TW200921141A - Antireflection film, polarizer, display, and process for producing antireflection film - Google Patents

Abstract

An antireflection film which comprises a transparent support and one or more layers formed thereon including an antireflection layer, characterized in that it has, as an outermost layer, a low-refractive-index layer comprising hollow silica particles and a silicone and having a refractive index of 1.20-1.49 and that the hollow silica particles are contained in an amount of 30-80 mass% based on the solid components. The antireflection film is further characterized in that when the film is examined by X-ray photoelectron spectroscopy, that average proportion of the Si-C bond peak intensity (Ros) for the depth range of from the outermost surface to a depth of 5 nm which is represented by the following equation (A) is 0.40 or higher and the average proportion of the Si-C bond peak intensity (Rot) for the range of from the outermost surface to a depth of 10-25 nm is 0.0005 to 0.10. Equation (A): (Proportion of Si-C bond peak intensity) = (Si-C bond peak intensity)/{(Si-C bond peak intensity)+(Si-O bond peak intensity)}

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film, and more particularly to an antireflection film which is excellent in scratch resistance, low in reflectivity, and excellent in visibility when used in a display device. [Prior Art] In an antireflection film used for the outermost surface of an image display device such as a liquid crystal, a technique in which an antireflection layer of an optical interference type is provided to form a low reflectance is proposed. As for the technique for lowering the reflectance, there is a method of lowering the refractive index of the outermost layer. Therefore, it has been proposed to use a low refractive index material in the outermost layer or to increase the refractive index by increasing the void. However, the film strength and the scratch resistance are disadvantageous. In order to directly maintain the film strength and reduce the refractive index due to the voids, it is further proposed to use an anthrone. Technology (for example, refer to Patent Document 1). However, in the low refractive index layer containing 20% by mass or more of the hollow cerium oxide particles in the solid content, the antifouling property contributed by the fluorenone is lowered. Therefore, the fluorenone is additionally added to adjust the relationship between the film strength and the antifouling property. Further, in addition to the deterioration of the strength of the film in the cerium oxide having a reactive base having high stain resistance, aggregation may easily occur. Further, the antireflection film can be used for versatility, and further improvement in film strength and stain resistance can be sought. -4 - 200921141 A method of forming a low refractive index layer by a sol-gel method using a film of a metal oxide is known as a method for improving the film strength (see Patent Document 2). Further, a technique of treating a hollow particle with a decane coupling agent using a fluorine-based resin as a binder component has been disclosed (for example, see Patent Document 3). However, even if such a method is combined, it is impossible to achieve a low refractive index and to satisfy the film strength and the antifouling property. Patent Document 1: JP-A-2002-79616 Patent Document 2: JP-A-2000-9 No. PCT Patent Publication No. JP-A No. 2000-119 SUMMARY OF THE INVENTION An object of the present invention is to provide an antireflection film which is excellent in scratch resistance, excellent in stain resistance, low in reflectance, and excellent in visibility when used in a display device. An aspect of the present invention for achieving the above object is an antireflection film having at least an antireflection layer on a transparent support, characterized in that it has at least a hollow cerium oxide particle and an anthrone at the outermost surface. a low refractive index layer having a refractive index of 1.20 to 1.49, wherein the hollow cerium oxide particle has a solid content of 30 to 80% by mass, and is determined by an X-ray photoelectron spectroscopy apparatus from the outermost surface to a depth of 5 nm. The average 値Ros of the Si-C bond peak intensity ratio represented by the formula (A) is 0.40 or more, and the average 値Rot of the Si-C bond peak intensity ratio in the most surface to depth 10 to 25 nm is 0.0005 to 0. . 1 0. 200921141 Formula (A) (Si-C bond peak intensity ratio) = (Si-C bond peak intensity) / {(Si-C bond peak intensity) + (Si-0 bond peak intensity)} Aspects of the Invention The above problems of the present invention are achieved by the following constitution. (1) An antireflection film which has at least an antireflection layer on a transparent support, and has a refractive index of at least 1 · 2 0 to 1 on the outermost surface including at least hollow cerium oxide particles and anthrone; a low refractive index layer of 49, the solid content of the hollow cerium oxide particle is 30 to 80% by mass, and is determined by an X-ray photoelectron spectroscopy apparatus from a surface to a depth of 5 nm and is represented by the following formula (A) The average 値R〇s of the Si-C bond peak intensity ratio shown is 0.40 or more' and the average 値Rot of the Si-C bond peak intensity ratio in the most surface to depth 1 〇 to 25 nm is 0.0005 to 0.10. Formula (A) (Si-C bond peak intensity ratio) = (Si-C bond peak intensity) / {(S i - C bond peak intensity) + (S i _ 〇 bond peak intensity)} (2 The antireflection film according to the above item (a), wherein the antireflection film has a hard coat layer (3) between the transparent support and the antireflection layer as described above (; [) or (2) The antireflection film, wherein the low refractive index layer is a condensate containing an organodecane represented by the following formula (1); and the formula (1) si(xi) 4, XI represents an alkoxy group. 200921141 (4) A method for producing an antireflection film, which comprises: a step of forming a high refractive index layer on a support, and an antireflection of the above (3) in a step of forming a low refractive index layer on the refractive index of the quotient The film forming method is characterized in that the low refractive index layer is formed by drying a coating liquid obtained by applying the coating step, and is hydrolyzed by an organic decane of the following formula (1) to have a weight average molecular weight of 500 Å. The step of lowering the condensate; mixing the hollow disulfide in the low condensate to further continue the steps of hydrolysis and condensation. (5) The method for producing an antireflection film according to the above (4), wherein the low condensate is mixed with hollow ceria and further hydrolyzed, and the organic decane represented by the formula (2) is mixed; 2) (R) mSi(X2)4-m R represents an organic group which is not hydrolyzed, X2 represents an alkoxy group, and m represents an integer. (6) The method of the antireflection film of the above (4) or (5) wherein the step of forming the aforementioned high refractive index layer has a step of forming a hard. (7) The method for producing an antireflection film according to the above (6), wherein the surface of the transparent support or the hard coat layer is formed into an uneven shape to prevent glare. (8) The antireflection thin manufacturing method according to any one of the above items (4) to (7) wherein, after the step of forming the low refractive index layer, the step of: winding the antireflection film in a roll shape And the step of heat-treating at a temperature of 50 to 160 ° C in a state in which the film is formed by a step of 1 to 4 in a step of 1 to 4 in which the film is formed in a roll-like state. . (9) A polarizing plate characterized by using the antireflection film according to any one of the above items (1) to (3). (10) The polarizing plate according to the above (9), wherein the anti-reflection film has anti-glare property. (11) A display device using the antireflection film according to any one of the above (1) to (3). (12) The display device according to the above (11), wherein the antireflection film has anti-glare property. The present invention provides an antireflection film, and more particularly to an antireflection film which is excellent in scratch resistance, low in reflectivity, and excellent in visibility when used in a display device. Hereinafter, the best mode for carrying out the invention will be described in detail, but the invention is not limited thereto. Conventionally, in order to reduce the reflectance, there is a technique of using hollow cerium oxide particles in a low refractive index layer. However, in this technique, it is necessary to further increase the content of hollow cerium oxide particles in order to reduce the reflectance. Generally, the surface of the display device is prevented from adhering to contamination, and an antifouling agent such as anthrone is used. However, if particles such as hollow ceria or colloidal ceria are added, the phenomenon of deterioration of the antifouling property occurs. The present inventors have studied the relationship between the increment of the hollow cerium oxide particles and the stain resistance. If the particles are increased, the amount of ketene which is the most surface of the antifouling task is reduced. Deterioration of sex. It is speculated that tartar is adsorbed on the surface of the hollow cerium oxide particles, which is caused by the lowest surface of the fluorescing layer -8-200921141. According to the present invention, it is found that the amount of the fluorenone on the outermost surface of the antireflection film can be increased by the antireflection film produced by the step of placing the hollow cerium oxide particles in the presence of the low condensate of the organic decane. This is considered to be due to a decrease in the amount of anthrone supported on the surface of the hollow ceria particles. The present invention is characterized in that the organic decane does not have a so-called functional group as a decane coupling agent. Further, the hydrolysis is carried out to some extent, and it is preferable to mix with the hollow cerium oxide particles at the time of forming the low condensate of the organic decane. This organic decane is formed into a main component of the original low refractive index layer and can be expected to have a function as a material having a low refractive index. However, in the present invention, it is found to function as a hollow cerium oxide particle. In general, the surface of the particles is treated with a decane coupling agent. However, in the use of the present invention, the effect of the treatment with a decane coupling agent is insufficient. It is not expected to be a low condensate of an organic decane which acts as a decane coupling agent. The time points formed are coexisting, and the effect on the particles can be exerted. Conventionally, after the hydrolysis of the organic decane is completely completed, the condensate of the organic decane is mixed with the hollow cerium oxide particles. The present invention will be described in detail below. The antireflection film of the present invention is composed of a high-, medium-, and low-refractive-index layer having an antireflection function, a hard coat layer thereunder, and a transparent support supporting the layers. 200921141 <low refractive index layer> The refractive index of the low refractive index layer of the present invention is preferably lower than the refractive index of the transparent support of the support, 23 ° C, wavelength 5 5 Onm, 1. 3 0 1 · The range of 4 5 . The film thickness of the low refractive index layer is preferably 5 nm to 0.5 # m, more preferably 10 〇 nm ~ 0 · 3 " ηι, most preferably 30 nm to 0.2 / zm. The low refractive index layer used in the present invention has hollow ceria particles, ketene, and a binder as a basic constitution. Further, it is preferable to contain hollow cerium oxide particles and contain at least two kinds of cerium oxide particles, and the other one type of cerium oxide fine particles is colloidal cerium oxide, and the average particle diameter of the colloidal cerium oxide is less than hollow two. The average particle diameter of the cerium oxide particles is 1.0 to 2 times 0 times. (The most surface Si-C bond peak intensity ratio) In the present invention, the outermost surface means the outermost surface of the antireflection layer and is the outermost surface of the low refractive index layer. The antireflection film of the present invention contains at least the hollow dioxide chopping particles and the ketene on the outermost surface. The ketene has a Si-C bond and a Si-0 bond in the molecule, and the cerium oxide particle has a Si-0 bond in the molecule. Therefore, the ratio of the intensity of the Si-C bond peak intensity to the sum of the si-0 bond peak intensity and the si-0 bond peak intensity is determined by using an X-ray photoelectron spectroscopy analyzer (hereinafter, slightly XPS). An indicator of the ratio of the presence of anthrone in the outermost surface of the antireflection film. In the present invention, the average 値R〇s of the Si-C bond peak intensity ratio shown by the following formula (A) is from -10-200921141 to 0.40 or more in the range from the outermost surface to the depth of 5 nm. Further, the average 値Rot of the aforementioned peak intensity ratio from the outermost surface to the depth of 10 to 25 nm is 0.0005 to 〇.1 〇. This table is not localized to the depth of the surface to a depth of 5 nm. The depth to 10 to 25 nm is only some amount below.

