JP2010008757A - Antidazzle antireflection film, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antidazzle antireflection film satisfying optical characteristics such as the widening of viewing angle and the enhancement of definition and remedying degradation in the surface hardness or chemical resistance after endurance test, and to provide a polarizing plate using the same, and an image display device. <P>SOLUTION: The antidazzle antireflection film is constituted in such a way that an antidazzle layer is provided on a film substrate, the ratio of scattering reflectance occupied in the integrated reflectance in the antidazzle layer is 2-60%, a low refractive index layer is laminated directly or through other layer on the antidazzle layer and a low refractive index layer forming material contains at least one kind of a cationic polymerizable compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antiglare antireflection film, a polarizing plate and an image display device.

  One of the various displays is a liquid crystal display. If the ease of viewing as a display device such as a wide viewing angle and high definition of a liquid crystal display is pursued, a decrease in contrast due to the surface reflection of the liquid crystal display surface, that is, the polarizing plate surface cannot be ignored. In particular, in car navigation monitors and video camera monitors that are frequently used outdoors, the visibility is significantly reduced due to surface reflection.

  For this reason, anti-reflection coatings are becoming indispensable for the polarizing plates mounted on these devices. For liquid crystal displays that are frequently used outdoors, there are polarizing plates that have undergone anti-glare treatment. The actual situation is being used.

  The antiglare treatment is to blur the outline of the image reflected on the surface, thereby reducing the visibility of the reflected image and reducing the reflection of the reflected image when the display device is used. In general, the surface is roughened by an appropriate method such as sandblasting, embossing roll, chemical etching, etc., and the surface is given a fine uneven structure, the surface is given a fine uneven structure by a mold transfer method, etc., resin There are some in which fine particles are dispersed and added to the surface to give a fine concavo-convex structure on the surface, and the surface concavo-convex structure is designed to scatter reflected light in the visible light region.

  Among these anti-glare treatments, a method of dispersing and containing particles in the resin layer is desirable because it can easily give a fine uneven structure.

  For example, Patent Document 1 and Patent Document 2 disclose anti-glare processing techniques using particles that improve optical characteristics such as wide viewing angle and high definition.

  Patent Document 1 defines the center line average roughness (Ra) and ten-point average roughness (Rz) of the uneven surface of the surface including particles having a refractive index difference with the resin, and in the bright room. There has been disclosed a technique in which both the effect of reducing the reflection of a reflected image and the prevention of surface glare are achieved.

  Patent Document 2 discloses an antiglare film having at least an antiglare layer on a transparent support, the haze value resulting from internal scattering of the antiglare layer is 0 to 40%, and surface scattering. An anti-glare film characterized in that the resulting haze value is 0.3 to 20% is disclosed.

Although these technologies certainly improve the optical characteristics such as wide viewing angle and high definition to some extent, LCDs that are frequently used outdoors are less likely to be scratched (high surface hardness), environment There is also a demand for characteristics that performance does not deteriorate due to changes in the temperature. However, with the technology described in the above-mentioned patent document, it is difficult to obtain a high surface hardness. In particular, under conditions that are assumed to be used outdoors (light irradiation after a durability test such as a cycle thermo test), surface hardness and resistance The decrease in chemical properties was significant.
JP 2000-338310 A JP 2007-45142 A

  Accordingly, an object of the present invention is to use an antiglare antireflection film that satisfies optical characteristics such as wide viewing angle and high definition, and that has improved surface hardness and chemical resistance reduction after a durability test. The object is to provide a polarizing plate and an image display device.

  The above object of the present invention is achieved by the following configurations.

  1. The film base has an antiglare layer, the ratio of the scattering reflectance to the integrated reflectance of the antiglare layer is 2 to 60%, and the antiglare layer has a direct or other layer on it. An antiglare antireflection film, wherein a low refractive index layer is laminated, and the low refractive index layer forming material contains at least one cationic polymerizable compound.

  2. 2. The antiglare antireflection film as described in 1 above, wherein the scattering reflectance ratio is 20 to 60%.

  3. 3. The antiglare antireflection film as described in 1 or 2 above, wherein the antiglare layer contains fine particles, and the fine particles are fluorine-containing acrylic resin particles.

  4). 4. The antiglare antireflection film as described in any one of 1 to 3, wherein the film substrate contains a cellulose ester resin.

  5. 5. The antiglare antireflection film as described in any one of 1 to 4, wherein the film substrate contains a cellulose ester resin and an acrylic resin.

  6). 5. The antiglare antireflection film as described in any one of 1 to 4, wherein the film substrate contains a cellulose ester resin, an acrylic resin, and acrylic particles.

  7). A polarizing plate characterized by using the antiglare antireflection film described in any one of 1 to 6 on at least one surface.

  8). The image display apparatus characterized by using the anti-glare antireflection film described in any one of 1 to 6 above or the polarizing plate described in 7 above.

  According to the present invention, an antiglare antireflection film satisfying optical characteristics such as a wide viewing angle and high definition and having improved deterioration of surface hardness and chemical resistance after a durability test is used. A polarizing plate and an image display device can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The antiglare antireflection film of the present invention is characterized in that the ratio of the scattered reflectance to the integrated reflectance of the antiglare layer (hereinafter abbreviated as the scattering reflectance ratio) is 2 to 60%.

  Until now, in order to improve contrast, it has been said that a smaller integrated reflectance is better. The integral reflectance is represented by the sum of the regular reflectance and the scattering reflectance (integral reflectance = regular reflectance + scattering reflectance). The present inventor has determined that the scattering reflectance is higher than the absolute value of the integral reflectance. When the scattering reflectance ratio (scattering reflectance ratio = scattering reflectance / integral reflectance), which is the ratio of the above, is within a certain range, it is found effective for suppressing the decrease in film strength after the durability test. As a result of proceeding, by laminating a low refractive index layer containing at least one cationic polymerization compound directly or via another layer on the antiglare layer having the scattering reflectance in the above range, It was found that the effect of suppressing the decrease in film strength was obtained, and the present invention was achieved.

  Details of the present invention will be described below.

  The antiglare antireflection film of the present invention is characterized in that the ratio of the scattered reflectance to the integrated reflectance of the antiglare layer (hereinafter abbreviated as the scattering reflectance ratio) is 2 to 60%. Furthermore, the ratio of the scattering reflectance is preferably in the range of 20 to 60% from the viewpoint that the target effect is more easily exhibited.

  The scattering reflectance ratio is SCI (integrated reflectance) and SCE (scattering reflectance) under the conditions of a measurement diameter of 8 mm and an observation field of view of 2 ° using a spectrocolorimeter CM-2500d manufactured by Konica Minolta Sensing Co., Ltd. It can be determined by measuring.

  Moreover, it is preferable that the anti-glare antireflection film of the present invention has a surface haze measured by transmitted light (haze caused by surface scattering of the film) of 0.5 to 15%. The surface haze is obtained by subtracting the internal haze, which is a haze caused by internal scattering, from the total haze.

  Further, as the surface irregularity shape of the antiglare layer, the center line average roughness (arithmetic average roughness) Ra is preferably 0.03 to 0.35 μm, more preferably 0.08 to 0.3 μm, and particularly preferably. 0.08 to 0.22 μm.

  Further, the 10-point average roughness Rz is 10 times or less the centerline average roughness Ra, and the average mountain valley distance Sm is preferably 50 to 150 μm, more preferably 50 to 120 μm, and the standard deviation of the height of the protrusion from the deepest part of the unevenness. Is 0.5 μm or less, the standard deviation of the average mountain-valley distance Sm with respect to the center line is preferably 20 μm or less, and the surface with the inclination angle of 0 to 5 degrees is preferably 10% or more.

  By designing in this way, sufficient antiglare property and contrast can be obtained. In particular, with respect to the center line average roughness Ra, a sufficient antiglare property can be obtained by setting it to 0.08 μm or more, and the smaller the value is 0.3 μm or less, the better.

  The center line average roughness Ra can be measured with an optical interference type surface roughness measuring instrument, for example, using an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO).

  The anti-glare property as used in the present invention is the use of an image display device such as a liquid crystal display, an organic EL display, a plasma display, etc. by reducing the visibility of the reflected image by blurring the outline of the image reflected on the surface of the film substrate At times, the reflection image does not matter.

<Anti-glare layer>
Next, the antiglare layer will be described.

  The antiglare layer is basically a binder layer mainly composed of a transparent resin, for example, an active energy ray curable resin, and the scattering reflection ratio can be easily controlled within the above range, and the object effects of the present invention can be easily exhibited. Therefore, it is preferable to contain fluorine-containing acrylic resin particles. First, the fluorine-containing acrylic resin particles will be described.

  The fluorine-containing acrylic resin particles are, for example, particles formed from a fluorine-containing acrylic ester or methacrylic ester polymer.

  Specific examples of the fluorine-containing acrylic ester or methacrylic ester include 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2-perfluorodecylethyl (Meth) acrylate, 3-perf Orobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylbutyl ) Ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) ) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) ) Acrylate, 1H-1- Trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctylethyl acrylate, 2- (perfluorobutyl) ethyl -Α-fluoroacrylate.

  Among the fluorine-containing acrylic resin particles, particles made of 2- (perfluorobutyl) ethyl-α-fluoroacrylate, fluorine-containing polymethyl methacrylate particles, and fluorine-containing methacrylic acid in the presence of a crosslinking agent are vinyl monomers. Particles copolymerized with are preferred, more preferably fluorine-containing polymethyl methacrylate particles.

  A vinyl monomer copolymerizable with a fluorine-containing (meth) acrylic acid ester may be copolymerized.

  These may be those having a vinyl group, specifically, alkyl methacrylates such as methyl methacrylate and butyl methacrylate, alkyl acrylates such as methyl acrylate and ethyl acrylate, styrene, α -Styrenes, such as methylstyrene, etc. are mentioned, These can be used individually or in mixture.

  The crosslinking agent used in the polymerization reaction is not particularly limited, but those having two or more unsaturated groups are preferably used. For example, bifunctional dimethacrylates such as ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate are used. And trimethylolpropane trimethacrylate, divinylbenzene and the like.

