TW201245756A - Antireflection film, polarizing plate, and image display device - Google Patents

Abstract

The purpose of the present invention is to provide an antireflection film that has a sufficient surface hardness and a uniform surface, comprises a low-refractive-index layer having a sufficiently low refractive index, and has excellent antireflection performance. An antireflection film wherein a hard coating layer is formed on a light-permeable substrate and a low-refractive-index layer is formed on the hard coating layer is characterized in that the low-refractive-index layer of the antireflection film comprises (meth)acrylic resin, hollow silica microparticles, reactive silica microparticles and an antifouling agent and the reactive silica microparticles in the low-refractive-index layer are unevenly distributed near the interface on the hard coating layer side and/or near the interface of the side opposite the hard coating layer.

Description

201245756 - VI. Description of the Invention: [Technical Field] The present invention relates to an anti-reflection film, a polarizing plate, and an image display device. [Prior Art] For a cathode ray tube display device (C RT ), a liquid crystal display (L c D ), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (ΡΕζ), a touch panel, The image display surface in an image display device such as a flat panel Pc or an electronic paper is required to reduce reflection caused by light irradiated by an external light source, thereby improving visibility. On the other hand, by using an antireflection film having an antireflection layer formed on a light-transmitting substrate, reflection of the image display surface of the image display device is reduced, and visibility is improved. As the antireflection film having an antireflection layer, a structure in which a low refractive index layer having a refractive index lower than that of a light-transmitting substrate is provided on the outermost surface is known. Such a low refractive index layer is required to have a low refractive index in order to improve the antireflection performance of the antireflection film, and is required to have a high hardness in order to prevent damage or the like because it is provided on the outermost surface, and is required to have Excellent optical properties such as transparency. As an antireflection film in which a low refractive index layer is formed on the outermost surface, for example, Patent Document 1 discloses an antireflection film using a coating liquid containing hollow smectite particles and a blistering resin such as acryl. An antireflection film having a low refractive index layer of a hollow cerium oxide material.

However, in recent years, the display quality required for the display device has become non-hanging, and the anti-reflection performance of rf? > c a several shots has become higher. 3 201245756 Level. However, the antireflection film which has been provided with a low refractive index layer containing hollow cerium oxide microparticles has insufficient antireflection performance and cannot sufficiently satisfy the demand for high display quality in recent years. Further, for example, Patent Document 2 or the like discloses a method of formulating a fluorine atom-containing polymer or a monomer in a material of a low refractive index layer. Since the fluorine atom-containing polymer or the monomer is a material having a relatively low refractive index, the low refractive index layer containing the lower refractive index layer can further reduce the refractive index as compared with the low refractive index layer containing the hollow hollow ceria microparticles. However, when the low refractive index layer containing a fluorine atom-containing polymer or a monomer contains such a compound to such an extent that the refractive index is sufficiently lowered, the hardness of the low refractive index layer becomes insufficient. Therefore, an antireflection film having a low refractive index 4' having a sufficient surface hardness and a lower refractive index and having high antireflection properties has been sought. Further, since such an antireflection film is usually provided on the outermost surface of the image display device, it is required to have excellent smoothness. Patent Document 1: JP-A-2003-29283 No. JP-A No. 2001-100004 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2001-100004 (Summary of the Invention) This is a continuation of the present invention, and is intended to provide an anti-reflection film and an anti-reflection film. a polarizing plate and an image display device made of a reflective film, which has a surface resistance, a surface hardness, and a uniform surface, and has a low refractive index (the refractive index of the refractive index layer is sufficiently low) The layer has excellent anti-reflection properties. 4 201245756 The present invention is an anti-reflection film which is formed by forming a hard coat layer on a light-transmitting substrate and forming a low-refractive-index layer on the hard coat layer, which is characterized by the above-mentioned low The refractive index layer contains a (fluorenyl) acrylic resin, hollow cerium oxide fine particles, reactive cerium oxide fine particles, and an antifouling agent, and the reactive cerium oxide fine particles in the low refractive index layer are biased to the hard coat layer. In the vicinity of the interface of the side and/or near the interface opposite to the hard coat layer. In the antireflection film of the present invention, it is preferred that the reactive cerium oxide microparticles in the low refractive index layer are biased to the side of the hard coat layer. phase Near the interface of the side, the hard coat layer has reactive ceria particles arranged neatly along the interface direction in the vicinity of the interface on the side of the low refractive index layer. Further preferably, the reactive ceria in the low refractive index layer is The content of the fine particles is 5 to 6 parts by mass based on 1 part by mass of the (fluorenyl) acrylic resin. Further, it is preferable that the average particle diameter of the hollow cerium oxide fine particles is 40 to 80 nm, and further The blending ratio of the (mercapto)acrylic resin (the content of the hollow cerium oxide fine particles/the content of the (meth)acrylic resin) is 0.90 to 1.60. Further, it is preferable that the above-mentioned antifouling agent is biased to the above low refractive index. Preferably, the antifouling agent contains a reactive functional group, a compound having a fluorine atom and/or a cerium atom, and is preferably 'the above (meth)acrylic acid. The resin is selected from the group consisting of neopentyl alcohol tris(mercapto) acrylate, dipentaerythritol hexakisyl acrylate, pentaerythritol tetrakis(meth) acrylate, and dipentaerythritol five (曱). Acrylate, At least one of a group consisting of trihydroxy 201245756 methyl propyl tris(meth) acrylate @ 、, diterpene tetraol tetra(meth) acrylate, and isotrimeric decanoic acid tri(meth) acrylate Further, the polymer or copolymer of one type of monomer is preferably a resin containing a fluorine atom in the low refractive index layer. Further, it is preferable that the content of the reactive cerium oxide microparticles in the hard coat layer is relative to The (meth)acrylic resin 丨 00 parts by mass is i 5 to 6 〇 parts by mass. The present invention is also a polarizing plate comprising a polarizing element, wherein the polarizing plate is provided on the surface of the polarizing element. Further, the present invention relates to an image display device comprising the above-described antireflection film or the above polarizing plate. The present invention will be described in detail below. The present invention is an antireflection film formed on a light-transmitting substrate. A hard coat layer forms a low refractive index layer on the hard coat layer. The inventors of the present invention conducted an effort to study the antireflection film having the above-described structure and found that the hard coat layer contains reactivity: oxygen-cut microparticles, and further, the low refractive index layer contains reactive ceria particles and hollow silica. In the case of the fine particles, the reverse n-oxidized oxide particles in the low refractive index layer are biased to the vicinity of the interface on the opposite side of the hard coat layer, and the t-shaped hollow oxide particles in the low refractive index layer are closely packed. The state, the desired effect is achieved', and the present invention is finally completed. Each of the layers constituting the antireflection film of the present invention is described. Low refractive index 0 201245756 The above-mentioned low refractive index layer refers to a refractive index lower than that of a constituent other than the low refractive index layer such as a light-transmitting substrate or a hard coat layer constituting the antireflection film of the present invention. . In the antireflection film of the present invention, the low refractive index layer contains (american acrylic resin, hollow silica fine particles, reactive dioxygen fine particles, and an antifouling agent. The hollow cerium oxide microparticles are maintained. The layer of the low refractive index layer has a degree of degree and reduces the refractive index. Further, in the present specification, the term "y hollow-shaped dioxy-cut microparticles" means a dioxo-cut microparticle: the inside of which is filled with a gas. The porous structure including the structure and/or the gas has a refractive index which decreases in proportion to the gas occupation rate as compared with the original refractive index of the silica fine particles. Further, in the present invention, the cerium oxide microparticles are used. The form, the structure, the agglomerated state, and the dispersed state in the interior of the coating film formed by using the low refractive index layer composition described later when the low refractive index layer is formed, and at least a part of the inside and/or the surface The oxidized cerium microparticles are formed in the antireflection film of the present invention, and the hollow cerium oxide microparticles are closely packed in the antireflection film of the present invention. The surface of the low refractive index layer is excellent in the uniformity of the surface of the low refractive index layer, and the surface hardness of the antireflection film of the present invention is excellent. Further, the term "closely filled state" means There is almost no state in which the above-mentioned reactive cerium oxide microparticles are formed in a state similar to the most densely packed structure between adjacent hollow cerium oxide microparticles. 201245756 It is presumed that the hollow cerium oxide microparticles are contained in the state of being closely packed in the low refractive index. The reason for the layer is that, as will be described later, the reactive ceria particles contained in the low refractive index layer are biased near the interface of the hard coat side of the low refractive index layer or near the interface opposite to the side of the hard coat layer. That is, the reason for the reason is that the low refractive index layer is formed by: forming the monomer component of the work--oxidized fine particles, the reactive dioxide #microparticles, and the (meth)acrylic resin in the package 3. The composition (hereinafter also referred to as a low-fold layer) is applied to the hard coat layer to form a coating film, and the coating film is dried and hardened. As will be described later, the reaction-containing oxidized fine particles contained in the coating film are moved to the vicinity of the interface on the side of the hard coat layer or to the interface on the opposite side of the hard coat layer 4, because & In the formed coating film, the hollow niobium oxide microparticles in the low refractive index layer formed by the formation of the reactive niobium oxide microparticles between the adjacent hollow oxidized fine particles are in a state of being closely packed. Specific examples of the hollow cerium oxide fine particles are not particularly limited. For example, cerium oxide fine particles prepared by the technique disclosed in Japanese Laid-Open Patent Publication No. Hm. Since the fine particles are easy to manufacture and their hardness is low, when the two-system adhesive is mixed to form a low refractive index layer, the layer strength of the low refractive index can be improved, and the refractive index can be adjusted to be low. In addition to the fine particles of the nitric oxide, the column for filling used for the production of a large specific surface area, the adsorbent for adsorbing various chemical substances, and the catalyst for the catalyst are used. A fixed dispersion of porous or coarse particles, or a dispersion or aggregate of the particles in the middle of a hot or low dielectric material. As a specific example, it is manufactured by Nippon Silica Industrial Co., Ltd. As a commercial item, it can be listed under the trade name Nipsil or