Si-C bond peak intensity ratio X-ray photoelectron spectroscopy (PSS) is used in an ion gun for sputtering of C 60 ions to determine the Si-C bonding energy of the etching conditions (Si-C bond peak intensity) : 〇 Bonding energy (S i - Ο bond peak intensity). The organic structure (S i - C bond) of fluorenone in the etching of Ar is easily determined by the destruction method to determine the correct organic fluorenone ratio. In the case of C 6 0 ion, the organic structure is difficult to be destroyed and can be more accurately determined. Formula (A ) (Si-C bond peak intensity ratio) = (Si-C bond degree) / {(Si-C Key spectrum peak intensity) + (Si-0 bond peak intensity) 丨 again, Si-C bond peak system is 102eV±0.5 eV, Si-Ο bond system is 103 eV±0.5 eV. (etching conditions) Device: ULVAC 06-C60 Accelerating voltage: l〇kV Ion beam current: 15mA Ion incident angle: 45° Etching speed · · minutes (in SiO)

Si-C bond, the device (in the following | with the su beam), so there is no f-grain peak spectrum peak 値-11 - 200921141 worm-inscribed area: 2.5 mm 2 (XP s measurement conditions) device · · Quantera SXM X-ray from ULVAC Company: A1 ( Monochro ) 2 5 W 1 5 k V Beam diameter: 1 0 0 # m The average ratio of Si-C bond peak intensity ratio of Ros in the range from the outermost surface to 5 nm.値, that is, the molecular ratio of the etching time of the above conditions. The XPS is based on the measurement of the outermost surface to obtain information of the depth of 5 nrn. The depth from the above surface is 1 Onm is equivalent to etching under the above conditions. The depth of 400 seconds, the depth from the outermost surface of 25 nm corresponds to a depth of 100 seconds of etching time. <Hollow cerium oxide particles> Description The hollow cerium oxide particles in which the inside is porous or void (hereinafter Also referred to as hollow particles. The hollow particle system (I) consists of a composite particle composed of a porous particle and a coating layer provided on the surface of the porous particle, or (II) has a void inside, and the content is solvent. , gas or porous matter The hollow particles are filled with particles with voids inside, and the voids are surrounded by the particle walls. The voids are filled with contents such as solvents, gases, or porous substances used for adjustment. - 200921141 The average particle size of such hollow particles is 5 to 200 nm, more preferably 10 to 70 nm. The particle size of the hollow particles should have a coefficient of variation of 丨 ~ "% of the monodisperse 〇 average particle size can be obtained from a scanning electron microscope ( Electron micrographs such as SE Μ ) are measured, and may be measured by a particle size distribution meter such as a dynamic light scattering method or a static light scattering method. When the hollow particles are composite particles, the thickness or void of the coating layer of the composite particles. The particle wall thickness of the particles is 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely coated, and the coating liquid component may easily enter the composite particles. In the inside, the internal porosity is reduced, and the effect of lowering the refractive index may not be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the coating liquid component is not formed. Although the porosity (pore volume) of the composite particles is lowered, the effect of lowering the refractive index may not be sufficiently obtained. In the case of void particles, when the thickness of the particle wall is less than 1 nm, the particle shape may not be maintained. When the thickness exceeds 20 nm, the effect of lowering the refractive index may not be sufficiently exhibited. The particle layer of the coating layer or the void particles of the composite particles preferably contains cerium oxide as a main component, and may contain a component other than cerium oxide. Specifically, for example, Al2〇3, B2〇3, Ti〇2, Zr〇2, Sn〇2, Ce〇2, P2〇3′ Sb203, Mo〇3, Zn〇2, W03, and the like can be given. The porous particle structure constituting the composite particles may be composed of, for example, cerium oxide, an inorganic compound other than cerium oxide and cerium oxide, 13-200921141, CaF2, NaF, NaAlF6, MgF or the like. Among them, a porous particle composed of a composite oxide of an inorganic compound other than cerium oxide and cerium oxide is particularly preferable. Examples of the inorganic compound other than cerium oxide include Al2〇3, B2〇3, Ti〇2, Zr02, Sn〇2, C e O 2 ' P 2 〇3 ' S b 2 0 3 'M0O3, Zn〇2 One or two or more kinds of WO3. Such a porous particle system has cerium oxide represented by S i Ο 2 and an inorganic compound other than cerium oxide in terms of oxide (MOx), and the molar ratio MOx/Si 〇 2 is 0.0001 to 1.0, preferably 0.001 〜 The range of 0.3. The molar ratio of the porous particles to MOx/SiO 2 is less than that of 〇·〇〇〇1, and even if it is available, the pore volume is small, and particles having a low refractive index cannot be obtained. Further, since the molar ratio of the porous particles to MOx/SiO 2 exceeds 1.0 and the ratio of cerium oxide is small, the pore volume becomes large, and it may be difficult to obtain a lower refractive index. The pore volume of such a porous particle is preferably in the range of 0.2 to 1.5 ml/g. When the pore volume is less than llml/g, the particles having a reduced refractive index cannot be sufficiently obtained, and if the thickness exceeds I·5 ml/g ′, the strength of the fine particles is lowered, and the strength of the film obtained is lowered. Further, the pore volume of such a porous particle can be determined by a mercury intrusion method. Further, examples of the content of the void particles include a solvent, a gas, a porous substance, and the like which are used in particle preparation. The solvent may also contain an unreacted product of the particles used in the preparation of the void particles, a catalyst to be used, and the like. Further, the porous material can be exemplified by a compound exemplified by the above porous particles. The grain system within this temple may be composed of a single component' but may also be a mixture of plural components. In the method for producing such a hollow particle, for example, a method of preparing a composite oxide colloidal particle disclosed in paragraph number [〇〇1〇卜 [0033] of JP-A-7-133901, It is preferable to carry out the heat treatment disclosed in paragraphs [0024] to [002 5] of JP-A No. 20 0 1 -23 36 1 1 . The content of the solid content in the low refractive index layer of the hollow particles of the present invention is preferably from 30 to 80% by mass. The solid content is used after the solvent to be applied is dried and completely removed. In the present invention, commercially available hollow particles described above can be used. Specific examples of the commercially available particles include, for example, ELEC OM V-8209 manufactured by Catalyst Chemical Industries, Ltd., and the like. <Colloidal cerium oxide> The colloidal cerium oxide which is preferably used in the present invention is a spherical, needle-like or bead-like shape in which cerium oxide is colloidally dispersed in water or an organic solvent. The average particle diameter of the colloidal cerium oxide is less than 1.1 to 20 times the average particle diameter of the hollow particles, and is preferably 1.5 to 5.0 times. Therefore, the average particle diameter of the colloidal ceria is preferably in the range of 50 to 300 nm. The particle size of the colloidal cerium oxide is preferably a single dispersion with a coefficient of variation of 1 to 40%. The average particle diameter can be measured from an electron microscope photograph such as a scanning electron microscope (SEM). -15- 200921141 Specifically, a microscope photograph (丨000 times transmission mode) containing the particles or the sample is photographed, and the diameter of the particles photographed in this photograph is measured by an image processing apparatus LUZEX-III (manufactured by Nireco). The average enthalpy was calculated as the average particle diameter. The measurement may be carried out by a particle size distribution method such as a dynamic light scattering method or a static light scattering method. However, the ratio of the average particle diameter of the colloidal ceria to the average particle diameter of the hollow particles must be determined in accordance with the same measurement method. The colloidal cerium oxide used in the present invention is commercially available, for example, the Sno wtech series of Nissan Chemical Industries Co., the Cataloid-S series of the Catalyst Chemical Industry Co., Ltd., and the Levasil series of Bayer Co., Ltd., and the like. Further, it is also preferred to use a primary particle of colloidal cerium oxide or cerium oxide modified with an alumina sol or aluminum hydroxide as a cation or a metal ion having two or more valences, and to bond the beads into a plurality of beads. Yttrium oxide. The beaded colloidal cerium oxide is the Snowtech-AK series, the Snowtech-PS series, and the Snowtech-UP series of Nissan Chemical Industries. The content in the low refractive index layer of the colloidal cerium oxide is preferably from 30 to 60% by mass based on the solid content of the low refractive index layer. When the effect of lowering the refractive index is obtained, it is preferably 30% by mass or more. If it exceeds 40% by mass, the binder component is small and the film strength is insufficient. The content ratio of the hollow particles to the colloidal cerium oxide in the low refractive index layer can be selected from the viewpoints of the effect of reducing the reflectance and the surface hardness, but is preferably 1: 0.1 to 10, more preferably 1: 0.8 to 5. -16- 200921141 <Alkane> The anthrone-based organic group used in the present invention is bonded to a siloxane-bonded organic polyoxyalkylene. The ketone ketone used in the present invention is a kind in which the type of the organic group bonded to the ruthenium atom can be roughly classified into a linear fluorenone oil and a modified guar oil. Linear fluorenone oil § The stomach is a combination of a methyl group, a phenyl group and a hydrogen atom as a substituent. Modified sesketone oil is a component which has a secondary derivatization from linear ketone oil. In addition, it can also be classified from the reactivity of chopped ketone oil. If you summarize this, as follows. Anthrone oil 1. Linear ketone oil 1 - 1. Non-reactive fluorenone oil · dimethyl 'methyl phenyl substitution, etc. 1-2_Reactive fluorenone oil: methyl hydrogen substitution, etc. 2. The ketone oil is introduced into various methyl groups in methyl ketone oil, modified cetyl oil 2 - 1 • Non-reactive fluorenone oil: alkyl, alkyl / aralkyl, alkyl / polyether , polyether, higher fatty acid ester substitution, etc., alkyl/aralkyl modified anthrone oil, one part of the methyl group of dimethyl fluorenone oil is substituted with a long chain alkyl or phenyl alkyl fluorenone oil, The polyether-modified fluorenone oil is a sulfonate-based polymer surfactant in which a hydrophilic polyoxyalkylene group is introduced into a hydrophobic dimethyl sol ketone, and a higher fatty acid-modified fluorenone oil-based dimethyl ketone. One of the methyl groups of the ketone oil-17- 200921141 The oxime oil partially substituted with the higher fatty acid ester, the amine-modified fluorenone oil has a structure in which one part of the methyl group of the fluorenone oil is substituted with an aminoalkyl group. The oxime oil and the epoxy-modified fluorenone oil have an oxime oil, a carboxyl group-modified or an alcohol-modified oxime having a structure in which one part of a methyl group of an oxime oil is substituted with an alkyl group containing an epoxy group. Oil-based silicone having a part of methyl ketone silicone oil substituted one configuration of an oil containing an alkyl group of the carboxyl group or hydrogen. 