  The polymerization reaction for producing the fluorine-containing polymethyl methacrylate particles may be either random copolymerization or block copolymerization. Specifically, for example, the method described in JP-A No. 2000-169658 can also be mentioned.

  As a commercial item, Negami Industrial Co., Ltd. product: MF-0043, Nippon Paint product: S-4000, FS-701, etc. are mentioned. These fluorine-containing acrylic resin particles may be used alone or in combination of two or more.

  Moreover, the state of these fluorine-containing acrylic resin particles may be added in any state such as powder or emulsion.

  Moreover, you may use the fluorine-containing crosslinked particle of Paragraphs 0028-0055 of Unexamined-Japanese-Patent No. 2004-83707.

  The refractive index of the fluorine-containing acrylic resin particles is preferably 1.38 to 1.44. As content of a fluorine-containing acrylic resin particle, 0.01-500 mass parts is preferable with respect to 100 mass parts of transparent resin which comprises a glare-proof layer, More preferably, it is 0.1-100 mass parts, Especially preferably, 1 to 60 parts by mass.

  The average particle diameter of the fluorine-containing acrylic resin particles is 1.5 to 6 μm, and preferably 2.0 to 4.0 μm. The average particle diameter is 100 particles obtained by taking a scanning electron micrograph of the particles (1000 particles or more), and using the image processing apparatus LUZEX-III (manufactured by Nireco) as the diameter of the particles in the photograph. The average value was measured and the average value was calculated.

  Further, other preferably contained particles are preferably particles having an average particle size of 0.01 to 1 μm, and specifically include inorganic particles mainly composed of silica.

  Examples of the silica particles include product names such as Nippon Aerosil Co., Ltd., Aerosil 200, 200V, 300, Degussa, Aerosil OX50, TT600, etc., Nippon Shokubai Co., Ltd., KEP-10, KEP-50, KEP-100 and the like.

  Colloidal silica may also be used. Colloidal silica is obtained by dispersing silicon dioxide in water or an organic solvent in a colloidal form, and is not particularly limited, and is spherical, acicular or beaded.

  Such colloidal silica is commercially available, and examples thereof include the Snowtex series of Nissan Chemical Industries, the Cataloid-S series of Catalytic Chemical Industries, and the Rebacil series of Bayer.

  Also, beaded colloidal silica in which primary particles of cation-modified with alumina sol or aluminum hydroxide are bonded in a bead shape by bonding the particles with divalent or higher metal ions.

  Examples of the beaded colloidal silica include SNOWTEX-AK series, SNOWTEX-PS series, SNOWTEX-UP series, etc. manufactured by Nissan Chemical Industries, Ltd. Specifically, IPS-ST-L (isopropanol silica sol, particle size 40-50 nm). , Silica concentration 30%), MEK-ST-MS (methyl ethyl ketone silica sol, particle diameter 17-23 nm, silica concentration 35%), etc. MEK-ST (methyl ethyl ketone silica sol, particle diameter 10-15 nm, silica concentration 30%), MEK- ST-L (methyl ethyl ketone silica sol, particle diameter 40-50 nm, silica concentration 30%), MEK-ST-UP (methyl ethyl ketone silica sol, particle diameter 9-15 nm (chain structure), silica concentration 20%) and the like can be mentioned.

  Particles having an average particle diameter of 0.01 to 1 μm are contained in 100 parts by mass of the transparent resin constituting the antiglare layer, because of the stability of the coating liquid forming the antiglare layer and the dispersibility of the dispersion. On the other hand, 0.01-500 mass parts is preferable, More preferably, it is 0.1-100 mass parts.

  The content ratio with respect to particles having an average particle diameter of 0.01 to 1 μm can be appropriately selected within a range of 0 to 500 mass% with respect to particles having an average particle diameter of 1.5 to 6 μm.

The particles may be added in any state such as powder or emulsion. Moreover, the density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

<Transparent resin>
The refractive index of the transparent resin constituting the antiglare layer is preferably 1.50 or more, more preferably 1.50 to 1.70.

  In order to make the refractive index within this range, the type and amount ratio of the transparent resin may be appropriately selected. If the refractive index is less than 1.50, it is difficult to obtain a resin with high hardness. If the refractive index is greater than 1.70, unevenness of the film tends to be noticeable.

  The refractive index of the transparent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry.

  The transparent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain.

  Particularly preferred is a resin that cures through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams.

  Examples of the curable resin include UV curable urethane acrylate resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, and UV curable epoxy resins. A type acrylate resin is preferably used.

  UV curable urethane acrylate resins are generally obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer and further adding 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter acrylate includes methacrylate). It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate.

  For example, those described in JP 59-151110 A can be used. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Those described in the publication can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in Japanese Patent No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of photopolymerization initiators for these curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used.

  The photopolymerization initiator or photosensitizer is used in an amount of 0.1 to 25 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the curable resin.

  As acrylate resins, methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyl dimethyl adiacrylate , Trimethylolpropane triacrylate, pentaerythritol tetraacrylic ester and the like.

  As these commercial products, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (manufactured by Asahi Denka Co., Ltd.); -101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG -1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20, DP -30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, KRM703 , KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122 RC-5152, RC-5171, RC-5180, RC-5181 (Dainippon Ink Chemical Co., Ltd.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), NK hard B-420, NK ester A-DOG, NK ester A-IBD-2E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used.

  Other examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dioxane glycol acrylate, ethoxylated acrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can do. Two or more of the acrylate resins may be used in combination. Further, in the antiglare layer composition, it is preferably 15% by mass or more and less than 70% by mass in the solid content from the viewpoint of stability, polymerization reactivity and the like in the antiglare layer composition.

  Further, the antiglare layer may contain a fluorine-acrylic copolymer resin. The fluorine-acrylic copolymer resin is a copolymer resin composed of a fluorine monomer and an acrylic monomer, and a block copolymer composed of a fluorine monomer segment and an acrylic monomer segment is particularly preferable. In addition, a cationically polymerizable compound described in the low refractive index layer may also be used.

<Other substances contained in the antiglare layer>
For the anti-glare layer, other organic particles include silicone resin powder, polystyrene resin powder, polycarbonate resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluorinated ethylene. An ultraviolet curable resin composition such as a resin powder can also be added. If necessary, the particles described in JP-A No. 2000-241807 may be further included.

  The refractive index of the other particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65.

  Note that the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in a solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. The refractive index of the solvent can be measured by measuring with an Abbe refractometer.

  Further, the antiglare layer preferably contains the following silicone surfactant, fluorine compound, polyoxyether compound and the like.

  These components increase productivity by imparting high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorine-based compound include fluoroaliphatic group-containing copolymers, and specifically, the compounds and description methods described in paragraphs 0053 to 0082 of JP-A-2007-45142 can be used.

  In addition, the compounds and description methods described in paragraphs 0008 to 0031 of JP-A No. 2000-119354 can also be used.

  Since these components are added in the range of 0.01 to 5% by mass with respect to the solid content component in the coating solution, the effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears. preferable.

  In addition, as the fluorine-based compound, a copolymer polymer obtained by grafting siloxane (including polysiloxane) and / or organosiloxane (including organopolysiloxane) to a fluororesin can also be preferably used.

  Specific examples include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Chemical Industry Co., Ltd. These compounds may be used as a mixture.

  Commercially available products of polyoxyethylene alkyl ether include Emulgen 1108, Emulgen 1118S-70 (manufactured by Kao Corporation), and commercially available products of polyoxyethylene lauryl ether include Emulgen 103, Emulgen 104P, Emulgen 105, and Emulgen 106. , Emulgen 108P, Emulgen 120P, Emulgen 120P, Emulgen 123P, Emulgen 147, Emulgen 150, Emulgen 130K (above, manufactured by Kao Corporation), and polyoxyethylene cetyl ether as commercially available products include Emulgen 210P, Emulgen 220 (above, Kao Corporation), polyoxyethylene stearyl ether commercially available products such as Emulgen 220, Emulgen 306P (above, Kao Corporation), polyoxyalkylene alkyl ether market As the products, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110 (manufactured by Kao Corporation), polyoxyethylene higher alcohol ether, commercially available products such as Emulgen 705, Emulgen 707, Emulgen 709 and the like.

  The polyoxyether compounds may be used alone or in combination of two or more. Moreover, you may use together an acetylene glycol type compound, a nonionic surfactant, a radically polymerizable nonionic surfactant, etc.

  The antiglare layer may contain a color tone adjusting agent (dye or pigment or the like) having a color tone adjusting function as a color correction filter for various display elements.

  Moreover, you may make it contain an electromagnetic wave shielding agent or an infrared absorber, etc. and to have each function.

  The antiglare layer may contain other functional thiol compounds as curing aids, such as 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1, 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like can be mentioned.

  Moreover, as a commercial item, Showa Denko Co., Ltd. make, brand name Karenz MT series, etc. are mentioned. The other functional thiol compound is preferably added in the range of 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin.

  By adding in the said range, it acts suitably as a hardening adjuvant and exists stably also in a glare-proof layer. The antiglare layer has at least one selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the organic particles, in order to improve hardness, prevent static electricity, and adjust the refractive index of the layer. Containing inorganic particles having an average particle size of 10 μm or less, for example 2 μm or less, preferably 0.2 μm or less, particularly preferably 0.1 μm or less, more preferably 0.06 μm or less. May be.

  Of the oxides of at least one metal selected from titanium, zirconium, indium, zinc, tin, and antimony, titanium and zirconium are preferable.

  The surface of the inorganic particles used in the antiglare layer is preferably subjected to silane coupling treatment or titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.

  The surface treatment agent may be used by mixing in the coating composition without coupling treatment in advance.

  When using these inorganic particles, the addition amount is preferably 10 to 90% of the total mass of the antiglare layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.

