WO2010087290A1 - Film anti-réflexion - Google Patents

Film anti-réflexion Download PDF

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Publication number
WO2010087290A1
WO2010087290A1 PCT/JP2010/050821 JP2010050821W WO2010087290A1 WO 2010087290 A1 WO2010087290 A1 WO 2010087290A1 JP 2010050821 W JP2010050821 W JP 2010050821W WO 2010087290 A1 WO2010087290 A1 WO 2010087290A1
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Prior art keywords
refractive index
index layer
high refractive
resin
film
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PCT/JP2010/050821
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English (en)
Japanese (ja)
Inventor
裕 矢賀部
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日本ゼオン株式会社
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Publication of WO2010087290A1 publication Critical patent/WO2010087290A1/fr

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    • 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

Definitions

  • the present invention relates to an antireflection film mainly used on the surface of a display device, and more particularly to an antireflection film having sufficient image clarity and surface hardness.
  • the display screen of a display device is often touched by the user's hand, and its surface may become dirty or scratched, making it difficult to see the displayed image, and its surface hardness needs to be improved. Yes.
  • the display screen of a display device is required to have an antireflection function because the visibility of a display image may be reduced due to a reflection image caused by reflection of external light from a fluorescent lamp. For this reason, conventionally, an antireflection film having an appropriate surface hardness may be applied to the display screen of a display device.
  • the antireflection film for example, a substrate film, a film provided on the substrate film, comprising a high refractive index layer, and a low refractive index layer provided on the high refractive index layer has been studied. Yes.
  • the high refractive index layer is also given a function as a hard coat layer in order to increase its surface hardness.
  • a curable material made of ultraviolet or thermosetting resin such as an acrylic oligomer or an acrylic urethane oligomer is used. It can be formed by curing.
  • Patent Document 1 discloses a composition in which, for example, scaly inorganic fine particles having an average particle diameter of 10 to 300 nm or less are added to a curable material for forming a hard coat layer. It is disclosed that a hard coat layer is formed using an object.
  • An object of the present invention is to provide an antireflection film having sufficient image clarity and surface hardness.
  • the present invention includes the following.
  • an antireflection film comprising a composition containing scaly inorganic particles having an average particle diameter of 3 to 10 ⁇ m, and the anti-reflection film has a clarity of image of 90% or more.
  • the antireflection film wherein the inorganic particles contain a silicon oxide component in an amount of 35% by weight or more.
  • the antireflection film, wherein the composition contains 3 to 30 parts by weight of the inorganic particles with respect to 100 parts by weight of the hard coat material.
  • the base film includes a first resin layer made of a composition including a thermoplastic acrylic resin or a resin having an alicyclic structure and elastic particles having a number average particle size of 2.0 ⁇ m or less, and the elasticity
  • the antireflection film which is a multilayer film having an average thickness of less than 100 ⁇ m, formed by a coextrusion method, and a second resin layer made of a thermoplastic resin not containing body particles.
  • the antireflection film of the present invention includes a high refractive index layer using a composition comprising a hard coat material as a main component and scaly or plate-like inorganic particles having an average particle diameter of 3 to 10 ⁇ m.
  • a composition comprising a hard coat material as a main component and scaly or plate-like inorganic particles having an average particle diameter of 3 to 10 ⁇ m.
  • display devices such as liquid crystal display devices, organic EL displays, plasma display devices, and touch panels.
  • the antireflection film of the present invention includes a base film, a high refractive index layer provided on the base film, and a low refractive index layer provided on the high refractive index layer, the refractive index R L and
  • the high refractive index layer includes a low refractive index layer in which a refractive index RH satisfies a relationship of (R H ⁇ 0.1) ⁇ RL .
  • the base film may be a single layer or a laminate composed of a plurality of layers.
  • a transparent resin having a thickness of 1 mm and a total light transmittance of 80% or more can be used.
  • the transparent resin include resins having an alicyclic structure, polyester resins, cellulose resins, polycarbonate resins, polysulfone resins, polyethersulfone resins, polystyrene resins, polyolefin resins, polyvinyl alcohol resins, polyvinyl chloride resins, and heat.
  • a plastic acrylic resin examples include a plastic acrylic resin.
  • a transparent resin used for the base film of the present invention a thermoplastic acrylic resin is preferable from the viewpoint of adhesion to a high refractive index layer described later.
  • Thermoplastic acrylic resins use (meth) acrylic acid ester as the main ingredient of raw material, and (meth) acrylic acid ester is derived from (meth) acrylic acid, alkanol having 1 to 15 carbon atoms and cycloalkanol. It is preferable that the structure be A structure derived from an alkanol having 1 to 8 carbon atoms is more preferable. When there are too many carbon numbers, the elongation at the time of the fracture
  • (meth) acrylic acid ester is methacrylic acid ester and acrylic acid ester.
  • thermoplastic acrylic resin a homopolymer of (meth) acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate; the hydrogen of the alkyl group is OH group, COOH group or NH 2 group
  • Homopolymer of (meth) acrylic acid alkyl ester substituted with a functional group such as: or (meth) acrylic acid alkyl ester and styrene, vinyl acetate, ⁇ , ⁇ -monoethylenically unsaturated carboxylic acid, vinyl toluene Mention may be made of copolymers with ⁇ -methylstyrene and vinyl monomers having an unsaturated bond such as maleic anhydride.