2-2. Reactive anthrone oil: For example, an amine group, an epoxy group, a carboxyl group, an alcohol substitution or the like can be mentioned. A reactive anthrone oil is preferably added to the anthrone of the present invention. The number average molecular weight of the anthrone of the present invention is, for example, 500 to 5,000, preferably 1,000 to 20,000 °. The specific products are: L-45, L-9300, FZ-3704, FZ-3703, FZ of Unicar, Japan. -3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ-3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499 Shin-Etsu Chemical Co., Ltd. KF96L, KF96, KF96H 'KF99, KF54, KF965, KF96 8, KF56 'KF995, KF351, KF3 52 ' KF3 5 3 ' KF3 5 4, KF355, KF615, KF618, KF945, KF6004, FL100, etc. Further, for example, it is manufactured by U Nicar Co., Ltd., an anthrone surfactant SILWET L-77, L-720, L-700 1, L-7002, L-7604 'Y-7006 &gt; FZ-210 1. FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120' FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ- 2614, FZ-2166, FZ-2191, etc. -18- 200921141 Further, for example, Supersilwet SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. = again, the hydrophobic group is dimethyl polyoxyalkylene, and the hydrophilic group is poly The preferred structure of the nonionic ceric acid composed of the oxygen hospital base is a linear block copolymer in which the dimethyl polyphosphonium structure portion and the polyoxymethylene support chain are alternately reciprocally bonded. Specific examples of such a product include, for example, Japanese Unicar Co., Ltd., anthrone interface activity, J ABN SILWET FZ-2203, FZ-2207, FZ-2208, FZ-2222, and the like. These ketones are preferably those having a polyether base. Also, 'BYK series made by BYK Chemie Japan, BYK-300/302, BYK-306, BYK-3 07, BYK-310, BYK-315, BYK-3 20, BYK-3 22, BYK-3 23 should be used. , BYK-3 25, BYK-3 3 0, BYK-331, BYK-3 3 3, BYK-3 3 7, BYK-3 40, BYK-3 44, BYK-370, BYK-3 75, BYK-3 77, BYK-3 52, BYK-3 54, BYK-3 5 5 /3 5 6, BYK-3 5 8N/361N, BYK-3 5 7, BYK-3 90, BYK-3 92, B YK-UV 3 500, BYK-UV 35 10, BYK-UV 3 5 70, BYK-Silclean 3 700, GE Toshiba Silicone dimethyl ketone series, XC96-723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897 . The anthrone of the present invention is preferably used in an amount of from 5 to 40% by mass, more preferably from 1 to 25% by mass, based on the binder. <Binder> The low refractive index layer should contain 5 to 80% by mass of the -19-200921141 binder for the entire low refractive index layer. The binder is combined with hollow particles, colloidal silica sand and cedar, and has a function of forming a low refractive index layer structure containing voids. The amount of binder used is adjusted so as not to fill the voids and maintain the strength of the low refractive index layer. The binder is a compound having a low refractive index per se, and an organic sand or a hydrolyzate or a condensate thereof which is not represented by the following formula (1). In the formula (1), si(xi)4 wherein XI is a decyloxy group, and is preferably a oxy group having 1 to 4 carbon atoms. As the specific compound, tetramethoxy decane, tetraethoxy cerium, tetraisopropoxy sand or the like is preferably used. Further, the low refractive index layer may contain an organic decane represented by the following formula (2) or a condensate thereof as a binder. The general formula (2) (R)mSi(X2)4-m R represents an organic group which is not hydrolyzed. X2 represents an alkoxy group. m represents an integer of 1 to 4. The organodecane represented by the formula (2) may, for example, be methyltrimethoxy chopped, methyldiethoxylate, methyldimethoxyethoxylate or methyltriacetin. Oxydecane, methyl tributoxydecane, ethyl trimethoxy decane, ethyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl triethoxy decane , vinyl trimethoxy ethoxy decane, phenyl trimethoxy decane, phenyl fluorenyl ethoxy decane, phenyl triethoxy decane, 7-chloropropyl trimethoxy decane, chloropropyl -20 - 200921141 Triethoxy decane, r-chloropropyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, glycidyloxypropyltrimethoxydecane, 7-glycidol Oxypropyltriethoxydecane, r-(/3-glycidyloxyethoxy)propyltrimethoxydecane, /3-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane, /3-(3,4-epoxycyclohexyl)ethyltriethoxydecane, γ-acryloxypropyltrimethoxydecane, r-methacryloxypropyltrimethoxydecane, R-amine Propyltrimethoxydecane, r-aminopropyltriethoxydecane, r-hydrothiopropyltrimethoxydecane, r-thiopropylpropyltriethoxydecane, N-/3-( Aminoethyl)-r-aminopropyltrimethoxydecane and /3-cyanoethyltriethoxydecane. Further, for example, dimethyldimethoxydecane, phenylmethyldimethoxydecane, dimethyldiethoxydecane, phenylmethyldiethoxydecane, and τ-glycidyloxypropane can be mentioned. Methyldiethoxydecane, r-glycidoxypropylmethyldimethoxydecane, r-glycidoxypropylphenyldiethoxydecane, r-chloropropylmethyldiethyl Oxydecane, dimethyldiethoxydecane, 7-propenylmethoxypropylmethyldimethoxydecane, 7-propenylmethoxypropylmercaptodiethoxydecane, r-methylpropene Mercaptooxypropylmethyldimethoxydecane, r-methylpropenyloxypropylmethyldiethoxydecane, r-hydrothiopropylmethyldimethoxydecane, r-hydrogen sulfur Propylmethyldiethoxydecane, r-aminopropylmethyldimethoxydecane, 7-aminopropylmethyldiethoxydecane, methylvinyldimethoxydecane and Vinyl diethoxy decane. Among these, it is preferably a vinyl trimethoxy decane having a double bond in the molecule, a vinyl triethoxy decane, a vinyl triethoxy decane, and a methyl-21 - 200921141 alkenyl trimethoxy ethoxy group. Base sand institute, propylene oxypropyl trimethoxy decane and 7-methacryl oxiranyl trimethoxy decane, 7-propylene methoxypropyl methyl dimethoxy fluorene, 7 propylene propylene Methyldiethoxy oxime, r-methylpropenyl methoxypropylmethyldimethoxy sand and r-methacryloxypropylmethyldiethoxylate, methylethylene Dimethoxy decane and methyl vinyl diethoxy decane. Particularly preferred is r-propylene oxypropyltrimethoxydecane and r-methacryloxypropyltrimethoxydecane, r-propylene methoxypropylmethyldimethoxydecane, r-propylene propylene oxide Methyldiethoxydecane, 7-methacryloxypropylmethyldimethoxydecane and 7-methacryloxypropylmethyldiethoxydecane. You can also use 2 or more types. Other organic decane may be used in addition to the organic decane shown above. Other organic decanes include, for example, alkyl esters of ortho-decanoic acid (for example, methyl ortho-decanoate, ethyl ortho-decanoate, n-propyl ortho-decanoate, isopropyl ortho-decanoate, n-butyl orthophthalate, Dibutyl phthalate, tert-butyl phthalate and its hydrolyzate. Other binders of the low refractive index layer include, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethacrylate, diethyl phthalocyanine, triethyl fluorenyl cellulose, and nitro group. Cellulose, polyester, alkyd resin In the present invention, the organodecane of the formula (2) is preferably used in an amount of 50% by mass relative to the organodecane of the formula (1), particularly preferably 5 to 40 by mass. The range of % is used. -22- 200921141 <Other Additives> (Fluorine-based surfactant) It is preferable to contain a fluorine-based surfactant in the low refractive index layer. It is effective in reducing coating unevenness or improving the stain resistance of the film surface. The fluorine-based surfactant may, for example, be a monomer containing a perfluoroalkyl group, an oligomer, a polymer as a core, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl allyl ether, or a polyoxygen. Derivatives such as ethylene. A commercially available product may be used as the fluorine-based surfactant, and examples thereof include Sarflon "S-381", "S-382", "SC-101", "SC-102", "SC-103", and "SC-". 104", (either is Asahi Glass Co., Ltd.), Fluorad "FC-430", "FC-431", "FC-173" (any one is Fluo Chemical Sumitomo 3M), EFTOP "EF352" ", "EF301", "EF303" (either one is New Akita Chemicals Co., Ltd.), Schwegolfer "8035", "8036" (all are manufactured by Schwegman), "BM1000", "BM1100" (Either BM.HyMl company), Megafack "F-171", "F-470", (all are manufactured by Dainippon Ink Chemical Industry Co., Ltd.), etc. The fluorine-containing ratio of the surfactant is 〇5~2% by mass, preferably 〇1 to 1% by mass. The above-mentioned fluorine-based surfactants may be used singly or in combination of two or more kinds, and may be used together with other surfactants. <Formation of Low Refractive Index Layer> The formation of the low refractive index layer of the present invention is basically carried out by directly applying a coating liquid containing a hydrolyzate containing organic decane by a method known in the ordinary -23-200921141. Specifically, the organic hydrazine is easily mixed with water, and the organometallic compound and water are used to coexist and dissolve a hydrophilic organic solvent of methanol, ethanol, and acetonitrile, and then, for example, a hydrolysis catalyst such as an acid is added to hydrolyze the organic decane. ,condensation. When a certain amount of hydrolysis is carried out by GPC measurement, the hollow particle is mixed to form a low refractive index layer coating liquid, and further condensation is carried out by continuing the hydrolysis step, and GPC is measured to observe the increase in molecular weight or the crosslinking. Then, it is coated on a substrate and dried to form a low refractive index layer. In the present invention, it is characterized in that the organic decane represented by the formula (1) is hydrolyzed by tetraethoxy decane or the like and condensed to form a low condensate of a specific molecular weight to make a hollow The particles are mixed in the coating liquid to further continue the hydrolysis and condensation. The specific molecular weight is a weight average molecular weight of 500-1000 in terms of styrene in terms of GPC measured under the following conditions. In the step of further continuing the hydrolysis and condensation, the weight average molecular weight is adjusted to more than 1,000 to 10,000 or less. <GPC measurement conditions> The weight average molecular weight measurement method by GPC was diluted with THF so that the sample solid concentration was 0.8% by mass, and the measurement was carried out under the following conditions at a column temperature of 25 °C. Column: Tosoh Corporation TSKgelG5000HXL-TSKgel -24- 200921141

G2000HXL

