JP2006047504A - Antireflective stack - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflective stack including a transparent low refractive index layer having a low refractive index and excellent adhesion property with a base material and mechanical strength, in which a coating layer of an ionization radiation-curing resin composition containing silsesquioxane containing a fluorine atom is formed. <P>SOLUTION: The antireflective stack has a low refractive index layer formed directly or with another layer interposed on at least one surface of a light-transmitting base material. The low refractive index layer is formed by using a low refractive index layer forming coating composition which contains: silsesquioxane having two or more perfluoroalkyl groups and two or more reactive groups in one molecule as a component (A); a fluorine-containing monomer as a component (B); and a filler as a component (C). The quantitative relation between the component (A) and the component (B) shows that the ratio of the component (A) to the component (B) is 50:50 to 95:5 by mass% and that the component (C) is included by 10 to 200 parts by mass with respect to total 100 parts by mass of the components (A) and (B). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antireflective laminate in which a low refractive index layer having a low refractive index and a high hardness is formed on a light transmissive substrate using a coating composition containing fluorine.

  A display surface of an image display device such as a liquid crystal display (LCD) or a cathode ray tube display device (CRT) is required to reflect less light emitted from an external light source such as a fluorescent lamp in order to improve its visibility. .

  It has been known that the reflectance is reduced by coating the surface of a transparent object with a transparent film having a low refractive index, and an antireflection film using such a phenomenon is provided on the display surface of the image display device. It is possible to improve visibility. The antireflection film is a single layer structure in which a low refractive index layer having a low refractive index is provided on the display surface, or a medium to high refractive index layer is provided on the display surface to further improve the antireflection effect. Or, it has a multilayer structure in which a plurality of layers are provided and a low refractive index layer is provided thereon.

  The single-layer type antireflection film has a simpler layer structure than the multilayer type, and thus has excellent productivity and cost performance. On the other hand, the multilayer type antireflection film can improve the antireflection performance by combining the layer structures, and can easily achieve higher performance than the single layer type.

  In general, methods for forming a low refractive index layer included in such an antireflection film are roughly classified into a vapor phase method and a coating method. Gas phase methods include physical methods such as vacuum deposition and sputtering, and chemical methods such as CVD, and coating methods include roll coating, gravure coating, slide coating, spraying, and immersion. And screen printing.

  When forming a low refractive index layer by a vapor phase method, it is possible to form a high-performance and high-quality transparent thin film, but it requires precise atmosphere control in a high vacuum system, and a special heating device or Since the ion generation accelerator is used, there is a problem that the manufacturing apparatus is complicated and large, and the manufacturing cost is inevitably increased. Further, when the vapor phase method is used, it is difficult to form a transparent thin film having a large area or to form a transparent thin film uniformly on the surface of a film having a complicated shape.

  On the other hand, in the case of forming by a spray method among the application methods, there are problems such as poor utilization efficiency of the coating liquid and difficulty in controlling film forming conditions. When using the roll coating method, gravure coating method, slide coating method, dipping method, screen printing method, etc., it is generally obtained by the coating method, although the use efficiency of the film forming raw material is good and the mass production and equipment cost are excellent. The transparent thin film obtained has a problem that its function and quality are inferior to those obtained by the vapor phase method.

  As a coating method, a coating liquid composed of an acrylic compound, an epoxy compound, or an organosilicon compound containing a fluorine atom in the molecule and containing a functional group that is cured by ionizing radiation or heat was applied to the surface of the substrate and dried. Thereafter, it is known that the compound is cured by UV irradiation or heat to form a low refractive index layer.

  Since the low refractive index layer is formed on the outermost surface of the display, it is necessary to have both low refractive index properties and antifouling properties such as scratch resistance and fingerprint wiping properties.

  A coating film made of a binder containing fluorine atoms has a lower refractive index as the fluorine atom content is higher, and at the same time, slipperiness and antifouling properties are improved. In particular, when there is a perfluoroalkyl group in which all or part of the hydrogen atoms in the hydrocarbon group are replaced with fluorine atoms on the coating film surface, it has a high level of anti-scratch property due to slipperiness and antifouling property due to reduced surface tension. I can expect. However, when the content of fluorine atoms in the coating film increases, there is a problem that the hardness and strength of the coating film decrease.

  In WO02 / 018457 (Patent Document 1), by using a fluoropolymer having an ethylenic carbon-carbon double bond in the side chain, a cured product having high hardness can be obtained without deteriorating the low refractive index. However, when many fluorine atoms are used in the polymer chain or in the side chain, the molecule itself becomes soft and the film strength of the cured film decreases.

  Japanese Patent Application Laid-Open No. 2003-147268 (Patent Document 2) discloses a cationic polymerizable monomer comprising an oxetane compound having a silyl group in its molecule or a hydrolysis condensate thereof and an epoxy compound, and porous silica for adjusting the refractive index. A composition for a low refractive index layer that has improved adhesion to the substrate with fine particles has been proposed, but when a large amount of porous silica used for the purpose of lowering the refractive index is used, the film strength of the coating film Decreases.

WO02 / 018457 JP 2003-147268 A

  The present invention has been accomplished in view of the above-mentioned actual situation, and the object thereof is to form a coating layer of an ionizing radiation curable resin composition containing a silsesquioxane containing a fluorine atom, and having a low refractive index. Another object of the present invention is to provide an antireflection laminate in which a transparent low refractive index layer having excellent adhesion to a substrate and mechanical strength is formed.

  In order to solve the above problems, an antireflection laminate according to the present invention is an antireflection laminate in which a low refractive index layer is formed directly on at least one surface side of a light-transmitting substrate or via another layer. The low refractive index layer comprises (A) component: silsesquioxane having two or more perfluoroalkyl groups and two or more reactive groups in one molecule, and (B) component: fluorine. Containing monomer and (C) component: It is formed using the coating composition for low refractive index layer formation containing a filler. The quantitative relationship of the component (A), the component (B), and the component (C) is such that the component (A) to the component (B) is 50% by mass to 50% by mass to 95% by mass to 5% by mass, It is preferable that (C) is 10 to 200 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

  The coating composition used for forming the low refractive index layer in the antireflection laminate of the present invention has a low refractive index (A) component having high hardness and high transparency, high elasticity, and transparency. Since it contains the component (B) having a high low refractive index, the low refractive index layer obtained by applying the coating composition has a high hardness, elasticity, and high transparency. Become a film.

  Since the component (A) has a perfluoroalkyl group covalently bonded to the skeleton of silsesquioxane, the compatibility with the fluorine-containing monomer as the component (B) is very high, and the formed low refractive index layer is transparent. The blending ratio of the fluorine-containing monomer can be increased without impairing the properties. For this reason, the coating film formed using the coating composition containing the component (A) and the component (B) can have both properties of high hardness and elasticity. It can be set as the coating film with high refractive index transparency.

  In the quantitative relationship in which the sum of the component (A) and the component (B) is 100% by mass, when the component (B) is more than 50% by mass than the component (A), the strength of the coating film is reduced and the film is damaged. When the component (B) is less than 5% by mass, it is not preferable because a brittle coating without elasticity is formed.

  The component (C) is used for adjustment for increasing the hardness of the low refractive index layer. For example, when the cured film is softened by increasing the amount of the component (B) for reducing the refractive index, the component (C) is filled within a range in which the refractive index of the obtained low refractive index layer is not impaired (not increased). By including the material, a low refractive index layer having a balance between hardness and elasticity can be obtained. When the total amount of the component (A) and the component (B) is 100 parts by mass, the hardness of the coating film is insufficient when (C) is less than 10 parts by mass. Decreases, and a fragile coating film is formed.

  Since component (A) has a perfluoroalkyl group covalently bonded to the silsesquioxane skeleton, the perfluoroalkyl group does not leave and collects on the surface of the low refractive index layer and exhibits water and oil repellency. And has a durable anti-stain performance. Further, since perfluoroalkyl groups are collected on the surface of the low refractive index layer, slipperiness occurs, and as a result, it becomes difficult to be damaged.

The present invention is described in detail below.
The coating composition used to form the low refractive index layer in the antireflective laminate of the present invention comprises (A) component having two or more perfluoroalkyl groups and two or more reactivity in one molecule. The silsesquioxane which has a group is contained, and this silsesquioxane is obtained as a condensate of the hydrolyzate of the compounds represented by the following general formulas (1) and (2).

（但し、Ｒ⁰ は（メタ）アクリロイル基、ビニル基、エポキシ基、及びオキセタニル基から選ばれた反応性基を有する有機官能基であり、Ｘは加水分解性基である。）

(However, R ⁰ is an organic functional group having a reactive group selected from a (meth) acryloyl group, a vinyl group, an epoxy group, and an oxetanyl group, and X is a hydrolyzable group.)

（但し、Ｒ¹ はパーフルオロアルキル基を有する有機官能基であり、Ｘは加水分解性基である。）

(However, R ¹ is an organic functional group having a perfluoroalkyl group, and X is a hydrolyzable group.)

  The silsesquioxane generally has a very low refractive index because it has two or more perfluoroalkyl groups in the molecular structure, and is suitable as a component for forming a low refractive index layer.

  In addition, the component (A) has a perfluoroalkyl group because it has two or more reactive groups in the silsesquioxane skeleton and one molecule as compared with ordinary fluorine-containing polymers, monomers, and oligomers. However, it has the property of forming a highly hard coating film when cured.