  • thermoplastic acrylic resin only 1 type may be used among these and it may use it in combination of 2 or more type. More preferably, the thermoplastic acrylic resin contains a methyl methacrylate unit and a butyl methacrylate unit as monomer units.
  • the transparent resin may contain other compounding agents in addition to the elastic particles described later.
  • Other compounding agents include, for example, inorganic particles; antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, UV absorbers, near infrared absorbers, and other stabilizers; resin modifiers such as lubricants and plasticizers Agents; coloring agents such as dyes and pigments; antistatic agents and the like. These compounding agents can be used alone or in combination of two or more.
  • the compounding amount of the compounding agent can be appropriately selected within a range not impairing the object of the present invention, and usually 0 to 5 parts by weight, preferably 0 to 3 parts by weight with respect to 100 parts by weight of the transparent resin. Examples of the method of incorporating these compounding agents include a method of previously compounding the compounding agent in a transparent resin, a method of directly supplying at the time of melt extrusion molding, and the like.
  • the base film preferably contains elastic particles having a number average particle diameter of 2.0 ⁇ m or less in addition to the transparent resin.
  • Elastic body particles are particles made of a rubber-like elastic body.
  • the rubber-like elastic material include an acrylate-based rubber-like polymer, a rubber-like polymer containing butadiene as a main component, and an ethylene-vinyl acetate copolymer.
  • the acrylic ester rubbery polymer include butyl acrylate, 2-ethylhexyl acrylate and the like as raw materials. Of these, acrylate polymers based on butyl acrylate and rubbery polymers based on butadiene are preferred.
  • the elastic particles may be formed by laminating two kinds of polymers, and representative examples thereof include an alkyl acrylate such as butyl acrylate and a grafted rubber elastic component of styrene, polymethyl Mention may be made of elastic particles in which a hard resin layer made of a methacrylate and / or a copolymer of methyl methacrylate and an alkyl acrylate forms a layer with a core-shell structure.
  • an alkyl acrylate such as butyl acrylate and a grafted rubber elastic component of styrene
  • polymethyl Mention may be made of elastic particles in which a hard resin layer made of a methacrylate and / or a copolymer of methyl methacrylate and an alkyl acrylate forms a layer with a core-shell structure.
  • the number average particle size of secondary particles dispersed in the transparent resin is 2.0 ⁇ m or less, preferably 0.1 to 1.0 ⁇ m, more preferably 0.1 to 0.5 ⁇ m. It is. Even if the primary particle size of the elastic particles is small, if the number average particle size of the secondary particles formed by aggregation or the like is large, the haze (cloudiness) of the base film becomes too high and the light transmittance becomes low. . Moreover, when the number average particle size becomes too small, the flexibility tends to decrease.
  • the base film is composed of a composition containing the transparent resin, preferably the thermoplastic acrylic resin or a resin having an alicyclic structure, and the elastic particles unevenly distributed in the thickness direction of the film.
  • the portion where the elastic particles are unevenly distributed may be a central portion in the thickness direction or a surface portion.
  • the elastic particles are unevenly distributed in the central portion, there are few elastic particles near the surface of the base film, and many elastic particles are distributed in the central portion in the thickness direction of the base film.
  • the elastic particles are unevenly distributed on the surface portion, there are few elastic particles in the central portion of the base film, and many elastic particles are distributed on at least one surface portion.
  • the distribution of the elastic particles may increase or decrease gradually from the surface toward the center, or may increase or decrease in stages.
  • the flexibility can be improved while sufficiently securing the surface hardness of the antireflection film.
  • the antireflection film of the present invention is bonded to a polarizing plate, a display device or the like, at least a high refractive index layer is laminated from the viewpoint of improving adhesion with a polarizer constituting the polarizing plate. It is preferable that a large amount of elastic particles be distributed on the surface of the base film opposite to the side.
  • a composition comprising a thermoplastic acrylic resin or a resin having an alicyclic structure and elastic particles having a number average particle size of 2.0 ⁇ m or less, A method of co-extrusion molding of a thermoplastic resin not containing the elastic particles; a composition comprising a thermoplastic resin and elastic particles having a number average particle size of 2.0 ⁇ m or less, and a thermoplastic not containing the elastic particles Examples thereof include a method of coextrusion molding with an acrylic resin or a resin having an alicyclic structure.
  • a composition comprising a thermoplastic acrylic resin or a resin having an alicyclic structure and elastic particles having a number average particle diameter of 2.0 ⁇ m or less and a thermoplastic resin not containing the elastic particles are coextruded.
  • Coextrusion method is used.
  • the co-extrusion method include a co-extrusion T-die method, a co-extrusion inflation method, and a co-extrusion lamination method, and among them, the co-extrusion T-die method is preferable.
  • the co-extrusion T-die method includes a feed block method and a multi-manifold method, but the multi-manifold method is more preferable in that variation in the thickness of the layer 1 containing elastic particles can be reduced.
  • the total thickness of the base film is preferably 10 to 300 ⁇ m, more preferably 15 to 150 ⁇ m as the total thickness.
  • the base film is composed of a multilayer resin layer formed using a composition comprising a thermoplastic acrylic resin or a resin having an alicyclic structure and elastic particles having a number average particle diameter of 2.0 ⁇ m or less
  • the total thickness of the layer composed of a plastic acrylic resin or a resin having an alicyclic structure and elastic particles having a number average particle size of 2.0 ⁇ m or less is preferably 60 ⁇ m or less, and preferably 20 ⁇ m or more and 60 ⁇ m or less.
