JP4961853B2 - Anti-reflection laminate - Google Patents

Description

  The present invention relates to an antireflection laminate. More specifically, the present invention relates to an antireflection laminate applied to the surface of a display device or the like.

  Conventionally, an antireflection laminate is known in which a low refractive index layer made of an inorganic oxide such as titanium oxide or silicon oxide is formed on a transparent substrate such as glass or plastic. Furthermore, it is known to form an antifouling layer on the low refractive index layer in order to impart an antifouling function. Further, it has been proposed that the low refractive index layer contains a fluororesin or the like to impart antifouling properties to the low refractive index layer.

Patent Document 1 discloses an antireflection film including a transparent substrate such as glass and an antireflection film formed on the transparent substrate. The antireflection film is formed by arranging a single particle layer of antireflection ultrafine particles having a fluorine-containing silane compound composited on the surface thereof. The ultrafine particles are bonded to the transparent substrate with a binder such as ethyl silicate. In the antireflection film of Patent Document 1, baking is performed at a high temperature in order to bond the fine particles and the transparent substrate with a binder such as ethyl silicate.
JP-A-8-211202

Patent Document 2 discloses an antireflection film in which a low refractive index layer is formed on a transparent plastic film substrate directly or via another layer. The low refractive index layer of this antireflection film contains silica fine particles having voids into which water- and oil-repellent groups are introduced by a compound having a perfluoroalkyl group or a hydrophobic compound containing a polydimethylsiloxane segment. It is.
JP 2006-106507 A

However, according to the study by the present inventors, the antireflection film described in Patent Document 1 requires firing at a high temperature in order to strengthen the bond between the transparent substrate and the fine particles, and from the viewpoint of heat resistance, It turned out that there is a limit in selection of the resin film which comprises a transparent substrate. Moreover, in the antireflection film described in Patent Document 2, it was found that as the introduction amount of the water / oil repellent group increased, the adhesion between the transparent substrate and the low refractive index layer was lowered and separated. . Further, it has been found that these conventional antireflection films have low alkali resistance and stains are caused by an alkaline detergent or the like.
Accordingly, an object of the present invention is to provide an antireflection laminate having high adhesion between a transparent substrate and a low refractive index layer, excellent antireflection properties and antifouling properties, and excellent alkali resistance. is there.

  As a result of intensive investigations to achieve the above object, the present inventor forms a low refractive index layer on a transparent substrate using fine particles coated with modified silicone oil and a monomer having a (meth) acryloyl group. Thus, it has been found that an antireflection laminate having high adhesion between the transparent substrate and the low refractive index layer, excellent in antireflection and antifouling properties, and excellent in alkali resistance can be obtained. The present invention has been completed by further research based on this finding.

That is, the present invention is as follows.
(1) having a transparent substrate and a low refractive index layer formed on the transparent substrate directly or via another layer;
An antireflective laminate comprising a cured product of a composition containing fine particles in which the low refractive index layer is coated with a modified silicone oil and a monomer having a (meth) acryloyl group.
(2) The antireflection laminate according to (1), wherein the modified silicone oil is (meth) acryl-modified dimethyl silicone oil.
(3) The antireflection laminate according to (1), wherein the fine particles are hollow silica fine particles.
(4) The antireflective laminate according to any one of (1) to (3), wherein the low refractive index layer has a refractive index of 1.45 or less.
(5) The antireflection laminate according to (1) to (4), wherein the maximum reflectance measured at an incident angle of 5 degrees at a wavelength of 430 to 700 nm is 2.5% or less.
(6) An optical member comprising the antireflection laminate according to any one of (1) to (5).
(7) A display device comprising the antireflection laminate according to any one of (1) to (5).

  The antireflection laminate of the present invention has high adhesion between the transparent substrate and the low refractive index layer, is excellent in antireflection properties and antifouling properties, and is excellent in alkali resistance. When this antireflection laminate is provided on the display surface of a display device typified by a liquid crystal display device, a plasma display device, an EL display device, etc., reflection of light emitted from an external light source such as a fluorescent lamp is reduced and visibility is improved. Greatly improved. Further, even when wiping and cleaning with an alkaline detergent or the like is performed, no spots or the like are generated, and functional problems such as peeling of the low refractive index layer from the transparent substrate are less likely to occur.

  The antireflection laminate of the present invention has a transparent substrate and a low refractive index layer formed on the substrate directly or via another layer.