  When the base material used in the antireflection laminate is a film base material, the cured coating film obtained by applying the coating composition consisting of silsesquioxane alone as the component (A) to the base material has high rigidity. Since it becomes a so-called brittle cured film that is hard and easily cracked, it is not suitable for a coating film applied to a film substrate. In the present invention, a fluorine-containing monomer is used as the component (B) together with the component (A) in order to impart elasticity to the coating film so that the component (A) is suitable for the coating film of the film substrate. Since the component (A) has a perfluoroalkyl group, the compatibility with the fluorine-containing monomer as the component (B) is very high, and the fluorine-containing monomer is obtained without impairing the transparency of the formed low refractive index layer. The mixing ratio of can be increased. Therefore, a fluorine-containing monomer is used as the component (B) from the viewpoint of reducing the refractive index of the coating film.

  As the component (B) according to the present invention, a fluorine-containing monomer represented by the following general formula (3) can be preferably used.

（式中、Ｒ² 及びＲ³ は、（メタ）アクリロイル基、ビニル基、エポキシ基、及びオキセタニル基から選ばれた反応性基を有する有機官能基であり、Ｒ⁴ 及びＲ⁵ は、単結合又は炭素原子数１〜５の２価の炭化水素、又は酸素であり、ｎは１〜３０の整数を示す。）

(Wherein R ² and R ³ are organic functional groups having a reactive group selected from a (meth) acryloyl group, a vinyl group, an epoxy group, and an oxetanyl group, and R ⁴ and R ⁵ are single bonds. Or it is a C1-C5 bivalent hydrocarbon or oxygen, and n shows the integer of 1-30.)

Furthermore, since the fluorine-containing monomer represented by the general formula (3) restricts the number of repeating units n of methylene (CF ₂ ) having fluorine atoms to 30 or less, the coating film is dried and cured during coating. Since it diffuses uniformly, it is possible to form a uniform coating film with no deviation in refractive index or film strength.

  The reactive groups of the component (A) and the component (B) may be the same or different, but those forming a copolymer with each other can form a uniform coating film with no deviation in refractive index or film strength. Is possible. The hydrolyzable groups X of the component (A) and the component (B) may be the same or different.

  The low refractive index layer, which is one of the constituent layers of the antireflection laminate of the present invention, has a refractive index of 1.45 by combining the component (A) as a main component and the component (B) containing a fluorine atom. It can be made very small as described below, and has hardness and strength that can withstand practical use, and has excellent adhesion and transparency of the coating film. When the refractive index needs to be 1.40 or less, the cured film becomes softer by increasing the amount of the component (B), and therefore further contains a filler of the component (C) for adjusting the hardness. . The filler is preferably contained in the coating composition for forming a low refractive index layer as long as the refractive index of the resulting low refractive index layer is not impaired (raised). When such a filler is contained, the strength and elasticity of the obtained low refractive index cured product are improved. Examples of the filler include inorganic fine particles having a refractive index of 1.45 or less, organic fine particles, or composite fine particles thereof. The average particle size of these fine particles is preferably 5 to 300 nm.

Component (A): Silsesquioxane having two or more perfluoroalkyl groups and two or more reactive groups in one molecule. A coating composition for forming a low refractive index layer used in the antireflection laminate of the present invention. The contained silsesquioxane is a silsesquioxane having at least two perfluoroalkyl groups and two or more reactive groups in one molecule.

  As such a silsesquioxane compound, various compounds can be used, and preferred compounds include condensates of the hydrolyzates of the general formula (1) and the general formula (2).

R ¹ in the general formula (2) is preferably an organic functional group represented by the structural formula shown in the following formula (4).

（但し、ｍは０〜１０の整数であり、Ｒ⁶ は炭素数１〜４のアルキレン基である。）

(Where, m is an integer of 0, R ⁶ is an alkylene group having 1 to 4 carbon atoms.)

  The hydrolyzable group X in the general formulas (1) and (2) is not particularly limited as long as it is a hydrolyzable group, and examples thereof include a halogen atom, an alkoxy group, a cycloalkoxy group, or an arylalkoxy group. is there. Further, three Xs are contained in one molecule of the general formulas (1) and (2), but they may all be the same group or two or more different groups.

  Examples of the “alkoxy group” include methoxy group, ethoxy group, n- and i-propoxy group, and the like. Examples of the “cycloalkoxy group” include a cyclohexyloxy group, and examples of the “aryloxy group” include a phenyloxy group.

  As the compound of the general formula (1), a silane coupling agent can be used particularly preferably since the raw material is easily available and the hydrolysis reaction is easily controlled.

  For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-ethyl (triethoxysilylpropoxymethyl) oxetane, and the like. Not.

  As the compound of the general formula (2), silica alkoxide having a fluoroalkyl chain can be used particularly preferably because the raw material is easily available and the hydrolysis reaction is easily controlled.

  Examples include, but are not limited to, TSL8256, TSL8257, TSL8232, and TSL8233 (trade names, manufactured by GE Toshiba Silicone).

Component (B): Fluorine-containing monomer The fluorine-containing monomer that is the component (B) contained in the coating composition for forming a low refractive index layer used in the antireflection laminate of the present invention is represented by the above general formula (3). .

  This fluorine-containing monomer generally has a very low refractive index because it contains fluorine in its molecular structure, and the low refractive index component in the coating composition for forming a low refractive index layer used in the present invention Function as. The fluorine-containing monomer contained in the coating composition for forming a low refractive index layer used in the present invention is polymerized by the polymerization reaction alone and / or fixed to the component (A), resulting in a decrease in the refractive index of the coating film. Let

  Since the fluorine-containing monomer represented by the general formula (3) has very high compatibility with the component (A), the options for other blending components are very wide. Therefore, the blending ratio of the fluorine-containing monomer can be increased without impairing the transparency of the antireflection laminate.

  Since the fluorine-containing monomer represented by the general formula (3) has two reactive groups in one molecule, the polymerization reactivity at the time of curing is large. For this reason, the fluorine-containing monomer represented by the general formula (3) does not need to add a large amount of a fluorine-free binder component for increasing the polymerizability unlike conventional fluorine-containing monomers. The low refractive index characteristic that is a characteristic of the contained monomer is not impaired.

Furthermore, since the fluorine-containing monomer represented by the general formula (3) limits the number of repeating units n of methylene (CF ₂ ) having fluorine atoms to 30 or less, it is uniform in the coating film during drying and curing. Easy to diffuse into.

  Therefore, the fluorine-containing monomer represented by the general formula (3) is excellent in compatibility, polymerization reactivity, and low refractive index property by forming a desired network in the coating film, and the refractive index and film strength. It is possible to form a uniform coating film with no bias.

In the general formula (3), R ² and R ³ may be the same or different as long as they are photoreactive groups that can be bonded to each other by light irradiation. Examples of the photoreactive group include those in which the reaction proceeds by a reaction mode such as polymerization reaction such as photo radical polymerization, photo cation polymerization, photo anion polymerization, and polymerization that proceeds via photodimerization.

  Examples of the photo-radical polymerizable reactive group include a functional group having an ethylenically unsaturated bond (preferably an ethylenic double bond), and specifically, an acryloyl group, a methacryloyl group, a vinyl group, a vinylcyclohexane. Examples thereof include an alkyl group and an allyl group. Among them, an acryloyl group and a methacryloyl group are preferable from the viewpoint of reactivity.

As the photocationic polymerization reactive group, for example, R ² and R ³ in the general formula (3) are both represented by the following general formula (5).

（式中、Ｒ⁷ は水素、フッ素、アルキレン基、又はフルオロアルキレン基である。）
で表されるエポキシ基、或いは何れも次の一般式（６）

(In the formula, R ⁷ is hydrogen, fluorine, an alkylene group, or a fluoroalkylene group.)
Or an epoxy group represented by the following general formula (6)

（式中、Ｒ⁸ は水素、フッ素、炭素数１〜１０のアルキル基、又はフルオロアルキル基であり、Ｒ⁹ は炭素数２〜６のアルキレン基である。）
で示されるオキセタニル基が挙げられる。

(In the formula, R ⁸ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group, and R ⁹ is an alkylene group having 2 to 6 carbon atoms.)
An oxetanyl group represented by

  These photo-cationically polymerizable reactive groups are uniformly incorporated in the binder component, and realize hardening acceleration of the oxetane compound, flexibility and elasticity imparted to the coating film, and a low refractive index.

  Among the fluorine-containing monomers represented by the general formula (3), those containing a (meth) acrylate group include 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol di (meth) acrylate, etc. However, those containing an epoxy group include 1,4-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-butane, and those containing an oxetanyl group include 1,4-bis (2 ′, 3 ′). -Oxetanylpropyl) -perfluoro-n-butane and the like are preferably used.

  The component (B) is preferably contained in an amount of 1 to 50% by weight with respect to the component (A). If it is 1% by weight or less, the coating film becomes brittle, and if it exceeds 50% by weight, it becomes soft and easily damaged.

Photopolymerization initiator The coating composition for forming a low refractive index layer for an antireflection laminate according to the present invention includes ionizing radiation (ultraviolet rays, visible rays, electron beams, β rays, energy quanta capable of polymerizing or crosslinking molecules, X-rays, γ-rays, α-rays and the like, and usually a photopolymerization initiator that initiates or accelerates polymerization or photodimerization reaction by ultraviolet rays or electron beams) is preferably added. The photopolymerization initiator is appropriately selected from a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanion polymerization initiator according to the type of photoreaction.