A collection of porous cerium oxide microparticles in Nipgel, manufactured by Nissan Chemical Industries Co., Ltd., having a structure in which the oxidized microparticles are joined to form a bond, and the colloidal niobium oxide series (the preferred particle size range of the trade name). Among these, the present invention can be used as the average particle diameter of the hollow cerium oxide microparticles, preferably 10 to 100 nm, by making the average particle diameter of the hollow smectite particles into the range Θ ' The low refractive index layer can be provided with excellent transparency. The lower limit is 40 nm. The upper limit is 8 〇 nm, and the lower limit is 45 nm. The upper limit is better than $ 75 nm. The lower limit is $ 5 〇. (10), the optimal upper limit is 70 nm. In addition, the average particle diameter of the above-mentioned hollow-shaped silica dioxide particles is the same as that of the hollow-shaped dioxygen particles alone, which means the value measured by dynamic light scattering method. On the other hand, the average particle diameter of the hollow-shaped silica fine particles in the low-refractive-index layer is as follows: using stem or the like: the profile of the refractive index layer 'select any 30 hollow-shaped dioxide In the case of the granules, the particle size of the cross-section is measured, and the average value is calculated. Further, the void ratio of the hollow zirconia particles is preferably 2.5 to 8 〇.〇%. The low refractive index: the refractive index of the layer and the refractive index of the layer are sufficiently reduced, and the anti-reflection performance of the anti-reflection film of the present invention is not slashed. If it exceeds 8 G G%, the strength of the hollow-shaped dioxide is reduced. Further, the strength of the entire low refractive index layer may be insufficient. The lower limit of the void ratio of the hollow cerium oxide fine particles 201245756 is 6.4%' of the upper limit & 76 4%' and thus the lower limit 丨2 〇〇%, and further preferably, the upper limit is 55.0%. By having a void ratio in this range, the low refractive index layer can be sufficiently lowered in refractive index, and the low refractive index layer can have excellent strength. The void ratio of the SiO2 particles can be calculated by the following formula: the thickness of the outer shell portion excluding the diameter and the void portion is measured by the hollow zirconia granule section § dicing observation or the like, and the hollow portion is determined. two The fossil granules are set as spheres, and the volume of the void portion of the hollow zirconia granules and the volume of the hollow zirconia granules when the void-free portion is set are calculated by {(t empty dicing microparticles) The gap (the volume of the knives) / (the volume of the hollow zirconia particles in the absence of the (four) portion) is calculated by xl 〇〇. Also, the average particle diameter and the outer shell portion are contained in the low refractive index layer. In the case of a plurality of hollow-shaped silica fine particles having different thicknesses, the void ratio of each of the hollow silica-containing fine particles calculated by the above method and the ratio of the void ratio of each of the hollow silica stones to the fine particles are calculated. The average value is taken as the void ratio of the hollow silica-containing fine particles (hereinafter, the void ratio is also referred to as "average void ratio"). Furthermore, even in this case, each of the hollow dioxo-particles preferably has a void having the above-mentioned range in the anti-reflection crucible of the present invention, and the average void ratio of the hollow-shaped silica fine particles is higher than (4) 10.0. When %1 is not satisfied, the refractive index of the low refractive index layer may not be sufficiently lowered, and the antireflection performance of the antireflection film of the present invention may be insufficient. When it exceeds 40.0%, the strength of the dimorphic cerium oxide microparticles in the above-mentioned 201245756 may be lowered, and the strength of the entire low refractive index layer may be insufficient. A lower limit is preferably 15.0%, and a lower limit is 35.0%. By having a void ratio in the range of B, the low refractive index layer can be sufficiently low in refractive index and the low refractive index layer can be made excellent in strength. From the viewpoint of low refractive index and strength, the lower limit of the average void ratio of the hollow dioxo fine particles is further preferably 20.0%, and more preferably the upper limit is 30.0%. Further, the hollow nitric oxide particles are The blending ratio of the (meth)acrylic resin to be described later (the content of the hollow cerium oxide fine particles/the content of the (meth)acrylic resin) is preferably 〇·90 to 1.6 G. . When the above-mentioned blending ratio is not satisfied, the refractive index of the low refractive index layer may not be sufficiently lowered, and the antireflection performance of the antireflection film of the present invention may be insufficient. When the compounding ratio exceeds 丨6〇, the uniformity of the surface of the low refractive index layer may be insufficient, and the surface hardness of the antireflection film of the present invention may be insufficient. The lower limit of the above-mentioned blending ratio is 1.0 0 ', and the upper limit is preferably 150. By being in this range, an antireflection film having more excellent antireflection properties, surface uniformity, and surface hardness can be obtained. Further, the surface hardness (scratch resistance) is improved by increasing the surface uniformity of the low refractive index layer. In the antireflection film of the present invention, the hollow ceria particles are preferably in a most densely packed structure in which two layers are laminated in the thickness direction of the low refractive index layer. By being contained in such a state, the antireflection film of the present invention can be extremely excellent in transparency, surface uniformity, and low refractive index. 11 201245756 The reactive ceria fine particles are biased to the vicinity of the interface of the low-refractive-index layer on the side of the hard coat layer and/or near the interface on the opposite side to the hard coat layer to be described later, and the refractive index of the low-refractive-index layer is lowered. Improve the surface hardness of the role. When the reactive ceria fine particles are in the vicinity of the interface on the hard coat layer side of the low refractive index layer and in the vicinity of the interface on the opposite side to the hard coat layer, the surface hardness and the antifouling property are excellent. Further, when the reactive cerium oxide fine particles are in the vicinity of the interface on the hard coat layer side of the low refractive index layer, the antifouling agent described later is biased to the vicinity of the interface of the low refractive index layer opposite to the hard coat layer, and In the case where the reactive cerium oxide is present on the outermost surface, the amount of the antifouling agent present on the outermost surface is increased, and therefore the antifouling property of the antireflective enamel of the present invention becomes extremely excellent. On the other hand, when the above-mentioned reactive cerium oxide microparticles are biased in the vicinity of the interface of the low refractive index layer opposite to the hard coat layer, the surface hardness of the low refractive index layer due to the biasing of the reactive cerium oxide microparticles can be obtained. Further, in the low refractive index layer, as described above, the hollow cerium oxide fine particles are in a state of being closely packed. Therefore, the surface due to the excellent surface uniformity of the low refractive index layer can be obtained. Increased hardness. As a result, the scratch resistance of the antireflection film of the present invention is excellent. Here, the above-mentioned "near the interface near the hard coat layer side or the vicinity of the interface on the side opposite to the hard coat layer described later" means that the above-mentioned reactive cerium oxide microparticles are present in close proximity in the low refractive index layer. In the filled state, the hollow cerium oxide microparticles are below (hard coat side) or above (opposite to 12 201245756 hard coat layer). More specifically, in the cross section of the low refractive index layer, the thickness of the low refractive index layer is divided into three, and the interface from the side of the hard coat layer is sequentially set to a 1/3 region and a 2/3 region. In the case of the 3/3 region, it is judged that the reactive cerium oxide fine particles are located near the interface of the hard coat layer side in the case where the i/3 region contains 75% or more of the reactive cerium oxide fine particles, which will be 3/3 above. In the case where the region 3 contains 75% or more of the reactive cerium oxide fine particles, it is judged that the reactive cerium oxide fine particles are in the vicinity of the interface on the opposite side to the hard coat layer. Further, the total of the above-mentioned reactive cerium oxide microparticles is more than 7 〇〇 / 〇 in the above-mentioned 1/3 region and 3 / 3 region, and is biased in the 1/3 region and the 3 / 3 region respectively. When the amount of the cerium oxide microparticles is more than the amount of the reactive cerium oxide microparticles contained in the 2/3 region, it is judged that the reactive cerium oxide microparticles are biased to the vicinity of the interface of the hard coating layer of the low refractive index layer and Near the interface on the opposite side of the hard coat. Further, the state in which such reactive cerium oxide fine particles are present in a biased state