited as long as the hollow particles are particles in the form of empty spaces on and / or inside the particles, but in one embodiment, the silicon compound or organic material is used to secure transparency and / or low refractive index of the low refractive index layer. Hollow silica particles derived from silicon compounds can be used.
  • the particle diameter of the hollow particles may be determined in a range capable of maintaining the transparency of the film while showing an antireflection effect.
  • the hollow particles may have a number average particle diameter, for example, of about 5 to 80 nm, or about 10 to 75 nm, or about 20 to 70 nm.
  • the hollow particles may be, for example, about 1 to 30 parts by weight, or about 1 to 25 parts by weight, or about 5 to 20 parts by weight based on 100 parts by weight of the low molecular weight (meth) acrylate compound described above. It may be included in the composition.
  • the content of the hollow particles can be adjusted in the above-described range so that the minimum distribution by the hollow particles can be exhibited, so that a desirable distribution according to phase separation can be formed.
  • the hollow particles may be included in a colloidal phase having a solid content of about 5 to 40% by weight in a form dispersed in a dispersion medium (water or an organic solvent).
  • a dispersion medium water or an organic solvent.
  • the organic solvent that can be used as a dispersion medium includes alcohols such as methanol, isopropyl alcohol (IPA), ethylene glycol and butanol; Ketones such as methyl ethyl ketone and methyl iso butyl ketone (MIB); Aromatic carbon hydrogens such as toluene and xylene; Amides such as dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone; Esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; Ethers such as tetrahydrofliran and 1,4-dioxane; Or combinations thereof.
  • alcohols such as methanol, isopropyl alcohol (IPA),
  • the above-described antireflective coating composition may further include a solvent.
  • the solvent serves to control the viscosity of the composition to an appropriate range, to control the erosion of the binder-forming compounds in the substrate, and to facilitate the smooth phase separation and distribution of the hollow particles.
  • a solvent having a dielectric constant (25 ° C.) of about 20 to 30 and a dipole moment of about 1.7 to 2.8 may be used.
  • the solvent capable of satisfying such physical properties include methyl ethyl ketone, ethyl acetate, acetyl acetone, and the like, and other solvents that satisfy the above physical properties may be used.
  • the other solvent is mixed together with the solvent which stirs the above-mentioned physical property, Can also be used.
  • Examples of such a mixed solvent that can be used include isobutyl ketone, methanol, ethanol, ⁇ -butanol, i-butanol, t-butane, and the like.
  • the solvent satisfying the dielectric constant and the dipole moment range is included in an amount of about 60 wt% or more based on the total weight of the solvent included in the composition.
  • the solvent is, for example, about 100 to 500 parts by weight, or about 100 to 450 parts by weight, or about 100 parts by weight based on 100 parts by weight of the low molecular weight (meth) acrylate compound. To 400 parts by weight. If the flowability of the composition is not good when the coating may cause defects such as streaks in the coating layer, in order to impart the minimum flowability required for the composition, the solvent may be included in a certain amount or more. In addition, when the solvent is added in an excessive amount, the solid content may be too low to cause defects during drying and curing, the distribution tendency of the hollow particles may be out of the preferred range.
  • the above-described anti-reflective coating composition may further include a polymerization initiator.
  • the polymerization initiator is a compound that can be activated by energy rays such as ultraviolet rays to induce a polymerization reaction of the compound for forming a binder, and a compound conventional in the art can be used.
  • polymerization initiators examples include 1-hydroxy cyclonuxylphenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin butyl ether, and the like. And various photopolymerization initiators may be used.
  • the content of the polymerization initiator may be, for example, about 5 to 25 parts by weight, or about 5 to 20 parts by weight, and black about 5 to 15 parts by weight based on 100 parts by weight of the low molecular weight (meth) acrylate compound. have.
  • the content of the polymerization initiation agent may be higher than a predetermined level.
  • mechanical properties such as scratch resistance or abrasion resistance of each layer forming the antireflection film may be lowered, which is not appropriate.