In the case of a photocationic polymerization system, an onium salt such as a diazonium salt, a sulfonium salt, or an iodonium salt represented by the following formulas is preferably used as the photopolymerization initiator. :
ArN ₂ ⁺ Z ⁻ ; (R) ₃ S ⁺ Z ⁻ ; (R) ₂ I ⁺ Z ⁻
(In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different, and Z ⁻ Represents a non-basic and non-nucleophilic anion.)

In each of the above formulas, the aryl group represented by Ar or R is also typically phenyl or naphthyl, and these may be substituted with an appropriate group. Specific examples of the anion represented by Z ⁻ include tetrafluoroborate ion (BF ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ), hexafluorophosphate ion. (PF ₆ ), hexafluoroarsenate ion (AsF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), hexachloroantimonate ion (SbCl ₆ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), perchlorate ion (ClO ₄ ⁻ ) and the like.

  Since many of these various initiators are commercially available, such commercial products can be used. Examples of commercially available initiators include “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd. and “Adekaoptomer SP-150” sold by Asahi Denka Kogyo Co., Ltd. (Product name), “ADEKA OPTMER SP-170” (product name), “RHODORSIL PHOTOINITIATOR 2074” (product name) sold by Rhodia Japan Co., Ltd., and the like. ) Etc. are used. In addition, the addition amount of this photoinitiator is 0.1-20 mass parts normally with respect to 100 mass parts of hardening components.

  Examples of radical polymerization photopolymerization initiators include acetophenones, benzophenones, ketals, imidazole derivatives, bisimidazole derivatives, N-arylglycine derivatives, organic azide compounds, titanocenes, alumina chelate complexes, N-alkoxypyridium salts Thioxanthone derivatives, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, and the like are used. Specific examples of such photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyl Dimethyl ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, benzophenone, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) Benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5 Triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc., among which 1-hydroxy-cyclohexyl-phenyl-ketone or 2-methyl-1 [4 Preferred is-(methylthio) phenyl] -2-morpholinopropan-1-one. In particular, 1-hydroxy-cyclohexyl-phenyl-ketone ((trade name) Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morphol. Linophenyl) -butan-1-one ((trade name) Irgacure 369, manufactured by Ciba Specialty Chemicals) or 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- When ON is used, a polymerization reaction due to irradiation with ultraviolet rays is initiated and accelerated even with a small amount of addition. These photopolymerization initiators may be used alone or in combination of two or more. Preferable examples of commercially available photo radical polymerization initiators include Irgacure 184 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd., which is 1-hydroxy-cyclohexyl-phenyl-ketone. In addition, the addition amount of a photoinitiator is 3-15 mass parts normally with respect to 100 mass parts of ionizing radiation curable resin components.

  Examples of photo radical polymerization initiators and photo cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, etc. More specifically, diphenyliodonium, ditolyliodonium, iodonium chloride such as bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, Iodonium salts such as hexafluoroantimonate salt, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butylphenylsulfonium, tris (4-methylpheni) sulfonium, bromide, borofluoride, hexafluoro Sulfonium salts such as phosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3 Examples include 2,4,6-substituted-1,3,5 triazine compounds such as 5-triazine and 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine. It is not limited. In addition, the addition amount of a photoinitiator is 3-15 mass parts normally with respect to 100 mass parts of ionizing radiation curable resin components.

  Photoanionic polymerization initiators include, for example, compounds that generate amines by ultraviolet rays, more specifically 1,10-diaminodecane, 4,4′-trimethylenedipiperidine, carbamates and derivatives thereof, and cobalt-amine complexes. , Aminooxyiminos, ammonium borates and the like, and commercially available products include NBC-101 (trade name) manufactured by Midori Chemical Co., Ltd. In addition, the addition amount of a photoinitiator is 3-15 mass parts normally with respect to 100 mass parts of ionizing radiation curable resin components.

Component (C): Filler The filler is added to improve the strength and elasticity of the resulting low refractive index cured product by being contained in the coating composition for forming a low refractive index layer. The filler is preferably contained in the coating composition for forming a low refractive index layer as long as the refractive index of the resulting low refractive index layer is not impaired (does not increase). Examples of the filler include inorganic fine particles, organic fine particles, and composite fine particles thereof. The average particle size of these fine particles is preferably 5 to 300 nm.

  The filler has a refractive index of 1.46 or less, more preferably 1.45 or less, such as inorganic fine particles (silica (1.42-1.46), magnesium fluoride (1.38), calcium fluoride (1 .36)) and organic fine particles (such as acrylic fine particles containing fluorine). Furthermore, fine particles that can be incorporated in the coating film with air having a refractive index of 1 as a nanoporous structure, for example, pores possessed by the particles themselves, or voids formed by the formation of aggregates between the particles, or It is possible to use fine particles that form pores of air that are generated by the diffusion of air from porous particles having a large specific surface area into the coating film during the coating formation process. This is preferable because the refractive index is lowered. At this time, the nanoporous structure may be independent or continuous as long as it is within a desired size range. These fine particles agglomerate slightly in the coating film, especially by forming fine irregularities on the outermost surface of the coating film that are less than or equal to the wavelength of visible light, resulting in the formation of a nanoporous structure inside and on the surface of the coating film. Since a structure in which air is taken in is realized as compared with only a resin that becomes a normal flat film, a decrease in the refractive index of the coating film can be expected to exceed the refractive index effect of the fine particles.

  In addition, conductive fine particles may be added to impart antistatic performance as long as the influence of coloring on the refractive index and coating film is not hindered.

  In the present specification, the term “fine particles” refers to those having a so-called ultra fine particle size in order to ensure sufficient transparency of the coating film. Here, “ultrafine particles” are particles of submicron order, and generally mean particles having a particle diameter smaller than particles having a particle diameter of several μm to several hundred μm, which are generally called “fine particles”. ing. The specific size of the ultrafine particles used in the present invention varies depending on the use and grade of the optical thin film to which the coating composition of the present invention is applied, but generally the primary particle diameter is in the range of 5 nm to 300 nm. Are preferably used. If the primary particle diameter is less than 1 nm, it becomes difficult to impart sufficient hardness and strength to the coating film. On the other hand, if the primary particle diameter exceeds 300 nm, the transparency of the coating film is impaired, and may not be applicable depending on the application. It may be possible. The primary particle size of the inorganic ultrafine particles may be measured visually from the secondary electron emission image photograph obtained by a scanning electron microscope (SEM) or the like, or a dynamic light scattering method or a static light scattering method is used. Mechanical measurement may be performed with a particle size distribution meter or the like.

  As long as the ultrafine particles can be dispersed in a colloidal form to ensure the hardness and strength of the coating film, and can ensure transparency with a size of the order of submicron, the particle shape is spherical. Any shape can be used in the present invention.

  These fine particles preferably have a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating film.

  A fine particle having a void itself, whether it is an inorganic fine particle or an organic fine particle, has a fine void outside or inside, and is filled with a gas, for example, air having a refractive index of 1. The refractive index of the coating film itself is low, and it is preferable because the refractive index of the coating film can be lowered even when dispersed uniformly without forming an aggregate in the coating film. The liquid filled in the gap may be liquid, but air is preferable from the viewpoint of lowering the refractive index.

  Preferable examples of the inorganic fine particles having voids include porous silica fine particles and hollow silica fine particles. For example, when silica is taken as an example, the silica fine particles having voids have a refractive index of 1.20 to 1.20 compared with ordinary silica ultrafine particles and colloidal silica particles (refractive index n = 1.46 or so) having no gas inside. As low as 1.45. The same applies to porous polymer particles and hollow polymer particles. In order to maintain air filled in the air gap, it is more preferable that the air gap has a closed structure (having an outer wall).

  From the above, fine particles having voids with a selected refractive index and / or addition amount, preferably fine particles having a refractive index of 1.20 to 1.45 having pores containing air having an average pore diameter of 0.01 nm to 100 nm, Alternatively, independent and / or continuous containing air having an average pore size of 0.01 nm to 100 nm and a refractive index of 1.20 to 1.45 resulting from the formation of aggregates of fine particles having an average particle size of 5 nm to 300 nm The coating composition for forming a low refractive index layer obtained by adding fine particle aggregates having pores to the binder component has no or very little influence on the refractive index of the binder component, but rather has a refractive index. Moreover, as described above, there is an effect of increasing the strength of the coating film as an effect of adding fine particles having voids as described above.

  Moreover, since the average particle diameter of the fine particles is 5 nm to 300 nm, the transparency of the coating film is also excellent. In addition, when these fine particles form aggregates before being added to the coating film or during coating film formation, it is possible to form fine irregularities on the outermost surface of the coating film, in particular, at a wavelength below the wavelength of visible light. Even in the case where it does not have voids, a structure in which air is taken in is realized as compared with only a resin that becomes a normal flat film, and therefore, the refractive index of the coating film can be expected to be lower than the refractive index of the fine particles.

  When the fine particles are an inorganic compound, it is preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or metal halide, and most preferably a metal oxide or metal fluoride. . As a metal atom, Na, K, Mg, Ca, Ba, Al, Si, and B are preferable, Mg, Ca, B, and Si are more preferable, and an inorganic compound containing two kinds of metals may be used.