can be easily discriminated by cross-sectional microscopic observation (STEM, TEM) of the low refractive index layer when the antireflection film of the present invention is cut in the thickness direction. The reason why the above-mentioned reactive cerium oxide fine particles are in the vicinity of the hard coat layer side interface and/or in the vicinity of the hard coat layer side interface in the low refractive index layer is not clear. However, 'for example, when the hard coat layer contains reactive cerium oxide microparticles, the reactivity in the low refractive index layer can be controlled by adjusting the amount of the reactive cerium oxide microparticles in the hard coat layer. The bias of the dioxide dioxide particles exists. That is, when the hard coat layer does not contain reactive cerium oxide microparticles, if a low refractive index layer is formed on the hard coat layer, the reactive refractive index of the low refractive index 13 201245756 layer can be made. Near the hard coating side interface. On the other hand, when the hard coat layer contains reactive redox oxide particles in a range of more than 25 parts by mass and 6 parts by mass or less with respect to the resin component 100 constituting the hard coat layer, The formation of the low refractive index layer on the hard coat layer allows the reactive rare earth oxide particles of the low refractive index layer to be biased near the interface with the opposite side of the hard coat layer. Further, when the hard coat layer contains reactive rare earth oxide particles in a range of 5 to 25 parts by mass based on the mass of the resin component constituting the hard coat layer, the low refractive index can be obtained. The layer of reactive SiO2 particles is located near the interface of the hard coat side of the low-profile ten-layer layer and near the interface with the opposite side of the hard coat layer. Commercially available products may be used as the above-mentioned reactive cerium oxide fine particles, and examples thereof include MIBK_SDL, MIBK_SDMS, and mibk sd (all of which are manufactured by Nissan Chemical Industries, Ltd.), Dpi〇21SIV, Dpi〇39siv, and DP1117SIV (all of which are The Japanese company has become a company to manufacture. The average particle diameter of the reactive nitric oxide granules is preferably from 1 to 25 nm. If not! In the case of nm, there is a case where aggregation is easy and the degree of filling is lowered, so that the obtained low refractive index layer cannot obtain sufficient strength. On the other hand, when it exceeds 25 nm, surface unevenness is formed in the low refractive index layer, and sufficient strength cannot be obtained. Further, when the reflectance is increased, it is difficult to exhibit sufficient antifouling property by containing an antifouling agent to be described later. A more preferred lower limit of the average particle diameter of the above reactive ceria particles is 5 nm, and a more preferred upper limit is 20 nm. By being in this range, the low reflectance and high hardness of the antireflection film of the present invention can be maintained. Furthermore, in the present specification, the above-mentioned reactive cerium oxide microparticles have a 201245756 flat sentence, and are observed by a cross section of BET (Brun_r E_emller) or STEM (the average of 3 〇) The value measured. 5 of the reactive trioxide 11 fine particles in the low refractive index layer is preferably 5 60 parts by mass based on 100 parts by mass of the (meth)acrylic resin to be described later. If it is less than 5 parts by mass, the surface hardness of the low refractive index layer may not be sufficiently increased, and the scratch resistance of the antireflection film of the present invention may be deteriorated. When the amount exceeds 6 G f, the above is not in the low refractive index. The amount of the reactive dioxygen microparticles in the state in which the layer is biased to exist is not in the state of the above-mentioned close filling, and as a result, the uniformity of the surface of the low refractive index layer is deteriorated. There is a possibility of causing an increase in reflectance. A more preferred lower limit of the amount of the above-mentioned reactive rare earth oxide particles is 丨0 parts by mass, and more preferably, the upper limit is 5 parts by mass. By containing reactive cerium oxide fine particles in this range, the surface hardness of the antireflection film of the present invention can be extremely excellent. The (mercapto)acrylic resin functions as a binder component of the hollow cerium oxide microparticles or the reactive cerium oxide microparticles in the low refractive index layer. Further, in the present specification, "(曱"Acrylate" means acrylate or methacrylate. The (meth)acrylic resin is a polymer or a copolymer of a (meth)acrylic acid monomer. The (early) acrylate monomer is not particularly limited, and for example, preferably, it is exemplified: Neopentyl alcohol tris(indenyl) acrylate bismuth, neopentyl pentoxide hexa(indenyl) acrylate vinegar, neopentyl alcohol tetrakis(mercapto) acrylate, dipentaerythritol (Mercapto) acrylate, trimethylol propyl tris (methyl 15 201245756 based) acrylic vinegar, dipentaerythritol tetrakis(meth) acrylate, tris (meth) acrylate, and the like. Moreover, the (mercapto) acrylate monomer may also be modified by one part of the molecular skeleton, and may also be used by ethylene oxide, propylene oxide, caprolactone, iso-cyanuric acid, alkyl, It is a modified one of a cyclic alkyl group, an aromatic group, and a bisphenol. The s-specific (meth) acrylate monomer may be used singly or in combination of two or more. These (fluorenyl) acrylate monomers satisfy the range of the refractive index described later, and are excellent in curing reactivity, and the hardness of the obtained low refractive index layer can be improved. Among them, a (meth)acrylic resin having a functional group number of 3 or more can be preferably used. The refractive index of the above (fluorenyl) acrylic resin (after hardening) is preferably 1.47 to 1.53. In fact, the refractive index cannot be set to less than 147. If it exceeds 1.53, a low refractive index having a sufficiently low refractive index cannot be obtained. Floor. The weight average molecular weight of the (meth)acrylic acid g-based monomer is preferably 250 to 1 Å. If it is less than 25 Å, the hardness of the obtained low refractive index layer is lowered due to the decrease in the number of functional groups. When the amount exceeds the chest, the functional group is usually 4 (the number of functional groups/molecular weight) is small, and there is a case where the crosslinking density is low and a low refractive index layer having sufficient hardness cannot be obtained. Further, the above (meth)acrylic acid The weight average molecular weight of the ester monomer can be determined by conversion of polystyrene by gel permeation chromatography (Gpc). It can be used in the solvent of the gpc mobile phase. Four mu# can be combined with tetrahydrofuran +, ^ ^4. It is used as a commercial column for the column. As the above-mentioned commercially available sigma, for example, Sh〇dexGPCKF_801 and GPC-KF800D (all are cheap · 0 々 (spoon is the trade name, Manufactured by Showa Denko Co., Ltd., etc. Detecting 16 201245756 The RI (differential refractive index) detector and UV detector can be used. This solvent, column, and detector are used, for example, by sh〇dexGpc_1〇1 (Showa Denko) The GPC system can be suitably measured for the weight average molecular weight. The low refractive index layer further contains an antifouling agent. The low refractive index layer further contains an antifouling agent, whereby the antireflection film of the present invention becomes antifouling property. 'especially When the reactive cerium oxide fine particles in the refractive index layer are in the vicinity of the interface on the side of the hard coat layer, the content ratio of the antifouling agent in the vicinity of the interface on the opposite side to the hard coat layer of the low refractive index layer becomes large. The antifouling property of the antireflection film of the present invention is particularly excellent. Further, in the case of the above low refractive index layer, when the reactive oxidized dreaming microparticles are in the vicinity of the interface opposite to the hard coat layer, the above prevention The same as the above-mentioned reactive cerium oxide microparticles, the stain is partially offset to the vicinity of the interface of the low refractive index layer opposite to the hard coat layer, and in this case, the antifouling property by the above antifouling agent can also be sought. To some extent, the reason for preventing the 5 agents from being biased to some extent near the interface with the opposite side of the hard coat layer is that the reaction film formed on the hard coat layer is not formed, but it is presumed that, for example, the reaction is as described above. The cerium oxide microparticles move in the coating film, and the movement of the reactive cerium oxide microparticles affects the deflection of the antifouling agent. Thus, in the antireflection film of the present invention, the low refractive index layer is a has an antifouling agent and is excellent in antifouling performance. The antifouling agent is preferably a compound containing a reactive functional group and a fluorine atom and/or a ruthenium atom. Further, the antifouling property of the low refractive index layer formed by the present invention is as follows. As the compound containing a reactive functional group and a fluorine atom, for example, a reactive decomposing compound, particularly an ethylenically unsaturated bond, can be widely used. The fluorine-containing monomer, more specifically, for example, a fluoroolefin (for example, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, total ruthenium 2,2-dimethyl (difluoro-2,2-dimethyl-l,3-diox〇le), etc.) Further, for example, (2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorobutyl)acetate (meth)acrylate, 2-(allylhexyl)ethyl (mercapto)acrylate, 2-(Perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorodecyl)ethyl (meth)acrylate, α-trifluoro(methyl)propene S The methyl ester (methyi _trifiu〇r〇(methyl)acrylate) is equivalent to a (fluorenyl) acrylate compound having a fluorine atom in the molecule; and has a fluorocarbon having a carbon number of 1 to 14 in the molecule; A fluorine-containing polyfunctional (meth) acrylate compound having a fluorocycloalkyl group or a fluoroalkyl group and at least two (meth) acryloxy groups. Further, a fluoropolymer or oligomer having a fluorinated alkyl group in the main chain, or a fluorinated polycondensate having a fluorinated alkyl group or a fluorinated alkyl group in the main chain and the side chain, Oligomers, etc. Among these, in particular, a fluorinated polymer having a chlorinated alkyl group and a fluorinated alkyl group in the primary and side bonds is less likely to cause bleed out from the low refractive index layer, and thus can be preferably used. Further, examples of the compound containing a reactive functional group and a ruthenium atom include a reactive polyoxo compound. Specific examples thereof include (poly)dimethyloxane, (poly)diethylene 201245756 sulfoxane, (poly)diphenylphosphorane, and (poly)methylphenyloxy siloxane. Alkyl modified (poly) dimethyl sulphur oxygen@ 'Azo-containing (poly) dimethyl oxa alkane, bis-f-polyoxyl, phenylmethyl polyoxyl, alkyl _ aryl Alkyl modified polyfluorene oxide, fluoropolyfluorene oxide, polyether modified polyfluorene oxide, fatty acid ester modified polyfluorene oxide, sulfhydryl f polyphosphorus, poly (m) alcohol-based polyphenol, containing alkoxy Poly-Wei, polyoxyl oxide containing phenolic group, (meth) acrylate modified poly-I, amine-modified poly-stone, (4) modified poly-money, methanol modified poly-money, epoxy modified Poly-stone oxygen, sulfhydryl-modified poly-oxygen, fluorine-modified poly-oxygen, polyether modified poly-oxygen, and the like. Among them, a structure having a dimethyl-dimension structure is less likely to cause bleeding from the low-refractive-index layer, and therefore is preferable. Further, the above-mentioned reactive compound may, for example, be an olefin copolymer obtained by reacting a reactive polyphosphonium compound. The content of the functional group, the reactive fluorine compound with the fluorine atom and the ruthenium atom, and the counter-generated polyoxymethylene-containing difluoroethylene as the antifouling agent are appropriately determined according to the target low refractive index layer: The hollow cerium oxide microparticles are all 100 parts by mass, preferably ^ parts by mass. = up to \, parts by mass, there is a case where it is impossible to impart a second:: property to the formed low refractive index layer. In the case of the mass portion, there is a case where the added prevention (4) oozes from the low refractive index layer... The effect of adding the antifouling agent, and the manufacturing] the hardness and appearance of the obtained low refractive index layer are not observed. Decline, and thus lead to reflectivity (four) sheep anti-pollution people θ 9 clear condition. Above