Dissolution: THF Lipu: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0 m 1 /min. Detection: RI Model 504 (manufactured by GL Science Co., Ltd.) Sample concentration: 0.8% Standard sample • Calibration curve: Standard polymerization Calibration curve for 13 samples of styrene STK Standand polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1,000,000 to 500. When the hollow particles are mixed in the coating liquid from the start of the hydrolysis, or the organic siloxane is a reactivity represented by the formula (2), it is almost impossible to observe the surface adsorption of the hollow particles as inhibited by the present invention. The role of anthrone. Further, the organodecane represented by the formula (2) is mixed with a low condensate having a weight average molecular weight of 500 to 1,000 as the organodecane represented by the formula (1), and is used as a binder. Film strength. <Layer Configuration of Antireflection Film> In the antireflection film of the present invention, the antireflection layer having an antireflection function must be the low refractive index layer of the present invention, but the other is provided with a medium refractive index layer and a high refractive index layer.俾 Improve anti-reflection function. A well-known layer can be used for each of a medium refractive index layer and a high refractive index layer. The composition examples include: a layer of a high refractive index layer/low refractive index layer from the transparent support side or a three-layer refractive index layer in which the refractive index is differently laminated (the refractive index is on the substrate or A hard coat layer having a lower refractive index than a layer of a high refractive index layer) / a height of -25 - 200921141 A refractive index layer / a low refractive index layer, etc. have been proposed to further laminate a plurality of antireflection layers. Among them, in terms of durability, optical properties, or productivity, it is preferable to sequentially laminate the medium refractive index layer/high refractive index layer/low refractive index layer on the substrate having a hard coat layer, and to refract in the laminate. Rate layer / low refractive index layer. If the reflectance can be reduced by optical interference, it is not particularly limited to the layer configuration. Further, the antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (e.g., Sn02, ITO, etc.), and may be provided by coating or atmospheric piezoelectric slurry treatment or the like. <Hard Coating Layer> In the antireflection film of the present invention, a hard coat layer is preferably provided between the transparent support and the antireflection layer such as a high refractive index layer or a low refractive index layer. The hard coat layer is preferably an active energy ray hardening resin layer. The active energy ray-hardening resin layer is a layer which is a main component of a resin which is cured by a crosslinking reaction or the like by an active line of ultraviolet rays or electron beams. The active energy ray-curable resin is preferably cured by irradiation with an active line containing ultraviolet rays or electron beams using a component containing a monomer having an ethylenically unsaturated double bond to form an active energy ray-curable resin layer. The active energy ray-curable resin may, for example, be an ultraviolet curable resin or an electron beam curable resin, but it is preferably a resin which is cured by ultraviolet irradiation. For the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin -26-200921141, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable multicomponent are preferably used. An alcohol acrylate resin or an ultraviolet curable epoxy resin. Among them, it is preferably an ultraviolet curable acrylic resin. The ultraviolet curable urethane urethane resin generally contains a 2-hydroxyethyl acrylate or a hydroxyethyl methacrylate in a product obtained by reacting an isocyanate monomer or a prepolymer with a polyester polyol. The ester (hereinafter, the acrylate-based only means that the acrylate is a methyl acrylate-containing ester) and the acrylate-based monomer having a hydroxyl group such as a propylpropionate are easily reacted. For example, it can be recorded by the special opening 59_151丨1〇. For example, it is preferable to use a mixture of 100 parts of Unidic 17-806 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and Coronate L (manufactured by Nippon p〇iyUrethane Co., Ltd.). The ultraviolet curable polyester acrylate resin is generally obtained by reacting a 2-polyethyl acrylate or a 2-hydroxy acrylate monomer with a polyester polyol. It can be used in the document No. 5 9 -1 5 1 1 1 2 . Specific examples of the ultraviolet curable epoxy acrylate-based resin include, for example, an epoxy acrylate as an oligomer, and a reactive diluent and a photopolymerization initiator are added to generate a reaction, and a special opening number can be used. Recorder. Specific examples of the ultraviolet curable polyol acrylate resin include, for example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, Alkyl-modified dipentaerythritol pentaacrylate or the like. -27- 200921141 The photopolymerization initiator of the ultraviolet curable resin, specifically, for example, benzoin and its derivatives, acetophenone, benzophenone, benzophenone, and micheler Ketones, alpha-amyloxim vinegar, thiopurine and the like and derivatives thereof. It can also be used together with a photosensitizer. The above photopolymerization initiator can also be used as a photosensitizer. Further, in the case of using a photopolymerization initiator of an epoxy acrylate type, a sensitizer such as n-butylamine, triethylamine or tri-n-butylphosphine can be used. The photopolymerization initiator and the photosensitizer used in the ultraviolet curable resin composition are 0.1 to 15 parts by mass, preferably 1 part by mass, per 100 parts by mass of the composition. The resin monomer is, for example, a monomer having one unsaturated double bond, and examples thereof include methacrylate, ethacrylate, butyl acrylate, benzyl methacrylate, cyclohexyl acrylate, and vinyl acetate. A general monomer such as styrene. Examples of the monomer having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, and 1,4 - Cyclohexyl dimethyl diacrylate, exemplified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and the like. A commercially available product of an ultraviolet curable resin which can be used in the present invention can be suitably selected and utilized, and Adeka op t omer KR · BY system J: KR-4 0 0, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Chemical Co., Ltd.); K Ο EIHARDA -1 (H - KK, A -1 0 1 - WS, C - 3 0 2 , (:-401-N, C-501) , M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (Guangrong Chemical Co., Ltd.); Seikabeam PHC 2210 (S), PHC X-9 ( -28- 200921141 Κ-3 ), PHC 22 13, DP-10, DP-20, DP-30, PI 000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900

(Daily Jinghua Industry Co., Ltd.); KRM703 3, KRM703 9, KRM7130, KRM7131, UVECRYL 2920 1 , UVECRYL 29202 (made by Daicel UCB); RC-5015, RC-5016, RC-502 0, RC - 5 03 1, RC-5100, RC - 5 1 0 2, RC - 5 1 2 0, RC 5122, RC-5152, RC-5171, RC-5180, RC-5181 (Daily Ink Chemical Industry Co., Ltd.) System; Olex No.340 Clear (China Coatings Co., Ltd.); Sanrad H-601, RC-75 0, RC-700, RC-600, RC-5 00, RC-61 1, RC-612 (Sanyo) Chemical Industry Co., Ltd.); SP-1509, SP-1507 (Showa Polymer Co., Ltd.); RCC-15C (made by Grace Japan Co., Ltd.), A r ο nix Μ-6 1 0 0, Μ - 8 0 3 0, Μ-8060 (East Asia Synthetic (stock) system); ΝΚ Hard Β-420, Β-500 (Xinzhongcun Chemical Industry Co., Ltd.). Further, specific examples thereof include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol. Pentaacrylate and the like. The cured resin layer thus obtained is adjusted to have scratch resistance, slipperiness, or refractive index, and imparts anti-glare properties to the antireflection film to be produced, and may contain fine particles of an inorganic compound or an organic compound. Examples of the inorganic fine particles used in the hard coat layer include cerium oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, I Τ 0, zinc oxide, cerium oxide, magnesium oxide, calcium carbonate, potassium carbonate, talc, clay, and burning. Cheng Gaoling, burn -29- 200921141 calcium citrate, water and calcium citrate, aluminum citrate, magnesium citrate, and calcium phosphate. In particular, it is preferable to use cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide or the like. Further, the organic particles may be added to polymethacrylic acid methacrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, anthrone resin powder, polystyrene resin powder, or polycarbonate. Ester resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamine resin powder, polyimide resin powder, or polyvinyl fluoride An ultraviolet curable resin composition such as a resin powder. More preferably, for example, crosslinked polystyrene particles (for example, SX-130H, SX-200H, and SX-350H manufactured by K.K.) and polymethyl methacrylate particles (for example, MX1 50 manufactured by Kokusai Chemical Co., Ltd.) MX3 00). The average particle diameter of the fine particle powder is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0/m, and particularly preferably 0.1 to 4. 〇vm. Further, it is preferable to contain two or more kinds of fine particles having different particle diameters. The ratio of the ultraviolet curable resin composition to the fine particles is preferably 0.1 to 30 parts by mass based on 1 part by mass of the resin composition. These hard coat layers can be applied by a known method such as a gravure coater, a dip coater, a reverse roll coater, a wire bar coater, a die coater, or an ink jet method. After coating, it is dried by heating and subjected to UV hardening treatment. The ultraviolet curable resin is hardened by photohardening reaction, and the light source for forming the hardened film layer is not limited to -30-200921141 and can be used as long as it is a light source for generating ultraviolet rays. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on the lamp, but the irradiation dose of the active wire is generally 5 to 500 mJ/cm 2 , preferably 5 to 150 mJ/cm 2 , but particularly preferably 20 to 100 mJ/cm 2 °, when the active line is irradiated. It is preferable to apply tension while carrying the film in the direction in which the film is conveyed, and it is preferable to apply tension to the width direction, and the tension to be applied is preferably 30 to 300 N/m. The method of imparting the tension is not particularly limited, and the tension may be applied to the transporting direction on the back roller, and the tension may be applied to the stretcher in the width direction or the biaxial direction. Further, a film having excellent planarity can be obtained by this. The hard coat coating liquid may further contain a solvent, and it is suitably contained as needed, and it is diluted. The organic solvent contained in the coating liquid may be suitably selected from, for example, hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol 'butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, Methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents are used in combination or in combination. It is preferable to use propylene glycol monoalkyl ether (alkyl group having 1 to 4 carbon atoms) or propylene glycol monoalkyl ether acetate (alkyl group having 1 to 4 carbon atoms), etc., and more preferably 5 or more. ～80% by mass or more of the above organic solvent. (Anti-glare property) The antireflection film of the present invention is preferably anti-glare. The anti-glare property reduces the visibility of the reflected image by blurring the contour of the image of the anti-31 - 200921141 on the surface, and does not detect the reflection when used in an image display device such as a liquid crystal display, an organic EL display, or a plasma display. Like it. By virtue of the surface having appropriate irregularities, the crucible can have such a property. The method of forming such irregularities can be selected from the processing of a transparent support, the processing of a hard coat layer, the processing of an anti-reflection film after coating an anti-reflection layer, etc., but the processing of the anti-reflection film has a convex portion of a concave-convex shape. The antireflection layer' or the antireflection layer is changed to impair the antireflection effect. Therefore, in the present invention, the processing of the transparent support and the processing of the hard coat layer are preferred. The concavo-convex shape of the present invention may be, for example, a structure selected from the group consisting of a straight cone, a slanted cone, a pyramid, a beveled cone, a wedge, a convex polyhedron, and a hemispherical shape, and a structure having a partial shape thereof. Further, the hemispherical shape is not necessarily a true spherical shape, and may be an elliptical shape or a deformed convex curved shape. Further, for example, the ridge line of the uneven shape may have a meander shape extending in a line shape, a columnar lens shape, or a fresnel lens shape. The slope from the ridgeline to the valley line may also be planar, curved, or a combination of the two. The hard coat layer is preferably an anti-glare hard coat layer having an arithmetic plane roughness (Ra) of 60 to 700 nm, preferably 80 to 400 nm, as defined by JIS B 0 0 0 1 : 2 0 0 1 . When Ra is less than 6 〇 nm, the effect of anti-glare is weak, and if it