  • Figure 2 schematically shows a method of manufacturing an antireflective film of one embodiment using the above-described antireflective coating composition as a flow chart.
  • the manufacturing method of such an anti-reflection film comprises the steps of preparing the composition for the anti-reflective coating described above; Applying the anti-reflective coating composition to at least one side of the substrate; Eroding a portion of the compound for forming a binder and the inorganic fine particles onto the substrate while drying the applied composition; And curing the eroded and dried composition to form a first layer corresponding to the eroded region of the substrate and a second layer comprising the vaporizing particles and covering the first layer. .
  • a solvent having a predetermined physical property in the composition may first dissolve a part of the substrate, and thus, a part of the compound for forming a binder (eg, a (meth) acrylate-based compound having a low molecular weight and a high molecular weight).
  • a part of the compound for forming a binder eg, a (meth) acrylate-based compound having a low molecular weight and a high molecular weight.
  • a portion of the compound) and at least a portion of the inorganic fine particles can be eroded into the substrate.
  • some of the non-eroded compound for binder formation, the inorganic fine particles, and the hollow particles may form a coating layer (eg, a second layer) on the substrate.
  • a coating layer may remain in a thin thickness on the substrate where the above components are eroded, and hollow particles may be densely present in the coating layer.
  • a first layer which is an erosion layer in the substrate serving as a hard coat layer, and a second layer including the hollow particles and covering the first layer may be formed.
  • an antireflection film of one embodiment can be formed.
  • the antireflective film of one embodiment may be formed in a simplified process by erosion and phase separation of the substrate in some components, even if a single coating and curing process using a single composition is applied.
  • the first layer acting as a hard coat layer is eroded in the substrate and formed in contact with the second layer, the reflective antiskid film may exhibit excellent interfacial adhesion and mechanical properties.
  • such an antireflection film has a first layer and a second layer Hollow particles may be densely present in the second layer without a separate layer in between, and thus may exhibit better refractive index and excellent antireflection properties.
  • the anti-reflective coating composition described above includes at least two compounds for forming a binder, a solvent having a predetermined physical property, and the like, so that erosion and phase separation in the substrate may be optimized.
  • the method of applying the composition to at least one side of the substrate may be performed using conventional coating apparatuses and methods in the art such as wire bars.
  • the drying step may be performed for about 0.1 to 60 minutes at a temperature of about 5 to 150 ° C, or about 0.1 to 20 at a temperature of about 20 to 120 ° C, to promote phase separation of the composition and erosion into the substrate. For minutes, or for about 1 to 10 minutes at a temperature of about 30 to 110 ° C.
  • the polymerization reaction may be initiated by adding energy to the dried composition by irradiation with light or the like, and through this, the erosion and dried composition may be cured.
  • This curing step takes about 1 to 600 seconds with an ultraviolet dose of about ⁇ to 2 J / ofl 2 or about 2 to 200 seconds with an ultraviolet dose of about 0.1 to 1.5 J / crf to induce a sufficient curing reaction.
  • the silver may be performed for about 3 to 100 seconds at an ultraviolet dose of about 0.2 to l J / ctf.
  • the antireflection film of the above-described embodiment can be obtained, and in this antireflection film, the cross-sectional area ratio of the hollow particles to any cross-sectional area of the second layer serving as the low refractive index layer. It is about 70 to 95%, or about 75 to 93%, to such an extent that a black is about 80 to 90%, the black is about 85 to 92%, can be hollow particles ppaek distributed ppaek 'in the low refractive index layer.
  • the method of manufacturing the above-described anti-reflection film may be performed by further including steps that may be commonly performed in the art before or after each step.
  • steps that may be commonly performed in the art before or after each step.
  • preferred embodiments are presented to help understand the invention.
  • the following examples are only intended to illustrate the invention, and the invention is not limited thereto.
  • Silica sol in which silica fine particles are dispersed (dispersion medium: methyl isobutyl ketone and methyl alcohol, solid content 40 wt%, number average particle diameter of silica fine particles: 10 rim, manufactured by Gaematech, product name: Purisol) about 15.87 parts by weight;