The transparent base material constituting the antireflection laminate of the present invention is not particularly limited as long as it has optical transparency. Glass and resin are mentioned as a material which comprises a transparent base material.
The resin is not particularly limited as long as it has a thickness of 1 mm and a total light transmittance of 80% or more. For example, a resin having an alicyclic structure, a polyester resin, a cellulose resin, a polycarbonate resin, a polysulfone resin, or a polyethersulfone. Examples thereof include resins, polystyrene resins, polyolefin resins, polyvinyl alcohol resins, polyvinyl chloride resins, and polymethyl methacrylate resins. These transparent resins can be used alone or in combination of two or more.

  The transparent substrate is usually in the form of a sheet, film or plate. The average thickness of the transparent substrate is preferably 30 to 300 μm, more preferably 40 to 200 μm, from the viewpoint of mechanical strength and the like. In the present invention, the transparent substrate may be composed of a single layer or a multilayer composed of two or more layers. Further, the substrate surface may be flat or uneven. The uneven shape can be obtained by a known saddle shape method such as embossing.

The transparent substrate may have a surface treated on one side or both sides. By performing the surface treatment, adhesion with other layers directly formed on the transparent substrate can be improved. Examples of the surface treatment include energy ray irradiation treatment and chemical treatment.
Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment are preferred, and corona discharge treatment is particularly preferred.
Examples of the chemical treatment include a method of immersing in an aqueous solution of an oxidizing agent such as potassium dichromate solution or concentrated sulfuric acid and then thoroughly washing with water. In addition, it is effective to shake in the soaked state, but if left soaked for a long time, the surface may dissolve or the transparency may be lowered. It is preferable to adjust treatment conditions such as immersion time and temperature according to the above.

  The low refractive index layer constituting the antireflection laminate of the present invention is composed of a cured product of a composition containing fine particles coated with a modified silicone oil and a monomer having a (meth) acryloyl group. (Meth) acryloyl is an abbreviation for acryloyl or methacryloyl. (Meth) acryl is an abbreviation for acrylic or methacrylic.

  Examples of the monomer having a (meth) acryloyl group contained in the composition for forming the low refractive index layer include acrylic acids such as acrylic acid and methacrylic acid; acrylate or methacrylate of ethylene oxide-modified phenol, acrylate of propylene oxide-modified phenol Or methacrylate, ethylene oxide modified nonylphenol acrylate or methacrylate, propylene oxide modified nonylphenol acrylate or methacrylate, 2-ethylhexyl carbitol acrylate, 2-ethylhexyl carbitol methacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl Acrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl Acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, diethylene glycol monoacrylate, diethylene glycol methacrylate, dipropylene glycol monoacrylate, dipropylene glycol methacrylate, triethylene Monoacrylate or methacrylate such as glycol monoacrylate, triethylene glycol monomethacrylate, tripropylene glycol, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethyl acrylate Hexyl methacrylate, acrylonitrile, glycidyl acrylate, monofunctional acrylate or methacrylate such as glycidyl methacrylate;

  Diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, Tripropylene glycol dimethacrylate, tetrapropylene glycol diacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentylglycoldia Relate, neopentyl glycol dimethacrylate, diacrylate or dimethacrylate of ethylene oxide modified neopentyl glycol, diacrylate or dimethacrylate of ethylene oxide modified bisphenol A, diacrylate or dimethacrylate of propylene oxide modified bisphenol A, hydrogenated ethylene oxide Bisphenol A diacrylate or dimethacrylate, trimethylolpropane diacrylate or dimethacrylate, trimethylolpropane allyl ether diacrylate, trimethylolpropane allyl ether dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide modified trimethylo Propanetriacrylate, ethylene oxide modified trimethylolpropane trimethacrylate, propylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetra Polyfunctional acrylates or methacrylates such as methacrylate and dipentaerythritol hexaacrylate;

Polyester acrylates such as polyester Aronix M-6400 (polyester acrylate manufactured by Toagosei Co., Ltd.); Urethane acrylates such as Aronix M-1200 (manufactured by Toagosei Co., Ltd.); 2,2,6,6-tetra having a cyclic hindered amine structure Methyl-4-piperidinyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2- (2′-hydroxy-5′-methacryloxyethylphenyl)-having a benzotriazole ring And 2H-benzotriazole.
The amount of the monomer having a (meth) acryloyl group is usually 30 to 70% by weight, preferably 40 to 60% by weight, based on the total amount excluding water and solvent in the composition for forming the low refractive index layer. It is.