In the coating composition for forming a low refractive index layer according to the present invention, it is possible to sufficiently improve the hardness and strength of a coating film by adding a relatively small amount of inorganic ultrafine particles. Thus, it is possible to completely eliminate the adverse effect that adversely affects the refractive index lowering action by diluting the binder component concentration or to a slight extent. However, when a relatively large amount of inorganic ultrafine particles is used, there is no possibility of adversely affecting the refractive index lowering effect of the binder component. Therefore, the inorganic ultrafine particles have a refractive index of 1.60 or less, preferably Is 1.46 or less, more preferably 1.45 or less. For example, alumina Al ₂ O ₃ (refractive index 1.53), silica SiO ₂ (refractive index 1.46), magnesium fluoride MgF ₂ (refractive index 1.38), calcium fluoride CaF ₂ (refractive index 1.36). Among these, as described above, it is preferable to select and use one that can be colloidally dispersed in a solvent or monomer and / or oligomer. When a particularly low refractive index is required, it is preferable to use colloidal silica (SiO ₂ ) fine particles among the inorganic ultrafine particles exemplified above. In addition, when priority is given to imparting sufficient hardness to the coating film, it is preferable to use alumina (Al ₂ O ₃ ) fine particles.

  As the fine particles, fine particles having an outer shell layer and porous or hollow inside are preferably used. The fine particles have a structure in which a gas is filled therein and / or a porous structure containing a gas. As a result, when the gas is air having a refractive index of 1.0, the fine particles have a higher refractive index than the original refractive index. It refers to fine particles whose refractive index has decreased in proportion to the occupation ratio of air.

  The silica fine particles used in the antireflection laminate according to the present invention are not particularly limited as long as the refractive index is 1.20 to 1.44. Examples of such silica fine particles include composite oxide sols or hollow silica fine particles disclosed in JP-A Nos. 7-133105 and 2001-233611.

  It is preferable to improve the affinity with the solvent or the binder or to impart reactivity with the binder by surface-treating at least a part of the inorganic fine particles.

  The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment in which a coupling agent, an organic low molecular weight compound, a polymer or the like is adsorbed or bonded to the surface. Furthermore, at least a part of the surface of the inorganic fine particles may be coated with inorganic or organic particles having a smaller particle diameter or composite fine particles thereof (these are collectively referred to as “surface treated product”). It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organometallic compound (eg, titanium coupling agent, silane coupling agent, aluminum chelating agent) is preferably used.

  When there are functional groups such as hydroxyl groups on the surface of the inorganic fine particles, the surface treatment product can be adsorbed stably, and by using a silane coupling agent or a polymer having reactivity with the functional groups, Since surface treatment by a stable chemical bond can be carried out particularly effectively, it is more preferable. As the silane coupling agent, a compound represented by the general formula (1) having the same reactive group as the reactive group of silsesquioxane can be particularly preferably used.

  When the fine particles are organic compounds, polymer fine particles having an average particle diameter of 5 nm to 300 nm can be used regardless of crosslinking or non-crosslinking, and can be used without any limitation. Polyvinyl alcohol-based, polyamide-based, polyimide-based, polyurethane-based, polyacryl-based, polystyrene-based, polyketone-based, silicone-based, polylactic acid-based, cellulose-based and the like, and copolymers thereof can be used. In particular, from the viewpoint of lowering the refractive index, it is more preferable to be made of a fluoropolymer or silicone. In addition, for example, polyacrylic resins are preferable because the refractive index of the fine particles can be lowered by using an acrylic monomer containing a fluorine atom.

  It is preferable that the organic fine particles are formed on the surface with a monomer polymer capable of obtaining affinity with the solvent or binder or reactivity with the binder. It is also preferable to perform a chemical surface treatment using a physical and / or surface treatment product similar to the inorganic fine particles.

  The organic hollow fine particles can be synthesized, for example, by the technique described in JP-A-2002-80503. Preferably, the addition amount of fine particles having an average particle diameter of 5 nm to 300 nm is in the range of 1 to 400 parts by mass, more preferably 30 to 300 parts by mass, and most preferably 50 to 200 parts by mass with respect to 100 parts by mass of the binder component. It is desirable.

Fluorine polymer additive and / or silicon polymer additive:
The low refractive index layer of the antireflection laminate according to the present invention may further contain a fluorine-based polymer additive and / or a silicon-based polymer additive that is compatible with both the composition and the filler. preferable. By including a fluorine-based polymer additive and / or a silicon-based polymer additive in this way, the antifouling property and scratch resistance required for the flattening of the coating surface used on the outermost surface and the antireflection laminate are improved. The slipperiness which is effective in can be provided. The “compatibility” means that the fluorine-based polymer additive and / or the silicon-based polymer additive is applied even when an amount capable of confirming the addition effect is added to the coating film containing the composition or filler. This means that the film has an affinity to such an extent that a decrease in transparency due to white turbidity of the film or an increase in haze cannot be confirmed.

  In the present invention, it is further preferable that at least a part of the fluorine-based polymer additive and / or the silicon-based polymer additive is fixed to the outermost surface of the coating film by forming a covalent bond with the composition by a chemical reaction. Preferably, this makes it possible to stably maintain the slipperiness required to improve the antifouling property and scratch resistance over a long period of time required after the antireflection laminate is commercialized.

Examples of the fluorine-based polymer additive include a perfluoroalkyl group represented by CdF ₂ d ⁺¹ (d is an integer of ¹ to 21), and-(CF ₂ CF ₂ ) _g (g is an integer of 1 to 50). perfluoroalkylene group represented or F, - (- CF (CF 3) CF 2 O-) e -CF (CF 3) ( where, e is an integer of 1 to 50) perfluoroalkyl ether represented by Group, CF ₂ = CFCF ₂ CF _2- , (CF ₃ ) ₂ C = C (C ₂ F ₅ )-, and ((CF ₃ ) ₂ CF) ₂ C = C (CF ₃ )- It is preferable to have a perfluoroalkenyl group.

  The structure of the fluorine-based polymer additive is not particularly limited as long as it is a compound containing the above functional group. For example, a polymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer can be used. It can also be used. Among them, in particular, a fluorine-containing polymer segment composed of either a homopolymer of a fluorine-containing monomer or a copolymer of a fluorine-containing monomer and a non-fluorine monomer, and a non-fluorine polymer segment, A block copolymer or graft copolymer consisting of is preferably used. In such a copolymer, the fluorine-containing polymer segment mainly has a function of improving antifouling properties and water / oil repellency, while the non-fluorine polymer segment is compatible with the binder component. Since it is high, it has an anchor function. Therefore, in the antireflection laminate using such a copolymer, even when the surface is repeatedly rubbed, it is difficult to remove these fluorine-based polymer additives, and the antifouling property and the like for a long time There is an effect that various performances can be maintained.

  The above-mentioned fluoropolymer additive can be obtained as a commercial product. For example, Nippon Oil & Fats Modiper F series (trade name), Dainippon Ink & Chemicals Co., Ltd. defender MCF series (trade name) and the like are preferably used. The fluorine-based polymer additive and / or the silicon-based polymer additive has the following general formula (7),

（式中、Ｒａはメチル基などの炭素数１〜２０のアルキル基を示し、Ｒｂは非置換、もしくはアミノ基、エポキシ基、カルボキシル基、水酸基、パーフルオロアルキル基、パーフルオロアルキレン基、パーフルオロアルキルエーテル基、または( メタ) アクリロイル基で置換された炭素数１〜２０のアルキル基、炭素数１〜３のアルコキシ基、またはポリエーテル変性基を示し、各Ｒａ、Ｒｂは互いに同一でも異なっていても良い。また、ｍは０〜２００、ｎは０〜２００の整数である。）
で示される構造を有することが好ましい。

(In the formula, Ra represents an alkyl group having 1 to 20 carbon atoms such as a methyl group, and Rb is unsubstituted, or an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, a perfluoro group. An alkyl ether group or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a polyether-modified group substituted with a (meth) acryloyl group. Each Ra and Rb are the same or different from each other. M is an integer from 0 to 200, and n is an integer from 0 to 200.)
It is preferable to have the structure shown by these.

  Polydimethylsilicone having a basic skeleton such as the above general formula (7) is generally known to have low surface tension and excellent water repellency and releasability, but various functional groups on the side chain or terminal. By introducing a group, further effects can be imparted. For example, reactivity can be imparted by introducing an amino group, epoxy group, carboxyl group, hydroxyl group, (meth) acryloyl group, alkoxy group, etc., and a covalent bond is formed by a chemical reaction with the ionizing radiation curable resin composition. it can. In addition, by introducing perfluoroalkyl groups, perfluoroalkylene groups, and perfluoroalkyl ether groups, oil resistance and lubricity can be imparted, and by introducing polyether-modified groups, leveling properties and lubricity can be provided. Can be improved.

  Such a compound can be obtained as a commercial product. For example, silicone oil FL100 having a fluoroalkyl group (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) or polyether-modified silicone oil TSF4460 (trade name, GE Toshiba). Various modified silicone oils can be obtained according to the purpose.

  As a preferred embodiment of the present invention, the fluorine-based polymer additive and / or the silicon-based polymer additive is represented by the following general formula (8),

（式中、Ｒａはパーフルオロアルキル基、パーフルオロアルキレン基、またはパーフルオロアルキルエーテル基を含む炭素数３〜１０００の炭化水素基を示し、Ｘはメトキシ基、エトキシ基、もしくはプロポキシ基等の炭素数１〜３のアルコキシ基、メトキシメトキシ基、もしくはメトキシエトキシ基等のオキシアルコキシ基、または、クロル基、ブロモ基もしくはヨード基等のハロゲン基等の加水分解性基であり、同一でも異なっていてもよく、ｎは１〜３の整数を示す。）
で示される構造であってもよい。

(In the formula, Ra represents a C3-1000 hydrocarbon group including a perfluoroalkyl group, a perfluoroalkylene group, or a perfluoroalkyl ether group, and X represents a carbon such as a methoxy group, an ethoxy group, or a propoxy group. A hydrolyzable group such as an alkoxy group of formulas 1 to 3, an oxyalkoxy group such as a methoxymethoxy group or a methoxyethoxy group, or a halogen group such as a chloro group, a bromo group or an iodo group, which may be the same or different; And n represents an integer of 1 to 3.)
The structure shown by may be sufficient.