exceeds 700 nm, it is impression that it is too thick. The arithmetic mean roughness (Ra) is preferably measured by an optical interference type surface roughness measuring instrument, and can be measured using, for example, an optical interference type surface roughness meter -32-200921141 RST/PLUS (manufactured by WYKO Co., Ltd.). The method of forming the uneven shape on the surface of the hard coat layer and the transparent support described later may be, for example, the following method. (1) A method of forming a negative mold of a desired shape on a roll or a master to emboss a shape. (2) A method in which a negative mold having a desired shape is formed on a roll or a master, and a thermosetting resin is filled in a negative mold to be peeled off from the negative mold after heat curing. (3) forming a negative mold of a desired shape on a roll or a master, applying an ultraviolet or electron beam hardening resin, filling the concave portion, and directly coating the transparent support on the intaglio plate through the resin liquid, irradiating ultraviolet rays or electron beams A method of peeling a cured resin and a transparent support adhered thereto from a negative mold. (4) A negative mold having a desired shape is formed on a vertical flow conveyor, and a solvent casting method is applied to the intended shape during casting. (5) A method in which a resin which is cured by light or heat is relief-printed on a transparent substrate and cured by light or heat to form irregularities. (6) A resin which is cured by light or heat on the surface of a transparent support. Printing by an ink-jet method, and curing by light or heat to form a concave-convex shape on the surface of the transparent support. (7) A method of cutting a surface by a working machine or the like. (8) A method in which particles of various shapes such as a sphere and a polygonal body are pressed into a state of being semi-buried to the surface of the transparent support, and the surface of the transparent support is formed into a concavo-convex shape. (9) A method in which particles of various shapes such as spheres and polyhedrons are dispersed in a small amount of a binder, and the surface of the transparent support is formed into a concave-convex shape by a surface of -33-200921141. (10) A method in which a surface of a transparent support is coated with a binder to spread particles of various shapes such as a sphere or a polygonal body to form a concave-convex shape on the surface of the transparent support. In the present invention, the anti-glare fine particles are preferably fluorine-containing acrylic resin fine particles other than the inorganic fine particles or the organic fine particles. The fluorine-containing acrylic resin fine particles are, for example, fine particles formed of a fluorine-containing acrylate or methacrylate monomer or polymer. Specific examples of the fluorine-containing acrylate or methacrylate include, for example, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, ih, 1H, 5H-octafluoropentyl (meth) acrylate, 1H,1H,7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorodecyl (meth) acrylate, 2,2,2-difluoroethyl (meth) acrylate Ester, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2-(perfluorobutyl)ethyl (meth) acrylate, 2-(perfluorohexyl)ethyl (A) Acrylate, 2-(perfluorooctyl)ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 3-perfluorobutyl 2 hydroxypropyl ( Methyl) acrylate, 3_perfluorohexyl-2-hydroxypropyl (meth) acrylate ' 3 - perfluorooctyl 2 -hydroxypropyl (meth) acrylate, 2-(perfluoro - 3 _Methylbutyl)ethyl (meth) acrylate, 2-(perfluoromethylhexyl)ethyl (meth) acrylate, 2-(perfluoro-7-methyloctyl)ethyl (A) Acrylate, 3-perfluoro-3-methylbutyl 2-hydroxypropyl (meth) acrylate, % (all -5-Methylhexyl)-2-hydroxypropyl (meth) acrylate, % (perfluoro-7-methyloctyl)-2-hydroxypropyl (meth) acrylate, ΐΗ_-34- 200921141 1-(Trifluoromethyl)trifluoroethyl (meth) acrylate, 111, 111, 311-hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate, tetrafluoropropyl Acrylate, perfluorooctylethyl acrylate, 2-(perfluorobutyl)ethyl-α-fluoroacrylate. Further, among the fluorine-containing acrylic resin fine particles, fine particles composed of 2-(perfluorobutyl)ethyl-fluoroacrylate, fluorine-containing polymethyl methacrylate fine particles, and fluorine-containing methacrylic acid are preferable. The fine particles copolymerized with the vinyl monomer in the presence of the crosslinking agent are more preferably fluorine-containing polymethyl methacrylate fine particles. The vinyl single system copolymerizable with the fluorine-containing (meth)acrylic acid may be any one having a vinyl group, and specific examples thereof include alkyl methacrylates such as methyl methacrylate and butyl methacrylate. An alkyl acrylate such as methyl acrylate or ethyl acrylate, or a benzene or the like of styrene or α-methyl styrene, etc., may be used singly or in combination. The crosslinking agent to be used in the polymerization reaction is not particularly limited, and those having two or more unsaturated groups are preferably used, and examples thereof include ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate. Bifunctional dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene, and the like. Further, in the present invention, the polymerization reaction system for producing fluorine-containing polymethyl methacrylate microparticles may be either random copolymerization or block copolymerization. Specifically, for example, the method described in JP-A-200- 1 696 585, and the like, and commercially available products such as FS-701, manufactured by Japan Paint, MF-0043, etc., may be mentioned. In addition, these fluorine-containing acrylic resin fine particles may be used alone or in combination of two or more. Further, the state of the fluorine-containing fine particles of the fluorine may be such that the average particle diameter of the fluorine-containing acrylic fine particle powder in any of the powder or the emulsion is preferably / m, more preferably 0.1 to 5.0 # m, particularly preferably For 0.1~4.0# m. Further, it is preferable to contain two or more kinds of fine particles having different particle diameters. The ratio of the ultraviolet curable resin composition to the fine particles is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the fat composition. &lt;Back Coating&gt; The antireflection film of the present invention is preferably provided with a back coat layer on the surface opposite to the side of the transparent support coat. The back coat layer is a roll produced by an active energy ray-curable resin layer or other layers, i.e., the surface provided with the back coat layer is made to have an inner side, and the curl can be balanced. Further, the back coat layer is preferably applied in layers, and in this case, it is functional in the back coat coating composition, and fine particles are preferably added. The back coat layer of the present invention can be used by a known person. The order of applying the back coat is applied before or after the hard coat layer is applied, but the back coat layer is also coated with the pressure-proof adhesive layer. Or, the back coat is applied more than once. BYK Japan's active agent BYK series and GE Toshiba Silicone Co., Ltd. described in the low refractive index layer are used for acrylic acid addition. It is 0.01~5. It has a hard bridge with respect to the tree. The curling property is set by the anti-pressure and anti-pressure adhesive. It can be divided into two types of interface methyl ketone-36-200921141 series. It is preferable to use an antireflection layer other than the low refractive index layer. &lt;Transparent support&gt; Next, a transparent support which can be used in the present invention will be described. The transparent support system used in the present invention is preferably a component which is easy to produce, and which has good adhesion to the gastric active line-curable resin layer, is optically isotropic, and is optically transparent. The term "transparent" as used in the present invention means that the transmittance of visible light is 60% or more, preferably 80% or more, and particularly preferably 90% or more. The above properties are not particularly limited, and examples thereof include a cellulose ester film, a polyester film, a polycarbonate film, a polyarylate film, and a polyether (also containing a polyether maple) film. Polyester film of ethylene phthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cerium, cellulose diacetate film, cellulose triacetate, cellulose acetate Ester propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, vinyl vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, cycloolefin polymer Film (Arton (manufactured by JSR), Zeonex, Zeonor (above, manufactured by Zeon, Japan), polymethylpentene film, polyetherketone film, polyether ketoximine film, polyamide film, fluororesin film , nylon film 'polymethyl methacrylate film, acrylic film or glass plate. Among them, it is preferable to contain a cellulose triacetate film, a polycarbonate film, a poly maple (also containing polyether maple), and in the present invention, a cellulose ester film (for example, 'Konica Minolta tack, product name KC8UX2MW, -37- 200921141 KC4UX2MW, KC8UY, KC4UY, KC5UN, KC12UR, KC8UCR-3 KC8UCR-4, KC8UCR-5 (Konica Minolta 〇pt〇 (share) system), from manufacturing, cost, transparency, isotropic, adhesive The point of view is better to use. These films may be films produced by film formation by squirting, or films produced by solution film formation. <Cellulose Vinegar> In the present invention, a cellulose ester film is preferably used as a transparent support. The cellulose ester is preferably cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, wherein cellulose acetate butyrate, cellulose acetate phthalate, Cellulose acetate propionate. It is particularly preferable to use an activity ratio in which the substitution degree of the ethyl thiol group is used as the substitution degree of X, a propyl fluorenyl group or a butyl fluorenyl group as Y, and a transparent support having a mixed fatty acid ester of cellulose having X and Y in the following ranges is provided. A low-reflective laminate of a hardened resin layer and an antireflection layer. It is preferably 2.3 ^ X + Y ^ 3.0 0.1 ^ Y ^ 1.2. When the cellulose ester is used as the transparent support system used in the present invention, the cellulose of the raw material of the cellulose ester is not particularly limited, but may, for example, cotton linter or wood. Pulp (from conifers, from eucalyptus), kenaf (kenaf), etc. Further, the cellulose esters obtained from these can be used in combination at any ratio of -38 to 200921141. The method for determining the degree of substitution of the thiol group can be determined in accordance with the provisions of ASTM-D817-96. The number average molecular weight of the cellulose ester is 70,000 to 250,000, and the mechanical strength during molding is strong, and it is a moderate doping viscosity, preferably 80,000 to 150,000. The cellulose ester film is preferably a cellulose ester dissolving solution (doped) generally referred to as a solution vertical flow film forming method, for example, on an endless metal conveyor belt for circulating transfer or a vertical flow support for a rotating metal drum. It is manufactured by a method of forming a film by a press die-type vertical flow doping (casting). The film formation should be extended after sag, and it is more than 1.2 times longer from the viewpoint of mechanical physical property improvement. The film width system is preferably 1 m or more from the viewpoint of productivity, but is more preferably 1.5 m or more, and most preferably l_8 m or more. <Plastic Agent> When the cellulose ester film is used for the antireflection film of the present invention, it is preferred to contain a plasticizer as described below. The plasticizer may be preferably