  Such inorganic particles have a particle size that is sufficiently smaller than the wavelength of light, so that scattering does not occur, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The antiglare layer may have a multilayer structure of two or more layers. One or both of them may be a so-called conductive layer containing, for example, conductive fine particles, a π-conjugated conductive polymer, or an ionic polymer. Examples of the π-conjugated conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene) , Poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3 Octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-di Ethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-dioctyloxythiophene), poly ( 3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4 4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4 -Ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene) , Polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-N-propylpyrrole), poly (3-butylpyrrole), poly (3-octyl) Pyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3 -Methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl 4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly ( 3-methyl-4-hexyloxypyrrole), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly (3-anilinesulfonic acid) and the like. . Each of these may be used alone, or two types of copolymers can be suitably used.

<Method for producing antiglare layer>
The antiglare layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a coating method for forming an antiglare layer is applied using a known method such as an inkjet method, and after application, is heated and dried. It is preferable to perform UV curing treatment. The antiglare layer may be composed of two or more layers.

  The coating amount is suitably 0.1 to 40 μm, preferably 0.5 to 30 μm, as the wet film thickness. Moreover, as a dry film thickness, it is an average film thickness of 0.1-30 micrometers, Preferably it is 1-20 micrometers. Within this range, lack of hardness, deterioration of curling and brittleness, and deterioration of workability are prevented.

  As the light source for the UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 50 to 300 mJ / cm ² . Further, the oxygen concentration may be reduced to 0.01% to 5% by nitrogen purge at the time of active ray irradiation.

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 500 N / m. More preferably, it is 250-500 N / m. At 250 to 500 N / m, the objective effect of the present invention is better exhibited after a more severe durability test. When it exceeds 500 N / m, it becomes difficult to maintain the flatness of the film. The width tension applying method is not particularly limited, and may be a free span, a back roll or the like. In addition, a method of applying tension using a width regulating device in the width direction is also effective, preferably stretching by 3.0% or less, more preferably by stretching by 0.05% to 1.0%. Is more effective. Thereby, a film excellent in blocking resistance can be obtained.

  The coating composition that forms the antiglare layer may contain a solvent. Examples of the organic solvent contained in the coating composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). , Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents may be appropriately selected or mixed for use.

  As the organic solvent, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is preferable. Moreover, as content of an organic solvent, 5-80 mass% is preferable in a coating composition.

<Low refractive index layer>
Next, the low refractive index layer will be described.

  The low refractive index layer in the present invention means a layer lower than the refractive index of the film substrate as a support, and the refractive index is in the range of 1.30 to 1.45 when measured at 23 ° C. and a wavelength of 550 nm. preferable.

  The film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably 30 nm to 0.2 μm.

  Next, the composition for forming a low refractive index layer will be described.

  First, a cationically polymerizable compound that is one of the features of the present invention will be described.

(Cationically polymerizable compound)
The low refractive index layer contains a cationic polymerizable compound as a binder. Any cationically polymerizable compound can be used as long as it undergoes cationic polymerization by irradiation with energy active rays or heat to form a resin. Specific examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group. Among them, a compound having a functional group such as an epoxy group or a vinyl ether group is preferably used in the present invention. Examples of the cationically polymerizable compound having an epoxy group or a vinyl ether group include phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, 3,4-epoxycyclohexylmethyl-3 ′. , 4′-epoxycyclohexanecarboxylate, bis- (6-methyl-3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1 , 4-cyclohexanedimethanol divinyl ether and the like. Moreover, as an epoxy compound, a polymer compound can also be used, for example, it is compoundable by the method currently disclosed by Unexamined-Japanese-Patent No. 7-247313.

  Moreover, an oxetane compound can also be mentioned as a cationically polymerizable compound. As the oxetane compound, any compound having at least one oxetane ring in the molecule may be used, and various compounds can be used as such an oxetane compound. Preferred compounds include the following general formula (I), Compounds of general formula (II) and general formula (III).

(Wherein R ⁷ represents hydrogen, fluorine, alkyl group, fluoroalkyl group, allyl group, aryl group or furyl group, m represents an integer of 1 to 4, Z represents oxygen or sulfur, R ⁸ Represents a monovalent to tetravalent organic group depending on the value of m.)

(In the formula, R ⁹ and R ¹⁰ each independently represent hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group, or a furyl group.)

(Wherein R ¹¹ represents hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group or a furyl group, R ¹² represents hydrogen or an inert monovalent organic group, and R ¹³ represents water Represents a decomposable functional group, n represents an integer of 1 to 5, and p represents an integer of 0 to 2.)
In the above general formulas (I) to (III), when R ⁷ , R ⁹ , R ¹⁰ and R ¹¹ are alkyl groups, the carbon number thereof can be about 1 to 6, specifically, methyl, Examples include ethyl, propyl, butyl and the like. The fluoroalkyl group can also have about 1 to 6 carbon atoms. Furthermore, the aryl group is typically phenyl or naphthyl, which may be substituted with other groups.

In addition, the organic group represented by R ⁸ in the general formula (I) is not particularly limited. For example, when m is 1, an alkyl group, a phenyl group, or the like, and when m is 2, the number of carbon atoms is When m is 3 or 4, 1 to 12 linear or branched alkylene groups, linear or branched poly (alkyleneoxy) groups, and the like, a similar polyvalent functional group is exemplified.

The inactive monovalent organic group represented by R ¹² in the general formula (II) typically includes an alkyl group having 1 to 4 carbon atoms, and is hydrolyzable represented by R ^13. Examples of the functional group include an alkoxy group having 1 to 5 carbon atoms including methoxy and ethoxy, and a halogen atom such as a chlorine atom and a bromine atom.

  Furthermore, if necessary, a (co) polymer containing a monomer having a hydrogen bond-forming group and a reactive polymer having an oxetanyl group in the main chain or side chain and having a number average molecular weight of 20,000 or more can also be used.

  Moreover, you may use the fluorine-containing vinyl ether compound as shown by the following general formula.

_{CH 2 = CH-O- (CH} 2) a-O- (CH 2) b-Rf- (CH 2) b-O- (CH 2) a-O-CH = CH 2
(In the formula, Rf represents a fluorine-containing alkyl group, a represents an integer of 1 to 2, and b represents an integer of 0 to 3. Rf may be a linear or branched alkyl group.)
Specific compounds are as follows.

_{CH 2 = CH-O-CH} 2 -O- (CF 2) k-O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O-CH 2 - (CF 2) k-CH 2 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O- (CH 2) 2 - (CF 2) k- (CH 2) 2 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O-CH} 2 -O- (CH 2) 3 - (CF 2) k- (CH 2) 3 -O-CH 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CF 2) k-O- (CH2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O-CH 2 - (CF 2) k-CH 2 -O- (CH 2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CH 2) 2 - (CF 2) k- (CH 2) 2 -O- (CH 2) 2 -O-CH = CH 2
_{CH 2 = CH-O- (CH} 2) 2 -O- (CH 2) 3 - (CF 2) k- (CH 2) 3 -O- (CH 2) 2 -O-CH = CH 2
In the above, k is preferably an integer of 2 or more and 12 or less, and more preferably, k is 4 or more and 10 or less. The fluorine-containing vinyl ether compound can be produced by reacting a fluorine-containing dialcohol and a vinyl ether having a halogen group in the presence of an alkali catalyst. Moreover, you may contain a fluorine-containing epoxy compound, for example, the compound as described in General formula (1)-(4) of Unexamined-Japanese-Patent No. 11-309830 can be used. Specific examples include the following fluorine-containing epoxy compounds 1 to 4, but are not limited thereto.

  Fluorine-containing epoxy compound 1

  Fluorine-containing epoxy compound 2

  Fluorine-containing epoxy compound 3

  Fluorine-containing epoxy compound 4

  In addition, the compounds described in JP-A-2007-254650, paragraph numbers [116] to [126] can also be mentioned.

  The above-mentioned cationically polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the low refractive layer coating composition from the viewpoint of the stability of the low refractive layer coating composition.

(Cationic polymerization accelerator)
Examples of the compound that accelerates the polymerization of the cationic polymerizable compound include known acids and photoacid generators. Examples of the photoacid generator include a cationic polymerization photoinitiator, a dye photodecoloring agent, a photochromic agent, a known compound used in a microresist, and a mixture thereof. Specific examples include onium compounds, organic halogen compounds, and disulfone compounds, and onium compounds are preferable. As the onium compound, diazonium salts, sulfonium salts, iodonium salts and the like represented by the following formulas are preferably used.

ArN ₂ ⁺ Z ⁻ ,
(R) ₃ S ⁺ Z ⁻ ,
(R) ₂ I ⁺ Z ⁻
In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different, and Z ⁻ Represents a non-basic and non-nucleophilic anion.

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

  Examples of other onium compounds include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, boron salts, and the like. For example, compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162 Etc.

  Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the material stability of the compound.

  Specific examples of onium salts that can be suitably used include, for example, an amylated sulfonium salt described in paragraph No. [0035] of JP-A No. 9-268205, and paragraph Nos. Of JP-A No. 2000-71366. 0010]-[0011] diaryl iodonium salt or triarylsulfonium salt, thiobenzoic acid S-phenyl ester sulfonium salt described in JP-A-2001-288205, paragraph number [0017], JP-A-2001-133696 Onium salts and the like described in paragraph numbers [0030] to [0033] of the publication.

  Other examples of the acid generator include organometallic / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], and a photoacid generator having an o-nitrobenzyl type protecting group. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.). Since many of these compounds are commercially available, such commercially available products can be used. Commercially available initiators include, for example, “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd., and “Adekaoptomer SP-150” (available from ADEKA Corporation) Product name), Adeka optomer SP-300 (product name), “RHODORSIL PHOTOINITIAOR 2074” (product name) sold by Rhodia Japan Co., Ltd., and the like.

  As the acid, Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate, Examples thereof include Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.

  Aromatic polycarboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, or anhydrides thereof, maleic acid, maleic anhydride, succinic acid, succinic anhydride Aliphatic polycarboxylic acids such as or anhydrides thereof are also included.

  As an acid, only 1 type may be used and 2 or more types may be used together.

  These acids and photoacid generators are preferably added in a proportion of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the cationic polymerizable compound. is there. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity, and the like.