  • colloidal solution in which hollow silica is dispersed (dispersion medium: methyl isobutyl ketone, solid content 20% by weight, number average particle diameter of hollow silica: 50 nm, manufacturer: Catalysis Industry, product name: MIBK-sol) about 11.33 parts by weight;
  • solvent specifically, about 179.63 parts by weight of methyl ketone (MEK), about 24.07 parts by weight of ethane, about 24.07 parts by weight of n-butyl alcohol and about 24.07 parts by weight of acetylacetone
  • MEK methyl ketone
  • a composition for preparation was prepared.
  • the anti-reflective coating composition was coated on a triacetate cell (Rose 80) using a wire bar (No. 9). After drying for 1 min at 90 ° C. Aubon, the composition was cured by irradiating with UV energy of 200 mJ / cuf for 5 seconds.
  • an antireflection film including a hard coat layer formed by erosion in a substrate and a low refractive index layer covering the hard coat layer was obtained.
  • the antireflection film according to Example 1 includes a binder hardened by erosion on the substrate 1 and a hard coat layer 2 (about 3.9) in which inorganic particles are dispersed in the binder; And a low refractive index layer 3 (about 0.15) in which the hollow particles 4 are dispersed in the binder, and a binder cured on the hard coat layer 2.
  • Penta in discrete little hex acrylate (molecular weight 298.3), 100 parts by weight of a fluorinated acrylate, a (trade name:: OPTOOL AR110, Manufacturer DAIKIN, solid content 15 wt. 0/0, and methyl isobutyl ketone solvent) 11.33 parts by weight, and a urethane functional group
  • a fluorinated acrylate 100 parts by weight of a fluorinated acrylate
  • a trade name:: OPTOOL AR110, Manufacturer DAIKIN, solid content 15 wt. 0/0, and methyl isobutyl ketone solvent
  • a urethane functional group To 100 weight part of (meth) acrylate type compounds containing 11.33 weight part of acrylate (manufacturer: KYOEISHA, product name: UA-306T, molecular weight 1000) which has;
  • Silica sol in which silica fine particles are dispersed (dispersion medium: methyl isobutyl ketone and methyl alcohol, solid content 40 wt%, number average particle diameter of silica fine particles: 10 nm, manufacturer: Gaematech, product name: Purisol) about 15.87 parts by weight;
  • colloidal solution in which hollow silica is dispersed (dispersion medium: methyl isobutyl ketone, solid content 20% by weight, number average particle diameter of hollow silica: 50 nm, manufacturer: Catalysis Industry, product name: MIBK-sol) about 11.33 parts by weight;
  • a coating composition was prepared. (Preparation of antireflection film)
  • solvent specifically, about 179.63 parts by weight of methyl ketone (MEK), about 24.07 parts by weight of ethane, about 24.07 parts by weight of n-butyl alcohol and about 24.07 parts by weight of acetylacetone
  • an anti-reflection film was prepared under the same conditions and methods as in Example 1.
  • the antireflection film according to Example 2 includes a binder hardened by erosion on the substrate 1 and a hard coat layer 2 (about 2.8 m) in which inorganic fine particles are dispersed in the binder; And a binder cured on the hard coat layer 2, and a low refractive index layer 3 (about 0.145) in which the hollow particles 4 are dispersed in the binder.
  • Example 3 the anti-reflection film according to Example 2 was confirmed that as the fluorine-based acrylate is included in the low refractive index layer, phase separation of the composition may occur more smoothly and scratch resistance is improved.
  • Pentaerythritol with respect to 100 parts by weight of a (meth) acrylate compound containing 100 parts by weight of nucleated acrylate (molecular weight 298.3) and 11.33 parts by weight of acrylate having a urethane functional group (manufacturer: KYOEISHA, product name: 510H, molecular weight 2000) ; Fine particles of silica are dispersed silica sol (dispersion medium: methyl isobutyl ketone and methyl alkoeul, solid content 40 wt. 0/0, the number average particle diameter of the silica fine particles: 10 nm, Manufacturer: Gaematech, product name: Purisol) about 15.87 parts by weight;
  • colloidal solution in which hollow silica is dispersed (dispersion medium: methyl isobutyl ketone, solid content 20 wt%, number average particle diameter of hollow silica: 50 nm, manufacturer: Catalysis Industry, product name: MIBK-sol) about 11.33 parts by weight; About 10.85 parts by weight of the photopolymerization initiator (specifically, about 1.1 parts by weight of Darocur-1173, about 6.48 parts by weight of Irgacure-184, about 2.15 parts by weight of Irgacure-819 and about 1.11 parts by weight of Irgacure-907); And
  • solvent specifically, about 179.63 parts by weight of methyl ethyl ketone (MEK), about 24.07 parts by weight of ethanol, about 24.07 parts by weight of n-butyl alcohol and about 24.07 parts by weight of acetylacetone