used, for example, a phosphate ester plasticizer, a phthalate plasticizer, a trimellitic acid ester plasticizer, a pyromellitic acid ester plasticizer, a glycolic acid plasticizer, and citric acid. An ester-based plasticizer, a polyester-based plasticizer, an aromatic polyester plasticizer, a sugar ester-based plasticizer, and the like. The amount of the plasticizer to be used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the film properties, workability, and the like. -39-200921141 <Ultraviolet absorber> The long film for the low refractive index layer of the present invention is preferably an ultraviolet absorber. The ultraviolet absorber is preferably one in which the absorption of visible light having a wavelength of 4 〇〇 nm or more is less than that of ultraviolet light having a wavelength of 370 nm or less and excellent liquid crystal display properties. Specific examples of the ultraviolet absorber to be preferably used in the present invention include, for example, an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylate-based compound, a benzophenone-based compound, and a cyanoacrylate-based compound. And a nickel-miss salt compound, etc., but it is not limited to this. The ultraviolet absorber which is preferably used in the present invention is preferably a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber which has high transparency and excellent effect of preventing deterioration of a polarizing plate or a liquid crystal, and is preferably used without coloring. A small amount of benzotriazole-based UV absorber. Further, the ultraviolet absorber having a partition coefficient of 9.2 or more as described in JP-A-2001-87-825 discloses an improved surface quality of the film and excellent coatability. It is particularly preferable to use a UV absorber having a partition coefficient of 1 〇.1 or more. In addition, it is also preferable to use the ultraviolet rays of the formulas (2), (6), and (7) described in the general formula (1) or the general formula (2) and the special purpose 2000-156039 described in JP-A-6-148430. Absorbent (or UV absorbing polymer). The polymer ultraviolet absorber is commercially available as P U V A - 30 Μ (manufactured by Otsuka Chemical Co., Ltd.). -40-200921141 <Microparticles> Further, the cellulose ester film used in the present invention is a microparticle to be used. Examples of the inorganic particles of the fine particles include, for example, dititanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, potassium carbonate 'soil, calcined kaolin, calcined calcium citrate, water and calcium citrate, magnesium citrate, and Calcium phosphate. When the microparticle system contains a ruthenium, the turbidity becomes low, and it is particularly suitable for the sulphur dioxide. The average diameter of the primary particles of the microparticles is preferably 5 to 5 Onm 7 to 20 nm. These systems preferably contain a body having a particle diameter of 0.05 to 0.3/zm. The content of such fine particles in the cellulose ester film is preferably: % by mass, particularly preferably 0.1 to 〇 5% by mass. In the case of a cellulose ester film composed of a layer of a common convection method, it is preferred that the surface contains such added amount of cerium oxide as, for example, Aerosil R972, R974, R812, 200, 200V, 300, R202, 0X50, or more Japanese Aerosil ( The product name of the product) is commercially available, and the zirconia fine particles are commercially available under the trade names of, for example, Aerosil R976 and Japan Aerosil Co., Ltd., and examples of the polymerizable polymer include, for example, an anthrone resin. Fluororesin and C. It is preferably an anthrone resin, particularly preferably having a three-dimensional network structure with T 〇sp e ar 1 1 〇3, T o sp e ar 1 1 5 5 'T 〇sp e ar 1 1 0 8 , slipperiness, Oxidized sand, talc, aluminum sulphate, and strontium are preferred. It is more suitable for the second agglomeration of 0.0 5 ~ 1 formed fine particles R972V, TT600 (and can use R81 1 (to use. Acetate, For example, the trade names of T ospearl -41 - 200921141 120 , Tospearl 145 , Tospearl 3120 and Tospearl 240 (above, Toshiba Silicone Co., Ltd.) are commercially available and can be used. In the cellulose ester film used in the present invention. The kinetic friction coefficient of the back side of the active energy ray-curable resin layer is 1.0 or less. <Method for Producing Cellulose Ester Film> Next, a method for producing a cellulose ester film will be described. The cellulose ester film of the present invention is preferably used. Any of the known solution vertical flow method, melt flow method, and film stretching method. <Alkali treatment method> In the production of the antireflection film of the present invention, it is preferable to perform alkali treatment before laminating the antireflection layer. Legal system as long as The method of immersing the hard coat layer in the aqueous alkali solution is not particularly limited. The aqueous alkali solution may be an aqueous sodium hydroxide solution, a potassium hydroxide aqueous solution, an aqueous ammonia solution or the like, and preferably an aqueous sodium hydroxide solution; The alkali concentration, for example, the concentration of sodium hydroxide is preferably 〇_1 to 25% by mass, more preferably 0.5 to 15% by mass. The alkali treatment temperature is generally 10 to 80 ° C, preferably 20 to 60 ° C °, and the alkali treatment time is 5 2 to 5 minutes, preferably 30 seconds to 3 minutes. After the alkali treatment, the film is neutralized with acidic water, and then it is preferably subjected to sufficient water washing. <Atmospheric piezoelectric slurry method> -42- 200921141 In the present invention, it is at atmospheric pressure. a high-frequency voltage having a frequency of 50 kHz to 150 MHz is applied between the opposing electrodes under pressure at or near the pressure to form a discharge, and the excitation gas formed by the discharge has a hard coat layer on the transparent support or the transparent support. After the film surface is formed, the anti-reflection layer is formed by coating, and the frequency is preferably 50 kHz to 27 MHz. The counter electrode is preferably composed of a first electrode and a second electrode, and a high-frequency voltage is applied to any of the electrodes. frequency Further, the frequency of the high-frequency voltage applied to the first electrode is 1 kHz to 200 MHz, and the frequency of the high-frequency voltage applied to the second electrode is 800 kHz to 150 MHz. The plasma discharge treatment under pressure is also referred to as the atmospheric piezoelectric slurry method. That is, the present invention is a film having a hard coat layer on a transparent support or a transparent support, and pressure at or near atmospheric pressure. A high-frequency voltage of a voltage component of the first frequency «1 is applied to the first electrode between the opposing electrodes composed of the first electrode and the second electrode, and a high-frequency voltage of a voltage component of the second frequency ω2 is applied to the second electrode. The discharge is formed such that the surface of the transparent support contacts the excitation gas formed by the discharge, and an antireflection layer is formed thereon. The atmospheric piezoelectric slurry system to which the present invention is applicable can be referred to Japanese Laid-Open Patent Publication No. Hei 11-133205, JP-A-2000-185362, JP-A No. Hei 1 1 - 6 1 4 06, and JP-A-2000. The technique disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2 000- 1 2 804. -43-200921141 &lt;Production Method of Antireflection Film&gt; The laminate of the antireflection layer of the present invention can be formed on a transparent support by a known method using a dip coating method, an air knife coating method, a curtain method, and a roll. A coating method, a wire scraper coating method, a gravure coating method, a dicavity method, or an extrusion coating method are formed by coating. At the time of coating, the transparent support is preferably wound up from a width of 1.4 to 4 m in a roll state. The coating is carried out, and after drying and hardening, it is taken. Further, the antireflection film of the present invention is preferably produced by a production method in which the antireflection layer is laminated on the transparent layer and then heated in a state of being wound up in a roll form at 50°. The period of the heat treatment is appropriately set as long as the temperature is set, for example, 50 ° C, preferably 3 days or more and less than 30 days, and 160 ° C is preferably 10 minutes or more and 1 day or less. The heat treatment effect of the outer part of the roll, the center part of the roll, and the core part of the roll is not biased. It should be set at a relatively low temperature. It is preferable to carry out 7 〇 in the vicinity of 50 to 60 ° C for the heat treatment to be stable. It is preferable to adjust the temperature and humidity. 'It should be carried out in a heat treatment room such as a dust-free clean room. The core for winding the anti-reflection film into a roll shape is not particularly limited, but is preferably a hollow plastic core, and the plastic material is preferably a heat-resistant plastic core having a heat treatment temperature, and may be, for example, a phenol resin or a resin. , melamine resin, polyester resin, epoxy resin, etc., for example, the coating roll coating roll-rolled support ~ 1 60 °C is determined during the period, generally, from the left and right sides The core can withstand xylene grease. Further, -44 - 200921141, it is a thermosetting resin which is reinforced by a glass fiber or the like. The number of rolls of such a core is preferably 100 or more, more preferably 5,000 or more, and the thickness of the roll is preferably 5 cm or more. In this manner, the long-volume anti-reflection film is subjected to the above-described heat treatment in a wound state, and the roller is rotated, and the rotation is preferably one or less rotations per minute, and may be continuous or intermittent rotation. Further, the roll was rolled one time or more during heating. The anti-reflection film taken up in the long roll of the core is rotated in the heat treatment, so that it is preferable to provide a dedicated rotary table in the heat treatment chamber. When the rotation system is intermittent, the stop time should be within 10 hours. The stop position should be uniform in the circumferential direction, and the stop time should be within 1 〇 minutes, and it is most suitable for continuous rotation. The time required for the rotation speed 1 of the continuous rotation is preferably 10 hours or less. If it is fast, the apparatus becomes a burden, and therefore it is preferably in the range of 15 minutes to 2 hours. Further, in the case of a dedicated trolley having a rotation function, it is preferable to rotate the optical film roll during movement or storage. In this case, the black belt generated during the storage period is rotated to be an effective function. &lt;Polarizing Plate&gt; A polarizing plate using the antireflection film of the present invention will be described. The polarizing plate is produced by a generally known method. The back side of the antireflection film of the present invention is alkalized to at least one of the polarizers prepared by immersing and stretching the treated antireflection film in an iodine solution. -45-200921141 Using a fully alkalized type The polyvinyl alcohol aqueous solution is attached. The antireflection film can also be used on the other side, and another polarizing plate can be used to protect the film. In the antireflection film of the present invention, the polarizing plate protective film used for the other surface is preferably in the in-plane direction with a retardation R 〇 of 5 90 nm, 20 to 70 nm, and a film thickness direction retardation Rt of 100. Optical