  • the total thickness of the thermoplastic resin layer not containing the elastic particles is preferably 20 ⁇ m or more, and preferably 20 ⁇ m or more and 60 ⁇ m or less. If the total thickness of the thermoplastic resin layer not containing elastic particles is less than 20 ⁇ m, heat resistance and strength are insufficient, and a thermoplastic acrylic resin or a resin having an alicyclic structure and a number average particle size of 2.0 ⁇ m or less. If the total thickness of the layers made of elastic particles is less than 20 ⁇ m, the flexibility becomes insufficient.
  • the “thermoplastic resin not containing elastic particles” can be a thermoplastic acrylic resin or a resin having an alicyclic structure.
  • the base film preferably has a residual solvent content of 0.01% by mass or less.
  • the residual solvent amount is in the above range, for example, it is possible to prevent the base film from being deformed in a high temperature / high humidity environment and to prevent the optical performance from being deteriorated.
  • the base film in which the residual solvent amount falls within the above range can be obtained, for example, by coextrusion molding of a plurality of resins. In the case of coextrusion molding, it is not necessary to go through a complicated process (for example, a drying process or a coating process). Therefore, there is little mixing of external foreign matters such as dust, and excellent optical performance can be exhibited.
  • the residual solvent content was determined by placing 50 mg of the base film in a glass tube sample container with an inner diameter of 4 mm from which moisture and organic substances adsorbed on the surface were completely removed, heating the container at a temperature of 200 ° C. for 30 minutes, This is a value obtained by continuously collecting the emitted gas and analyzing the collected gas with a thermal desorption gas chromatography mass spectrometer (TDS-GC-MS).
  • TDS-GC-MS thermal desorption gas chromatography mass spectrometer
  • the substrate film preferably has a moisture permeability of 10 g ⁇ m ⁇ 2 day ⁇ 1 or more and 200 g ⁇ m ⁇ 2 day ⁇ 1 or less. Adhesiveness with the layer laminated
  • the moisture permeability can be measured by the cup method described in JIS Z 0208 under the test conditions for 24 hours in an environment of 40 ° C. and 90% RH.
  • the surface of the base film may have a concavo-convex structure from the viewpoint of reducing interference unevenness.
  • the uneven structure may be formed only on one surface of the base film, or may be formed on both surfaces.
  • a method of imparting a concavo-convex structure on the surface of the base film a nip molding method using a shaping roll having concavo-convex, a sandwich lamination method using a film having concavo-convex, The blast method can be applied.
  • the surface on the uneven structure side can have an arithmetic average surface roughness (Ra) of 0.05 ⁇ m or more and 0.5 ⁇ m or less.
  • the average period (Sm) of the structure can be 10 ⁇ m or more and 200 ⁇ m or less.
  • the arithmetic average surface roughness and average period of the base film are values measured in accordance with JIS B 0601: 2001.
  • the base film having an uneven structure on the surface preferably has a haze of 1% or more and less than 50%, and more preferably 3% or more and less than 40%.
  • the surface of the base film on the side where the high refractive index layer is provided can be subjected to surface modification treatment.
  • the surface modification treatment include energy beam irradiation treatment and chemical treatment.
  • the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like. Corona discharge treatment and plasma treatment are preferable from the viewpoint of treatment efficiency.
  • the chemical treatment include a method of immersing the agent film in an aqueous oxidizing agent solution such as potassium dichromate solution or concentrated sulfuric acid, and then sufficiently washing with water. When shaken in an immersed state, the treatment can be performed in a short time. However, if the treatment is carried out excessively, the surface is dissolved or the transparency is lowered.
  • the high refractive index layer is a composition containing a hard coat material as a main component and scaly inorganic particles having an average particle diameter of 3 to 10 ⁇ m (hereinafter sometimes referred to as a composition for forming a high refractive index layer). ).
  • the hard coat material an inorganic material, a resin material, or a mixture thereof can be used, but a resin material is preferable from the viewpoint of excellent productivity.
  • a resin material a material having sufficient strength as a film after the formation of the high refractive index layer and having transparency can be used.
  • the resin material include a thermosetting resin, a thermoplastic resin, and an ionizing radiation curable resin, and a thermosetting resin or an ionizing radiation curable resin is preferable in terms of film strength and workability. .
  • Thermosetting resins include phenolic resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicone resin, polysiloxane Resin. Moreover, you may add hardening agents, such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc. to these thermosetting resins as needed.
  • hardening agents such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc.
  • the ionizing radiation curable resin is a resin in which a prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is cured by irradiation with ionizing radiation.
  • Ionizing radiation refers to electromagnetic waves or charged particle beams having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet rays or electron beams are used.
  • Examples of the ultraviolet curable resin include a photopolymerizable prepolymer or a photopolymerizable monomer and a photopolymerization initiator or a photosensitizer, and examples of the electron beam curable resin include a photopolymerizable prepolymer or a photopolymer. The thing containing a polymerizable monomer is mentioned.
  • Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These photopolymerizable prepolymers may be used alone or in combination of two or more.
  • Examples of the photopolymerizable monomer include polymethylolpropane triacrylate, polymethylolpropane trimethacrylate, hexanediol acrylate, hexanediol methacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedi
  • urethane acrylate as the prepolymer and dipentaerythritol hexaacrylate or dipentaerythritol hexamethacrylate as the monomer.