The fine particles contained in the composition for forming the low refractive index layer are fine particles coated with a modified silicone oil.
The fine particles coated with the modified silicone oil are inorganic or organic fine particles having a low refractive index. From the viewpoint of achieving both a low refractive index and scratch resistance, silica fine particles are preferred, and hollow silica fine particles are particularly preferred.
The hollow silica fine particles preferably have a refractive index of 1.20 to 1.35, particularly preferably 1.20 to 1.30. The refractive index of the fine particles can be calculated by the method described in JP-A-2002-79616.

  The number average particle diameter of the hollow silica fine particles is usually 100 nm or less, preferably 5 to 100 nm, and more preferably 15 to 90 nm. When the number average particle diameter of the hollow silica fine particles exceeds 100 nm, the particle diameter of the hollow silica fine particles becomes larger than the coating thickness, and it becomes difficult to perform the coating. The particle size distribution of the hollow silica fine particles is preferably narrow and monodispersed, but may be polydispersed. Therefore, two or more types of hollow silica fine particles having different average particle diameters can be used in combination. Further, agglomerated particles may be used as long as a predetermined particle size is satisfied. The hollow silica fine particles are most preferably spherical, but may be indefinite. The particle size of the hollow silica fine particles can be determined from an electron micrograph.

The silica forming the outer shell (shell) of the hollow silica fine particles may be crystalline or amorphous. The shell may be porous so that the outside and the hollow portion can communicate with each other, but it is preferable that the shell can be blocked from the outside.
The hollow silica fine particles used in the present invention can be obtained, for example, by the methods described in JP-A Nos. 2001-233611 and 2002-79616.

  The modified silicone oil coated on the fine particles is a silicone oil having a functional group. Silicone oils include those in which a dimethylsiloxane structure is contained in a repeating unit, those in which a methylphenylsiloxane structure is contained in a repeating unit, and those in which a methylhydrosiloxane structure is contained in a repeating unit. Those in which only the structure is contained in the repeating unit are preferred.

  Modified silicone oils include long chain alkyl modified dimethyl silicone oil, fluorine modified dimethyl silicone oil, methacryl modified dimethyl silicone oil, acrylic modified dimethyl silicone oil, carbinol modified dimethyl silicone oil, polyol modified dimethyl silicone oil, methylstyryl modified dimethyl silicone. An oil etc. are mentioned. The site of denaturation may be any site such as the end of the main chain or the end of the side chain. A combination of the above modifications may also be used. Of these, long-chain alkyl-modified dimethyl silicone oil, fluorine-modified dimethyl silicone oil, methacryl-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, and polyol-modified dimethyl silicone oil are preferred. Is preferred.

  The amount of the modified silicone oil to be coated is 10 to 100 parts by weight, preferably 10 to 60 parts by weight with respect to 100 parts by weight of the fine particles. When the amount of the modified silicone oil is small, fine particles that cannot be completely coated exist, and the slipping property, stain resistance, and alkali resistance tend to decrease. On the contrary, when the amount of the modified silicone oil increases, the modified silicone oil comes to exist independently from the fine particles, and this tends to decrease the surface strength of the antireflection laminate.

  The fine particles coated with the modified silicone oil can be obtained by mixing and stirring the fine particles and the modified silicone oil. When mixing and stirring the fine particles and the modified silicone oil, a silane coupling agent and a silylating agent may be added and stirred.

  As silane coupling agents, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltri Ethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, Examples include γ-chloropropyltrimethoxysilane and γ-ureidopropyltriethoxysilane. The amount of the silane coupling agent is usually 0.5 to 10 parts by weight with respect to 100 parts by weight of the fine particles.

  Examples of silylating agents include trimethylsilyl chloride, 1,1,1,3,3,3-hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) trifluoroacetamide, trimethylsilyl. Trifluoromethanesulfonate, triethylsilyl chloride, tri-i-butylsilyl chloride, t-butyldimethylsilyl chloride, tri-i-propylsilyl chloride, texyldimethylsilyl chloride, 1,3-dichloro-1,1,3 Mention may be made of 3-tetra-i-propyldisiloxane. The amount of the silylating agent is usually 0.5 to 10 parts by weight with respect to 100 parts by weight of the fine particles.

  The amount of fine particles coated with the modified silicone oil may be appropriately adjusted according to the refractive index value required for the low refractive index layer.

  The composition for forming the low refractive index layer may contain other components. Examples of other components include a photopolymerization initiator, a solvent, a dispersant, and a thickener.

  The photopolymerization initiator can be selected from known photopolymerization initiators. As the photopolymerization initiator, aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyl) Benzoins, benzoin ethers, benzyl dimethyl ketals, benzoyl benzoates, α-acyloxime esters, etc.); sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.); acylphosphine oxide light A polymerization initiator etc. are mentioned. The amount of the photopolymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer having a (meth) acryloyl group. These photopolymerization initiators can be used in combination with a photosensitizer such as amines.