The lower limit of Sr is preferably 2 parts by mass, and the upper limit is more preferably 15 19 201245756. Further, the antifouling agent may be added together with the above-mentioned compound containing a reactive functional group and a fluorine atom and/or a ruthenium atom. It is used without containing a compound of a reactive S-energy group. In the antireflection film of the present invention, the refractive index of the low refractive index layer is preferably less than 1.45 Å, and if it is 1.45 or more, the antireflection property of the antireflection film of the present invention is insufficient to cope with recent years. The image shows the display quality of the level between the devices. A lower limit is preferably 丨 2 5 and a higher limit is 1.43. The film thickness (nm) dA of the low refractive index layer preferably satisfies the following formula dA = m λ / ( 4nA) (I) (in the above formula, nA represents the refractive index of the low refractive index layer, and m represents a positive odd number, Preferably, it is 1, and is also a wavelength, preferably a value in the range of 480 to 580 nm. Further, in the present invention, in terms of low reflectance, the low refractive index layer preferably satisfies the following formula (Π): 120 < nAdA < 145 (II) Further, the haze value of the above low refractive index layer It is preferably 1% or less. If it is over ~, there is a case where the anti-reverse (four) of the present invention is inferior to (4), and the display quality of the image is not lowered. Better & 0,. the following. In the present specification, the haze value is determined according to mK7136, and the hardness of the low refractive index layer is preferably determined by the pencil hardness test according to JIS K5600-5-4 (1999). 'More preferably 2H or more. 20 201245756 The upper return low refractive index layer is preferably not damaged by the friction load of the steel wool 3 # #_〇. Rubbing one round back and forth scratch-resistant test, on the reverse side: the ruthenium layer can be prepared by preparing a monomer-forming coating liquid containing the above-mentioned hollow dioxin particles and = ray powder, base) . ― Use of the low refractive index layer The low refractive index layer I composition preferably contains a solvent. As the solvent, a mixed solvent of methyl isobutyl hydrazine (stupid κ), propylene glycol monomethyl bond (PGME) or propylene glycol monomethyl ether acetate vinegar PGMEA) is preferred. By using such a mixed solvent, since the drying time of the solvent is different, the low refractive index layer of the above configuration can be preferably formed. The mixing ratio of MIBK and pGME or pgmea in the above mixed solvent is preferably a mass ratio (MIBK/pGME or pgmea) = /5 ) (30/70 ). The low refractive index layer of the above structure can be particularly preferably formed by satisfying the mixing ratio of the above range. More preferably (8〇/2〇)~(4〇/6〇). Further, the composition for a low refractive index layer may contain other solvents as long as it does not inhibit the formation of the low refractive index layer having the above structure. Examples of such other solvents include alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, second butanol, and benzyl alcohol, acetone, and mercaptoethyl ketone cyclohexanone. Ketones such as heptanone, diisobutyl ketone, and diethyl ketone; methyl hydrazine acetate, ethyl acetate, propyl acetate, butyl acetate, decyl decanoate, acetaminophen citrate, propyl citrate, Butyl formate, PGMEA and other esters; hexane, cyclohexane, etc. 21 201245756, aliphatic hydrocarbons; dentate hydrocarbons such as gas, gas, and gasification; aromatic hydrocarbons such as benzene, toluene, and diphenylbenzene ; dimethyl decylamine, dimethyl acetamide, n-methyl.嘻 嘻 _ _ 醯 醯 醯 醯 匕 匕 匕 匕 匕 匕 匕 匕 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Further, the composition for a low refractive index layer may further contain other components as needed. Examples of the other components include a photopolymerization initiator, a leveling agent, a polymerization accelerator, a viscosity modifier, an antiglare agent, an antistatic agent, an ultraviolet absorber, and a resin other than the above (monomer, oligomerization). In the case where the composition for a low refractive index layer contains a resin having a radical polymerizable unsaturated group, for example, an acetophenone (for example, As a trade name of Irgacurel 84 (manufactured by BAsF & s), ruthenyl-cyclohexyl phenyl ketone, benzophenone, hydrazinone, benzoin, benzoin methyl ether, etc. In the case where the composition for a low refractive index layer contains a resin having a cationically polymerizable functional group, the photopolymerization initiator may, for example, be an aromatic diazo. The salt, the aromatic sulfonium salt, the aromatic sulfonium salt, the metallocene compound, the benzoin sulfonate, etc. may be used alone or in combination of two or more. Specific examples thereof include those manufactured by BASF Corporation.

IrgaCure907, Irgacure369, lrgacure379, Irgacure819, IrgaCUrel27, Irgacure500, Irgacure754, Irgacure25〇,

Irgacurel800, Irgacurel870, ilgacureOXEOl, daROCUR 22 201245756 • ΤΡΟ, DAROCUR1173; SpeedcureMBB, SpeedcurePBZ, SpeedcurelTX, SpeedcureCTX 'SpeedcureEDB ' Esacure ONE ' Esacurc KIP150, Esacure KT046 manufactured by Siber Hegner, Japan; KAYACURE DETX-S, KAYACURE manufactured by Nippon Kayaku Co., Ltd. CTX, KAYACURE BMS, KAYACURE DMBI. Among them, 'irgacure369, irgacurei27, Irgacure907, Esacure ONE, SpeedcureMBB, SpeedcurePBZ, KAYACURE DETX-S are preferred.尤佳 is Irgacurel27 (2-hydroxy-1-{4-[4-(2-hydroxy-2-indolyl-propionyl)-benzyl]phenyl}_2-methyl-propane-1 manufactured by BASF -ketone), Irgacurel 84 (hydroxy-cyclohexyl-phenyl-ketone manufactured by BASF Corporation). The amount of the photopolymerization initiator to be added is preferably 0.1 to 10 parts by mass based on 1 part by mass of the solid content of the resin component contained in the coating liquid for the low refractive index layer. The above-mentioned leveling agent, polymerization accelerator, viscosity adjuster, antiglare agent, antistatic agent, ultraviolet absorber, and other resins (monomer, oligomer, polymer) other than the above may be used. The method for producing the composition for a low refractive index layer is not particularly limited. For example, the hollow silica fine particles, the reactive silica fine particles, and the (meth)acrylic resin may be borrowed. It is obtained by using a monomer component, an anti-agent, a solvent, and a photopolymerization initiator which is added as needed. A known method such as a paint shaker or a bead mill can be used. The composition for a low refractive index layer is coated on the hard coat layer described later by applying the composition for the low refractive index layer, and the formed coating film is dried, and the coating film is hardened by irradiation and/or heating of ionizing radiation 23 201245756 line. Thereby, the low refractive index layer β can be formed. Here, 'the preferred drying condition as the coating film' is 40 to 80 ° C for 10 seconds to 2 minutes. By drying the above coating under such conditions, the low refractive index layer of the above configuration can be preferably formed. The method of applying the composition for the low refractive index layer is not particularly limited, and examples thereof include a spin coating method, a dipping method, a spray method, a gravure coating method, a die coating method, a bar coating method, and a roll coating method. Various methods such as a method and a liquid surface bending coating method. Hard coat layer The antireflection film of the present invention has a hard coat layer between the light-transmitting substrate and the low refractive index layer.

"Hard-coating" refers to the hardness of 2h or more in the pen hardness test specified in K5600-5-4 (1999) in this specification. The above pencil hardness is more preferably 3H or more. Further, the film thickness of the hard coat layer is 〜1 5 β m. In the case of curing, it is preferably 1 to 3 Å. In the antireflection film of the present invention, the hard coat layer preferably contains reactive dioxygen particles. The hard coat layer contains reactive dioxygen microparticles*, whereby the reactive dioxygen microparticles in the low refractive index layer are biased to the vicinity of the interface on the opposite side to the hard coat layer. The reactive dioxygen fine particles are the same as those of the reactive ceria particles in the above-mentioned low-fold layer. The content of the reactivity in the hard coat layer: the content of the oxygen-cut fine particles, 24 201245756 is preferably 15 to 60 parts by mass based on 1 part by mass of the resin component constituting the hard coat layer. When the amount is less than 15 parts by mass, the hardness of the hard coat layer may be insufficient, and if it exceeds 60 parts by mass, the adhesion to the light-transmitting substrate and the adhesion to the low refractive index layer may be obtained. In the case of deterioration, the lower limit of the hard coat layer which is liable to be broken or the total light transmittance is lowered and the haze is increased is preferably 20 parts by mass, and more preferably the upper limit is 55 parts by mass. The hard coat layer preferably has reactive cerium oxide microparticles contained in a state in which the vicinity of the interface on the low refractive index layer side is aligned in the interface direction. The low refractive index layer of the above configuration can be more preferably obtained by having the thus arranged reactive ceria particles. Here, the above-mentioned "state in which the vicinity of the interface on the side of the low refractive index layer is aligned in the direction of the interface" is preferably a