  By including such a hydrolyzable group, it is particularly easy to form a covalent bond or a hydrogen bond with the hydroxyl group of the inorganic component, more preferably, the silica component, and there is an effect that the adhesiveness can be maintained. Specific examples of such a compound include fluoroalkylsilanes such as TSL8257 (trade name, manufactured by GE Toshiba Silicone).

  The fluorine-based polymer additive and / or the silicon-based polymer additive is 0.01 to 10% by mass, preferably 0.1 to 3.0% by mass, based on the total mass of the composition and the filler. It is preferable that When the content is less than 0.01% by mass, sufficient antifouling property and slipperiness cannot be imparted to the antireflection laminate, and when it exceeds 10% by mass, the strength of the coating film is extremely lowered. .

  These fluorine-based polymer additives and silicon-based polymer additives may be used alone or in combination of two or more depending on the expected effect. By appropriately combining these additives, various properties such as antifouling property, water and oil repellency, slipperiness, scratch resistance, durability, and leveling property can be adjusted to achieve the intended function.

Other Components The low refractive index layer constituting the antireflection laminate according to the present invention contains the above composition component, the above filler component, and the above fluorine and / or silicon compound as essential components. In addition, a binder component other than the composition component as described above may be included, and the low refractive index layer forming coating solution further includes a solvent, a polymerization initiator, a curing agent, a crosslinking agent, an ultraviolet blocking agent, An ultraviolet absorber, a surface conditioner (leveling agent), or other components may be contained.

Preparation of coating composition for forming low refractive index layer, solvent, coating, forming method of low refractive index layer:
The low refractive index layer comprising the above components is prepared by preparing a composition for forming a low refractive index layer in which each of the above components is dissolved in a solvent, and dispersing the composition according to a general preparation method. It can be formed by preparing a liquid and applying and drying the coating liquid on a substrate.

  Hereinafter, the adjustment method of a solvent, a coating composition, and the formation method of a coating film are demonstrated.

(1) Solvent When a relatively large amount of the binder component is used, the monomer and / or oligomer can also function as a liquid medium for preparing the coating liquid, so that the coating composition can be solid without using a solvent. In some cases, the components can be dissolved, dispersed, or diluted to prepare a coating solution. Accordingly, in the present invention, a solvent is not always necessary, but in many cases, a solvent is used to dissolve and disperse solid components, adjust the concentration, and prepare a coating solution having excellent coating suitability.

  The solvent used for dissolving and dispersing the solid component of the low refractive index layer in the present invention is not particularly limited, and various organic solvents such as alcohols such as isopropyl alcohol, methanol and ethanol; methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ketones such as; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatic hydrocarbons such as toluene and xylene; or a mixture thereof.

  As the solvent, a ketone-based organic solvent is preferably used. When the coating composition for forming a low refractive index layer used in the present invention is prepared using a ketone solvent, it can be applied thinly and uniformly on the surface of the substrate, and the evaporation rate of the solvent after coating is high. This is because it is moderate and hardly causes uneven drying, and a large-area coating film having a uniform thickness can be easily obtained.

  In order to impart a function as an antiglare layer to the hard coat layer that is a support layer of the antireflection laminate, the surface of the hard coat layer is formed in a fine uneven shape, and a medium refractive index layer or a high refractive index is formed thereon. A low refractive index layer may be formed by applying a composition for forming a low refractive index layer with or without a layer. When the composition is prepared using a ketone solvent, it can be applied evenly on such fine uneven surfaces, and uneven coating can be prevented.

  As a ketone solvent, it contains a single solvent composed of one kind of ketone, a mixed solvent composed of two or more kinds of ketones, and other solvents together with one or more kinds of ketones, and has lost the properties as a ketone solvent. Those that are not can be used. Preferably, a ketone solvent in which 70% by mass or more, particularly 80% by mass or more of the solvent is occupied by one or two or more ketones is used.

  The amount of the solvent is appropriately adjusted so that each component can be uniformly dissolved and dispersed, does not cause aggregation during storage after preparation, and does not become too dilute during coating. Prepare a coating composition for forming a low-refractive index layer with a high concentration by reducing the amount of solvent used within the range that satisfies this condition, store it in a state that does not take up the capacity, and take out the necessary amount when using it and apply it. It is preferable to dilute to a concentration suitable for the work. When the total amount of the solid content and the solvent is 100 parts by mass, the solvent is 50 to 95.5 parts by mass with respect to the total solids of 0.5 to 50 parts by mass, and more preferably the total solid content is 10 to 30 parts by mass. By using the solvent at a ratio of 70 to 90 parts by mass with respect to parts, a coating composition for forming a low refractive index layer that is particularly excellent in dispersion stability and suitable for long-term storage can be obtained.

(2) Preparation of coating composition for forming low refractive index layer Each essential component and each desired component are mixed in an arbitrary order, and if the filler is in the form of a colloid, it can be mixed as it is, If it is, the composition for forming a low refractive index layer for coating can be obtained by putting a medium such as beads into the obtained mixture and appropriately dispersing it with a paint shaker or a bead mill.

(3) Formation of coating film In order to form a coating film using the coating composition for forming a low refractive index layer, a coating liquid containing a composition and various additives is applied to the surface of an object to be coated. Curing of a film mainly containing an ionizing radiation curable resin composition, surface-treated silica fine particles, a fluorine-based polymer additive and / or a silicon-based polymer additive after being dried and cured by irradiation with ionizing radiation and / or heating. It is a thing.

  Examples of the method for applying the coating composition for forming the low refractive index layer include spin coating, dipping, spraying, slide coating, bar coating, roll coater, meniscus coater, flexographic printing, and screen printing. Method, bead coater method and the like.

Light-transmitting base material The light-transmitting base material constituting the antireflection laminate according to the present invention may be plate-shaped or film-shaped. Preferred substrates include, for example, triacetate cellulose (TAC), polyethylene terephthalate (PET), diacetyl cellulose, acetate butyrate cellulose, polyethersulfone, acrylic resin; polyurethane resin; polyester; polycarbonate; polysulfone; Examples thereof include films formed of various resins such as trimethylpentene; polyetherketone; (meth) acrylonitrile; cyclic polyolefin. The thickness of a base material is about 30 micrometers-200 micrometers normally, Preferably it is 50 micrometers-200 micrometers.

  The coating liquid of the composition for forming a low refractive index layer is applied directly to the surface of the substrate, which is an object to be coated, or through another layer such as a hard coat layer, and dried to thereby form an oxetanyl group. By the action, a coating film having excellent adhesion to the surface of the object to be coated can be obtained.

Antireflective laminate The antireflective laminate of the present invention is a layer having a light transmittance and a refractive index different from each other directly or via another layer on at least one side of a light transmissive substrate ( At least one of the single layer type or multilayer type antireflection film formed by laminating one or more light transmission layers) is a low refractive index layer. The antireflection laminate can be used as an antireflection film. In the present invention, in the multilayer antireflection film, the layer having the highest refractive index is referred to as a high refractive index layer, the layer having the lowest refractive index is referred to as a low refractive index layer, and other intermediate refractions. A layer having a refractive index is referred to as a medium refractive index layer. The base material and the light transmission layer need to have light transmittance that can be used as a material for the antireflection film, and are preferably as transparent as possible.

  In the antireflection laminate obtained in the present invention, as the other layer, a hard coat layer may be provided for the purpose of imparting hard performance such as scratch resistance and strength to the antireflection laminate. Alternatively, an antiglare layer may be provided as another layer for the purpose of imparting antiglare properties to the antireflection laminate.

Hard coat layer The hard coat layer in the antireflection laminate of the present invention is preferably formed using an ionizing radiation curable resin composition. In the present specification, the “hard coat layer” means a layer having a hardness of H or higher in a pencil hardness test shown in JIS 5600-5-4: 1999.

  The ionizing radiation curable resin composition suitable for forming the hard coat layer is preferably one having an acrylate functional group, such as a relatively low molecular weight polyester resin, polyether resin, acrylic resin, epoxy resin. , Urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyether resins, polyhydric alcohols, di (meth) acrylates such as ethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate; Tri (meth) acrylates such as methylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate derivatives and dipentaerythritol penta (meth) acrylate Etc. may be used polyfunctional (meth) oligomer, such as monomers, epoxy acrylates and urethane acrylates such as multifunctional compounds such as acrylates rates.

  The hard coat layer in the antireflection laminate of the present invention has a cured film thickness of 0.1 to 100 μm, preferably 0.8 to 20 μm. When the film thickness is 0.1 μm or less, sufficient hard coat performance cannot be obtained, and when the film thickness is 100 μm or more, it is not preferable because it easily breaks against an external impact.

  The refractive index of the hard coat layer in the antireflection laminate of the present invention is preferably 1.50 to 1.70, for example, 1.57 to 1.70, a medium refractive index layer or a high refractive index layer. It is preferable for the antireflection property of the antireflection laminate.