compensation film (phase difference film) with a phase difference of ~400 nm. These can be produced, for example, by the method described in Japanese Patent Application Laid-Open No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film having an optical compensation film which has an optically different layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, an optical anisotropic layer can be formed by the method described in JP-A-2003-98348. By using it in combination with the antireflection film of the present invention, it is possible to obtain a polarizing plate having an excellent planarity and a stable viewing angle expansion effect. The polarizing plate protective film used for the back side is preferably KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5 (Konica Minolta) for the commercially available cellulose ester film. Opto (share) system)). The polarizer of the main constituent elements of the polarizing plate is a component that passes only the light of the deflecting surface in a certain direction. A representative polarizer is a polyvinyl alcohol-based polarizing film, which has a dyed iodine on a polyvinyl alcohol-based film. And dyed dichroic dyes, but are not limited thereto. The polarizer can be formed by using a film-forming polyvinyl alcohol aqueous solution, followed by uniaxial stretching and dyeing, or after uniaxial stretching after dyeing, preferably with a boron compound for durability treatment. The film thickness of the polarizer is 5 to 30 / / m, preferably a polarizer of 8 to 15 #m - 46 - 200921141. A polarizing plate is bonded to the antireflection film of the present invention on the surface of the polarizer. Preferably, it is bonded by an aqueous adhesive which is completely alkalized with polyvinyl alcohol or the like. <Image display device> By combining the film-preventing surface of the polarizing plate using the antireflection film of the present invention on the viewing surface side of the image display device, it is possible to produce an image display device excellent in each. The antireflection film of the present invention preferably uses various types of driving methods such as a reflective type, a transmissive type LCD or a TN type, an STN type, an OCB type, a HAN type, a (PVA type, an MVA type), an IPS type, and the like. The antireflection film of the invention has less obvious reflection light, and has low reflectivity and excellent planarity, and is also suitable for various displays such as an indicator, a field emission display, an organic EL display, an inorganic EL, an electronic paper, and the like. Device. In particular, images with a large screen size of 30 or more display uneven color or wavy lines, and have an eye effect even for a long time of appreciation. [Embodiment] Embodiment 1 Single-sided and mainly reflective thin-type identification type, semi-VA type β LCD color-free plasma display display is not worn -47-200921141 The cellulose ester film of the material is provided with a hard coating layer and an antireflection layer. (coating composition for hard coating 1) pentaerythritol triacrylate 30 parts by mass pentaerythritol tetraacrylate 45 parts by mass of urethane acrylate (U-4HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass 1- Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass of 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinylpropane- 1-ketone (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) (Emulgen 404 'polyoxyethylene oleyl ether propylene glycol monomethyl ether methyl acetate acetone 3 parts by mass of Kao Co., Ltd.) 〇. 5 parts by mass 1 〇 45 parts by mass of 45 parts by mass of polymethyl methacrylate fine particles (average particle diameter 4 &quot; m) 2 〇 by mass &lt; formation of hard coat film H-1 &gt; die-stitching hard coating on a substrate After the coating composition 1 was applied and dried at 80 - 48 - 200921141 ° C, the high-pressure mercury lamp was irradiated with ultraviolet rays of 3030 J/cm 2 , and the hard coat layer 1 was applied so that the film thickness after hardening became 12 / zm. Further, the surface of the coating layer for coating the hard coating composition 1 is coated with the coating composition for a back coating layer described below so as to have a wet film thickness of 14/zm. The back coat layer was prepared by coating a hard coat film (HC film) H-1 having a hard coat layer and a back coat layer on a cellulose ester film. (coating composition for back coat layer) acetone 30 parts by mass of ethyl acetate 45 parts by mass of isopropanol 1 part by mass of diacetyl cellulose 0.6 parts by mass of ultrafine particle cerium oxide 2% acetone dispersion 0.2 parts by mass (Aerosil 200V manufactured by Aerosil Co., Ltd., Japan) &lt;Production of anti-glare hard coat film H-2&gt; In the preparation of H-1, the coating composition 1 for hard coating was changed to the following anti-glare hard Coating composition 2 was applied. 3 5 parts by mass of 3 5 parts by mass of 15 parts by mass of 15 parts by mass (coating composition for anti-glare hard coating 2) acetone ethyl acetate cyclohexanone toluene-49- 200921141 pentaerythritol triacrylate pentaerythritol tetrapropyl acid Ester urethane acrylate 3 〇 parts by mass 45 parts by mass of 25 parts by mass (trade name U-4HA, 8 parts by mass of Xinzhongcun Chemical Industry Co., Ltd.) 1-hydroxycyclohexyl-phenyl-ketone (Irgacure 184) 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) 8 parts by mass Fluorine-containing polymethyl methacrylate microparticles (manufactured by K.K.), average particle diameter 3 · 5 // m 2 parts by mass &lt;Production of anti-glare hard coat film Η-3] In the production of Η-2, The fluorine-containing polymethyl methacrylate fine particles were changed to 5 parts by mass. <Preparation of anti-glare hard coat film Η - 4> In the production of Η-3, fluorine-containing polymethyl methacrylate was used. The fine particles were changed to 1 part by mass. &lt;Production of anti-glare hard coat film Η-5&gt; In the production of Η-2, fluorine-containing polymethyl propylene was used. The amount of the methyl ester microparticles is changed to 15 parts by mass. -50-200921141 (Production of the intermediate film Μ-1) <Atmospheric piezoelectric slurry treatment> The atmosphere piezoelectric blade surface described in 7 is supplied to the discharge gas shown in the following atmospheric pressure. The source was used, and the frequency was 13.5 MHz, 1.5 W / cm 2 to form a discharge using the schematic device of No. 2〇〇5-351829, and the above-made Η-1 self-spray _ plasma treatment. The clearance is 〇 _ 5 mm, and the following household space is surface treated with a high g _ , a voltage of Vp = 9.5 kV and an output density. (Discharge gas) Nitrogen 80.0 vol% Oxygen 20.0 vol% The above-mentioned high-refractive-index layer coating liquid 1 was applied to the H-1 surface of the above-mentioned atmospheric piezoelectric slurry treatment, and dried at 50 ° C, and then irradiated with ultraviolet rays of 120 mJ/cm 2 with a high-pressure mercury lamp to cure the film. A high refractive index layer is provided in a manner of a thickness of 130 nm to obtain an intermediate film M-1 having a high refractive index layer. The refractive index of the high refractive index layer is 1.56. (High refractive index layer coating liquid 1) Tannic acid Zinc sol (CX-Z610M-F2, Nissan Chemical Industry Co., Ltd.) 50 parts by mass of dioxane glycol diacrylate (NK ester A-DOG, manufactured by Shin-Nakamura Chemical Co., Ltd. - 51 - 200921141), 12 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, Ciba specialtychemicals (manufactured by the company)) 2 parts by mass of 3-propenyl propyl trimethoxy decane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass of polyoxyalkylene dimethyl polyoxyalkylene copolymer (FZ-2207, T〇ray

Dow Corning (propylene glycol monomethyl ether isopropanol methyl ethyl ketone) 10% propylene glycol monomethyl ether liquid 2 parts by mass 3 60 parts by mass 3 60 parts by mass 200 parts by mass (intermediate film M-2 ~M-5 production) In the production of M-1, the hard coat film was changed to H-2 to H-5 to prepare an intermediate film Μ-2~Μ-5. (Production of Μ-6) In the production of Μ-1, the zinc silicate sol used for the preparation of the particle dispersion Α of the high refractive index layer coating liquid 1 is changed to the phosphorus-doped tin oxide (Sn〇2) (P2〇s) x) A sol was used to prepare an intermediate film M-6. "Preparation of Antireflection Film Coated with Low Refractive Index Layer" (Preparation of Antireflection Film 1 0 1) Also on the intermediate film Μ-1 produced above, die-stitch coating -52-200921141 The low refractive index layer coating liquid 1 was irradiated with ultraviolet rays of 190 mJ/cm 2 at a dry lamp of 50 ° C, and a low refractive film 101 (Comparative 1) was provided so as to have a film thickness of 92 nm. Further, the organodecane represented by the formula (2) is _trimethoxydecane, and the reactive anthrone is a -butylo(hydroxymethyl)butoxy)propyl]polydimethylguanidine (low refractive index) Layer coating solution 1) Propylene glycol monomethyl ether isopropanol acetic acid hydrolyzate A (solid content 8.6% conversion) r · Methyl propylene propyl propyl trimethoxy oxime (KBM5 03, manufactured by Shin-Etsu Chemical Co., Ltd.) « -butyl-0-[3-(2,2-bis(hydroxymethyl)dimethyloxane (FM-DA21 Chisso® ELCOM V-8209 (Isopropanol system manufactured by Catalyst Chemical Industries, Ltd.) Microparticles, solid fraction 20%) Alethylethyl acetonylacetone ligand · Diisopropyl Chemical Co., Ltd. ALCH) Isopropyl S 10%) After drying, the heat treatment rate layer is performed at a commercial pressure of mercury 1 2 ° °c. Preparation of anti-reflection r-methacryl decyl propyl-ω-[3- (2,2-double «院. 4 3 7 parts by mass 4 3 7 parts by mass 3 〇〇 parts by mass 7 5.0 parts by mass 1.25 parts by mass Butoxy)propyl]German Co., Ltd.) 1.05 parts by mass of dispersed hollow silica sand 30.0 parts by mass of acid ester (Chuanchuan Fine (diluted liquid (solid content 2.2 5 parts by mass -53- 200921141 FZ-2207 (10%) Propylene glycol monomethyl acid solution 2,40 parts by mass of the preparation of the hydrolysate A. The tetraethoxy bromide l47g (trade name: KBE〇4, manufactured by Shin-Etsu Chemical Co., Ltd.) was added with ethanol and an aqueous acetic acid solution to form 5 0 0 g 'The mixture was stirred at room temperature (2 5 T:) for 25 hours to prepare a hydrolysate A ° condensate of the condensate, the weight average molecular weight Mw was 2000, and the deciduous system was all hydrolyzed 'no residue. (Anti-reflective film (Production of 102) In the production of the antireflection film 1 〇1, the low refractive index layer coating liquid 1 was changed to the following low refractive index layer coating liquid 2'. Liquid 2) 43 7 parts by mass of 347 parts by mass 3 · 〇〇 parts by mass 165 parts by mass 1.2 5 parts by mass of propylene glycol monomethyl ether isopropanol acetate hydrolyzate B (solid content: 8.6% conversion) T-methyl propylene thiol Tris-methoxydecane (KBM5 03, manufactured by Shin-Etsu Chemical Co., Ltd.) α-butyl-ω-[3-(2,2-bis(hydroxymethyl)butoxy)propyl]polydimethyloxane (FM-DA21 Chisso Co., Ltd.) 1 . 0 5 parts by mass -54- 200921141 Aluminum ethyl acetoxyacetone ligand. Diisopropyl Isopropyl ester diluent (WH Sichuan Fine Chemical Co., Ltd. ALCH) the (solid content 10%) 2.25 parts by mass of FZ-2207 (10% propan glycol monomethyl ether a solution, Toray Dow