(Radically polymerizable compound)
Next, the radical polymerizable compound will be described. Examples of the radical polymerizable group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a compound having a (meth) acryloyl group is preferable. Moreover, as a radically polymerizable compound, it is preferable to contain the polyfunctional monomer which contains a 2 or more radically polymerizable group in a molecule | numerator. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Examples of the polyfunctional acrylate monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. , Tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerol triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Lithol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate Acrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, isobornyl acrylate and the like preferably. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  Commercially available polyfunctional acrylates include Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka Co., Ltd.); Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8 MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP-10, DP-20 DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KRM7033, RM 7039, KRM 7130, KRM 7131, UVECRYL 29201, UVECRYL 29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC- 5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.); B420 (manufactured by Shin-Nakamura Chemical Co., Ltd.) or the like can be appropriately selected and used.

  The addition amount of the radical polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the low refractive layer coating composition from the viewpoint of the stability of the low refractive layer coating composition.

(Radical polymerization accelerator)
In order to accelerate the curing of the radical polymerizable compound, it is preferable to use a photopolymerization initiator in combination with the radical polymerizable compound. When the photopolymerization initiator and the radical polymerizable compound are used in combination, it is preferable to contain the photopolymerization initiator and the radical polymerizable compound in a mass ratio of 20: 100 to 0.01: 100.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

  Furthermore, a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (OSi-2) can also be used as a binder.

  The fluorine-substituted alkyl group-containing silane compound represented by the general formula (OSi-2) will be described.

In the formula, R ^{1 to} R ⁶ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and 6 to 12 carbon atoms, preferably 6 carbon atoms. 10 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkylaryl groups, arylalkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkenyl groups, or 1 to 6 carbon atoms, preferably 1 to 3 alkoxy groups, a hydrogen atom or a halogen atom.

Rf represents-(CaHbFc)-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, examples of such a fluorine-containing silicone compound include (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ and (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H. ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (MeO) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H ₄ Si _(OC 2 _{H 5) 3,} include methoxy disilane compound or the like represented by _{(H 5 C 2 O) 3} SiC 2 H 4 C 6 F 12 C 2 H 4 Si (OC 2 H 5) 3.

  If the fluorine-containing alkyl group-containing silane compound is included as a binder, the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer which is the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.

  In addition, when a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only the hydrophobic property but also the slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch strength can be obtained. Can do. Further, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage rate of the binder is equivalent to that of the conductive layer. Therefore, it is possible to form a transparent film having excellent adhesion to the conductive layer. Furthermore, when the transparent film is heat-treated, the conductive layer is not peeled off due to the difference in shrinkage rate, and a portion having no electrical contact is not generated in the transparent conductive layer. For this reason, sufficient electroconductivity can be maintained as a whole film.

  A transparent film containing a fluorine-substituted alkyl group-containing silane compound and hollow silica-based fine particles having the outer shell layer and being porous or hollow inside has high scratch strength and is evaluated by eraser strength or nail strength. The film strength is high, the pencil hardness is high, and a transparent film excellent in strength can be formed.

  The low refractive index layer may contain a silane coupling agent. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

The low refractive index layer may contain a silicon compound represented by CF ₃ (CF ₂ ) nCH ₂ CH ₂ Si (OR ₁ ) ₃ . (In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 12.) Specific examples of the compound include trifluoropropyltrimethoxysilane and trifluoropropyl. Examples include triethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and these are used alone or in combination of two or more. Can be used. _{It may} also contain H 2 NCONH (CH) mSi ( OR2) silicon compound in the terminal position represented by ₃ having a ureido group _(H 2 NCONH-). (In the formula, R2 represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 5.) Specific compounds include γ-ureidopropyltrimethoxysilane and γ-ureido. Examples thereof include propyltriethoxysilane and γ-ureidopropyltripropoxysilane. Among these, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and the like are particularly preferable.

  In addition, the low refractive index layer can use, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, etc. as a binder. .

  In addition, the low refractive index layer includes, for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, fluoroacrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin as a binder.

  The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder has a function of maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is suitably adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap.

  The composition for forming a low refractive index layer used in the present invention may contain at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles. Particles having a shell layer and porous or hollow inside are preferably hollow silica-based fine particles.

(Hollow silica fine particles)
The hollow silica-based fine particles are (I) a composite particle comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the content is a solvent, gas or porous It is a hollow particle filled with a porous material. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or both.

  Note that the cavity particles are particles having a cavity inside, and the cavity is covered with a coating layer (also referred to as a particle wall). The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such hollow fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The average particle diameter of the hollow fine particles to be used is desirably 3/2 to 1/10, preferably 2/3 to 1/10, of the average film thickness of the low refractive index layer to be formed. These hollow fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohol (for example, diacetone alcohol), or a mixed solvent containing these is preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. In some cases, the refractive index of the particles is increased by entering the voids inside the composite particles, and the effect of low refractive index may not be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. .

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. Moreover, components other than silica may be contained, and specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O _3. , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ and WO _3. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, a pore volume is small and particles having a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a material having a lower refractive index. is there.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or higher, and then an aqueous solution of the compound is added to the above-mentioned alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and an inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, Preferably it is in the range of 0.2-2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing the hollow particles, the molar ratio of MO _X / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organic silicon compound used for the silica protective film formed of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, such as acrylic group An alkoxysilane represented by a hydrocarbon group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, a hollow particle precursor). When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. As the hollow silica-based fine particles, those commercially available from Catalyst Kasei Co., Ltd. can be preferably used.

  The content of the hollow silica-based fine particles having an outer shell layer and porous or hollow inside is preferably 10 to 50% by mass. In order to obtain the effect of a low refractive index, the content is preferably 15% by mass or more. Most preferably, it is 20-50 mass%.

  As a method of adding to the low refractive index layer, for example, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of the tetraalkoxysilane, pure water, and alcohol is added to the dispersion of the hollow silica fine particles. The silicic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles. At this time, tetraalkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used. Silica-based fine particles may be those produced by the production method described in WO2007 / 099814.

(solvent)
The low refractive index layer preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The solid content concentration in the low refractive index layer coating composition is preferably 1 to 4% by mass. By making the solid content concentration 4% by mass or less, coating unevenness is less likely to occur, and the content is 1% by mass or more. By doing so, the drying load is reduced.

  The low refractive index layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a known method such as an inkjet method, and the above coating composition for forming the low refractive index layer is applied, and after coating, It is formed by heat drying and curing treatment as necessary.

  The coating amount is suitably 0.05 to 100 μm, preferably 0.1 to 50 μm, as the wet film thickness. Further, the solid content concentration of the coating composition is adjusted so that the dry film thickness becomes the above film thickness.

Moreover, you may include the process of heat-processing at the temperature of 50-160 degreeC after forming a low-refractive-index layer. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably a period of 3 days or more and less than 30 days, and if it is 160 ° C., a range of 10 minutes or more and 1 day or less is preferable . Examples of the curing method include a method of thermosetting by heating, a method of curing by irradiation with light such as ultraviolet rays, and the like. When thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, and more preferably 80 to 150 ° C. When curing by light irradiation, exposure of the irradiation light is ^{preferably, 100mJ / cm 2 ~500mJ / cm} 2 and more preferably ^{10mJ / cm 2 ~10J / cm 2} .

Here, the wavelength range of the irradiated light is not particularly limited, but light having a wavelength in the ultraviolet region is preferably used. Specifically, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² , and particularly preferably 20 to 100 mJ / cm ² .

(High refractive index layer)
In addition to the above-described low refractive index layer, the following high refractive index layer may be included.

  The high refractive index layer preferably contains metal oxide fine particles. The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a minute amount of atoms. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is particularly preferable to use it as the main component. In particular, it is preferable to contain zinc antimonate particles.

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the film as the support, and is preferably in the range of 1.5 to 2.2 when measured at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. Two or more kinds of surface treatments may be combined.

  The thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The ratio of the metal oxide fine particles to be used and a binder such as an actinic ray curable resin to be described later varies depending on the kind of metal oxide fine particles, the particle size, etc. The latter one is preferable.

  The amount of the metal oxide fine particles used is preferably 5% by mass to 85% by mass, more preferably 10% by mass to 80% by mass, and most preferably 20% by mass to 75% by mass in the high refractive index layer. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength deteriorates.

  The metal oxide fine particles are supplied to a coating solution for forming a high refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder. It is also preferable to contain a dispersant.

  Furthermore, metal oxide fine particles having a core / shell structure may be contained. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, etc. can be used. Titanium may be the main component.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated. Two or more inorganic fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, U.S. Pat. No. 3,410,708, JP-B-58-47061, U.S. Pat. No. 2,885,366, and U.S. Pat. No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. Can do.

  The high refractive index layer or the low refractive index layer described above can contain a compound represented by the following general formula (CL1) or a chelate compound thereof, and can improve physical properties such as hardness.

General formula (CL1) AnMBx-n
In the formula, M represents a metal atom, A represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. x represents the valence of the metal atom M, and n represents an integer of 2 or more and x or less.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. The metal compound belonging to the general formula (CL1) includes an alkoxide having two or more alkoxyl groups directly bonded to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxide, zirconium alkoxide, or chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of promoting the reaction of the ultraviolet curable resin and metal alkoxide, the physical properties of the coating film can be improved by adding a small amount.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound that is stable against water mixing and is excellent in the effect of reinforcing the coating film.

  The addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.

  The high refractive index layer preferably contains a radical polymerizable compound as a binder for the metal oxide fine particles in order to improve the film forming property and physical properties of the coating film. As the radically polymerizable compound, a monomer or oligomer having two or more functional groups that cause a polymerization reaction directly by irradiation with actinic rays such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator is used. Specifically, polyol acrylate, epoxy acrylate, urethane acrylate, polyester acrylate or a mixture thereof is preferable. For example, the polyfunctional acrylate compound described in the hard coat layer described above is preferable.

  The addition amount of the radical polymerizable compound is preferably 15% by mass or more and less than 50% by mass in the solid content in the high refractive index composition.

  In order to accelerate curing of the radically polymerizable compound, it is preferable to contain a photopolymerization initiator. The addition amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: radically polymerizable compound = 3: 7 to 1: 9.