state in which the reactivity is in the vicinity of the interface between the hard coat layer and the low refractive index layer. The oxygen-cut microparticles are arranged neatly in such a manner as to be adjacent to each other in the interfacial direction, and more preferably as follows: 1. The reactive nitric oxide granules have an upper end contacting the interface of the hard coat layer with the low refractive index layer, H h π β The mutually adjacent states are arranged neatly along the interface (Fig. I 1 Λ Further, the hard coat layer preferably also contains a ruthenium containing a state other than the above-mentioned neatly arranged state, and is 炙-reactive As the hard coat layer, it can be used as a hard coat layer, and it can be exemplified by a hard coat layer containing the above-mentioned reactive oxidized granules, and a component of the same. The composition is formed as the above-mentioned resin, and the transparency is used. Specifically, it can be listed as 25 201245756: ionizing radiation-curable resin which is a resin which is hardened by ultraviolet rays or electron beams, and ionizing radiation. A mixture of a curable resin and a solvent-drying resin (a resin which is a resin to be dried by adjusting a solid content component during coating to form a film, or a thermosetting resin) is preferably an ionizing radiation curable resin. Specific examples of the ionizing radiation-curable resin include those having a functional group of a propionate vinegar type, for example, a polyester resin having a relatively low molecular weight, a polyether resin, an acrylic resin, an epoxy resin, or an amine ester resin. a monomer, an oligomer, a prepolymer or the like of a (meth) acrylate such as a polyfunctional compound such as a polyhydric alcohol, etc. In addition, the (meth)acrylic resin used in the low refractive index layer may be used. Among the hard coat layers, a (meth)acrylic resin having a functional group number of 3 or more is preferred. When the above ionizing radiation curable resin is used as the ultraviolet curable resin, it is preferred to use photopolymerization. The starting agent. As the photopolymerization initiator, for example, acetophenone, diphenyl ketone, and M. benzoyl benzoate (Michler, s benZQy) l benzoate) 'a-amyloxime ester, tetramethylthiuram monosulfide, sulfonium sulfonium, etc. Preferably Irgacure 184 (1-carbo-cyclohexyl) manufactured by Basf -Phenyl-ketone). It is preferable to use a photosensitizer in combination, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like. The reactive polymer is used in combination with the ionizing radiation-curable resin. Examples of the non-reactive polymer include polyacrylic acid, polyacrylic acid, polyacrylate, polymethacrylic acid vinegar, and 26 201245756. Olefin, polystyrene, polyamine, mm ^ ^ bearing sub-private, polyvinyl chloride, polyethylene, polyethylene shrink disk, polycarbonate: polyethylene polymer, and can inhibit curl. "Add... non-reactive as the above-mentioned thermosetting tree resin, phthalic acid 1..." Listed. Benzene resin, gland grease, non-polyamine resin 'melamine resin, dimerization, resin, poly Amine vinegar resin, epoxy resin, amino strontium silicate-< gland co-condensation resin, Shixi resin, polymethane resin, and the like. In the case of using the above-mentioned thermosetting resin, q may be added as needed, such as a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, or the like. The above hard coat layer can be formed by applying the above-mentioned respective materials: the prepared hard coat layer composition onto the above-mentioned light-transmitting substrate, and drying the formed coating film as needed. It is hardened by irradiation with radiation or heating. In addition, as a method of preparing the composition for a hard coat layer, a method for forming a coating film, and the like, the same method as the above-described low refractive index layer can be mentioned. Further, the hard coat layer may further contain a high hardness or a low crimp material such as a known antistatic agent or a high refractive index agent. Translucent enamel The antireflection film of the present invention has a light-transmitting substrate. The light-transmitting substrate preferably has smoothness, heat resistance, and mechanical strength. Specific examples of the material for forming the light-transmitting substrate include polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, cellulose diacetate, Cellulose acetate butyrate, polyester, 27 201245756 Polyamide, polyimide, polyethersulfone, polyfluorene, polypropylene, polydecylpentene, polyethylene oxide, polyvinyl acetal, polyether ketone, A thermoplastic resin such as polymethyl methacrylate or polycarboethyl methacrylate (PMMA, Poly Methyl Methacrylate) or polyamino phthalate. Preferred examples are polyester (polyethylene terephthalate, polyethylene naphthalate) and cellulose triacetate. It is preferable that the above-mentioned thermoplastic resin is used in the form of a film body rich in flexibility, but a plate of the thermoplastic resin or a plate of a glass plate may be used depending on the use form of the curable property. Shaped person. In addition, as the light-transmitting substrate, a non-Japanese olefin polymer (Cycl〇 finlefin_p〇lymer: C〇p) film having an alicyclic structure w may also be mentioned. In the case of using a norbornene-based polymer, a monocyclic cyclic olefin polymer, a cyclic copolymer, a vinyl alicyclic polymer, or a vinyl alicyclic hydrocarbon polymer, for example, Japan is used. ZE〇N company's ζΕ〇ΝΕχ or ZEONOR (norbornene resin), Sumitomo's SUMILITEFS-1700, jSR company's art〇n (modified borneol thin resin)' Mitsui Chemicals 8n AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP AP The tree stagnation is a substitute substrate of acetyl cellulose, and the Asahi Kasei Chemical Corporation, the FV system 低 (low birefringence, low photoelastic modulus film) is also preferably used as the thickness of the light transmissive substrate, preferably Bu Bujia is the lower limit of 9 η 妒 妒 妒 , , , , , , , , , , , , , , , 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限 上限When the above-mentioned hard coat layer or the like is formed thereon, in order to improve adhesion, in addition to corona discharge treatment, In addition to the physical treatment such as chemical treatment, coating of a coating called a tackifier or a primer may be carried out in advance. The structure of the hard coat layer is formed between the light-transmitting substrate and the low refractive index layer. The antireflection film of the present invention may further comprise a structure in which an antistatic layer composed of a known antistatic agent and an adhesive resin is formed between the hard coat layer and the photosensitive substrate. Further, the antireflection film of the present invention. If necessary, it may be any other hard coat layer, anti-contamination layer, high refractive index layer, medium refractive index layer or the like which is different from the hard coat layer as an optional layer. The anti-fouling layer, the high refractive index layer, The intermediate refractive index layer can be prepared by adding a composition containing a commonly used antifouling agent, a high refractive index agent, a medium refractive index agent, a low refractive index agent, a resin, or the like, and each layer is formed by a known method. The total light transmittance is preferably 9% or more. If it is less than 90%, there is a possibility that the color is relinearized or visually recognized when it is mounted on the surface of the display. The total light transmittance is preferably Μ. More than % and further preferably 95% The anti-reflection film of the present invention preferably has a haze of less than about 5%, more preferably less than 0.5%. As a method for producing the antireflection film of the present invention, the above method is applied to a light-transmitting substrate. a step of forming a hard coat layer by using a composition for a hard coat layer and a step of applying a composition for the low refractive index layer on the formed hard coat layer to form a low refractive index, as a method of forming the hard coat layer and The method of the low refractive index layer is as described above. 29 201245756 The antireflection film of the present invention is provided by the present invention on the surface of the polarizing element opposite to the surface on which the low refractive index layer in the antireflection film exists. The polarizing plate can be made into a polarizing plate. The polarizing plate is also one of the inventions. The polarizing element is not particularly limited, and examples thereof include polyethylene which is dyed by iodine or the like and stretched. An alcohol film 'polyethylene formaldehyde film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, or the like. In the lamination treatment of the above polarizing element and the antireflection film of the present invention, it is preferred to subject the light-transmitting substrate (preferably triacetyl cellulose film) to a saponification treatment. By the saponification treatment, the adhesion becomes good, and an antistatic effect can also be obtained. The present invention may be an image display device comprising the antireflection film or the polarizing plate. The image display device may be an image display device such as an LCD, a pDp, an eld (organic EL, an inorganic EL), a CRT, a touch panel, a flat panel, or an electronic paper. The LCD has a transmissive display and is illuminating from the back. The light source device is not the body. In the case where the image display device of the present invention is an LCD, the antireflection film of the present invention or the polarizing plate of the present invention is formed on the surface of the transparent display body. In the case where the present invention is a liquid crystal display device having the above antireflection film, the light source of the temple light source device is irradiated from the lower side of the optical laminate. Further, in the STN type liquid crystal display device, a phase difference plate can also be inserted into the liquid crystal display element and the polarized light 1. An adhesive layer may be provided between the layers of the liquid crystal display device as needed. 