2.40 parts by mass of the preparation of the hydrolyzate B. The addition of ethanol and an aqueous solution of acetic acid to 4.7 g of tetraethoxy decane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) to form 500 g at room temperature (25 °) C) The hydrolyzate was prepared by stirring for 15 hours. The weight average molecular weight Mw of the condensate of decane was 800. At this point, 'Mixed ELC Ο Μ V - 8 2 0 9 (Isopropanol-dispersed hollow cerium oxide particles manufactured by Catalyst Chemical Industries, Ltd., solid content 20%) 5 8 8 g, further stirred for 2 hours' The solvent was distilled off, the concentration was adjusted, and the hydrolyzate B was prepared. (Preparation of Antireflection Film 103) In the production of the antireflection film 102, the hollow cerium oxide particles were mixed with the decane weight average molecular weight Mw of the hydrolyzate b, and the other was produced in the same manner. (Preparation of Antireflection Film 1 0 4) In the preparation of the antireflection film 1 〇2, the weight average molecular weight M w of the hydrolyzate b is 10000, and the hollow cerium oxide particles are mixed at -55 to 200921141. In the department, other departments make the same thing. (Preparation of anti-reflection film 105) In the production of the anti-reflection film 102, the sand of the hydrolyzate B "when the weight average molecular weight Mw is 450" is mixed with the hollow silica sand particles in the system, and the other processes are the same. Production. (Preparation of the anti-reflection film 106) In the production of the anti-reflection film 1〇2, the hydrolyzate B had a decane weight average molecular weight Mw of 1,100, and the hollow cerium oxide particles were mixed, and the other methods were produced in the same manner. (Preparation of the anti-reflection film 107) In the production of the anti-reflection film 1 〇 2, the hollow silica sand particles of the mixed hydrolyzate B are simultaneously mixed with 〇; -butyl_0_[3_(2, 2_ double (Hydroxymethyl)butoxy)propyl]polydimethyl oxalate (manufactured by FM-DA21 Chis so Co., Ltd.) was prepared in an amount of 1.05 parts by mass. (Preparation of anti-reflection film 108) In the production of the anti-reflection film 1 〇 2, the hollow cerium oxide particles of the mixed hydrolyzate b are simultaneously mixed with α-butyl _ω_[3_(2, 2_double ( Hydroxymethyl)butoxy)propyl]polydimethyl oxalate (made by FM-DA21 chiSS〇 Co., Ltd.) and r-methyl propyl hydroxypropyltrimethoxy sulfonium-56 - 200921141 alkane (KBM5 03 'Shin-Etsu Chemical Industry Co., Ltd., other systems are produced in the same way. (Preparation of Antireflection Film 109) In the preparation of the antireflection film 102, the hollow ceria particles of the hydrolyzate b are mixed and mixed with r-methylpropenylpropyltrimethoxydecane (KBM503 'Shin-Etsu Chemical Co., Ltd. Industrial company system), other systems are produced in the same way. (Anti-reflection film) 1) In the production of the anti-reflection film 1 〇 2, the amount of the low-refractive-index layer coating liquid 2 to be hydrolyzed B was 1.5 times. . (Preparation of the anti-reflection film 1 11) In the production of the anti-reflection film 1 〇 1, the amount of the low-refractive-index layer coating liquid 1 to be added to the hydrolyzate A was half, and the other processes were carried out in the same manner. (Preparation of the antireflection film π 2 ) The hollow cerium oxide particles described in the specification [0164] of JP-A-2006- 1 1 7924 are prepared in the same manner as in the production of the antireflection film 010. The results of evaluation regarding the above antireflection film are shown in Table 1. -57- 200921141 &lt;Evaluation Method&gt; "Refractive Index" Using Konica Minolta (share) and spectrophotometer CM- 2 5 00d ', the measurement is performed by measuring the diameter φ 8 mm and observing the field of view 2° to determine the SCI (integration). reflection). It is preferably 0.7% or less in the transparent film and 1.0% or less in the anti-glare film. "Stain Resistance" The stain resistance is judged by the contact angle of pure water. Those with large contact angles are excellent in stain resistance. The contact angle meter CA-X type manufactured by Kyowa Interface Chemical Co., Ltd. was used in an environment of 23 ° C and 5 5 % RH to measure the contact angle of pure water at a droplet diameter of 1.5 mm. "Abrasion resistance" A load of 500 g/cm2 was applied to the steel wool (SW) of #〇〇〇〇 in a 23 t, 55% RH environment, and every 1 cm width was measured 10 times round trip. The number of scratches. Further, the number of scratches was measured at a position where the number of scratches in the applied load portion was large. A: The number of scratches is 〇B: The number of scratches is less than 1~5 C: The number of scratches is 5 or more~ Less than 10 0 D: The number of scratches is 1 or more -58- 200921141 "Pencil Hardness" According to JI SK 5 600, pencils of known hardness are pencil hardness tester (HA-301, Clemence type scratch hardness tester, Tester industry), 1 kg The load was scratched to visually assess the presence or absence of scratches. If the scratch is 5 times or less, it is acceptable if it is one or less. (Example: A pencil with a 5H has a scratch of 2 or more times, and a pencil with a 4H has a scratch of 1 or less when it is one or less.) -59 - 200921141 [1®

PREPARATORY COMPARING The present invention The present invention The present invention The present invention The present invention comparatively evaluates 1_____ 11 X inch κ inch inch X inch m ffi m &lt;N rub resistance Q &lt;&lt;&lt;&lt; CQ &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt;&lt;&lt;&gt;&lt;&lt;&gt;&gt;&lt;&gt;&gt; Q 琅 〇 〇 · · · · · s s s s s s s s s s s s s s s s s s s s s s s s ο Ό 〇ooo 〇iio Si-C bond peak intensity ratio 'g 0.086 0.033 1 :0.033 0.033 0.041 1 1 0.039 0.044 0.041 0.033 0.033 0.045 0.045 C/D 0.353 0.651 I ;0.609 0.614 O 0.562 0.659 0.661 0.658 0.637 0.659 0.385 Hollow When the particles are mixed, the mixture is the same as the formula (2), organic decane 〇 I &lt; I 1 1 1 〇〇i 〇〇 reactive fluorenone oxime I 1 I 1 1 〇〇 1 1 〇〇 organic decane low condensate Mw 2000 Ο 00 Ο yrt Ο Ο o 1100 〇00 o 00 〇00 o oo 2000 2000 Contains the mass % of hollow particles 〇ο ο ο 〇oooo § 40 ※ Anti-reflective film No. ◦ 1 i SS Η sg 1 ig 丨H ov 1 r—H (N —_H _ί collar蘅&lt;π®遐 give ※ -60- 200921141 Example 2 The high refractive index layer and the hard coat layer were changed to evaluate the antiglare property as follows (Production of the antireflection film 200) In the production of the antireflection film 102, M-1 was changed to M-6. The rest of the film was produced in the same manner. (Preparation of the anti-reflection film 201) In the production of the anti-reflection film 102, except that H-1 was changed to H-2, the same method was used. In the production of the antireflection film 102, except that H-1 is changed to H-3, the same method is used. (Production of the antireflection film 203) In the production of the antireflection film 102, H-1 was changed to H-4, and the rest was produced in the same manner. (Preparation of anti-reflection film 204) In the production of the anti-reflection film 102, except that H-1 was changed to H-5, the same procedure was followed. The results of the evaluation are shown in Table 2. -61 - 200921141 t^2]

Sample No. ''——The reflectance of HC film is written through the image (width 0.25mm) pencil hardness, 200 Η-1 0-6% C 90% 4H , 201 H-2 0.7% B 70% 6H . ^ 202 H-3 0.8% A 3 5% 6H , 203 H-4 1.0% A 2 0% 6H L_ 204 H-5 1.3% A 8% 5H &lt;Evaluation Method &gt; "Write" Posted in Black Image The upper g-type material 'is written in the self-view evaluation in the room where the fluorescent lamp is lit. A: The outline of the fluorescent lamp is blurred and the writing is not noticed at all. B: The outline of the fluorescent light is slightly visible but not noticed. C: The outline of the fluorescent lamp can be seen but tolerable. D: The outline of the fluorescent light is slightly visible, and the writing is noticed. "Imagination" Using the Suga tester (manufactured by the Suga Tester Co., Ltd.), the image quality measuring device 1CM-IDP was used to measure the transmission power in the pitch width 2 2 5 m m. By writing the parameters related to the sex system. The write image should be more than 20% (width 〇 · 2 5 m m). INDUSTRIAL APPLICABILITY -62- 200921141 According to the present invention, it is possible to provide an antireflection film which is excellent in scratch resistance, low in reflectance, and excellent in visibility when used in a display device. -63-

Claims (1)

200921141 X. Patent Application No. 1. An antireflection film having at least an antireflection layer on a transparent support, characterized in that it has a refractive index of at least 1 part of hollow ceria particles and anthrone on the outermost surface. a low refractive index layer of 2 0 to 1 · 4 9 , which contains 30 to 80% by mass in the solid content of the hollow cerium oxide particles, and is determined by X-ray photoelectron spectroscopy from the surface to the depth of 5 nm, and the following The average 値Ros of the Si-C bond peak intensity ratio shown in the above formula (A) is 0.4 〇 or more, and the average 値Rot of the Si-C bond peak intensity ratio in the most surface to depth 1 〇 to 25 nm is 0.0005 to 0.10; Formula (A) (Si-C bond peak intensity ratio) = (Si-C bond peak intensity) / { (Si-C bond peak intensity) + (Si-Ο bond peak intensity)} . 2. The antireflection film of claim 1, wherein the antireflection film has a hard coat layer on the transparent support and the antireflection layer. 3. The antireflection film according to claim 1 or 2, wherein the low refractive index layer is a condensate containing an organic decane represented by the following formula (1); and the general formula (1) Si(Xl) 4 , X1 represents the hospitaloxy. 4 _ A method for producing an antireflection film, comprising: a step of forming a high refractive index layer on the transparent eraser and a step of forming a low refractive index layer on the high refractive index layer; The method for producing an antireflection film is characterized in that the low refractive index layer is formed by drying a coating liquid obtained by applying the following steps, and is produced by hydrolyzing an organic decane represented by the following formula (1). The step of lowering the condensate of the weight average molecular weight of -64 - 200921141 5 0 0~1 0 0 0; mixing the hollow cerium oxide in the low condensate to further continue the hydrolysis and condensation. 5. The method for producing an antireflection film according to the fourth aspect of the invention, wherein the step of further mixing the hollow cerium oxide particles in the low condensate to further hydrolyze, mixing the organic decane represented by the formula (2); The general formula (2) ( R ) mSi ( Χ 2 ) 4-m R represents an organic group which is not hydrolyzed, X 2 represents an alkoxy group, and m represents an integer of 1 to 4. 6. The method of producing an antireflection film according to claim 4 or 5, wherein the step of forming the hard coat layer is performed before the step of forming the high refractive index layer. The method for producing an antireflection film according to the sixth aspect of the invention, wherein the surface of the transparent support or the hard coat layer is formed in a concavo-convex shape to impart anti-glare properties. 8. The method for producing an antireflection film according to any one of claims 4 to 7, wherein after the step of forming the low refractive index layer, the method comprises the steps of: winding the antireflection film in a roll shape; ; with a roll-like state of 50 to 160. (A step of performing a heat treatment process.) A polarizing plate characterized by using an antireflection film according to any one of claims 1 to 3. 10 The anti-reflection film has an anti-glare property. 1 1 A display device using the anti-reflection film according to any one of claims 1 to 3. -65- 200921141 12. The display device of item 1 wherein the anti-reflection film has anti-glare property. -66 - 200921141 The list of the single-character table of the seven-character table is the table of the representative figure of the generation of the table: the table of the generation, the table of the case, and the generation of Nly Set one or two fingers ✓iv Nothing. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none