  • photopolymerization initiator examples include acetophenones, benzophenones, ⁇ -amyloxime esters, tetramethylchuram monosulfide, thioxanthones, and the like.
  • photosensitizer n-butylamine, triethylamine, poly-n-butylphosphine and the like can be used alone or in combination.
  • the composition for forming a high refractive layer contains scaly inorganic particles having an average particle diameter of 3 to 10 ⁇ m.
  • the average particle diameter of the inorganic particles can be determined by observing 100 inorganic particles using a scanning electron microscope (SEM), obtaining the length of the major axis, and averaging these major axes. .
  • the scaly shape can be said to be a thin shape, and the average aspect ratio between the thickness and the length in the long side direction (the length in the longest direction among the directions perpendicular to the thickness direction) is 40 to 200, the film thickness is 2 ⁇ m or less.
  • the inorganic particles preferably contain a silicon oxide component of 35% by weight or more.
  • a silicon oxide component of 35% by weight or more.
  • adhesion between the low refractive index layer and the layer can be further increased, and the surface strength can be further improved.
  • the low refractive index layer has a silicon oxide component of 40% by weight. In the case of including the above, there is an advantage that the adhesion can be further improved.
  • the upper limit of the content rate of a silicon oxide component is not specifically limited, It can be 80 weight% or less.
  • the inorganic particles are preferably contained in an amount of 3 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the hard coat material. By setting it as the said suitable range, surface hardness and image clarity can be improved further.
  • the inorganic particles include mascobite, phlogopite, biotite, fluorine phlogopite, kaolinite, talc, sericite, organically treated mica, silica, bentonite, montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite. , Stevensite, vermicularite, and synthetic smectite. One of these may be used, or two or more may be used in combination. Moreover, you may provide a silane coupling agent to an inorganic particle.
  • the composition for forming a high refractive index layer may contain conductive fine particles in addition to the inorganic particles.
  • conductive fine particles By including the conductive fine particles, not only a function as a high refractive index layer but also a function as an antistatic layer can be imparted.
  • the conductive fine particles are not particularly limited as long as they are conductive fine particles, but metal oxide fine particles are preferable in terms of excellent transparency. Examples of the metal oxide include antimony pentoxide, tin oxide, tin oxide doped with phosphorus (PTO), tin oxide doped with antimony (ATO), indium oxide doped with tin (ITO), and zinc.
  • Indium oxide doped with IZO
  • zinc doped with aluminum AZO
  • tin doped with fluorine FTO
  • zinc oxide / aluminum oxide zinc antimonate, and the like.
  • metal oxide fine particles can be used singly or in combination of two or more.
  • antimony pentoxide fine particles and / or tin oxide fine particles doped with phosphorus are preferable because of excellent transparency.
  • the metal oxide fine particles fine particles imparted with conductivity by coating the surface of the metal oxide fine particles having no conductivity with a conductive metal oxide can also be used.
  • the surface of fine particles of titanium oxide, zirconium oxide, cerium oxide or the like having a high refractive index but no conductivity can be used by coating the conductive metal oxide to impart conductivity.
  • the number average particle diameter of the conductive fine particles is preferably 200 nm or less, more preferably 50 to 15 nm.
  • the number average particle size is determined by visual observation from a secondary electron emission image photograph obtained by a transmission electron microscope (TEM) or image processing of the image photograph, or a dynamic light scattering method, a static light scattering method, or the like. It can be measured by a particle size distribution meter using
  • the high refractive layer forming composition may contain other inorganic particles in addition to the inorganic particles.
  • inorganic particles inorganic oxides are generally used.
  • SiO 2 , Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , CeO 2 , P 2 O 5 , MoO 3 , ZnO 2 , WO 3 or the like can be mentioned.
  • the number average particle diameter of the other inorganic particles is preferably 500 nm or less, more preferably 30 to 15 nm. The number average particle diameter can be measured in the same manner as described above.
  • the high refractive index layer is prepared by diluting the composition for forming a high refractive index layer with a solvent, and diluting the diluted product directly or on the surface of one surface of the base film, preferably the surface on which the concavo-convex structure is formed. It can be obtained by coating on another layer formed on the material film to obtain a coating film and irradiating the coating film with heat or ionizing radiation.
  • the solvent examples include alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; glycols such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether; aromatic hydrocarbons such as toluene and xylene. Aliphatic hydrocarbons such as n-hexane and n-heptane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and combinations of two or more of these; .
  • alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol
  • glycols such as ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether
  • aromatic hydrocarbons such as toluene and
  • a leveling agent or a dispersant may be contained for the purpose of improving the uniformity of the layer thickness or improving the adhesion.
  • the leveling agent include compounds that lower the surface tension, such as silicone oil, fluorinated polyolefin, and polyacrylic acid ester.
  • the dispersing agent include a surfactant and a silane coupling agent.
  • the refractive index of the high refractive index layer is preferably 1.5 to 1.7.
  • the refractive index can be obtained by measuring using, for example, a known spectroscopic ellipsometer.
  • the high refractive index layer preferably exhibits a hardness of “2H” or more at a load of 500 g of a pencil hardness test (test plate is a glass plate) shown in JIS K5600-5-4.
  • a pencil hardness test test plate is a glass plate
  • the high refractive index layer can also serve as a hard coat layer, and the thickness of the entire antireflection film can be reduced.