  Solvents include ethers such as propylene glycol monomethyl ether and ethylene glycol monomethyl ether; alcohols such as diacetone alcohol, isobutyl alcohol, isopropyl alcohol, n-butyl alcohol, and n-propyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as acetylacetone; ethyl acetate, butyl acetate, xylene, toluene and the like. What is necessary is just to adjust the quantity of a solvent suitably with the coating conditions (for example, appropriate viscosity, appropriate film thickness) of the coating machine to be used.

  The low refractive index layer can be obtained by applying the composition on a transparent substrate directly or via another layer, drying, and curing. The coating method is not particularly limited, and examples thereof include a spin coating method, a dip method, a spray method, and a bar coating method. Examples of the curing means include heat and ionizing radiation, and ionizing radiation is preferred.

  The average thickness of the low refractive index layer is usually 10 to 1000 nm, preferably 20 to 500 nm. The refractive index of the low refractive index layer is preferably 1.45 or less. When the refractive index of the low refractive index layer is in the above range, it is possible to achieve the hardness and strength required for the polarizing plate protective film, and to obtain an antireflection laminate excellent in adhesion and transparency. The refractive index can be determined by measuring using a known spectroscopic ellipsometer.

Other layers may be laminated on the antireflection laminate of the present invention. Examples of the other layer include a high refractive index layer. In the present invention, the high refractive index layer refers to a layer having a refractive index of 1.55 or more. The high refractive index layer is usually formed between the transparent substrate and the low refractive index layer.
Examples of the material constituting the high refractive index layer include inorganic materials and resin materials, but resin materials are preferred from the viewpoint of excellent productivity.
As a resin material for forming the high refractive index layer, it has properties as a binder in the high refractive index layer, has sufficient strength as a film after the formation of the high refractive index layer, and is further transparent, There is no particular limitation. For example, a thermosetting resin, a thermoplastic resin, and an ionizing radiation curable resin can be used, but a thermosetting resin or an ionizing radiation curable resin is preferable in terms of the strength and workability of the film.

  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 cocondensation resin, silicone resin, polysiloxane Resin. Further, these thermosetting resins may contain a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like.

The ionizing radiation curable resin contains a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule, and these are cured by irradiation with ionizing radiation. Ionizing radiation has energy quanta that can polymerize or crosslink molecules of electromagnetic waves or charged particle beams. Usually, ultraviolet rays or electron beams are used.
The ultraviolet or electron beam curable resin is not particularly limited, and can be appropriately selected from known ultraviolet or electron beam curable resins. The ultraviolet curable resin contains a photopolymerizable prepolymer or a photopolymerizable monomer, a photopolymerization initiator, and a photosensitizer. The electron beam curable resin contains a photopolymerizable prepolymer or a photopolymerizable monomer.

Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These photopolymerizable prepolymers can be used singly 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-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol di Methacrylate etc. It is.
In the present invention, urethane acrylate is preferably used as the photopolymerizable prepolymer, and dipentaerythritol hexaacrylate or dipentaerythritol hexamethacrylate is preferably used as the photopolymerizable monomer.

  Examples of the photopolymerization initiator include acetophenones, benzophenones, α-amyloxime esters, tetramethylchuram monosulfide, thioxanthones, and the like. Moreover, n-butylamine, triethylamine, poly-n-butylphosphine, etc. are mentioned as a photosensitizer.

  The high refractive index layer preferably contains conductive fine particles in addition to the thermosetting resin or ionizing radiation curable resin. By containing the conductive fine particles, an antistatic function is imparted to the high refractive index layer, and the mechanical strength is excellent.

  The conductive fine particles are not particularly limited as long as they are conductive fine particles, but metal oxide fine particles are preferable because of excellent transparency.

  Examples of the metal oxide constituting the conductive metal oxide fine particles include antimony pentoxide, tin oxide, tin oxide doped with phosphorus (PTO), tin oxide doped with antimony (ATO), and tin doped. Indium oxide (ITO), zinc-doped indium oxide (IZO), aluminum-doped zinc oxide (AZO), fluorine-doped tin oxide (FTO), zinc oxide / aluminum oxide, zinc antimonate Etc. These metal oxide fine particles can be used singly or in combination of two or more. Among these, at least one selected from antimony pentoxide fine particles and tin oxide fine particles doped with phosphorus is preferable because of excellent transparency.