  As the photopolymerization initiator, specifically, the compounds described in the above-described antiglare layer can be used.

  Examples of the organic solvent used for coating the high refractive index layer include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol). , Benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thio Diglycol, etc.), polyhydric alcohol ethers (eg, ethylene glycol monomethyl ether, Lenglycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ether) Range amine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) ), Heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) , Sulfones (for example, sulfolane), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

  For the high refractive index layer, the above composition is applied to the hard coat layer surface with a wet film thickness of 0.1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. Then, after coating, it is dried by heating and cured as necessary. The content described in the low refractive index layer can be used in the curing step. The dry film thickness is adjusted to the above film thickness by adjusting the solid content concentration of the coating composition.

(Antistatic layer)
An antistatic layer may be provided on the film substrate. The antistatic layer is composed of zinc antimonate sol, tin phosphate sol, tin oxide sol, π-conjugated conductive polymer, ionic polymer compound, etc. according to the method for producing the antiglare layer, such as ultraviolet rays and electron beams. It is preferable to contain in resin which hardens | cures through a crosslinking reaction etc. by an irradiation.

The antistatic layer imparts a function of preventing the film from being charged when the support (resin film or the like) is handled. The surface resistivity of the antistatic layer is preferably adjusted to 10 ¹¹ Ω / □ (25 ° C., 55% RH) or less, and more preferably 10 ¹⁰ Ω / □ (25 ° C., 55% RH) or less. Particularly preferably, it is 10 ⁹ Ω / □ (25 ° C., 55% RH) or less.

  Here, although details of the measurement of the surface specific resistance value are described in the Examples, the sample was conditioned for 24 hours under the conditions of 25 ° C. and 55% RH, and a terraohm meter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. was used. Use to measure.

  On the conductive layer, an overcoat layer is further provided as the outermost surface layer. The surface specific resistance value is measured by substantially conducting the surface specific resistance value on the outermost surface layer on the side where the conductive layer is provided. It is defined as the surface resistivity value of the conductive layer.

[Back coat layer]
The antiglare antireflection film may be provided with a backcoat layer on the surface opposite to the side on which the antiglare layer is provided. The back coat layer is provided in order to correct the curl generated by providing the antiglare layer. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward.

  The backcoat layer is preferably applied also as an antiblocking layer, and in this case, particles of an inorganic compound or an organic compound are added to the backcoat layer coating composition in order to provide an antiblocking function. Is preferred. Examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, indium oxide, zinc oxide, ITO, hydrated silica Mention may be made of calcium acid, aluminum silicate, magnesium silicate and calcium phosphate.

  These inorganic compounds are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can. Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large anti-blocking effect while keeping haze low. In the hard coat film of the present invention, the dynamic friction coefficient on the back side of the actinic ray curable resin layer is preferably 0.9 or less, particularly preferably 0.1 to 0.9.

  It is preferable that 0.1-50 mass% of inorganic compounds contained in a backcoat layer are contained with respect to a binder, and it is more preferable that it is 0.1-10 mass%. The increase in haze when a backcoat layer is provided is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Examples of the solvent used for coating the backcoat layer include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, Examples include chloroform, water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or hydrocarbons (toluene, xylene). Are used in appropriate combinations.

  It is preferable to apply these coating compositions on the surface of the hard coat film with a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like with a wet film thickness of 1 to 100 μm. Is particularly preferably 5 to 30 μm.

  Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin , Polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile Examples thereof include, but are not limited to, rubber resins such as resins, silicone resins, fluorine resins, and the like.

  As the binder, it is preferable to use a blend of acetylated cellulose such as cellulose diacetate and cellulose acetate proionate and an acrylic resin, and the refractive index difference between the fine particles and the binder is 0 to 0 using fine particles made of acrylic resin. By setting it to less than 0.02, a highly transparent back coat layer can be obtained.

  The order in which the backcoat layer is applied may be before or after the hardcoat layer is applied, but when the backcoat layer also serves as an anti-blocking layer, it is preferably applied first. Alternatively, the backcoat layer can be applied in two or more steps. Moreover, it is also preferable that the backcoat layer also serves as an easy-adhesion layer for improving the adhesion with the polarizer.

(Reflectance)
The reflectance of the antiglare antireflection film can be measured with a spectrophotometer or a spectrocolorimeter. At that time, after the surface on the measurement side of the sample is roughened, the light absorption treatment is performed by attaching a black spray, a black acrylic plate, etc., and then the reflected light in the visible light region (400 to 700 nm) is measured. To do.

  The antiglare antireflection film of the present invention is preferably as low in reflectance as possible, but an average value in the visible light region wavelength of 2.0% or less was used for the outermost surface of an image display device such as an LCD. In this case, it is preferable because the function of preventing reflection of external light can be suitably obtained. The minimum reflectance is preferably 0.8% or less.

  Moreover, it is preferable to have a flat reflection spectrum in the wavelength region of visible light. In addition, the reflection hue on the surface of the display device that has been subjected to the antireflection treatment is often colored red or blue because the reflectance in the short wavelength region and the long wavelength region is high in the visible light region due to the design of the antireflection film. The color tone of the reflected light varies depending on the application, and when used on the outermost surface of a flat-screen television or the like, a neutral color tone is preferred. In this case, generally preferred reflection hue ranges are 0.17 ≦ x ≦ 0.27 and 0.07 ≦ y ≦ 0.17 on the XYZ color system (CIE1931 color system). Further, the range in which the distance Δxy of (x, y) = (0.31, 0.31) on the xy plane is 0.05 or less is preferable because it is closer to neutral with no color, and 0.03 or less is preferable. Further preferred. The color tone can be calculated from the refractive index of each layer in accordance with a conventional method in consideration of the reflectance and the color of reflected light.

(surface hardness)
As the surface hardness of the antiglare antireflection film in the present invention, it can be expressed by pencil hardness, and when it is 3H to 8H, it is difficult to be scratched in use on the surface of a display device such as an LCD or in a polarizing plate forming step. It is a preferable structure, More preferably, it is 4H-8H, More preferably, it is 5H-8H.

  The pencil hardness is determined by JIS K 5400 using a test pencil specified by JIS S 6006 after conditioning the prepared anti-glare antireflection film sample for 24 hours or more at a temperature of 23 ° C. and a relative humidity of 55%. It is a value measured according to the pencil hardness evaluation method specified.

<Surface treatment and coating>
You may surface-treat before apply | coating each layer. Examples of the surface treatment method include a cleaning method, an alkali treatment method, a flame plasma treatment method, a high frequency discharge plasma method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure glow discharge plasma method. It is done.

  The corona treatment can be performed by using a device commercially available from a corona treatment having a multi-knife electrode of SOFTAL (Sophthal), Kasuga Electric Co., Ltd., Toyo Electric Co., Ltd. or the like. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency.

As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of ceramic, silicon, EPT rubber, hyperon rubber or the like on a roll made of aluminum, stainless steel, or a metal thereof. It is done. The frequency used for the corona treatment is a frequency of 20 kHz or more and 100 kHz or less, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Occurs. The output of the corona treatment is 10 to 500 W · min / m ² , but an output of ^{20 to} 400 W · min / m ² is preferable. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap opens, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. On the other hand, if the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film contacts the electrode and scratches are generated.

  The alkali treatment method is generally performed in a cycle in which the film is immersed in an alkali solution, then washed with water and dried. Further, after the alkali treatment, neutralization in an acidic water step may be performed, followed by washing with water and drying. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably 0.1 to 3N, and more preferably 0.5N to 2N. Adhesiveness between the antiglare layer and the low refractive index layer can be obtained by setting the content in the above range. The temperature of the alkaline solution is preferably in the range of 25 to 90 ° C., more preferably 40 to 70 ° C., from the viewpoint of precipitation of the alkaline solution. The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes.

  Moreover, you may use the method as described in Unexamined-Japanese-Patent No. 2003-313326 and Unexamined-Japanese-Patent No. 2007-332253, for example, for alkali treatment.

  Plasma treatments such as flame plasma treatment, high-frequency discharge plasma, and atmospheric pressure glow discharge plasma are disclosed in JP-A-2004-352777, JP-A-2004-352777, JP-A-2007-314707, and the like. You can refer to the technology. Moreover, AP-T series etc. which are the atmospheric pressure plasma processing apparatus by Sekisui Chemical Co., Ltd. can be used as a processing apparatus.

<Film base>
As the film base material, it is preferable that the production is easy, the adhesiveness with the antiglare layer is good, the optical isotropic property, the optical transparency, and the like.

  The term “transparent” as used herein means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, cellulose ester-type films, such as a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polyester-type film, a polycarbonate Film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol Film, syndiotactic polystyrene film, cycloolefin polymer fill (Arton (manufactured by JSR)), ZEONEX, ZEONOR (manufactured by Nippon Zeon), polyvinyl acetal, polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, A polymethyl methacrylate film, an acrylic film, a glass plate, etc. can be mentioned.

  Among these, a cellulose ester film, a polycarbonate film, a polysulfone (including polyether sulfone) film, and a cycloolefin polymer film are preferable.

  In particular, it is preferable to use a cellulose ester film (hereinafter also referred to as a cellulose ester film) as the film substrate.

  Cellulose ester film (for example, Konica Minolta Tack, product names KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC12UR (above, manufactured by Konica Minolta Opto Co., Ltd.) It is preferably used from the viewpoints of surface, transparency, adhesiveness, and the object effects of the present invention.

  Hereinafter, the cellulose ester film which is a preferable film substrate will be described in detail.

  The cellulose ester film may be a film produced by melt casting film formation or a film produced by solution casting film formation.

  As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used.

  In particular, when the substitution degree of the acetyl group is X and the substitution degree of the propionyl group or butyryl group is Y, it is preferable to use a cellulose ester film in which X and Y are in the following ranges.