  • the average thickness of the high refractive index layer is usually 0.3 to 20 ⁇ m, preferably 0.8 to 10 ⁇ m.
  • the surface of the high refractive index layer can be subjected to surface treatment.
  • the surface treatment include the surface modification treatment exemplified in the above-described base film.
  • the antireflection film of the present invention includes a low refractive index layer provided on the high refractive index layer.
  • the refractive index RL of the low refractive index layer and the refractive index RH of the high refractive index layer satisfy the relationship of (R H ⁇ 0.1) ⁇ RL . That is, the refractive index of the low refractive index layer is 0.1 or more smaller than the refractive index of the high refractive index layer.
  • the material for forming the low refractive index layer (hereinafter sometimes referred to as a composition for forming a low refractive index layer) preferably contains mainly a thermosetting resin or an ionizing radiation type curable resin.
  • the silicon oxide component of the low refractive index layer is preferably 40% by weight or more. By setting it as such a suitable range, adhesiveness with a high refractive layer can be improved.
  • the upper limit of the content ratio of the silicon oxide component in the low refractive index layer is not particularly limited, but can be 60% by weight or less.
  • thermosetting resin R 1 nSi (OR 2 ) m (wherein R 1 is a monovalent hydrocarbon group which may have a substituent, OR 2 is a hydrolyzable group) N, m represents an integer, m is 1 to 4, and m + n is 4.)
  • R 1 nSi (OR 2 ) m (wherein R 1 is a monovalent hydrocarbon group which may have a substituent, OR 2 is a hydrolyzable group) N, m represents an integer, m is 1 to 4, and m + n is 4.)
  • a silicon compound obtained by hydrolyzing all or part of the silicon compound can be used. .
  • the monovalent hydrocarbon group which may have a substituent includes an alkyl group, a phenyl group, a cycloalkyl group, an aryl group, a haloalkyl group; an alkenylcarbonyloxyalkyl group; an alkyl group having an epoxy group, and a mercapto group.
  • Examples thereof include an alkyl group, an alkyl group having an amino group, and a perfluoroalkyl group.
  • an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a perfluoroalkyl group are preferable from the viewpoint of ease of synthesis and availability.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent hydrocarbon group.
  • an alkoxyl group is preferable from the viewpoint of availability.
  • nSi (OR 2 ) m a silicon compound in which n is an integer of 0 to 2 is preferable.
  • Specific examples thereof include alkoxysilanes, acetoxysilanes, oxime silanes, enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Among these, alkoxysilanes are more preferable from the viewpoint of availability.
  • Examples of the tetraalkoxysilane in which n is 0 include tetramethoxysilane and tetraethoxysilane.
  • Examples of the organotrialkoxysilane in which n is 1 include methyltrimethoxysilane, methyltriethoxysilane, and methyltriisopropoxysilane.
  • Examples of the diorganodialkoxysilane in which n is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane.
  • the silicon compound preferably contains fluorine.
  • the silicon compound containing fluorine include fluorine-containing alkylalkoxysilanes.
  • trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxy Examples include silane. Of these, compounds in which n is 2 to 6 are preferred.
  • the silicon compounds may be used alone or in combination of two or more. Also, the order of mixing and hydrolysis of two or more silicon compounds may be sequential or simultaneous.
  • Resins curable by ionizing radiation curability include monomers having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; monomers having a carboxyl group such as acrylic acid and methacrylic acid; hydroxyl groups such as hydroxyalkyl acrylate and hydroxyalkyl methacrylate.
  • a monomer having a vinyl group such as allyl acrylate and allyl methacrylate; a monomer having an amino group; a monomer having a sulfonic acid group; and the like.
  • the composition for forming a low refractive index layer may contain a filler.
  • the filler is not particularly limited as long as it is fine particles of an inorganic compound.
  • an inorganic oxide is generally used.
  • ZnO 2 and WO 3 can be mentioned.
  • hollow fine particles may be added to the composition for forming a low refractive index layer.
  • the hollow fine particles have a hollow structure in which cavities are formed inside the outer shell.
  • silica-based hollow fine particles can be suitably used. By containing silica-based hollow fine particles, it is possible to improve scratch resistance in addition to low refractive index properties.
  • the hollow fine particles include (A) a single layer of an inorganic oxide, (B) a single layer of a composite oxide composed of different types of inorganic oxides, and (C) a double layer of the above (A) and (B). Things can be used.
  • the average particle diameter of the hollow fine particles is not particularly limited, but is preferably 5 to 2000 nm, and more preferably 20 to 100 nm. If it is smaller than 5 nm, the effect of lowering the refractive index due to hollowness is reduced. If it is larger than 2000 nm, the transparency is lowered and the contribution due to diffuse reflection is increased.
  • the average particle diameter can be determined by the number average particle diameter by observation with a transmission electron microscope.
  • the addition amount of the hollow fine particles is not particularly limited, but is preferably 40 to 200% by weight, more preferably 40 to 150% by weight, based on the solid content of the composition for forming a low refractive index layer. Within this range, both low refractive index properties and scratch resistance can be achieved.
  • the low refractive index layer is obtained by diluting the composition for forming a low refractive index layer with a solvent, coating the diluted product on the high refractive index layer, and then drying and curing the coating film. A cured film of a rate layer can be formed.