  Moreover, in this invention, what provided electroconductivity can be used by coat | covering electroconductive metal oxide to the metal oxide microparticles | fine-particles which do not have electroconductivity as electroconductive metal oxide microparticles | fine-particles. For example, the surface of fine particles of titanium oxide, zirconium oxide, cerium oxide or the like having a high refractive index but no conductivity is coated with the conductive metal oxide to impart conductivity.

  The number average particle diameter of the conductive fine particles is preferably 200 nm or less, and 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. Can be measured with a particle size distribution meter using

In the present invention, the amount of conductive fine particles contained in the high refractive index layer is preferably 30% by volume or more, and more preferably 40-60% by volume. The amount of the conductive fine particles contained in the high refractive index layer is a value obtained by the following formula.
Content of conductive fine particles (volume%) = (C−A) / (B−A) × 100
However, C is the refractive index of the high refractive index layer, A is the refractive index of the resin material forming the high refractive index layer, and B is the refractive index of the conductive fine particles.

  Moreover, the high refractive index layer may contain particles for imparting antiglare properties. The particles for imparting antiglare properties are not particularly limited as long as they can form irregularities on the surface of the high refractive index layer. The number average particle diameter of the particles for imparting antiglare properties is preferably 0.5 to 10 μm, and more preferably 1 to 7 μm.

  The high refractive index layer may contain a leveling agent and a dispersing agent for the purpose of improving the uniformity of the layer thickness and improving the adhesion. Examples of the leveling agent include compounds that lower the surface tension, such as silicone oil, fluorinated polyolefin, and polyacrylate. Examples of the dispersant include a surfactant and a silane coupling agent.

  The high refractive index layer is formed by applying a composition containing the above-described components for forming the high refractive index layer directly on the transparent substrate or on the other layer formed on the surface of the transparent substrate and drying. Then, it can be formed by irradiation with heat or ionizing radiation. Examples of the coating method include a spin coating method, a dip method, a spray method, and a bar coating method.

  The refractive index of the high refractive index layer is preferably 1.55 or more, more preferably 1.60 or more. When the refractive index of the high refractive index layer is within this range, reflection of external light can be suppressed and reflection can be prevented when the low refractive index layer is laminated on the high refractive index layer. 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 “HB” or higher in a pencil hardness test (test plate is a glass plate) shown in JIS K5600-5-4. The high refractive index layer having a pencil hardness of “HB” or higher can serve as a hard coat layer and can be thinned by reducing the number of layers of the antireflection laminate. The average thickness of the high refractive index layer is usually 0.3 to 20 μm, preferably 0.8 to 10 μm.

  In the antireflection laminate of the present invention, the maximum reflectance at an incident angle of 5 degrees at a wavelength of 430 to 700 nm is preferably 2.5% or less, more preferably 2.0% or less. The reflectance at an incident angle of 5 degrees at a wavelength of 550 nm is preferably 1.5% or less.

  Since the antireflection laminate of the present invention is excellent in antireflection performance, physical strength of the surface layer, and antifouling resistance, it is useful as an antireflection film for flat panel displays. More specifically, various liquid crystal displays such as a mobile phone, a digital information terminal, a pager (registered trademark), a navigation system, an in-vehicle liquid crystal display, a TV liquid crystal monitor, a light control panel, a display for OA equipment, and a display for AV equipment. It is suitable as an antireflection film used for panels, electroluminescence display elements, touch panels and the like.

  The optical member of the present invention comprises the antireflection laminate. Examples of the optical member include an antireflection film in a touch panel, a plasma panel display front plate in a plasma panel display, and a polarizing plate with an antireflection function in a liquid crystal display device. Especially, the polarizing plate with an antireflection function in a liquid crystal display device is preferable.

The display device of the present invention includes the antireflection laminate.
The display device includes members unique to each of a liquid crystal display device, a plasma display device, an EL display device, and the like. For example, in a liquid crystal display device, a cold cathode tube, a light diffusion plate, a light guide plate, a brightness enhancement film, a prism array sheet, a liquid crystal cell, a phase difference plate, and the like can be given. One layer or two or more layers can be arranged at appropriate positions. The mode of the liquid crystal used for the liquid crystal cell is not particularly limited. Liquid crystal modes include TN (Twisted Nematic), STN (Super Twisted Nematic), HAN (Hybrid Alignment Nematic), VA (Vertical Alignment), MVA (Multiple Alignment). OCB (Optical Compensated Bend) type and the like. The display device of the present invention is configured by applying the antireflection laminate of the present invention alone or in combination with a member specific to the display device.