2.3 ≦ X + Y ≦ 3.0
0.1 ≦ Y ≦ 2.0
In particular,
2.5 ≦ X + Y ≦ 2.9
3.0 ≦ Y ≦ 1.2
It is preferable that

  In addition, the measuring method of the substitution degree of an acyl group can be measured according to the prescription | regulation of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably 50000 to 250,000, since it has a high mechanical strength when molded and an appropriate dope viscosity, and more preferably 80000 to 150,000.

  Since the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the mass average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 1,000,000-500 calibration curves with 13 samples were used. The 13 samples are preferably used at approximately equal intervals.

  The raw material cellulose of the cellulose ester may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable. A cotton linter is preferably used from the viewpoint of peelability during film formation. The cellulose ester made from these can be mixed suitably or can be used independently.

  For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.

  Moreover, it is preferable that a cellulose-ester film contains an acrylic resin from the point which the objective effect of this invention is exhibited more effectively.

(acrylic resin)
Acrylic resin also includes methacrylic resin. Although it does not restrict | limit especially as resin, What consists of 50-99 mass% of methyl methacrylate units and 1-50 mass% of other monomer units copolymerizable with this is preferable.

  Other monomers that can be copolymerized include alkyl methacrylates having 2 to 18 carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, acrylic acid, methacrylic acid, and the like. Saturated acids, maleic acids, fumaric acids, unsaturated divalent carboxylic acids such as itaconic acid, aromatic vinyl compounds such as styrene, α-methylstyrene, and nucleus-substituted styrene, α, β- such as acrylonitrile, methacrylonitrile, etc. Examples thereof include unsaturated nitrile, maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, and the like. These can be used alone or in combination of two or more.

  Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer. n-Butyl acrylate is particularly preferably used.

  The acrylic resin preferably has a weight average molecular weight (Mw) of 80000 to 1000000 from the viewpoint of mechanical strength as a film and fluidity when producing the film. A weight average molecular weight (Mw) can be measured using said high performance liquid chromatography.

  There is no restriction | limiting in particular as a manufacturing method of an acrylic resin (A), You may use any well-known methods, such as suspension polymerization, emulsion polymerization, block polymerization, or solution polymerization. Here, as a polymerization initiator, a normal peroxide type and an azo type can be used, and a redox type can also be used. Regarding the polymerization temperature, suspension or emulsion polymerization may be performed at 30 to 100 ° C, and bulk or solution polymerization may be performed at 80 to 160 ° C. Further, in order to control the reduced viscosity of the produced copolymer, polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent. With this molecular weight, both heat resistance and brittleness can be achieved. A commercially available thing can also be used as an acrylic resin. For example, Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dialal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .

  Furthermore, it is preferable to contain acrylic particles from the viewpoint of the brittleness resistance and surface hardness of the film substrate.

  Next, the acrylic particles will be described. Acrylic particles, for example, a PTFE membrane having a pore diameter less than the average particle diameter of acrylic particles when a predetermined amount of the prepared acrylic resin-containing film is collected, dissolved in a solvent, stirred, and sufficiently dissolved and dispersed. It is preferable that the weight of the insoluble matter filtered and collected using a filter is 90% by mass or more of the acrylic particles added to the acrylic resin-containing film.

  The acrylic particles are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and particularly preferably the following multilayer structure acrylic granular composite.

  The multilayer structure acrylic granular composite is formed by laminating the innermost hard layer polymer, the cross-linked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer from the central portion toward the outer peripheral portion. This refers to a particulate acrylic polymer having a structure.

  A commercially available thing can also be used as an acrylic particle. For example, metabrene W-341 (C2) (manufactured by Mitsubishi Rayon Co., Ltd.), Chemisnow MR-2G (C3), MS-300X (C4) (manufactured by Soken Chemical Co., Ltd.) and the like can be mentioned.

  The acrylic particles preferably contain 0.5 to 45% by mass of acrylic particles with respect to the total mass of the cellulose ester resin and the acrylic resin.

  Moreover, the film which consists of a cellulose-ester resin and an acrylic resin (henceforth a cellulose-ester resin and an acrylic resin film) has a tension softening point of 105-145 degreeC, and a film which does not produce a ductile fracture is preferable. Ductile fracture is caused by the application of a greater stress than the strength of a certain material, and is defined as a fracture that involves significant elongation or drawing of the material before final fracture. As a specific measurement method of the tension softening point temperature, for example, using a Tensilon tester (ORIENTEC Co., RTC-1225A), the acrylic resin-containing film is cut out at 120 mm (length) × 10 mm (width), and 10N The temperature can be raised at a rate of 30 ° C./min while pulling with tension, and the temperature at 9 N is measured three times, and the average value can be obtained.

  Moreover, it is preferable that the film consisting of a cellulose ester resin and an acrylic resin has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, it is 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.

  The glass transition temperature is determined by using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer) at a heating rate of 20 ° C./min, and determined in accordance with JIS K7121 (1987). Tmg).

  A film composed of a cellulose ester resin and an acrylic resin preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, in the measurement based on JIS-K7127-1999. The upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming. The thickness of the film made of cellulose ester resin and acrylic resin is preferably 20 μm or more.

  More preferably, it is 30 μm or more. The upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 μm from the viewpoint of applicability, foaming, solvent drying, and the like. The thickness of the film can be appropriately selected depending on the application.

  The film comprising a cellulose ester resin and an acrylic resin preferably contains an acrylic resin and a cellulose ester resin in a mass ratio of 95: 5 to 30:70 from the viewpoint of both workability and heat resistance. The total substitution degree (T) of the acyl group is 2.00 to 3.00, the acetyl group substitution degree (ac) is 0 to 1.89, the number of carbons of the acyl group other than the acetyl group is 3 to 7, and the weight The average molecular weight (Mw) is preferably 75,000 to 280000. Moreover, the total mass of an acrylic resin and a cellulose-ester resin is 55-100 mass% of an acrylic resin containing film, Preferably it is 60-99 mass%.

  A film made of a cellulose ester resin and an acrylic resin may contain other acrylic resins.

  A cellulose ester film or a film made of a cellulose ester resin and an acrylic resin may be produced by a solution casting method or a melt casting method. For example, when cellulose ester is used as a film base material In the case of cellulose ester, the solvent used for dissolution tends to remain. Since the elastic modulus of the film is lowered and plastic deformation is likely to occur due to the influence of the remaining solvent, the film is preferably produced by a melt casting method. Methods formed by melt casting can be classified into melt extrusion molding methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like. Among these, the melt extrusion method is preferable, in which a film having excellent mechanical strength and surface accuracy can be obtained.

  In the present invention, a method of forming a film after the film forming material is heated to exhibit its fluidity and then extruded onto a drum or an endless belt is also included as a melt casting film forming method.

  Further, in film formation of the film substrate, it is preferable to stretch at least in the width direction, and in the solution casting process, 1.01-1 in the width direction when the amount of residual peeling is 3 to 40% by mass. The film is preferably stretched 5 times. More preferably, it is biaxially stretched in the width direction and the lengthwise direction, and when the amount of residual dissolution is 3 to 40% by mass, it is stretched by 1.01 to 1.5 times in the width direction and the lengthwise direction, respectively. It is to be.

  Although the film thickness of a film base material is not specifically limited, the thing of the range of 10-200 micrometers is used. In particular, the film thickness is particularly preferably 10 to 100 μm. More preferably, it is 20-80 micrometers.

  The length of the film substrate is preferably 100 m to 5000 m, and the width is preferably 1.2 m or more, more preferably 1.4 to 4 m. By making the length and width of the film base within the above ranges, the handleability and productivity are excellent. The film substrate is preferably a transparent support having a light transmittance of 90% or more, more preferably 93% or more.

(Plasticizer)
The film substrate preferably contains the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, and the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, and other trimellitic acid plasticizers include tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethylglycolate, butylphthalylbutylglycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid, and the like can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The polyhydric alcohol ester plasticizer comprises an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid. Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, 2-n-butyl-2-ethyl- Examples include 1,3-propanediol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol, and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable. There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention. Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto. As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is more preferable that it is C1-C20, and it is especially preferable that it is C1-C10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid. Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof. Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. And aromatic monocarboxylic acids possessed by them, or derivatives thereof. Particularly preferred is benzoic acid. The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified with carboxylic acid, or a part of the OH groups may be left as they are. These plasticizers are preferably used alone or in combination. The amount of these plasticizers used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film performance, processability and the like.

(UV absorber)
The film substrate may contain an ultraviolet absorber. Next, the ultraviolet absorber will be described.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, and the like.

  Although the following specific examples are given as a benzotriazole type ultraviolet absorber, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba Japan)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba Japan)
Moreover, although the following specific examples are shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the UV absorber, a benzotriazole UV absorber and a benzophenone UV absorber, which are highly transparent and excellent in preventing the deterioration of polarizing plates and liquid crystals, are preferable, and benzotriazole UV absorption with less unnecessary coloring is preferable. An agent is particularly preferably used.

  Further, an ultraviolet absorber having a distribution coefficient of 9.2 or more described in Japanese Patent Application No. 11-295209 can be used, and in particular, an ultraviolet absorber having a distribution coefficient of 10.1 or more is the surface quality of the film substrate. Is preferable from the standpoint that it can be maintained well.

  Moreover, the polymer ultraviolet absorber (or the general formula (1) or the general formula (2) of JP-A-6-148430 and the general formulas (3), (6) and (7) described in Japanese Patent Application No. 2000-156039 (or A UV-absorbing polymer) is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  Moreover, you may give an internal haze to a film base material.

(particle)
Internal haze, for example, by adding particles with a refractive index different from that of the film base to the film base and controlling the addition amount and particle size of the particles, generating haze due to internal scattering, and adjusting this Can be achieved. The particles are classified into inorganic particles and organic particles. The inorganic particles are not particularly limited, and examples thereof include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. The organic particles are not particularly limited. For example, fluorinated acrylic resin powder, polystyrene resin powder, polymethacrylic acid methyl acrylate resin powder, silicone resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin Examples thereof include powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, and polyfluoroethylene resin powder. These inorganic particles and organic particles may be used in combination of two or more different types and average particle diameters, and those obtained by surface-treating the surface of the particles with an organic substance are also preferably used.