  • the coating method is not particularly limited, and includes usual methods such as a doctor blade method, a gravure roll coater method, a dipping method, a spin coating method, a brush coating method, a flexographic printing method, and the like.
  • a cured film having a low refractive index layer can be obtained by forming the obtained coating film by irradiating it with heat or ionizing radiation.
  • Examples of the solvent include the same solvents as those exemplified above for the composition for forming a high refractive index layer.
  • the solid content concentration in the composition for forming a low refractive index layer diluted with a solvent can be appropriately adjusted within a range not impairing the solution stability. Since the composition for forming a low refractive index layer is preferably formed into a thin film with a good thickness accuracy, it is usually from about 0.1 to 20% by weight, preferably from about 0.5 to 10% by weight because it is easy to handle. .
  • the composition for forming a low refractive index layer may contain other components.
  • other components include surfactants, photopolymerization initiators, dispersants such as silane coupling agents, leveling agents, and thickeners.
  • the content of the surfactant is preferably 500 ppm or more and more preferably 1000 ppm or more with respect to the solid content of the composition for forming a low refractive index layer.
  • the surfactant include a fluorine-based surfactant and a silicone-based surfactant.
  • Fluorosurfactants include non-ionic perfluoroalkylsulfonic acid amide group-containing nonions such as Fluorad FC-431 manufactured by 3M, MegaFac F-171, F-172, F-173, F manufactured by Dainippon Ink, Inc.
  • Perfluoroalkyl group-containing oligomers such as -176PF, F-470, and F-471.
  • silicone surfactant include polydimethylsiloxane in which the side chain or the end of the main chain is modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.
  • photopolymerization initiator examples include known photopolymerization initiators. Specifically, aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers) , Benzyldimethyl ketals, benzoylbenzoates, ⁇ -acyloxime esters, etc.); sulfur-containing photopolymerization initiators (for example, sulfides, thioxanthones, etc.); acylphosphine oxide photopolymerization initiators; other light There is a polymerization initiator.
  • aryl ketone photopolymerization initiators for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers
  • sulfur-containing photopolymerization initiators for example, sulfides,
  • the photopolymerization initiator can also be used in combination with a photosensitizer such as amines.
  • the content of the photopolymerization initiator is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
  • Curing can be performed by heating and / or actinic ray irradiation according to the composition for forming a low refractive index layer.
  • the drying conditions and curing conditions can be appropriately determined depending on the boiling point of the solvent to be used, the saturated vapor pressure, the type of the base material, and the like. In the case of irradiation, it is usually preferably 2 J / cm 2 or less.
  • the refractive index RL of the low refractive index layer and the refractive index RH of the high refractive index layer satisfy the relationship of (R H ⁇ 0.1) ⁇ RL . That is, the refractive index of the low refractive index layer is 0.1 or more smaller than that of the high refractive layer.
  • the refractive index of the low refractive index layer is preferably less than 1.4, preferably 1.25 to 1.38, more preferably 1.30 to 1.38. By setting the refractive index of the low refractive index layer in the above range, in addition to antireflection properties, scratch resistance can be imparted.
  • the average thickness of the low refractive index layer is usually 10 to 1000 nm, preferably 20 to 500 nm.
  • an antifouling layer may be provided on the low refractive index layer.
  • the antifouling layer is provided for protecting the low refractive index layer and enhancing the antifouling performance.
  • the material for forming the antifouling layer is not particularly limited as long as the function of the low refractive index layer is not inhibited and the required performance as the antifouling layer is satisfied.
  • a compound having a hydrophobic group can be preferably used.
  • a perfluoroalkylsilane compound, a perfluoropolyethersilane compound, or a fluorine-containing silicone compound can be used.
  • the antifouling layer for example, a physical vapor deposition method such as vapor deposition or sputtering; a chemical vapor deposition (CVD) method; a wet coating method;
  • the thickness of the antifouling layer is not particularly limited, but is usually preferably 20 nm or less, more preferably 1 to 10 nm.
  • the minimum value measured at an incident angle of 5 ° at a wavelength of 430 to 700 nm is less than 1.5%, and preferably 1.3% or less.
  • the image clarity of the antireflection film of the present invention is 90% or more. If it is less than 90%, the irregular reflection of the display image becomes intense and the visibility is lowered.
  • the upper limit of image clarity is not particularly limited, but can be 100% or less.
  • the antireflection film of the present invention includes a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode tube display (CRT), a field emission display (FED), electronic paper, a touch panel, and the like. It can be used by directly bonding to the display device or by replacing with a surface member incorporated in the display device such as a polarizing plate protective film or a front plate.
  • LCD liquid crystal display
  • PDP plasma display panel
  • ELD electroluminescence display
  • CRT cathode tube display
  • FED field emission display
  • the resin was molded into a single layer and measured using a prism coupler (product name “model 2010” manufactured by Metricon) under the conditions of a temperature of 20 ° C. ⁇ 2 ° C. and a humidity of 60 ⁇ 5%.
  • Image clarity According to JIS K 7105, measurement was performed with an optical comb having a width of 0.5 mm using a image clarity measuring device (manufactured by Suga Test Instruments Co., Ltd.). Higher values mean higher clarity.
  • the image clarity is measured through an optical comb that moves the transmitted light from the sample, and the value is obtained by calculation.