30 201245756 * The PDP is provided with a surface glass substrate (the surface forming electrode is wider than the back glass substrate in which the discharge gas is sealed between the surface glass substrate (the electrode is formed on the surface and the minute groove is formed in the groove). When the image display device of the present invention is pdp, the surface of the surface glass substrate or the front panel (glass substrate or film substrate) thereof is provided. The image display device may be an ELD device that performs vapor deposition on a glass substrate, such as a vulcanization or a diamine-based substance that emits light when a voltage is applied, and controls display of a voltage applied to the substrate. Or an image display device such as a CRT that converts an electrical signal into light and produces an image visible to the human eye. In this case, the anti-reflection film is provided on the outer surface of each of the display devices as described above or on the surface of the front panel thereof. The image display device of the present invention can be used for display display of televisions, computers, word processors, etc., in any case. Good for use in the surface of displays for high-definition images such as CRT, touch panel, tablet pc, electronic paper, liquid crystal panel, pDp, ELD, FED, etc. [Effects of the Invention] In the antireflection film of the present invention, low refractive index The layer has reactive rare earth oxide particles in the vicinity of the surface thereof, whereby the surface hardness is excellent. Further, in the antireflection film of the prior art, fine irregularities are present on the surface of the low refractive index layer, which causes One of the causes of poor scratch resistance, but in the low refractive index layer of the above-mentioned structure, the hollow oxidized fine particles are in a state of being closely packed, and thus have an extremely uniform surface. Therefore, the antireflection film of the present invention becomes a surface hardness. Further, in the antireflection 31 201245756 film of the present invention, the 'low refractive index layer is mainly composed of the above hollow cerium oxide microparticles and reactive oxidized cerium oxide microparticles, so that the refractive index can be sufficiently low. The antireflection film of the present invention is excellent in antireflection properties. Therefore, the antireflection film of the present invention can be preferably used for a cathode ray tube display device. CRT), liquid crystal display (LCD), plasma display (pdp), electroluminescent display (ELD), field emission display (FEI), touch panel, tablet PC, electronic paper, etc. [Embodiment] The following examples illustrate the contents of the present invention, but the contents of the present invention are not limited to those explained in the embodiments. Unless otherwise stated, "parts" and "%" are quality benchmarks. Further, each component is a solid content component unless otherwise specified. (Preparation of composition (1) for hard coat layer) Each component shown below was mixed to prepare a composition for a hard coat layer (^. Reactive cerium oxide microparticles (Z7537, solid content component manufactured by JSR Corporation, 50%, reaction)二 二 含有 含有 含有 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Parts by mass · mercapto ethyl ketone 3.3 parts by mass of methyl isobutyl ketone 2.3 parts by mass Further, the solid content component of the leveling agent in the composition for hard coat layer (1) 32 201245756 mass ratio is 0.10%. Preparation of Layer Composition (2) A composition for the hard coat layer (2) was prepared by mixing the components shown below. Polyester acrylate (ARONIX M-9050, manufactured by Toagosei Co., Ltd., 3-functional) 5 parts by mass of an amine Urethane acrylate (UV1700B, manufactured by Nippon Synthetic Co., Ltd., 1 〇 functional) 11 parts by mass of a polymerization initiator (Irgacurel 84, manufactured by BASF Corporation) 0.5 parts by mass of mercaptoethyl ketone 10 parts by mass, further, hard coat layer In the composition (2) The mass ratio of the solid content of the flat agent is 0.10%. (Preparation of the composition (3) for hard coat layer) Each component shown below is mixed to prepare a composition (3) for a hard coat layer. Microparticles (Z7537, manufactured by JSR, Solids Knife 50/ί», Reactive Nitric Oxide Microparticles 60%), 4 parts by mass of amino acid styrene acrylate (UV1700B, manufactured by Nippon Synthetic Co., Ltd., 10 functional) 5.7 A part by mass of a polymerization initiator (Irga CUrei 84, manufactured by BASF Corporation) 〇 6 parts by mass of mercaptoethyl ketone 3.3 parts by mass of mercaptoisobutyl ketone 2.3 parts by mass, and a composition for hard coat layer (3) 'τi碉The mass ratio of the solid content of the ten doses was 0.10%. 33 201245756 (Preparation of composition for low refractive index layer (1)) The composition (1) for preparing a low refractive index layer was prepared by mixing the components shown below. Cerium oxide microparticles (the solid content of the hollow ceria microparticles is 20% by mass solution: methyl isobutyl ketone, average particle diameter: 55 nm 'average void ratio: 23.3%) 0.8 parts by mass of pentaerythritol Acrylate (PETA) 0.05 parts by mass Pentaerythritol hexaacrylate (DPHA) 〇. 〇 5 parts by mass of reactive oxidized cerium microparticles (the solid content of the reactive oxidized pulverized microparticles is 30% by mass solution: decyl isobutyl ketone, average particle diameter : 12 nm ) 0_1 mass parts of antifouling agent (X-22-164E, manufactured by Shin-Etsu Chemical Co., Ltd.) 〇〇 1 part by mass of polymerization initiator (lrgacurel27, manufactured by BASF) 〇〇 1 part by mass MIBK 3 parts by mass PGME2 mass Parts (Preparation of Composition (2) for Low Refractive Index Layer) A component (2) for preparing a low refractive index layer was prepared by mixing the components shown below. Hollow-shaped cerium oxide microparticles (the solid content of the hollow cerium oxide microparticles is 20% by mass solution: decyl isobutyl ketone, average particle diameter: 60 nm, average void ratio: 29.6%) 0.8 parts by mass of neodymium Tetrahydrin triacrylate (PETA) 0.1 part by mass of reactive cerium oxide microparticles (the solid content of the reactive cerium oxide microparticle is 30% by mass solution: decyl isobutyl ketone, average particle diameter: 34 201245756 12 nm 0.1 part by mass of antifouling agent (RS-74, manufactured by DIC, 20% by mass solution: methyl ethyl ketone) 0.01 part by mass of antifouling agent (TU2225, manufactured by JSR Corporation) 15% by mass solution: mercaptoisobutyl Ketone) 0,01 parts by mass of a polymerization initiator (Irgacurel 27, manufactured by BASF Corporation) 〇 1 part by mass of MIBK 3 parts by mass of PGME 2 parts by mass (preparation of composition for low refractive index layer (3)) A composition (3) for a low refractive index layer was prepared. Hollow-shaped silica dioxide granules (the solid content of the hollow zirconia granules is 20% by mass solution: methyl isobutyl ketone, average particle diameter: 55 nm, average void ratio: 23.3%) 0.8 parts by mass Neopentyl alcohol triacrylate (PETA) 0_08 parts by mass of dipentaerythritol hexaacrylate (DPHA) 〇·〇 8 parts by mass of reactive dioxygen microparticles (the solid content of the reducing dioxygen microparticles is 30) Mass % solution: decyl isobutyl ketone, average particle diameter: 12 nm) 0.1 part by mass of an antifouling agent (X-22-164E, manufactured by Shin-Etsu Chemical Co., Ltd.) Amount of polymerization initiator (Irgaeurel 27, manufactured by BASF Corporation). MIBK 3 parts by mass 35 201245756 PGME 2 parts by mass (preparation of composition for low refractive index layer (4)) The composition (4) for the low refractive index layer was prepared by mixing the components shown below. Hollow cerium oxide microparticles (this) The solid content of the hollow cerium oxide microparticles is 2 G mass% solution: decyl isobutyl ketone, average particle diameter: 60 nm 'average void ratio: 29 6%) 〇 8 parts by mass of pentaerythritol triacrylate ( PETA) 0.17 parts by mass of reactive dioxide矽Microparticles (the solid content of the reactive cerium oxide microparticles is 30% by mass solution: methyl isobutyl ketone, average particle diameter: 12 nm) 0.2 parts by mass of antifouling agent (RS-74, manufactured by DIC Corporation, 20 Mass % solution: methyl ethyl ketone) 0.01 parts by mass of antifouling agent (TU2225, manufactured by JSR, 15 mass 0 / 〇 solution: mercapto isobutyl ketone) 0. 01 parts by mass of polymerization initiator (lrgacure 127, BASF (manufactured by the company) 〇〇1 part by mass of MIBK, 3 parts by mass of PGME, 2 parts by mass (preparation of composition for low refractive index layer (5)) The composition shown below is prepared by mixing the components shown below to prepare a composition (5) for a low refractive index layer. Cerium oxide microparticles (the solid content of the hollow ceria microparticles is 20% by mass solution: methyl isobutyl _, average particle diameter: 60 nm, average void ratio: 29.6%) 0.8 parts by mass of pentaerythritol Acrylate (PETA) 0.1 parts by mass 36 201245756 Reactive cerium oxide microparticles (the solid content of the reactive cerium oxide microparticles is 30% by mass solution: methyl isobutyl ketone, average particle diameter: 12 nm) 0.02 mass Antifouling agent (RS-74, DIC) Manufacture, 20% by mass solution: methyl ethyl ketone) 0.01 parts by mass of antifouling agent (TU2225, manufactured by JSR Corporation, 15% by mass solution: methyl isobutyl ketone) 0.01 parts by mass of polymerization initiator (Irgacurel 27, BASF Corporation (manufactured) 〇. 〇 1 part by mass of MIBK 3 parts by mass of PGME 2 parts by mass (preparation of composition (6) for low refractive index layer) The component (6) for the low refractive index layer was prepared by mixing the components shown below. Hollow cerium oxide microparticles (the solid content of the hollow cerium oxide microparticles is 20% by mass solution: methyl isobutyl ketone, average particle diameter: 5 5 nm 'average void ratio: 23 3%) 〇 8 mass Pentaerythritol triacrylate (ΡΕΤΑ) 〇·〇 5 parts by mass of dipentaerythritol hexaacrylate (DPHA) 0.05 parts by mass of reactive cerium oxide microparticles (the solid component of the reactive cerium oxide microparticles is 30% by mass solution: methyl isobutyl ketone, average particle diameter: 12 nm) 0.1 part by mass of antifouling agent (RS-74, manufactured by DIC Corporation, 20% by mass solution: mercaptoethyl ketone) 0.01 part by mass of antifouling Agent (TU2225, manufactured by JSR, 15% by mass solution: A 37 201245756 isobutyl ketone) ο·οι mass part polymerization initiator (Irgacurel 27, manufactured by BASF Corporation) 〇〇 1 part by mass MIBK 4 parts by mass PGMEA 1 part by mass ( Preparation of Composition (7) for Low Refractive Index Layer) A component (7) for a low refractive index layer was prepared by mixing the components shown below. Hollow cerium oxide microparticles (the solid content of the hollow cerium oxide microparticles is 20% by mass solution: methyl isobutyl ketone, average particle diameter: 60 nm 'average void ratio: 29 6%) 〇 8 parts by mass Neopentyl alcohol triacrylate (PETA) 2. 2 parts by mass of reactive oxidized cerium microparticles (the reactive solid dioxide component of the solar oxidized microparticles is 30% by mass solution: methyl isobutyl ketone, average particle Diameter: 12 nm) 0.1 part by mass of antifouling agent (RS-74, manufactured by DIC, 20% by mass solution: methyl ethyl ketone) 0_01 parts by mass of antifouling agent (TU2225, manufactured by JSR, 15% by mass solution: 曱Isobutyl ketone) 〇. 〇 1 part by mass of a polymerization initiator (Irgacure 127, manufactured by BASF Corporation) 〇·〇ι parts by mass ΜΙΒΚ 3 parts by mass of PGME 2 parts by mass (preparation of composition for low refractive index layer (8)) A composition (8) for a low refractive index layer was prepared as shown below. 38 201245756 Hollow ceria particles (the solid content of the hollow ceria particles is 20 mass. /〇 solution: methyl isobutyl ketone, average particle size: 60 nm 'average void ratio: 29.6%) 0.8 Parts by mass of pentaerythritol triacrylate (PETA) 0.1 parts by mass of reactive cerium oxide microparticles (the solid content of the reactive cerium oxide microparticles is 30% by mass solution: methyl isobutyl ketone, average particle diameter: 12 nm) 0.25 parts by mass of antifouling agent (RS-74, manufactured by DIC, 20% by mass solution: methyl ethyl ketone) 0.01 parts by mass of antifouling agent (TU2225, manufactured by JSR, 15% by mass solution: methyl Butyl ketone) 〇. 