  Particularly preferred inorganic particles are silicon dioxide. Specific examples of silicon dioxide include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.), Sea Hoster KEP-10, Sea Hoster KEP-30, Commercial products having trade names such as Seahoster KEP-50 (above, made by Nippon Shokubai Co., Ltd.), Silo Hovic 100 (made by Fuji Silysia), Nip Seal E220A (made by Nippon Silica Kogyo), Admafine SO (made by Admatechs), etc. Can be preferably used. The shape of the particles can be used without any particular limitation, such as indefinite shape, needle shape, flat shape, spherical shape, etc. However, the use of spherical particles is particularly preferable because it is easy to adjust the haze.

  The average particle size of the particles added to the support is preferably from 0.3 to 1 μm, more preferably from 0.4 to 0.7 μm.

  The average particle size can be determined by visual observation from an image photograph of secondary electron emission obtained by scanning electron microscope (SEM) or the like of 500 particles or by image processing, or by dynamic light scattering, static It can be measured by a particle size distribution meter using an automatic light scattering method or the like. The average particle diameter here refers to the number average particle diameter. In addition, an average particle diameter means the average particle diameter of an aggregate, when particle | grains are the aggregates of a primary particle. Moreover, when a particle is not spherical, it means the diameter of a circle corresponding to the projected area.

  The refractive index of the particles is preferably 1.45 to 1.70, more preferably 1.45 to 1.65. Note that the refractive index of the particles is measured by measuring the turbidity by dispersing the same amount of particles in a solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. The refractive index of the solvent can be measured by measuring with an Abbe refractometer.

  In addition, the refractive index difference between the resin used for the support and the particles is preferably 0.02 or more and 0.20 or less in order to increase the internal haze using the light scattering effect. A more preferable range of the refractive index difference is 0.05 or more and 0.15 or less.

  The content of the inorganic or organic particles is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin for producing the film base material, and more preferably 5 parts by mass to 25 parts by mass for obtaining the internal haze. Part.

  The particles may be dispersed together with cellulose ester, other additives and an organic solvent at the time of preparing a composition (dope) for producing a film substrate, or may be dispersed alone in a solution. . As a method for dispersing the particles, it is preferable that the particles are preliminarily dispersed in an organic solvent and then finely dispersed by a disperser (high pressure disperser) having a high shearing force.

  As a dope preparation method, it is preferable to disperse particles in a large amount of an organic solvent, merge with a cellulose ester solution, and mix with an in-line mixer to form a dope. In this case, an ultraviolet absorbent may be added to the particle dispersion to form an ultraviolet absorbent liquid.

  In addition, the above plasticizer and ultraviolet absorber may be added together with a solvent in the preparation of a solution composed of cellulose ester or cellulose ester resin and an acrylic resin. It may be added during or after preparation.

(Organic solvent)
When the cellulose ester film is produced by a solution casting method, the dope preferably contains an organic solvent from the viewpoint of film forming property and productivity. Any organic solvent can be used without limitation as long as it dissolves cellulose ester and other additives simultaneously. For example, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3 , 3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3 , 3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane and the like. Among these organic solvents, methylene chloride, methyl acetate, ethyl acetate, and acetone are preferably used.

  The dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. When the proportion of alcohol in the dope increases, the web gels, facilitating peeling from the metal support, and when the proportion of alcohol is small, the role of promoting dissolution of cellulose esters in non-chlorine organic solvents There is also. Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the boiling point being relatively low, good drying properties, and no toxicity. The concentration of the cellulose ester in the dope is preferably adjusted to 15 to 40% by mass, and the dope viscosity is preferably adjusted to a range of 10 to 50 Pa · s in order to obtain good film surface quality.

<Polarizing plate>
A polarizing plate using the antiglare antireflection film of the present invention will be described.

  The polarizing plate can be produced by a general method. The back side of the antiglare antireflection film of the present invention is subjected to alkali saponification treatment, and the antiglare antireflection film thus treated is immersed and stretched in an iodine solution. It is preferable to bond using an aqueous polyvinyl alcohol solution.

  The polarizing plate protective film used on the other surface of the antiglare antireflection film of the present invention can be an optical film in which in-plane retardation (Ro) and thickness direction retardation (Rt) are appropriately selected. .

  The retardation values Ro and Rt can be measured using an automatic birefringence meter. For example, using KOBRA-21ADH (manufactured by Oji Scientific Instruments Co., Ltd.), the wavelength can be obtained at 590 nm in an environment of a temperature of 23 ° C. and a humidity of 55% RH.

  As a polarizing plate protective film used on the back side, as a commercially available cellulose ester film, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4F-1, -2 (manufactured by Konica Minolta Opto) is preferably used.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this.

  As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound.

  A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used. On the surface of the polarizing film, one side of the antiglare antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

<Image display device>
By incorporating the antiglare antireflection film of the present invention on the viewing surface side of the image display device, various display devices of the present invention having excellent visibility can be produced.

  The antiglare antireflection film of the present invention is incorporated in a polarizing plate, and is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), It is preferably used in various drive system LCDs such as IPS type.

  Further, it has low reflectance and excellent flatness, and is preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
[Production of cellulose ester film (film substrate 1)]
(Synthesis of cellulose ester C1)
With reference to Example B of JP-T-6-501040, the amount of propionic acid and acetic acid was adjusted to synthesize cellulose ester C1 with the acetyl group substitution degree and propionyl group substitution degree adjusted as follows. .

C1: acetyl group substitution degree 1.9, propionyl group substitution degree 0.7, total acyl group substitution degree 2.60
The substitution degree of the obtained cellulose ester was calculated based on ASTM-D817-96.

  The weight average molecular weight of the cellulose ester C1 was 130,000 as a result of measurement using the high performance liquid chromatography.

(Preparation of cellulose ester film 1)
Cellulose ester film 1 was produced by melt casting with the following composition.

<Cellulose ester film 1 composition>
Cellulose ester: C1 94 parts by mass Plasticizer: Glycerin tribenzoate 5 parts by mass Irganox 1010 (manufactured by Ciba Japan) 0.5 part by mass Irgafos P-EPG (manufactured by Ciba Japan) 0.3 part by mass HP-136 ( 0.2 parts by mass The above cellulose ester was dried under reduced pressure at 70 ° C. for 3 hours and cooled to room temperature, and then each additive was mixed.

  The above mixture was formed into a film by a manufacturing apparatus using an elastic touch roll. Under a nitrogen atmosphere, it was melted at 240 ° C., extruded from the casting die onto the first cooling roll, and formed by pressing the film between the first cooling roll and the elastic touch roll. Further, silica particles (manufactured by Nippon Aerosil Co., Ltd.) were added as a slip agent from the hopper opening in the middle of the extruder so as to be 0.1 part by mass.

  The heat bolt was adjusted so that the gap width of the casting die was 0.5 mm within 30 mm from the end in the width direction of the film and 1 mm at other locations. As an elastic touch roll, 80 degreeC water was poured as cooling water inside.

  The position of the first cooling roller from the position P1 where the resin extruded from the casting die contacts the first cooling roll to the position P2 at the upstream end in the first cooling roll rotation direction of the nip between the first cooling roll and the elastic touch roll The length L along the peripheral surface was set to 20 mm. Thereafter, the elastic touch roll was separated from the first cooling roll, and the temperature T of the melted portion immediately before being sandwiched between the first cooling roll and the elastic touch roll was measured. The temperature T of the melted portion immediately before being sandwiched between the first cooling roll and the elastic touch roll is 1 mm upstream from the nip upstream end P2, and a thermometer (HA-200E manufactured by Anritsu Keiki Co., Ltd.). ). As a result of the measurement, the temperature T was 141 ° C. The linear pressure of the touch roll against the first cooling roll was 14.7 N / cm. Furthermore, after being introduced into a tenter and stretched 1.3 times at 160 ° C in the width direction, it was cooled to 30 ° C while relaxing 3% in the width direction, and then released from the clip. Was subjected to a knurling process having a width of 20 mm and a height of 25 μm, and wound on a winding core with a winding tension of 220 N / m and a taper of 40%. The winding core had an inner diameter of 152 mm, an outer diameter of 165 to 180 mm, and a length of 1550 mm. A prepreg resin obtained by impregnating glass fibers and carbon fibers with an epoxy resin was used as the core material for the core. The surface of the core was coated with an epoxy conductive resin, the surface was polished, and the surface roughness Ra was finished to 0.3 μm. In addition, the film thickness was 60 micrometers, the winding length was 3500 m, and the cellulose-ester film 1 of refractive index 1.49 was produced.

[Preparation of antiglare antireflection film]
(Preparation of antiglare antireflection film 1)
(Formation of antiglare layer)
After producing an anti-glare film by the following procedure using the cellulose ester film 1, the following low refractive index layer coating composition 1 is applied on the anti-glare layer surface to form a low refractive index layer. An antiglare antireflection film 1 was produced.

The following antiglare layer coating composition 1 is prepared, applied to the cellulose ester film 1 using a micro gravure coater, dried at 80 ° C. for 1 minute, and then irradiated with an ultraviolet lamp to illuminate the irradiated part. It was cured under the conditions of 150 mW / cm ² and an irradiation amount of 0.2 J / cm ² to form an antiglare layer having a dry film thickness of 15 μm. Next, the following back coat layer coating composition 1 was applied to the surface opposite to the surface coated with the antiglare layer so as to have a wet film thickness of 9 μm, coated with an extrusion coater, dried at 50 ° C., and an antiglare film was formed. It produced and wound up in roll shape.