  • the slit image formed on the optical comb becomes thick due to the blur. Therefore, both ends of the slit image are applied to the opaque part at the position of the transmission part, and the amount of light is 100%. Decrease. Further, at the position of the opaque portion, light leaks from the opaque portion at both ends of the slit image, and the amount of light of 0% increases.
  • the sharpness value is defined by the following equation from the maximum value M of the transmitted light of the transparent portion of the optical comb and the minimum value m of the opaque portion.
  • the image clarity can be determined to be good when the following value C is 90% or more (more preferably 95% or more).
  • Value of map clarity C (%) ((M ⁇ m) / (M + m)) ⁇ 100
  • each layer constituting the base film 1 is such that the thickness of one surface layer (surface layer 1) is 5 ⁇ m, the intermediate layer is 10 ⁇ m, and the other surface layer (surface layer 2) is 5 ⁇ m.
  • the total thickness was 20 ⁇ m.
  • the refractive index of the surface layer 1 of the base film 1 was 1.49.
  • Production Example 2 Production of Substrate Film 2
  • a norbornene-based polymer (product name “ZEONOR 1420R”, manufactured by Nippon Zeon Co., Ltd .: glass transition temperature Tg 136 ° C.) is used to make 110 using a hot air dryer in which air is circulated. Dry at 4 ° C. for 4 hours. Thereafter, the pellet was melt-extruded at 260 ° C. using a single screw extruder to obtain a base film 2. Moreover, the film thickness of this base film 2 was 20 micrometers.
  • composition 1 for Forming High Refractive Layer To 100 parts of an oligomer containing acryloyl group (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “UV-1700B”), scaly inorganic particles (Yamaguchi mica) 7 parts by Sangyo Kogyo Co., Ltd., SJ-005, average particle size 5 ⁇ m, silicon oxide component 45%), 150 parts zirconia (Cai Kasei Co., Ltd., average particle size 20 nm), photopolymerization initiator (Ciba Specialty Chemicals) 2 parts of a product name “IRGACURE184” manufactured by the company) and another 1 part of methacryl-modified dimethyl silicone oil (trade name “X-22-164A” manufactured by Shin-Etsu Chemical Co., Ltd.) are added and stirred for 5 minutes at 5000 rpm with a stirrer. By doing this, the composition 1 for high refractive index layer
  • Production Example 4 Preparation of High Refractive Layer Forming Composition 2
  • a high refractive index layer forming composition 2 was obtained in the same manner as in Production Example 3 except that the scale-shaped inorganic particles were changed to 35 parts.
  • the refractive index was 1.63.
  • composition 5 for forming a high refractive layer Scale-like inorganic particles were replaced with other scale-like inorganic particles (manufactured by Coop Chemical Co., MK-300, average particle size 15 ⁇ m, silicon oxide component 52%).
  • a composition 5 for forming a high refractive index layer was obtained in the same manner as in Production Example 3, except for changing to.
  • the refractive index was 1.62.
  • composition 6 for forming a high refractive index layer For forming a high refractive index layer in the same manner as in Production Example 3 except that the scale-shaped inorganic particles were changed to a biotite pulverized product (average particle diameter 6 ⁇ m).
  • Composition 6 was obtained.
  • the biotite pulverized product is obtained by pulverizing biotite (manufactured by Lingju Prefectural Tianjin Mining Co., Ltd., silicon oxide component 35%) with a ball mill and passing through an 8 ⁇ m sieve to obtain an average particle size of 6 ⁇ m.
  • the refractive index was 1.62.
  • composition 1 for forming a low refractive index layer By adding 200 parts of ethanol to a four-necked reaction flask equipped with a reflux tube and adding 120 parts of oxalic acid to this ethanol in small amounts. An ethanol solution of oxalic acid was prepared. The solution was then heated to the reflux temperature, and a mixture of 20 parts tetraethoxysilane and 4 parts tridecafluorooctyltrimethoxysilane (GE Toshiba Silicone, trade name “TSL8257”) was added dropwise to the refluxed solution. did.
  • composition 3 for forming a low refractive index layer A composition 3 for forming a low refractive index layer was obtained in the same manner as in Production Example 10 except that the hollow silica fine particles were changed to 80 parts.
  • the silicon oxide component of the low refractive index layer obtained by drying this composition and forming a film was 42%.
  • the refractive index of the low refractive index layer was 1.43.
  • Production Example 13 Preparation of Low Refractive Index Layer Composition 4
  • a low refractive index layer composition 4 was obtained in the same manner as in Production Example 10 except that the hollow silica fine particles were changed to 60 parts.
  • the silicon oxide component of the low refractive index layer obtained by drying this composition and forming a film was 35%.
  • the refractive index of the low refractive index layer was 1.44.
  • Example 1 After applying the composition 1 for forming a high refractive layer obtained in Production Example 3 to the surface of the base film 1 obtained in Production Example 1 with a bar coater, using an ultraviolet irradiator. Ultraviolet irradiation was performed so that the integrated light amount was 200 mJ / cm 2, and a high refractive layer having a thickness of 5 ⁇ m was formed to obtain a laminate of base film / high refractive index layer. Next, on the high refractive index layer, the low refractive index layer forming composition 1 obtained in Production Example 10 was applied with a bar coater, and the obtained coating film was dried and cured at 60 ° C. for 1 minute, A low refractive index layer having a thickness of 100 nm was formed to obtain the antireflection film 1 of the present invention. The evaluation results of the antireflection film 1 are shown in Table 1.