Antiglare layer The hard coat layer in the antireflection laminate of the present invention may have antiglare properties described below, and an antiglare layer may be provided separately from the hard coat layer.

  The antiglare layer of the present invention can be constituted using an ionizing radiation curable resin composition and resin beads having a refractive index of 1.40 to 1.60. By including resin beads, in addition to hard coat properties, antiglare properties can be imparted. The ionizing radiation curable resin composition can be appropriately selected from those preferably used for the hard coat layer.

  The reason why the refractive index of the resin beads is in such a range is that the ionizing radiation curable resin, in particular, the refractive index of the acrylate or methacrylate resin is usually 1.45 to 1.55. This is because if resin beads having a refractive index as close as possible to the refractive index are selected, the transparency of the coating film is not impaired and the antiglare property can be increased. Examples of resin beads having a refractive index close to that of ionizing radiation curable resin include polymethyl methacrylate beads (1.49), polycarbonate beads (1.58), polystyrene beads (1.50), and polyacrylstyrene beads. (1.57), polyvinyl chloride beads (1.54), etc., but those within the above range can be used.

  The particle diameter of these resin beads is preferably 3 to 8 μm, and is 2 to 10 parts by mass, usually about 4 parts by mass with respect to 100 parts by mass of the resin. When resin beads such as paint are mixed, it is necessary to agitate and disperse the resin beads precipitated on the bottom of the container when using the paint. In order to eliminate such inconvenience, silica beads having a particle diameter of 0.5 μm or less, preferably 0.1 to 0.25 μm may be included in the coating material as an anti-settling agent for resin beads. Note that the more silica beads are added, the more effective the prevention of sedimentation of the organic filler is, but it adversely affects the transparency of the coating film. Therefore, the amount of less than 0.1 parts by mass, which is a range capable of preventing sedimentation, is preferable to the extent that the transparency of the coating film is not impaired with respect to 100 parts by mass of the resin.

  The antiglare layer in the antireflection laminate of the present invention desirably has a film thickness after curing of 0.1 to 100 μm, preferably 0.8 to 20 μm. When the film thickness is 0.1 μm or less, sufficient hard coat performance cannot be obtained, and when the film thickness is 100 μm or more, it is not preferable because it easily breaks against an external impact.

Antistatic layer The antireflective laminate of the present invention has no need to generate static electricity and prevent dust from adhering to it, or when it is incorporated into a liquid crystal display, etc. An antistatic layer may be formed. As the performance of the antistatic layer in this case, the surface resistance after the formation of the antireflection laminate is preferably 10 ¹² Ω / □ or less. However, even if it exceeds 10 ¹² Ω / □, dust adhesion can be prevented as compared with the case where no antistatic layer is provided.

  Examples of the antistatic agent contained in the antistatic resin composition include various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and first to third amino groups, and a sulfonate group. , Anionic antistatic agents having anionic groups such as sulfate ester base, phosphate ester base, phosphonate base, amphoteric antistatic agents such as amino acid and aminosulfate esters, amino alcohols, glycerols, polyethylene glycols Nonionic antistatic agents such as various surfactant type antistatic agents such as organometallic compounds such as tin and titanium alkoxides and metal chelates such as acetylacetonate salts, and the above-mentioned charging High molecular weight antistatic agent having a high molecular weight, and tertiary amino groups and quaternary amines. Sulfonium groups, polymerizable antistatic agents such as an organic metal compound such as a coupling agent having polymerizable monomer or oligomer by ionizing radiation has a metal chelate portion, the same polymerizable functional groups by ionizing radiation may also be used. Other antistatic agents contained in the antistatic resin composition include ultrafine particles having a particle size of 100 nm or less, such as tin oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and indium-doped zinc oxide (AZO). Antimony oxide, indium oxide, or the like can be used. In particular, it is preferable that the particle diameter is 100 nm or less, which is equal to or less than the wavelength of visible light, since it becomes transparent after film formation and the transparency of the antireflection film is not impaired.

  By mixing the antistatic agent in the coating material for forming the hard coat layer and the antiglare layer, two properties of antistatic performance and hard coat property, and similarly two properties of antistatic performance and antiglare property. It becomes possible to obtain a coating film that improves the above simultaneously.

High refractive index layer to medium refractive index layer (refractive index layer in the range of refractive index 1.46 to 2.00)
Between the hard coat layer and the low refractive index layer, a refractive index in the range of 1.46 to 2.00 and a film thickness in the range of 0.05 to 0.15 μm to a high refractive index layer, It is desirable in terms of antireflection properties that at least one layer is provided.

  The middle to high refractive index layer in the antireflection laminate of the present invention can be constituted mainly by containing ionizing radiation curable resin and medium to high refractive index ultrafine particles having a particle diameter of 100 nm or less. Examples of ultrafine particles with medium to high refractive index include zinc oxide (refractive index 1.90, the following numerical values indicate refractive index), titania (2.3-2.7), ceria (1.95), tin-doped Examples include indium oxide (1.95), antimony-doped tin oxide (1.80), yttria (1.87), and zirconia (2.0). The ultrafine particles preferably have a higher refractive index than the ionizing radiation curable resin binder. The refractive index is determined by the content of the fine particles in the refractive index layer, that is, the refractive index increases as the content of the fine particles increases. Therefore, the refractive index is set to 1 by controlling the composition ratio of the ionizing radiation curable resin and the fine particles. It can be freely controlled in the range of .46 to 2.00.

  If these ultrafine particles have conductivity, the high refractive index layer and the medium refractive index layer formed using the ultrafine particles have antistatic properties.

  The medium refractive index layer and the high refractive index layer are formed by depositing an inorganic oxide having a high refractive index such as titanium oxide or zirconium oxide formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). It can be formed into a film or a coating film in which inorganic oxide fine particles having a high refractive index such as titanium oxide are dispersed. As the medium refractive index layer, a light transmissive layer having a refractive index of 1.46 to 1.80 can be used, and as the high refractive index layer, a light transmissive layer having a refractive index of 1.65 or more can be used. .

An antifouling layer may be provided on the surface of the low refractive index layer opposite to the substrate side for the purpose of antifouling the surface of the low refractive index layer. Although the antifouling layer is provided on the surface opposite to the substrate side of the low refractive index layer, it has an effect on antifouling properties and scratch resistance of the antireflection film, but ionizing radiation having fluorine atoms in the molecule Fluorine polymer additive and / or silicon polymer additive that has low compatibility with curable resin composition and cannot be added to low refractive index layer, and ionizing radiation curable resin composition having fluorine atom in molecule A fluorine-based polymer additive and / or a silicon-based polymer additive having compatibility with both fine particles and fine particles may be used, and provided on the surface opposite to the substrate side of the low refractive index layer. Further improvement in antifouling properties and scratch resistance required for the antireflection laminate can be expected.

  FIG. 3 schematically shows a cross section of an example of the antireflection laminate of the present invention as an antireflection film. The antireflective film 102 has a high refractive index layer 22 formed on one surface side of a base film 21 having optical transparency, and further a coating for forming a low refractive index layer used in the present invention on the high refractive index layer. The low refractive index layer 23 is provided by applying the composition. In this example, there are only two light transmissive layers having different refractive indexes, a high refractive index layer and a low refractive index layer, but three or more light transmissive layers may be provided. In that case, not only the low refractive index layer but also the middle refractive index layer can be formed by applying the coating composition for forming a low refractive index layer used in the present invention.

Image Display Device The antireflective laminate of the present invention is a display surface of an image display device such as a liquid crystal display device (LCD), a cathode ray tube display device (CRT), a plasma display panel (PDP), or an electroluminescence display (ELD). It is suitably used for forming at least one of the multilayer antireflection coatings, particularly the low refractive index layer.

  FIG. 1 schematically shows a cross section of an example (101) of a liquid crystal display device in which a display surface is covered with a multilayer antireflection film containing the antireflection laminate of the present invention as a light transmission layer. The liquid crystal display device 101 prepares a color filter 4 in which an RGB pixel portion 2 (2R, 2G, 2B) and a black matrix layer 3 are formed on one surface of a glass substrate 1 on the display surface side, and the pixel of the color filter. The transparent electrode layer 5 is provided on the part 2, the transparent electrode layer 7 is provided on one surface of the glass substrate 6 on the backlight side, and the transparent electrode layers 5 and 7 face each other with the glass substrate on the backlight side and the color filter. The liquid crystal L is sealed in the gap, the alignment film 9 is formed on the outer surface of the glass substrate 6 on the back side, and the glass substrate on the display surface side. The polarizing film 10 is affixed on the outer surface of 1, and the backlight unit 11 is arrange | positioned back.

  FIG. 2 schematically shows a cross section of the polarizing film 10 attached to the outer surface of the glass substrate 1 on the display surface side. The polarizing film 10 on the display surface side covers both surfaces of a polarizing element 12 made of polyvinyl alcohol (PVA) or the like with protective films (light-transmitting base films) 13 and 14 made of triacetyl cellulose (TAC) or the like. An adhesive layer 15 is provided on the back side, and a hard coat layer 16 and a multilayer antireflection film 17 are sequentially formed on the viewing side. The adhesive layer 15 is provided on the glass substrate 1 on the display surface side. It is stuck.

  Here, in order to reduce the glare by diffusing the light emitted from the inside as in a liquid crystal display device, the hard coat layer 16 is formed by forming the surface of the hard coat layer into an uneven shape, or the hard coat layer. It is good also as an anti-glare layer (anti-glare layer) which gave the function to which an inorganic or organic filler is disperse | distributed inside a layer and to scatter light inside a hard-coat layer. The hard coat layer may be composed of two or more layers, and the hard coat layers can be used in appropriate combination.