〇 1 part by mass of a polymerization initiator (Irgacurel 27, manufactured by BASF Corporation) 〇〇1 mass fraction of M1BK 3 parts by mass of PGME 2 parts by mass (preparation of composition for low refractive index layer (9)) A composition (9) for a low refractive index layer was prepared as shown below. Hollow-shaped white oxide fine particles (the hollow-shaped silica dioxide solid particles composition is 20% by mass solution: methyl isobutyl, average particle scale. 60 nm, average void ratio: 29.6%) 〇·8 mass Parts/diameter. Pentaerythritol triacrylate (ΡΕΤΑ) 〇. 1 part by mass, reactive dioxygen microparticles (compared to pure dioxate microsolids component of 30 mass. /0 solution: thiol iso 12 nm) 0.22 Amount of isobutyl ketone, average particle size: 39 201245756 Anti-fouling agent (RS-74 'Manufactured by DIC Corporation' 20% by mass solution: mercaptoethyl ketone) 0.01 parts by mass of antifouling agent (TU2225, manufactured by JSR Corporation, 15 mass% solution: methyl isobutyl ketone) hydrazine, hydrazine 1 part by mass of a polymerization initiator (lrgacurel 27, manufactured by BASF Corporation) 〇〇 1 part by mass MIBK 3 parts by mass PGME 2 parts by mass (a composition for a low refractive index layer (i Preparation of 〇)) A composition for a low refractive index layer (1 Å) was prepared by mixing the components shown below. Hollow cerium oxide microparticles (the solid content of the hollow cerium oxide microparticles is 20% by mass solution: decyl isobutyl ketone, average particle diameter: 60 nm 'average void ratio: 29.6%) 0.8 parts by mass of new pentylene Tetrahydrin triacrylate (PETA) 0.1 part by mass of reactive dioxygen fine particles (the reactive disulfide fine particles solid component is 30% by mass solution: mercaptoisobutyl ketone, average large diameter. 12 nm) 0.01 parts by mass of antifouling agent (RS-74, manufactured by DIC Corporation, 20% by mass solution: methyl ethyl ketone) 0.01 parts by mass of antifouling agent (TU2225 'manufactured by JSR Corporation' 15% by mass solution. Methyl isobutyl ketone 0.01 parts by mass of a polymerization initiator (Irgacurel 27, manufactured by BASF Corporation) 〇〇1 mass MI part MIBK 3 parts by mass 40 201245756 PGME 2 parts by mass (preparation of composition for low refractive index layer (11)) The components shown below are mixed, A composition (ii) for a low refractive index layer was prepared. Medium jade-like nitric oxide granules (the solid content of the hollow-shaped cerium oxide granules is 20% by mass solution: methyl isobutyl ketone, average particle diameter: 55 nm, average void ratio: 23.3%) 0.8 mass Pentaerythritol triacrylate (PETA) 0.05 parts by mass of dipentaerythritol hexaacrylate (DPHA) 0.05 parts by mass of reactive cerium oxide microparticles (the solid content of the reactive oxidized fine particles is 30 Mass% solution: mercaptoisobutyl ketone, average particle size: 12 nm) 0.1 mass part of anti-/depletion agent (RS·74, manufactured by DIC, 20 mass 〇/0 solution: mercapto ethyl ketone 1) 0.01 mass Antifouling agent (TU2225 'manufactured by JSR, 15% by mass solution: methyl isobutyl ketone) 0.01 parts by mass of t-starting agent (Irgacurel 27, manufactured by BASF Corporation) 〇. 1 part by mass of MIBK 1 part by mass of MEK 4 parts by mass (Example 1) A composition for a hard coat layer (1) was applied to one side of a cellulose diacetate film (thickness 8 〇M m ) to have a wet weight of 30 g/m 2 (dry weight of 15 g/m 2 ). It was dried at 50 C for 30 seconds and irradiated with ultraviolet rays of 50 mJ/cm 2 to form a hard coat layer. And then 'dry on the hard coating formed (25. (: x30 seconds ~ 70 201245756

The composition (1) for the low refractive index layer was applied in such a manner that the film thickness after Cx3 〇 second was 0.1 / zm. In addition, the ultraviolet ray irradiation device (manufactured by Fusi〇n UV System Japan Co., Ltd., light source η valve) is irradiated with ultraviolet rays at an irradiation dose of 192 mJ/m 2 to obtain an anti-reflection film. The film thickness is extremely small at a reflectance. Adjust by the way around the wavelength of 5 50 nm. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow zirconia particles to the (fluorenyl) acrylate resin (the content of the hollow cerium oxide microparticles / (meth)acrylic acid The content of the resin was 1 (Example 2) An antireflection film was obtained in the same manner as in Example 1 except that the composition (2) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer. . In the low refractive index layer of the obtained antireflection film, the ratio of the hollow cerium oxide microparticles to the (meth)acrylic resin (the content of the hollow cerium oxide microparticles / (meth)acrylic resin) The content) is 16 〇. (Example 3) The composition for hard coating layer (2) was applied to one side of a cellulose diacetate film (thickness 80 // m) to have a wet weight of 30 g/m 2 (dry weight of 15 g/m 2 ). An anti-reflection film was obtained in the same manner as in Example 1 except that a hard coat layer was formed, and then a low refractive index layer was formed on the formed hard coat layer using the low refractive index layer composition (2). (Example 4) An antireflection film 42 201245756 Λ film was obtained in the same manner as in Example 使用 except that the composition (3) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow cerium oxide microparticles to the (fluorenyl) acrylate resin (the content of the hollow cerium oxide microparticles / (fluorenyl) acrylic resin The content) is 1 〇〇. (Example 5) An antireflection film was obtained in the same manner as in Example 1 except that the composition (4) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow cerium oxide microparticles to the (fluorenyl) acrylate resin (the content of the hollow cerium oxide microparticles / (fluorenyl) acrylic resin The content) is 〇94. (Example 6) An antireflection film was obtained in the same manner as in Example 使用 except that the composition (5) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow cerium oxide microparticles to the (fluorenyl) acrylate resin (the content of the hollow cerium oxide microparticles / (fluorenyl) acrylic resin The content) is 16 〇. (Example 7) A composition for hard coating layer (3) was applied to one side of a cellulose triacetate film (thickness of 8 Å in m) to have a wet weight of 30 g/m 2 (dry weight: 15 g/m 2 ) to form a hard An antireflection film was obtained in the same manner as in Example 1 except that the coating layer was used to form a low refractive index layer on the formed hard coat layer using the low refractive index layer composition (2). 43 201245756 (Example 8) An antireflection film was obtained in the same manner as in Example " except that the composition (6) for the low refractive index layer was used instead of the composition (1)' for the low refractive index layer. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow cerium oxide microparticles to the (meth)acrylic resin (the content of the hollow cerium oxide microparticles / (mercapto) acrylic resin) The content) is 16 〇. (Comparative Example 1) The low refractive index layer composition (1) was used instead of the low refractive index layer composition (1), and the low refractive index layer composition (?1) was dried at 120 °C. An antireflection film was obtained in the same manner as in Example i except that a low refractive index layer was formed in 1 minute. (Comparative Example 2) A composition for low refractive index layer (丨2) having the same composition as that of the composition (1) for a low refractive index layer other than the reactive cerium oxide microparticles was used, and the low refractive index layer was used. An antireflection film was obtained in the same manner as in Example 1 except for the composition (12). (Comparative Example 3) In the composition (1) for a low refractive index layer, the reactive cerium oxide fine particles are cerium oxide fine particles having a surface having no reactive functional groups (MEK-ST 'Medical Chemical Industry Co., Ltd.) An antireflection film was obtained in the same manner as in Example 1 except that the composition for low refractive index layer (13) was used to prepare the composition for low refractive index layer (Ref. 3) (Reference Example 1) 201245756 An antireflection film was obtained in the same manner as in Example 除 except that the composition (1) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow zirconia particles to the (fluorenyl) acrylic resin (the content of the hollow zirconia particles / (meth) acrylate The content of the resin is 〇8〇. (Reference Example 2) An antireflection film was obtained in the same manner as in Example 1 except that the composition (8) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow silica dioxide particles to the (fluorenyl) acrylic resin (the content of the hollow cerium oxide microparticles / (mercapto) acrylic) The content of the resin was 1.60. Further, the content of the reactive ceria fine particles in the low refractive index layer was 75 parts by mass based on 10 parts by mass of the (fluorenyl) acrylic resin. (Reference Example 3) The composition (1) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer, and other examples were used! An antireflection film was obtained in the same manner. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow zirconia particles to the (meth)acrylic resin (the content of the hollow cerium oxide microparticles / (meth)acrylic acid) The content of the resin was 1.60. In addition, the content of the reactive cerium oxide fine particles in the low refractive index layer is 65 parts by mass based on 00 parts by mass of the (meth)acrylic resin. (Reference Example 4) 45 201245756 An antireflection film was obtained in the same manner as in Example 除 except that the composition (10) for the low refractive index layer was used instead of the composition (1) for the low refractive index layer. In the low refractive index layer of the obtained antireflection film, the ratio of the hollow zirconia particles to the (meth)acrylic resin (the content of the hollow zirconia particles/(meth)acrylic acid) The content of the resin is 1.60. The content of the reactive cerium oxide microparticles in the low refractive index layer is 3 parts by mass based on 100 parts by mass of the (meth)acrylic resin. (Evaluation) The respective evaluations shown below were carried out for the antireflection films obtained in the examples and the comparative examples. The results are shown in Table 1. (Measurement of reflectance) The black tape of the back surface of each of the obtained anti-reflection films is prevented from being adhered to the surface of the low refractive index layer, and the spectral reflectance measuring machine "MCP3100" manufactured by Shimadzu Corporation is used to measure the wavelength band 380. 