  • MEK methyl ethyl ketone
  • the anti-reflective coating composition was coated with a triacetate cell on a rose film (thickness: 80 kPa) using a wire bar (9). After drying for 1 minute in a 90 ° C oven, the composition was cured by irradiating UV energy of 200 mJ / ciif for 5 seconds.
  • an antireflection film including a hard coat layer formed by erosion in a substrate and a low refractive index layer covering the hard coat layer was obtained.
  • the anti-reflection film according to Example 3 includes a binder hardened by erosion by a substrate and a hard coat layer (about 3.1 ⁇ m) in which inorganic particles are dispersed in the binder; And it was confirmed that it comprises a binder cured on the hard coat layer, and a low refractive index layer (about 0.16 // m) in which hollow particles are dispersed in the binder.
  • Pentae Ritri is 100 parts by weight of nucleacrylate (molecular weight 298.3) and an acrylate having an ester functional group (manufacturer: SK Cytec, product name: DPHA, Molecular weight 524) to 100 parts by weight of a (meth) acrylate compound including 11.33 parts by weight;
  • Silica particulate self sol dispersed silica (dispersion medium: methyl isobutyl ketone and methyl alcohol, the solid content of 40 wt. 0/0, the silica particulate number average particle diameter's: 10 nm, Manufacturer: Gaematech, product name: Purisol) about 15.87 wt. part;
  • the colloid solution dispersed the hollow silica (dispersion medium: methyl isobutyl ketone, solids content 20 wt. 0/0, the number average particle diameter of the hollow silica: 50 nm, Manufacturer: Catalyst Chemical Industry, Product name: MIBK-sol) about 1 L33 weight part;
  • solvent specifically, about 179.63 parts by weight of methyl ethyl ketone (MEK), about 24.07 parts by weight of ethanol, about 24.07 parts by weight of n -butyl alcohol and about 24.07 parts by weight of acetylacetone
  • MEK methyl ethyl ketone
  • the antireflective coating composition was coated on a triacetate cell (Rose 80) using a wire bar (No. 9). After drying for 1 minute in a 90 ° C oven, the composition was cured by irradiating UV energy of 200 mJ / oif for 5 seconds.
  • an antireflection film including a hard coat layer formed by erosion in a substrate and a low refractive index layer covering the hard coat layer was obtained.
  • the antireflection film according to Example 4 includes a binder hardened by erosion on the substrate 1 and a hard coat layer 2 having inorganic particles dispersed therein (about). 2.78 ⁇ 1); And a low refractive index layer (3) (about 0.18 tm) in which the hollow particles 4 are dispersed in the binder, and the binder cured on the hard coat layer 2.
  • Silica particulate sol self-dispersed silica (dispersion medium: methyl isobutyl ketone and methyl alcohol, and solids content of 40 wt. 0/0, the number average particle diameter: 10 nm, Manufacturer: Gaematech, product name: Purisol) 15.87 parts by weight
  • the colloid solution dispersed the hollow silica (dispersion medium: methyl isobutyl ketone, solids content 20 wt. 0/0, the number average particle diameter of the hollow silica: 50 nm, Manufacturer: Catalyst Chemical Industry, Product name: MIBK-sol) about 11.33 increase unit
  • solvent specifically, about 125.91 parts by weight of methyl isobutyl ketone, about 41.98 parts by weight of ethanol, about 41.98 parts by weight of n-butyl alcohol and about 41.98 parts by weight of acetylacetone
  • solvent specifically, about 125.91 parts by weight of methyl isobutyl ketone, about 41.98 parts by weight of ethanol, about 41.98 parts by weight of n-butyl alcohol and about 41.98 parts by weight of acetylacetone
  • an anti-reflection film was prepared under the same conditions and methods as in Example 1. And the cross-sectional photograph of the said antireflection film was shown to FIG. 6 (a), and the photograph which expanded and observed the part is shown to FIG. 6 (b).
  • the antireflective film according to Comparative Example 1 did not properly undergo phase separation of the composition (see the circle portion of FIG. 6 (a)), and in particular, the hollow particles 4 in the low refractive index layer were excessive. As it spreads out (see the circled portion of Figure 6 (b)), the appearance of the film was opaque, and the scratch resistance and The antireflection effect was also found to be inferior (see Experimental Example). In this anti-reflection film of Comparative Example 1, it was confirmed that the ratio of the cross-sectional area of the hollow particles to the arbitrary cross-sectional area in the total area where the hollow particles were distributed was about 30 to 60%. Experimental Example
  • the anti-reflection film according to the embodiments was lower than the film of the comparative examples, while the transmittance was higher, scratch resistance and adhesion was excellent.