  The multilayer antireflection film 17 has a three-layer structure in which a middle refractive index layer 18, a high refractive index layer 19, and a low refractive index layer 20 are sequentially laminated from the backlight side to the viewing side. The multilayer antireflection film 17 may have a two-layer structure in which a high refractive index layer 19 or a medium refractive index layer 18 and a low refractive index layer 20 are sequentially stacked. When the surface of the hard coat layer 16 is formed in an uneven shape, the multilayer antireflection film 17 formed thereon also has an uneven shape as shown in the drawing.

  The low refractive index layer 20 is a coating film formed by applying the coating composition of the present invention on the high refractive index layer 19, drying, and photocuring, and has a refractive index of 1.45 or less, preferably 1. .41 or less, and can be lowered to about 1.20. Further, the medium refractive index layer 18 and the high refractive index layer 19 are made of an inorganic oxide having a high refractive index such as titanium oxide or zirconium oxide formed by a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). Or a coating film in which inorganic oxide fine particles having a high refractive index such as titanium oxide are dispersed. The medium refractive index layer 18 has a refractive index of 1.46 to 1.80. A light transmissive layer having a refractive index of 1.65 or more is used for the light transmissive layer in the range and the high refractive index layer 19.

  Furthermore, when it is necessary to impart antistatic properties or electrostatic properties, a conductive layer may be provided on the base film, or conductive particles may be included in the hard coat layer. The same properties can also be obtained by using a conductive material for the inorganic oxide fine particles having a high refractive index dispersed in the medium refractive index layer or the high refractive index layer. Furthermore, if the desired refractive index is within the range, an antistatic agent composed of an organic component is added directly to the low refractive index layer, or an antistatic layer is applied to the outermost surface of the low refractive index layer, affecting the performance of the antireflection film. Similar properties can be obtained by providing the film thickness within a range of 30 nm or less.

  Due to the action of the antireflection film, the reflectance of light emitted from the external light source is reduced, so that the reflection of scenery and fluorescent light is reduced and the visibility of the display is improved. Moreover, the reflected light of external light is reduced by the light scattering effect by the unevenness | corrugation of the hard-coat layer 16, and the visibility of a display improves further that external light is reflected on the display surface, or is a dazzling state. .

  In the case of the liquid crystal display device 101, the intermediate refractive index layer 18 having a refractive index adjusted in the range of 1.46 to 1.80 and a refractive index of 1.65 are provided on the laminate including the polarizing element 12 and the protective films 13 and 14. The low refractive index layer 20 can be provided by forming the high refractive index layer 19 adjusted as described above and further applying the coating composition for forming a low refractive index layer used in the present invention. Then, the polarizing film 10 including the antireflection film 17 can be stuck on the glass substrate 1 on the viewing side through the adhesive layer 15.

  On the other hand, since an orientation plate is not attached to the display surface of the CRT, it is necessary to directly provide an antireflection laminate. However, applying the coating composition of the present invention to the display surface of the CRT is a complicated operation. In such a case, an antireflection film containing the antireflection laminate of the present invention is prepared, and the antireflection film is formed by sticking it to the display surface. It is not necessary to apply the coating composition for forming a low refractive index layer.

  Examples and Comparative Examples of the present invention are shown below, but the scope of the present invention is not limited thereto.

1. Preparation of surface-treated colloidal silica dispersion Isopropyl alcohol-dispersed chain colloidal silica (IPA-ST-UP: trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15%, silica having a primary particle size of 9 to 15 nm is chain-like Was introduced into a rotary evaporator, and the solvent was replaced from isopropyl alcohol to methyl isobutyl ketone to obtain a dispersion of 20% by mass of silica fine particles. By adding 5 parts by mass of 3-methacryloxypropylmethyldimethoxysilane to 100 parts by mass of this methyl isobutyl ketone dispersion and subjecting it to a heat treatment at 50 ° C. for 1 hour, the surface-treated chain silica fine particles 20% by mass of methyl isobutyl A ketone dispersion (surface-treated colloidal silica dispersion) was obtained.

2. Preparation of coating solution for forming low refractive index layer Coating solutions 1 to 5 were prepared by mixing the following compositions. The surface-treated colloidal silica dispersion is prepared by the step What was prepared in (1) was used.

Coating liquid 1 [ (A) component: (B) component: (C) component = 80: 20: 100]
Silsesquioxane compound having a perfluoroalkyl chain and an acryloyl group: AC-SQ-F (trade name; manufactured by Toagosei; functional group concentration 678 g / mol, inorganic fraction 15%, refractive index 1.39) 4 mass Part Fluorine-containing monomer: 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol di (meth) acrylate 1 part by mass Surface-treated colloidal silica dispersion 25 parts by weight Initiator: Irgure Cure 184 (trade name; 0.25 parts by mass Solvent: 70 parts by mass of methyl isobutyl ketone

Coating liquid 2 [(A) component: (B) component: (C) component = 90: 10: 100]
3. Silsesquioxane compound having a perfluoroalkyl chain and an acryloyl group: AC-SQ-F (trade name; manufactured by Toagosei; functional group concentration: 678 g / mol, inorganic fraction: 15%, refractive index: 1.39) 75 parts by mass Fluorine-containing monomer: 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol di (meth) acrylate 0.25 part by mass Surface-treated colloidal silica dispersion 25 parts by weight Initiator: ILGERCURE 184 (Product name; manufactured by Ciba Specialty Chemicals) 0.25 parts by mass Solvent: 70 parts by mass of methyl isobutyl ketone

Coating liquid 3 [(A) component: (B) component: (C) component = 50: 50: 100]
1. Silsesquioxane compound having a perfluoroalkyl chain and an acryloyl group: AC-SQ-F (trade name; manufactured by Toagosei; functional group concentration 678 g / mol, inorganic fraction 15%, refractive index 1.39) 5 parts by mass Fluorine-containing monomer: 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol di (meth) acrylate 2.5 parts by mass Surface-treated colloidal silica dispersion 25 parts by weight Initiator: Irgure Cure 184 (Product name; manufactured by Ciba Specialty Chemicals) 0.25 parts by mass Solvent: 70 parts by mass of methyl isobutyl ketone

Coating liquid 4 [(A) component: (B) component: (C) component = 80: 20: 20]
Silsesquioxane compound having a perfluoroalkyl chain and an acryloyl group: AC-SQ-F (trade name; manufactured by Toagosei; functional group concentration 678 g / mol, inorganic fraction 15%, refractive index 1.39) 4 mass Part Fluorine-containing monomer: 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol di (meth) acrylate 1 part by weight Surface-treated colloidal silica dispersion 5 parts by weight Initiator: Irgure Cure 184 (trade name; 0.25 parts by mass Solvent: 80 parts by mass of methyl isobutyl ketone

Coating liquid 5 [(A) component: (B) component: (C) component = 80: 20: 180]
Silsesquioxane compound having a perfluoroalkyl chain and an acryloyl group: AC-SQ-F (trade name; manufactured by Toagosei; functional group concentration 678 g / mol, inorganic fraction 15%, refractive index 1.39) 4 mass Part Fluorine-containing monomer: 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol di (meth) acrylate 1 part by mass Surface-treated colloidal silica dispersion 45 parts by weight Initiator: Iruger Cure 184 (trade name; 0.25 parts by mass Solvent: 50 parts by mass of methyl isobutyl ketone

Coating liquid 6 [(A) component: (B) component: (C) component = 80: 20: 100]
Silsesquioxane compound having a perfluoroalkyl chain and an oxetanyl group: OX-SQ-F (trade name; manufactured by Toagosei; functional group concentration 708 g / mol, inorganic fraction 15%, refractive index 1.39) 4 mass Part Fluorine-containing monomer: 1,4-bis (2 ′, 3′-epoxypropyl) -perfluoro-n-butane 1 part by mass Surface-treated colloidal silica dispersion: 25 parts by mass Initiator: triallylsulfonium hexafluoro Phosphine salt 0.05 parts by weight Fluoropolymer additive: Modiper F3035 (trade name, manufactured by NOF Corporation; solid content 30% by weight) 0.3 parts by weight Solvent: 70 parts by weight of methyl isobutyl ketone

Coating liquid 7
Except for adding 0.3 parts by mass of a fluorine-based polymer additive (Modiper F3035 (trade name, manufactured by Nippon Oil & Fats Co., Ltd .; solid content: 30% by mass) in the composition of the coating solution, the same manner as in the coating solution 1 was applied. A coating solution 7 was prepared.

Coating liquid 8
The composition of the coating liquid is the same as that of the coating liquid 1 except that Methacryl-POSS (trade name, manufactured by Sigma Aldrich Japan) having only a methacryloyloxypropyl group as the silsesquioxane compound is used as the silsesquioxane compound. Thus, a coating solution 8 was prepared.

Coating liquid 9
In the composition of the coating liquid, OX-SQ (trade name, manufactured by Toagosei; functional group concentration 283 g / mol, inorganic fraction 34%, refractive index) having no fluoroalkyl group and having only an oxetanyl group as a silsesquioxane compound A coating solution 9 was prepared in the same manner as the coating solution 6 except that 1.46) was used.

3. Formation of Hard Coat Layer on Light-Transparent Substrate The following components were mixed to prepare a hard coat layer forming coating solution.