About 90% of touch panels currently use the resistive film method. In general, the resistive film type touch panel has an input side resin base material in which a transparent conductive thin film such as indium tin oxide (ITO) film is coated on one side of a transparent resin base material, and an ITO film on one side of a transparent base material such as glass. The pressure-receiving side transparent base material coated with a transparent conductive thin film such as the above has a structure in which the transparent conductive thin films face each other through insulating spacers. Then, when the input surface of the input side resin base material (referred to as the surface opposite to the transparent conductive thin film side) is pressed with a pen or a finger, the transparent conductive thin film of the input side resin base material and the pressure receiving side transparent base material The transparent conductive thin film is in contact with each other and information is input.
As an aspect of applying the antireflection laminate of the present invention as an antireflection film of the touch panel, the antireflection laminate of the present invention is formed on the input side of the input side resin substrate, and the transparent substrate is on the input side. A mode in which the low-refractive index layer is provided on the surface side of the resin base and the transparent base-side surface constituting the antireflection laminate of the present invention (a surface on which the low-refractive index layer is not formed) Further, there is an embodiment in which a transparent conductive thin film such as an ITO film is formed and used as it is as an input side resin base material of the touch panel.

  When the antireflection laminate of the present invention is applied to the front plate of a plasma display panel, the antireflection laminate of the present invention is usually arranged so that the surface on which the low refractive index layer is formed is the viewing side. In addition, it is used by being laminated on a transparent substrate. The transparent substrate is not particularly limited as long as it is a transparent plate. For example, a substrate having a thickness of 1 mm and a total light transmittance of 80% or more, preferably 90% or more can be used. More specifically, a glass plate and a transparent resin plate are mentioned.

  The antireflection laminate of the present invention and the transparent substrate can be laminated by bonding them using an appropriate adhesive means such as an adhesive or a pressure-sensitive adhesive. Examples of the adhesive or pressure-sensitive adhesive include acrylic, silicone, polyester, polyurethane, polyether, and rubber. Among these, acrylic adhesives or pressure-sensitive adhesives are preferable because they are excellent in heat resistance and transparency.

  In the liquid crystal display device, a polarizing plate is provided on the exit side or the entrance side of the liquid crystal cell. This polarizing plate includes a polarizer made of a stretched film of polyvinyl alcohol dyed or adsorbed with dichroic materials such as iodine and organic dyes, and triacetyl cellulose (TAC) bonded to both sides of the polarizer. It consists of a protective film.

  When the antireflective laminate of the present invention is applied to a polarizing plate in a liquid crystal display device, the antireflective laminate of the present invention is antireflective on the polarizer instead of one protective film bonded to the polarizer. The laminate is used so that the transparent substrate is on the polarizer side. The lamination of the antireflection laminate of the present invention and a polarizer and the lamination of a polarizer and a protective film can be bonded using an appropriate adhesive means such as an adhesive or a pressure-sensitive adhesive. Examples of the adhesive or pressure-sensitive adhesive include acrylic, silicone, polyester, polyurethane, polyether, and rubber. Among these, acrylic adhesives or pressure-sensitive adhesives are preferable because they are excellent in heat resistance and transparency.

  In addition, although it does not restrict | limit especially as a material which comprises a protective film, Cellulosic resins, such as a cellulose triacetate, and resin which has an alicyclic structure are preferable from a viewpoint of transparency, low birefringence, and dimensional stability. The protective film may have optical isotropy or optical anisotropy. A protective film having optical illegality can be used as a retardation film.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified.
(1) Scratch resistance (steel wool test)
In a state where steel wool # 0000 is pressed to the surface of the antireflection laminate with a load of 0.025 MPa, the steel wool is rubbed 10 times on the surface of the antireflection laminate. The surface state of the antireflection laminate after rubbing was visually observed and evaluated by the following indices.
○: Scratches are not recognized.
X: Scratches are observed.

(2) Pencil hardness Measured with a 1 kg load according to JIS K5600-5-4.

(3) Reflectance Using a spectrophotometer (ultraviolet visible near infrared photometer V-550, manufactured by JASCO Corporation), the reflectance at an incident angle of 5 degrees at a wavelength of 430 to 700 nm is measured (measurement wavelength interval). 1 nm), the maximum reflectance in the wavelength range, and the reflectance at a wavelength of 550 nm were calculated.