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Abstract

La présente invention concerne un film anti-éblouissement. Chaque couche du film anti-éblouissement présente une force adhésive superficielle et une résistance à l'abrasion améliorées. Le film anti-éblouissement peut être fabriqué par un procédé simplifié.
PCT/KR2012/004764 2011-08-26 2012-06-15 Film anti-éblouissement WO2013032120A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2014527054A JP2014531608A (ja) 2011-08-26 2012-06-15 反射防止フィルム
CN201280041661.8A CN103765250B (zh) 2011-08-26 2012-06-15 防眩膜
EP12827399.2A EP2749913B1 (fr) 2011-08-26 2012-06-15 Film anti-éblouissement
US13/842,758 US20130222915A1 (en) 2011-08-26 2013-03-15 Anti-reflective coating film

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2011-0085788 2011-08-26
KR20110085787 2011-08-26
KR20110085788 2011-08-26
KR10-2011-0085787 2011-08-26
KR10-2012-0036337 2012-04-06
KR1020120036337A KR101226230B1 (ko) 2011-08-26 2012-04-06 반사 방지 필름

Related Child Applications (1)

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US13/842,758 Continuation US20130222915A1 (en) 2011-08-26 2013-03-15 Anti-reflective coating film

Publications (1)

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WO2013032120A1 true WO2013032120A1 (fr) 2013-03-07

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PCT/KR2012/004764 WO2013032120A1 (fr) 2011-08-26 2012-06-15 Film anti-éblouissement

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WO (1) WO2013032120A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016061794A (ja) * 2014-09-12 2016-04-25 富士フイルム株式会社 反射防止フィルム、偏光板、カバーガラス、画像表示装置、及び反射防止フィルムの製造方法
US10338276B2 (en) 2014-09-12 2019-07-02 Fujifilm Corporation Antireflective film, polarizing plate, cover glass, image display device, and method of manufacturing antireflective film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006106714A (ja) * 2004-09-13 2006-04-20 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板、および液晶表示装置
JP2006308832A (ja) * 2005-04-28 2006-11-09 Asahi Kasei Corp 反射防止膜
JP2007133236A (ja) * 2005-11-11 2007-05-31 Fujifilm Corp 光学フィルム、偏光板、及び画像表示装置
KR20070065858A (ko) * 2006-05-31 2007-06-25 쇼꾸바이 카세이 고교 가부시키가이샤 투명 피막 형성용 도료 및 투명 피막부 기재

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006106714A (ja) * 2004-09-13 2006-04-20 Fuji Photo Film Co Ltd 反射防止フィルム、偏光板、および液晶表示装置
JP2006308832A (ja) * 2005-04-28 2006-11-09 Asahi Kasei Corp 反射防止膜
JP2007133236A (ja) * 2005-11-11 2007-05-31 Fujifilm Corp 光学フィルム、偏光板、及び画像表示装置
KR20070065858A (ko) * 2006-05-31 2007-06-25 쇼꾸바이 카세이 고교 가부시키가이샤 투명 피막 형성용 도료 및 투명 피막부 기재

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016061794A (ja) * 2014-09-12 2016-04-25 富士フイルム株式会社 反射防止フィルム、偏光板、カバーガラス、画像表示装置、及び反射防止フィルムの製造方法
US10338276B2 (en) 2014-09-12 2019-07-02 Fujifilm Corporation Antireflective film, polarizing plate, cover glass, image display device, and method of manufacturing antireflective film

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