Pentaerythritol triacrylate (PETA) 5 parts by weight Photopolymerization initiator (Irgacure 184: trade name, manufactured by Ciba Specialty Chemicals) 0.25 parts by weight Methyl isobutyl ketone 94.75 parts by weight

The hard coat layer forming coating solution prepared in the above step is bar coated on a 80 μm thick triacetate cellulose (TAC) film, and after removing the solvent by drying, an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd., Using a light source H bulb, ultraviolet irradiation was performed at an irradiation dose of 108 mJ / cm ² to cure the hard coat layer to obtain a substrate / hard coat layer laminate having a thickness of 2 μm.

4). Preparation of antireflection laminate [Example 1]
3. above. The substrate / hard coat layer laminate prepared in Step 1 is bar-coated with the coating solution 1 for forming a low refractive index layer prepared in the above step and dried to remove the solvent, and then an ultraviolet irradiation device (fusion UV Using System Japan Co., Ltd., light source H bulb), UV irradiation is performed at an irradiation dose of 200 mJ / cm ² , the coating film is cured, and the antireflection laminate of the substrate / hard coat layer / low refractive index layer Got. The film thickness was adjusted so that the minimum value of the reflectance was around 550 nm.

[Example 2]
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating solution 2 for forming a low refractive index layer prepared in the above step was used.

Example 3
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating solution 3 for forming a low refractive index layer prepared in the above step was used.

Example 4
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating solution 4 for forming a low refractive index layer prepared in the above step was used.

Example 5
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating solution 5 for forming a low refractive index layer prepared in the above step was used.

Example 6
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating solution 6 for forming a low refractive index layer prepared in the above step was used.

Example 7
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating solution 7 for forming a low refractive index layer prepared in the above step was used.

[Comparative Example 1]
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating liquid 8 for forming a low refractive index layer prepared in the above step was used.

[Comparative Example 2]
An antireflection laminate was prepared in the same manner as in Example 1 except that the coating liquid 9 for forming a low refractive index layer prepared in the above step was used.

5. Evaluation Test The following physical properties were measured and evaluated for each of the antireflection laminates of Examples 1 to 7 and Comparative Examples 1 and 2, and the results are shown in Table 1 below.

Evaluation 1: Reflectance measurement The absolute reflectance of the outermost surface of the antireflection laminate was measured using a spectrophotometer (UV-3100PC: trade name) manufactured by Shimadzu Corporation.

Evaluation 2: Haze value measurement
The haze value of the outermost surface of the antireflection laminate was measured according to JIS K 7136: 2000 “How to Obtain Haze of Transparent Plastic Material”.

Evaluation 3: Scratch resistance evaluation test The surface of the antireflection laminate was subjected to 10 reciprocating frictions using # 0000 steel wool with a predetermined friction load (changed every 200 g within a range of 200 to 1000 g). Thereafter, the haze value was measured. Then, the scratch resistance of the antireflection laminate was evaluated by examining the minimum load when a change of 3% or more was recognized as compared with the haze value of the antireflection laminate before friction.

Evaluation 4: Contact angle measurement The water contact angle of the antireflection laminate was measured according to JIS R 3257: 1999 “Wetting test method for substrate glass surface” using an antireflection film fixed on a glass plate with double-sided tape. It was measured.

  The antireflection laminate of the present invention is coated with a fluorine-containing low refractive index composition having a low refractive index and a high altitude, which can be applied to an image display device such as a liquid crystal display (LCD) or a cathode ray tube display (CRT). It is useful as an antireflection laminate such as an antireflection film having a low refractive index layer formed thereon.

It is the figure which showed typically the cross section of an example of the liquid crystal display device which coat | covered the display surface with the multilayer type antireflection film containing the low refractive index layer of this invention as a light transmissive layer. It is the figure which showed typically the cross section of the polarizing film affixed on the outer surface of the glass substrate of the display surface side. It is the figure which showed typically the cross section of an example of the antireflection film containing the coating film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,6 Glass substrate 2 Pixel part 3 Black matrix layer 4 Color filter 5,7 Transparent electrode layer 8 Sealing material 9 Orientation film 10 Polarizing film 11 Backlight unit 12 Polarizing element 13,14 Protective film 15 Adhesive layer 16 Hard coat layer DESCRIPTION OF SYMBOLS 17 Multilayer type antireflection film 18 Medium refractive index layer 19 High refractive index layer 20 Low refractive index layer 21 Transparent base film 22 High refractive index layer 23 Low refractive index layer 101 Liquid crystal display device 102 Antireflection film

Claims (24)

An antireflective laminate in which a low refractive index layer is formed directly on at least one surface side of a light-transmitting substrate or via another layer,
The low refractive index layer is
(A) component: silsesquioxane having two or more perfluoroalkyl groups and two or more reactive groups in one molecule;
(B) component: a fluorine-containing monomer, and
Component (C): An antireflective laminate characterized by being formed using a coating composition for forming a low refractive index layer containing a filler. The component (A) to the component (B) is 50% by mass to 50% by mass to 95% by mass to 5% by mass, and the total amount of the component (A) and the component (B) is 100 parts by mass. (C) is 10-200 mass parts, The reflection preventing laminated body of Claim 1 characterized by the above-mentioned. The reactive group of the component A has any reactivity selected from the group consisting of photoradical polymerization, photocationic polymerization, photoanion polymerization, polymerization that proceeds through photodimerization, and thermal polymerization. Item 3. The antireflection laminate according to Item 1 or 2. The antireflection laminate according to any one of claims 1 to 3, wherein the reactive group of the component A is selected from a (meth) acryloyl group, a vinyl group, an epoxy group, and an oxetanyl group. The said A component is silsesquioxane which consists of a condensate of the hydrolyzate of the compound represented by the following general formula (1) and (2), The any one of Claim 1 thru | or 4 characterized by the above-mentioned. The antireflection laminate as described in 1.

(However, R ⁰ is an organic functional group having a reactive group selected from a (meth) acryloyl group, a vinyl group, an epoxy group, and an oxetanyl group, and X is a hydrolyzable group.)

(However, R ¹ is an organic functional group having a perfluoroalkyl group, and X is a hydrolyzable group.) 2. The antireflection according to claim 1, wherein the component B contains one or more (meth) acryloyl group, vinyl group, epoxy group, oxetanyl group, or a reactive group selected from a combination thereof in one molecule. Laminated body. The antireflection laminate according to claim 1, wherein the component B is a fluorine-containing monomer represented by the following general formula (3).

(Wherein R ² and R ³ are organic functional groups having a reactive group selected from a (meth) acryloyl group, a vinyl group, an epoxy group, and an oxetanyl group, and R ⁴ and R ⁵ are single bonds. Or it is a C1-C5 bivalent hydrocarbon or oxygen, and n shows the integer of 1-30.) The antireflection laminate according to claim 5, wherein R ¹ in the general formula (2) is represented by the following general formula (4).

(Where, m is an integer of 0, R ⁶ is an alkylene group having 1 to 4 carbon atoms.) The reflection according to claim 7, wherein R ² and R ³ in the general formula (3) are both an epoxy group represented by the following general formula (5) or an oxetanyl group represented by the following general formula (6). Prevention laminate.

(In the formula, R ⁷ is hydrogen, fluorine, an alkylene group, or a fluoroalkylene group.)

(In the formula, R ⁸ is hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group, and R ⁹ is an alkylene group having 2 to 6 carbon atoms.) The antireflection laminate according to claim 1, wherein the C component is silica fine particles, and at least a part of the C component has voids therein. The antireflection laminate according to any one of claims 1 to 10, wherein the coating composition for forming a low refractive index layer further contains a fluorine-based compound and / or a silicon-based compound. The antireflection laminate according to claim 11, wherein at least a part of the fluorine-based and / or silicon-based compound forms a covalent bond by a chemical reaction with the coating composition for forming a low refractive index layer. . The antireflection laminate according to any one of claims 1 to 12, wherein a refractive index of the low refractive index layer is 1.45 or less. The antireflection laminate according to any one of claims 1 to 12, wherein a refractive index of the low refractive index layer is 1.40 or less. The antireflection laminate according to any one of claims 1 to 14, wherein the other layer is a hard coat layer. The antireflection laminate according to claim 15, wherein the refractive index of the hard coat layer is in the range of 1.50 to 1.70. The antireflection laminate according to claim 15 or 16, wherein the hard coat layer has an antiglare property. The antireflection laminate according to any one of claims 1 to 17, wherein an antifouling layer is provided on the surface of the low refractive index layer opposite to the substrate side. A medium to high refractive index layer having a refractive index in the range of 1.46 to 2.00 and a film thickness in the range of 0.05 to 0.15 μm between the hard coat layer and the low refractive index layer. The antireflection laminate according to any one of claims 15 to 18, wherein at least one layer is provided. The antireflection laminate according to any one of claims 15 to 19, wherein at least one layer selected from the hard coat layer, the medium to high refractive index layer, and the low refractive index layer has antistatic performance. . 21. The antireflection laminate according to any one of claims 15 to 20, wherein an antistatic layer is provided between the substrate and the hard coat layer. The antireflection laminate according to any one of claims 1 to 21, wherein a film thickness of the low refractive index layer is in a range of 0.05 to 0.15 µm. The minimum load amount at which a change in haze value of the low refractive index layer is observed when the surface of the low refractive index layer is rubbed 10 times with # 0000 steel wool is 200 g or more. 23. The antireflection laminate according to any one of 1 to 22. The antireflection laminate according to any one of claims 1 to 23, wherein the substrate is a plastic film.

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