(4) Contamination resistance A 10 cm long line was drawn with oil-based magic on the surface of the antireflection laminate. The state of the line drawing was visually observed. Further, the cloth was rubbed with a cloth to wipe the line drawing. The line drawing after rubbing was visually observed. The observation results were evaluated in the following four stages.
◎: Repel (wipe off)
○: Not repelled but wiped off △: Slightly wiped off ×: Not wiped off

(5) Alkali resistance 2 ml of a 1% by weight aqueous solution of sodium hydroxide is dropped onto the outermost surface of the antireflection laminate (the surface on which the low refractive index layer is laminated), left for 30 minutes, and then wiped with a cloth soaked in water. The surface state was visually observed to determine whether the surface was attacked.
○: No trace △: Only outline can be confirmed ×: Overall trace is visible

(6) Dispersion stable state The coating agent for forming a low refractive index layer was placed in a 100 ml transparent bottle, stored at 40 degrees for 3 days, and it was visually confirmed whether or not it was separated.

(Production Example 1) Preparation of High Refractive Index Layer Composition 100 parts of an acryloyl group-containing oligomer (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., UV-1700B), Sb ₂ O ₅ particles (manufactured by Catalyst Kasei Kogyo Co., Ltd., average) 100 parts of a particle size of 30 nm) and 2 parts of a photopolymerization initiator (IRGACURE 184 manufactured by Ciba Specialty Chemicals) were added and stirred at 2000 rpm for 5 minutes with a stirrer to obtain a composition for forming a high refractive index layer. .

(Production Example 2)
(Preparation of film-forming fine particles A)
Impurity ions were removed from the hollow silica fine particles (number average particle diameter 30 nm, refractive index 1.29) using an ion exchange resin (AG1 × 8, BIO-Rad Laboratories). Next, 40 parts of methacryl-modified dimethyl silicone oil (X-22-2404, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts of the hollow silica fine particles, and the mixture is stirred for 1 hour in a dissolver mixer to prepare a fine particle dispersion A. did.

(Preparation of film-forming fine particles B)
10 g of an acryloyl group-containing silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 g of an aqueous solution containing 0.1% acetic acid and stirred for about 1 hour in a dissolver mixer until the aqueous solution becomes transparent.
Impurity ions were removed from the hollow silica fine particles (number average particle size 30 nm, refractive index 1.29) using an ion exchange resin (AG1 × 8, BIO-Rad Laboratories). To 100 parts of the hollow silica fine particles, 2 parts (solid content) of the above-mentioned coupling agent solution was added and stirred for 1 hour in a dissolver mixer. Next, 40 parts of methacryl-modified dimethyl silicone oil (X-22-2404, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was further stirred for 1 hour in a dissolver mixer to prepare a fine particle dispersion B.

(Preparation of film-forming fine particles C)
Impurity ions were removed from the hollow silica fine particles (number average particle diameter 30 nm, refractive index 1.29) using an ion exchange resin (AG1 × 8, BIO-Rad Laboratories).
1 part of a trimethylsilyl group-containing silylating agent (KA31, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 40 parts of methacryl-modified dimethyl silicone oil (X-22-2404, manufactured by Shin-Etsu Chemical Co., Ltd.), and the mixture was stirred for 1 hour in a dissolver mixer. . 100 parts of the hollow silica fine particles were added to this liquid, and stirred for 1 hour in a dissolver mixer to prepare a fine particle dispersion C.

(Preparation of film-forming fine particles D)
Using ion exchange resin (AG1 × 8, BIO-Rad Laboratories), pretreatment for increasing the activity of silanol groups of hollow silica fine particles (number average particle diameter 30 nm, refractive index 1.29) was performed. A fine particle dispersion D was prepared by adding 40 parts of a fluororesin (manufactured by Novec 1720 3M) to 100 parts of the hollow silica fine particles and stirring for 1 hour in a dissolver mixer.

(Production Example 3) Preparation of Coating Agent 1 for Low Refractive Index Layer 100 parts of an acryloyl group-containing monomer (Adekaoptomer KR566, manufactured by Asahi Denka Kogyo Co., Ltd.) is added to a photopolymerization initiator (IRGACURE 184, Ciba Specialty Chemicals). (Manufactured) 2 parts, 70 parts of the fine particle dispersion A were added, and the mixture was stirred with a stirrer at 2000 rpm for 30 minutes to obtain a coating agent 1 for a low refractive index layer.

(Production Example 4) Preparation of coating agent 2 for low refractive index layer A coating agent for low refractive index layer was produced in the same manner as in Production Example 3 except that the fine particle dispersion A was replaced with the fine particle dispersion B in Production Example 3. 2 was obtained.

(Production Example 5) Preparation of coating agent 3 for low refractive index layer A coating agent for low refractive index layer was produced in the same manner as in Production Example 3 except that the fine particle dispersion A was replaced with the fine particle dispersion C in Production Example 3. 3 was obtained.