5° positive reflection Y value in ~780 nm. The results were evaluated on the basis of the following criteria ^5. The specular reflection gamma value was measured in the wavelength range of 380 to 780 nm. The regular reflectance, and thereafter, the value expressed by the visual reflectance calculated by the software for calculating the brightness perceived by the human eye (built in the MCP3 100). Evaluation standard 〇: 5° positive reflection Y value is less than 1.5% X : 5° positive reflection Y value is 1.5% or more (scratch resistance) Steel wool with #〇〇〇〇, with a specified friction load of 300 g/ Cm2 46 201245756 The surface of the low refractive index layer of the antireflection film obtained in the examples and the comparative examples was rubbed for 10 times. Then, the coating film was visually observed for peeling, and the results were evaluated by the following criteria. ◎: no scars: slightly injured X: wounded (anti-staining property) After attaching the fingerprint to the surface of the antireflection film obtained in the examples and the comparative examples, Kimwipe (registered trademark) manufactured by Nippon Paper Paper CRECIA Co., Ltd. was The load of 150 g/cm2 was rubbed back and forth 30 times, and the black tape was pasted, and the rubbing property (residence of the fingerprint) was evaluated by visual inspection under the fluorescent light according to the following criteria. ◎ 'The fingerprint is not left 〇··The fingerprint is slightly residual X: The fingerprint remains 47 201245756 vg Μ Μ tn 〇§π Left 荃 £ 芸Μ 芸Μ V0 V0 V0 V0 V0 V0 叫 v§ V0 shouting and Lingling Ridge Ridge ^ Φ 岭岭4 Η" 荃荃WU leather extract V0 grass 5 leather V0 extract €: leather extraction ε e ε Μ 〇§〇要要要要要要要要· Butterfly· δ3 Qgm Djn leather {$〇萃茶〇^〇钿m Sword and sword like 1 Right and right Ί LfilJ W tfhi w 蜊b xsaJ w \〇xJ vp> / ^hJ w 铽硪i£lJ w 硪铼朱\B^J Zhu Zhu竦t埂牮竣1 Μ ±! k 〇〇◎ 〇〇〇〇〇X 〇〇〇XXX ◎ ◎ 〇〇 ◎ 〇〇〇XXX 〇XXX 跻〇〇〇〇 〇〇〇〇〇〇X hacker W. 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201245756 (Sectional observation of the low refractive index layer) The antireflection film obtained in the examples and the comparative examples in the thickness direction (4) was observed by STEM (applied voltage: 3 〇〇 kv, magnification: 2 million times). The results of Example 1 are shown in Fig. 1, the results of Example 7 are shown in Fig. 2, the results of Comparative Example 1 are shown in Fig. 3, and the results of Comparative Example 2 are shown in Fig. 4. Further, the antireflection film obtained in the 'Comparative Example' was formed into a vapor deposition layer having a thickness of about 15 carbons when observed in a cross section. Further, in the lower right of Figs. 1 to 4, the scale 1 indicates the scale of 20_. It is confirmed from FIGS. 1 and 2 that in the antireflection film of Example 1, the reactive silica fine particles are biased to the vicinity of the interface of the low refractive index layer opposite to the hard coat layer, and further, the antireflection of Example 7. In the film, the reactive smectite particles are in the vicinity of the interface on the hard coat side of the low refractive index layer and in the vicinity of the interface with the side of the hard coat layer, and both of the hollow oxy-cut particles are intimately filled. In the state, the surface of the low refractive index layer is in an extremely uniform state. Further, although not shown in the drawings, it was confirmed that in the antireflection film of Example 3, the reactive cerium oxide microparticles were in the vicinity of the interface on the hard coat layer side of the low refractive index layer, and the work of the cerium oxide microparticles was also tight. In the filled state, the surface of the low refractive index layer is in an extremely uniform state. Further, although not shown in the drawings, it was confirmed that in the antireflection films of Examples 2, 4 to 6, and 8, the reactive silica fine particles were all biased to the vicinity of the interface of the low refractive index layer on the opposite side to the hard coat layer. The hollow-shaped silica dioxide particles are also in a state of close filling, and the surface of the low refractive index layer is extremely uniform. Further, it has been found that the antireflection film of the examples has sufficient antifouling properties, antireflection properties and scratch resistance. 49 201245756 Further, as a result of the examples, the scratch resistance was optimized in the following cases. In the case where the reactive cerium oxide microparticles are biased on the opposite side of the low refractive index layer from the hard coat layer, and the amount of reactive cerium oxide microparticles present in a biased manner is optimal (relative to the (fluorenyl) acrylic resin 丨〇 〇 mass parts are more than 3 parts by mass). In the case where the hard coat layer contains reactive cerium oxide fine particles, the layer which becomes the underlayer of the low refractive index layer (translucent substrate and hard coat layer) has a high hardness as a whole. Further, it is found that the antifouling property is optimized when the reactive cerium oxide fine particles are biased to the hard coat layer side of the low refractive index layer, and it is presumed that there is no reaction on the outermost surface of the low refractive index layer. The cerium oxide microparticles are such that the antifouling agent itself easily comes to the surface of the low refractive index layer, and the antifouling agent is present on the entire outermost surface of the low refractive index layer. On the other hand, as shown in Fig. 3, in the antireflection film of Comparative Example, the reactive silica fine particles were dispersed throughout the low refractive index layer, and the hard coat layer biased to the low refractive index layer was not confirmed. The side of the side or the reactive cerium oxide microparticles near the interface opposite the hard coat layer, and the surface thereof is also uneven. 1 It is presumed that the reason is that the solvent or drying conditions used are not appropriate and the drying speed is fast. Further, the antireflection film of Comparative Example 1 was also inferior in antifouling property. Further, as shown in FIG. 4, in the antireflection film of Comparative Example 2, although the hollow cerium oxide microparticles were in a state of being closely packed and the surface was uniform, since no reactive cerium oxide microparticles were contained in the low refractive index layer. 'So the financial scratch is poor. Further, although not illustrated, in the antireflection film of Comparative Example 3, although the hollow cerium oxide microparticles of 201245756 are in a state of being closely packed and the surface is uniform, since the low refractive index layer contains a non-reactive functional group. Based on the cerium oxide microparticles, the scratch resistance is poor. Further, in the antireflection film of Reference Example 1, the ratio of the hollow cerium oxide microparticles of the (fluorenyl)acrylic resin to the low refractive index layer was small, and the antireflection property was inferior. In the antireflection film of Reference Examples 2 and 3, the content of the reactive cerium oxide microparticles in the low refractive index layer is large, and the bias of the reactive oxidized cerium microparticles is insufficient, and is dispersed in the low refractive index layer. In the middle of the process, the hollow cerium oxide microparticles are not in a state of close filling, and the scratch resistance and the antifouling property are inferior. Moreover, in the anti-reflection film of the reference 4, the content of the reactive oxidized cerium particles in the low refractive index layer is small, and the bias of the reactive cerium oxide microparticles is insufficient, and is dispersed in the low refractive index layer. In all cases, the hollow cerium oxide fine particles are not in a state of being closely packed, and the scratch resistance and the antifouling property are inferior. [Industrial Applicability] The antireflection film of the present invention has an excellent antireflection property and surface hardness because it has a low refractive index layer composed of the above configuration. Therefore, the antireflection film of the present invention can be preferably applied to a cathode ray tube display device (CRT), a liquid crystal display (LGD), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED). , touch panel, tablet pc, electronic paper, etc. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photomicrograph of a cross section of an antireflection film of Example 1. 2 is a photomicrograph of a cross section of the antireflection film of Example 7. 201245756 FIG. 3 is a photomicrograph of a cross section of the antireflection film of Comparative Example 1. 4 is a photomicrograph of a cross section of the antireflection film of Comparative Example 2. [Main component symbol description] None 52

Claims (1)

201245756 * VII. Patent application scope: 1. An anti-reflection film is formed on a light-transmitting substrate to form a hard coating layer and a low refractive index layer is formed on the hard coating layer, wherein the low refractive index layer contains a (meth)acrylic resin, hollow cerium oxide microparticles, reactive cerium oxide microparticles, and an antifouling agent, and the reactive cerium oxide microparticles in the low refractive index layer are biased near the interface of the hard coat layer side And/or near the interface on the opposite side of the hard coat layer. 2. The antireflection film of claim 1, wherein the reactive smectite particles in the low refractive index layer are biased near the interface on the side opposite to the side of the hard coat layer, the hard coat layer being at the low refractive index Near the interface on the rate layer side, there are reactive cerium oxide microparticles arranged neatly along the interface direction. 3. The antireflection film according to claim 1 or 2, wherein the content of the reactive cerium oxide microparticles in the low refractive index layer is 1.0 part by mass relative to the (fluorenyl) acrylic resin. , for 5 to 6 〇 by mass. 4. The anti-reflection film of the second, third or third aspect of the patent application, wherein the average particle diameter of the hollow-shaped oxidized fine particles is 40 to 80 nm, and further relative to the (fluorenyl) acrylic resin. The blending ratio (the content of the hollow cerium oxide microparticles / the content of the (meth)acrylic resin) is 〇9 〇 to 1.60. 5. The antireflection film of claim 2, 2, 3 or 4, wherein the antifouling agent is biased near the interface of the low refractive index layer opposite to the hard coat layer. 6. For anti-reflection film of the scope of the patent, the second item, the third item, the fourth item or the fifth item, wherein the antifouling agent contains a reactive functional group, 53 201245756 and the atom and/or The compound of Shi Xi atom. 7. For the patent application, item 1, item 2, item 3, item 4, item 5 or item 6 of the antireflection film, wherein the (meth)acrylic resin is selected from the group consisting of neopentyl alcohol Tris(fluorenyl) acrylate, dipentaerythritol hexa(indenyl) acrylate, neopentyltetrakis(mercapto) acrylate, dipentaerythritol quinone (mercapto) propylene S 夂曰, 曱 曱 丙 丙 丙 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 之 之 之 之 之 之 之 之 之 之 之 之A polymer or copolymer of at least one monomer. 8. For anti-reflection film of claim 1, item 1, item 3, item 4, item 5, item 6, or item 7, wherein the low refractive index layer further contains a fluorine atom Resin. 9. For the anti-reflection film of claim 1, item 1, item 3, item 4, item 5, item 6, item 7, or item 8, wherein the reaction in the hard coat layer The content of the cerium oxide fine particles is 15 to 60 parts by mass based on 100 parts by mass of the (fluorenyl) acrylic resin. The polarizing plate of the 10th type is provided with a polarizing element, and the polarizing plate has the first, second, third, fourth, fifth, and sixth patent claims on the surface of the polarizing element. Item, item 7, item 8, or item 9 of the antireflective film. 11. Anti-reflection of the 1st, 2nd, 3rd, 4th, 5th, 6th, 7th, 8th or 9th item of the 1 π-rq target Film or polarizing plate 54 of the scope of patent application