  • Example 2 Example except that the low refractive index layer forming composition 2 obtained in Production Example 11 was used instead of the low refractive index layer forming composition 1 and the steps for forming the low refractive index layer were changed as follows.
  • an antireflection film 2 was obtained.
  • the low refractive index layer is formed by applying the low refractive index layer forming composition on the high refractive index layer with a bar coater, and drying the obtained coating film at 60 ° C. for 1 minute to obtain an integrated light amount of 100 mJ / cm 2 . It was obtained by curing with ultraviolet irradiation.
  • the evaluation results of the antireflection film 2 are shown in Table 1.
  • Example 3 instead of the base film 1, an antireflection film 3 was obtained in the same manner as in Example 1 except that the base film 2 obtained in Production Example 2 was used. The evaluation results of the antireflection film 3 are shown in Table 1.
  • Example 4 An antireflection film 4 was obtained in the same manner as in Example 1 except that the low refractive index layer forming composition 3 obtained in Production Example 13 was used instead of the low refractive index layer forming composition 1. The evaluation results of the antireflection film 4 are shown in Table 1.
  • Example 5 An antireflection film 5 was obtained in the same manner as in Example 1 except that the high refractive layer forming composition 6 obtained in Production Example 8 was used instead of the high refractive layer forming composition 1.
  • the evaluation results of the antireflection film 9 are shown in Table 1.
  • Example 1 An antireflection film 11 was obtained in the same manner as in Example 1 except that the high refractive layer forming composition 2 obtained in Production Example 4 was used instead of the high refractive layer forming composition 1. The evaluation results of the antireflection film 11 are shown in Table 2.
  • Example 2 An antireflection film 12 was obtained in the same manner as in Example 1 except that the high refractive layer forming composition 3 obtained in Production Example 5 was used instead of the high refractive layer forming composition 1. The evaluation results of the antireflection film 12 are shown in Table 2.
  • Example 3 An antireflection film 13 was obtained in the same manner as in Example 1, except that the high refractive layer forming composition 4 obtained in Production Example 6 was used instead of the high refractive layer forming composition 1. The evaluation results of the antireflection film 13 are shown in Table 2.
  • Example 4 An antireflection film 14 was obtained in the same manner as in Example 1 except that the high refractive layer forming composition 5 obtained in Production Example 7 was used instead of the high refractive layer forming composition 1. The evaluation results of the antireflection film 14 are shown in Table 2.
  • the antireflection films of Examples 1 to 4 have good adhesion, a minimum reflectance of 1.3% or less, a high surface strength of 3H or more, and image clarity. Is as high as 90% or more, it has sufficient image clarity and surface hardness. Therefore, it is understood that the visibility is difficult to be lowered when used in a display device. Moreover, although Example 5 is slightly lowered in terms of adhesion, there is no practical problem, and it can be seen that other points are sufficient. On the other hand, as shown in Comparative Examples 1 and 4, when the content of the scale-shaped inorganic particles is large or the particle diameter is larger than the predetermined range, it is found that the image clarity is inferior.
  • Comparative Examples 2 and 3 it can be seen that the surface hardness is insufficient when the content of the scale-like inorganic particles is small or the particle diameter is smaller than the predetermined range. Furthermore, as shown in Comparative Example 5, it can be seen that when the difference in refractive index is smaller than 0.1, the minimum reflectance is 1.5%, and the performance as an antireflection film is slightly inferior.

Abstract

Le film anti-réflexion qui fait l'objet de l'invention comporte un film de base, une couche d'indice de réfraction élevé, placée au dessus dudit film de base, ainsi qu'une couche d'indice de réfraction faible, placée au dessus de ladite couche d'indice de réfraction élevé, qui est telle que, RL correspondant à l'indice de réfraction de ladite couche à indice de réfraction faible, et RH correspondant à l'indice de réfraction de ladite couche à indice de réfraction élevé, la condition(RH-0,1)≥ RL soit satisfaite. Ladite couche à indice de réfraction élevé consistant en une composition contenant un matériau de revêtement dur en tant que ingrédient principal et des particules inorganiques squamiformes dont le diamètre moyen se situe entre 3 et 10μm, la netteté de l'image du film anti-réflexion est égale ou supérieure à 90%.
PCT/JP2010/050821 2009-01-30 2010-01-22 Film anti-réflexion WO2010087290A1 (fr)

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KR101526650B1 (ko) * 2012-11-21 2015-06-05 (주)엘지하우시스 광학특성이 우수한 반사방지 필름
KR102280262B1 (ko) 2018-05-18 2021-07-21 주식회사 엘지화학 반사 방지 필름, 편광판 및 디스플레이 장치
WO2020027085A1 (fr) * 2018-07-31 2020-02-06 コニカミノルタ株式会社 Film optique, plaque de polarisation et procédé de production de film optique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002275409A (ja) * 2001-03-16 2002-09-25 Nippon Soda Co Ltd 親水性ハードコート膜及びその製造方法
WO2007119560A1 (fr) * 2006-03-31 2007-10-25 Zeon Corporation Plaque de polarisation, écran à cristaux liquides et film protecteur

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002275409A (ja) * 2001-03-16 2002-09-25 Nippon Soda Co Ltd 親水性ハードコート膜及びその製造方法
WO2007119560A1 (fr) * 2006-03-31 2007-10-25 Zeon Corporation Plaque de polarisation, écran à cristaux liquides et film protecteur

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