(Production Example 6) Preparation of coating agent 4 for low refractive index layer A coating agent for low refractive index layer was produced in the same manner as in Production Example 3 except that the fine particle dispersion A was replaced with the fine particle dispersion D in Production Example 3. 4 was obtained.

(Production Example 7) Preparation of Coating Agent 5 for Low Refractive Index Layer In Production Example 3, 50 parts of hollow silica fine particles (number average particle size 30 nm, refractive index 1.29) not coated with the fine particle dispersion A were prepared. Other than having changed, it carried out similarly to manufacture example 3, and obtained the coating agent 5 for low refractive index layers.

Example 1
A 70 μm thick polyethylene terephthalate (PET) film (A4300, manufactured by Toyobo Co., Ltd.) was used as the transparent substrate. The composition for forming a high refractive index layer obtained in Production Example 1 was applied on this transparent substrate with a bar coater. Using a UV irradiator, the UV light was irradiated and cured so that the accumulated light amount was 300 mJ / cm ² to obtain a transparent substrate / high refractive index layer laminate. The high refractive index layer had a thickness of 2 μm and a refractive index of 1.70. Next, the coating agent 1 for the low refractive index layer obtained in Production Example 3 was applied on the high refractive index layer with a bar coater, and the obtained coating film was dried at 90 ° C. for 3 minutes, and then irradiated with ultraviolet rays. The antireflection laminate 1 comprising transparent substrate / high refractive index layer / low refractive index layer was obtained by irradiating with ultraviolet rays so as to obtain an integrated light quantity of 300 mJ / cm ² using a machine and curing the coating film. The obtained antireflection laminate 1 was evaluated. The evaluation results are shown in Table 1.

(Example 2)
An antireflection laminate 2 was obtained in the same manner as in Example 1, except that the low refractive index layer coating agent 2 obtained in Production Example 4 was used instead of the low refractive index layer coating agent 1. The obtained antireflection laminate 2 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 3)
An antireflection laminate 3 was obtained in the same manner as in Example 1 except that the low refractive index layer coating agent 3 obtained in Production Example 5 was used instead of the low refractive index layer coating agent 1. The obtained antireflection laminate 3 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 1)
An antireflection laminate 4 was obtained in the same manner as in Example 1 except that the coating agent 4 for low refractive index layer obtained in Production Example 6 was used instead of the coating agent 1 for low refractive index layer. The obtained antireflection laminate 4 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 2)
An antireflection laminate 5 was obtained in the same manner as in Example 1 except that the low refractive index layer coating agent 5 obtained in Production Example 7 was used instead of the low refractive index layer coating agent 1. The obtained antireflection laminate 5 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Table 1 shows the following.
As shown in the examples, the antireflective laminate of the present invention is excellent in surface strength (abrasion resistance and pencil hardness), and thus has sufficient physical strength, as well as excellent contamination resistance and alkali resistance, and reflectivity. Is found to be good. On the other hand, in the antireflection laminate of Comparative Example 1, it can be seen that the coating liquid is separated and a coating on fine particles is not formed. Further, in Comparative Example 2, it can be seen that the surface strength (scratch resistance, pencil hardness), stain resistance, and alkali resistance are insufficient when the fine particles are not coated.

Claims (8)

A transparent substrate and a low refractive index layer formed on the transparent substrate directly or via another layer;
Fine particles coated low refractive index layer by modified silicone oil (average particle size except those is 50 to 200 nm), and (meth) Ri Do a cured product of a composition containing a monomer having an acryloyl group, 40 to 100 parts by weight of der Ru antireflection stack against coverages fine particles 100 parts by weight of the modified silicone oil.   The antireflection laminate according to claim 1, wherein the modified silicone oil is (meth) acryl-modified dimethyl silicone oil.   The antireflection laminate according to claim 1, wherein the fine particles are hollow silica fine particles.   The antireflective laminate according to any one of claims 1 to 3, wherein the low refractive index layer has a refractive index of 1.45 or less.   The antireflection laminate according to any one of claims 1 to 4, wherein the maximum reflectance measured at an incident angle of 5 degrees at a wavelength of 430 to 700 nm is 2.5% or less.   An optical member comprising the antireflection laminate according to claim 1.   A display apparatus provided with the antireflection laminated body in any one of Claims 1-5.   6. The method according to claim 1, comprising removing impurity ions from the fine particles with an ion exchange resin, coating the fine particles with a modified silicone oil, and then mixing it with a monomer having a (meth) acryloyl group. A method for producing an antireflection laminate.