(Coating composition 1 for anti-glare layer)
After mixing 7 parts by mass of particles A in a solvent having the following blending ratio, the mixture was stirred with an air disper for 30 minutes to obtain a particle dispersion. Other raw materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 1.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
Particle A 7 parts by mass (Coating composition 1 for back coat layer)
Acetone 30 parts by weight Methyl ethyl ketone 45 parts by weight Isopropyl alcohol 10 parts by weight Diacetylcellulose 0.6 part by weight Ultrafine silica 2% acetone dispersion 0.2 part by weight (formation of a low refractive index layer)
The roll-shaped antiglare film produced above is drawn out again, and the following low refractive index layer coating composition 1 is applied on the surface of the antiglare layer with a microgravure coater so that the film thickness after drying is 85 nm. Apply, dry at 80 ° C. for 1 minute, and then purge with nitrogen so that the oxygen concentration is 0.5 volume% or less, while using an ultraviolet lamp to irradiate the irradiated part with an irradiance of 150 mW / cm ² and an irradiation dose. Curing was performed under conditions of 0.3 J / cm ² , and after curing, heat treatment was performed at a temperature of 120 ° C. for 2 minutes, and winding was performed to produce an antiglare antireflection film 1.

(Preparation of low refractive index coating composition 1 (cationic polymerizable compound-containing low refractive index layer coating composition))
(Preparation of fluorine-containing epoxy compound 1)
81.03 g of 1,3-dihydroxyhexafluoroisopropylbenzene and 185 g of epichlorohydrin were mixed, 16.27 g of sodium hydroxide and 40 ml of water were added, and the mixture was heated to reflux with stirring. After reacting at 130 ° C. for 3 hours, the mixture was naturally cooled, and the produced sodium chloride was removed by suction filtration. The obtained filtrate was extracted with chloroform-water, and the organic layer was dried, filtered and concentrated to obtain 95.7 g of fluorine-containing epoxy compound 1.

(Cationically polymerizable compound)
[1- (3-Ethyl-3-oxetanyl) methyl] ether 6.7 parts by mass 3,4-epoxy-6-methylcyclohexylmethylcarboxylate
0.3 part by mass Fluorine-containing epoxy compound 1 2 parts by mass (cationic polymerization initiator)
Triallylsulfonium hexafluorophosphine salt 0.2 parts by mass (fine particles)
Isopropyl alcohol-dispersed hollow silica fine particle sol 6.9 parts by mass (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209)
(Additive)
Silicone compound (FZ-2207, 10% propylene glycol monomethyl ether solution manufactured by Nippon Unicar Co., Ltd.) 0.9 parts by mass (solvent)
Methyl isobutyl ketone 80 parts by weight Methyl ethyl ketone 40 parts by weight Among the above coating composition 2 for low refractive index layer, a compound other than isopropyl alcohol-dispersed hollow silica fine particle sol is added to methyl isobutyl ketone and methyl ethyl ketone at the above-mentioned blending ratio. After dissolution, the isopropyl alcohol-dispersed hollow silica fine particle sol was added at the above blending ratio. Moreover, the refractive index of the low refractive index layer of the low refractive index layer coating composition 1 was 1.37.

(Preparation of antiglare reflective film 2)
An antiglare antireflection film 2 was prepared in the same manner except that the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 2 in the production of the antiglare film 1.

(Coating composition 2 for anti-glare layer)
After mixing 10 parts by mass of particles B in a solvent having the following blending ratio, the mixture was stirred with an air disper for 30 minutes to obtain a particle dispersion. Other raw materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 2.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
10 parts by mass of particle B (Preparation of antiglare reflective film 3)
In the production of the antiglare film 1, an antiglare antireflection film 3 was produced in the same manner except that the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 3.

(Coating composition 3 for anti-glare layer)
After mixing particles A, 4 parts by mass, particles C, and 10 parts by mass with a solvent having the following blending ratio, the mixture was stirred with an air disper for 30 minutes to obtain a particle dispersion. Other materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 3.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
Particle A 4 parts by mass Particle C 10 parts by mass (Preparation of antiglare reflective film 4)
An antiglare antireflection film 4 was prepared in the same manner except that the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 4 in the production of the antiglare film 1.

(Coating composition 4 for anti-glare layer)
Particle D, 7 parts by mass, particle E, and 3 parts by mass were mixed in a solvent having the following blending ratio, and then stirred with an air disper for 30 minutes to obtain a particle dispersion. Other raw materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 4.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
Particle D 7 parts by mass Particle E 3 parts by mass (Preparation of antiglare reflective film 5)
In preparation of the anti-glare film 1, the anti-glare layer coating composition 1 was changed to the anti-glare layer coating composition 5, and the film thickness after drying of the anti-glare layer was changed to 8.5 μm. An antiglare antireflection film 5 was produced.

(Coating composition 5 for anti-glare layer)
After mixing 5 parts by mass of particles A in a solvent having the following blending ratio, the mixture was stirred with an air disper for 30 minutes to obtain a particle dispersion. Other raw materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 5.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
5 parts by mass of particle A (production of antiglare reflective film 6)
In the production of the anti-glare film 1, the anti-glare layer coating composition 1 was changed to the anti-glare layer coating composition 6 and the film thickness after drying of the anti-glare layer was changed to 17 μm. Antireflection film 6 was produced.

(Coating composition 6 for anti-glare layer)
Particles A, 2.5 parts by mass and particles C and 10 parts by mass were mixed in a solvent having the following blending ratio, and then stirred with an air disperser for 30 minutes to obtain a particle dispersion. Another material was mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 6.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
Particle A 2.5 parts by mass Particle C 10 parts by mass (Preparation of antiglare reflective film 7)
In the production of the antiglare film 1, an antiglare antireflection film 7 was produced in the same manner except that the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 7.

(Coating composition 7 for anti-glare layer)
After mixing 12 parts by mass of particles G in a solvent having the following blending ratio, the mixture was stirred with an air disper for 30 minutes to obtain a particle dispersion. Other materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 7.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
Particle G 12 parts by mass (Preparation of antiglare reflective film 8)
An antiglare layer coating composition 8 was prepared with reference to the antiglare layer coating solution B of Example 1 of JP-A-2007-45142, except that the particle size was changed. Next, an antiglare antireflection film 8 was produced in the same manner as in Example 1.

(Coating composition 8 for antiglare layer)
After mixing 6.3 parts by mass of particles F in a solvent having the following blending ratio, the mixture was stirred with an air disper for 30 minutes to obtain a particle dispersion. Other raw materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 8.

(solvent)
Methyl isobutyl ketone 54.7 parts by mass Propylene glycol 6.3 parts by mass (resin)
DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 25.4 parts by mass (photopolymerization initiator)
1.3 parts by mass of 1-hydroxycyclohexyl-phenyl-ketone (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Fluorine surface modifier (FP-149) 0.04 parts by mass Silane coupling agent (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
5.2 parts by mass Cellulose acetate butyrate (CAB-531-1, manufactured by Eastman Chemical Co., Ltd.) 0.5 parts by mass (particles)
6.3 parts by mass of particle F (production of antiglare reflective film 9)
In the production of the antiglare film 1, the antiglare layer coating composition 1 was changed to the antiglare layer coating composition 9 and the film thickness after drying of the antiglare layer was changed to 6.5 μm in the same manner. An antiglare antireflection film 9 was produced.

(Coating composition 9 for antiglare layer)
After mixing particles A, 5 parts by mass, particles E, and 22 parts by mass with a solvent having the following blending ratio, the mixture was stirred with an air disper for 30 minutes to obtain a particle dispersion. Other raw materials were mixed and stirred in this particle dispersion to prepare a string-proof layer coating composition 9.

(solvent)
Methyl ethyl ketone 50 parts by mass Ethyl acetate 20 parts by mass Cyclohexanone 15 parts by mass Toluene 15 parts by mass (resin)
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 100 parts by mass (photopolymerization initiator)
1-hydroxycyclohexyl-phenyl-ketone 8 parts by mass (Irgacure 184: manufactured by Ciba Japan)
(Additive)
Polyether-modified silicone (KF-354L: manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by mass (particles)
Particle A 5 parts by mass Particle E 22 parts by mass (production of antiglare antireflection films 10 and 11)
In the antiglare antireflection films 2 and 3, a low refractive index layer on the surface of the antiglare layer of the produced antiglare film, and the following low refractive index layer using a commonly used radical polymerizable compound as a binder Antiglare and antireflection films 10 and 11 were prepared in the same manner except that the coating composition 2 was applied.

(Preparation of low refractive index layer coating composition 2 (radical polymerizable compound-containing low refractive index layer coating composition))
(Preparation of fluoropolymer 1)
In an autoclave with a stirrer made of stainless steel having an internal volume of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether, and 0.55 g of dilauroyl peroxide were charged, and the reaction system was degassed and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The temperature inside the autoclave was maintained as it was, and the reaction was continued for 8 hours. When the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature decreased to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out.

  The obtained reaction solution was put into a large excess of hexane, and the solvent was removed by decantation to take out the precipitated polymer. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove residual monomers and dried to obtain 28 g of a polymer. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of fluorinated polymer 1.

(Coating composition 2 for low refractive index layer)
(solvent)
Methyl ethyl ketone 460 parts by mass Cyclohexanone 300 parts by mass (radical polymerizable compound)
Fluoropolymer 1 30 parts by mass Pentaerythritol triacrylate 20 parts by mass Pentaerythritol tetraacrylate 14 parts by mass (photopolymerizable initiator)
Irgacure 907 (Ciba Japan) 3 parts by weight (additive)
6.5% by mass of 10% propylene glycol monomethyl ether solution of silicone compound (FZ-2207, Nippon Unicar Co., Ltd.) (fine particles)
50 parts by mass of isopropyl alcohol-dispersed hollow silica fine particle sol (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209)
Of the above coating composition 1 for low refractive index layer, with respect to methyl ethyl ketone and cyclohexanone, the previously prepared fluorine-containing polymer 1, methacrylate group-containing silicone resin, photopolymerization initiator, pentaerythritol triacrylate and pentaerythritol tetra After the acrylate was added and dissolved at the above blending ratio, the isopropyl alcohol-dispersed hollow silica fine particle sol was added at the above blending ratio. Moreover, the refractive index of the low refractive index layer of the low refractive index layer coating composition 2 was 1.37.

  The details of the particles A to G used in Example 1 are as follows.

Particle A: Fluorine-containing acrylic resin particles having an average particle size of 3.5 μm Particle B: Fluorine-containing acrylic resin particles having an average particle size of 2.0 μm Particle C: Fluorine-containing acrylic resin particles having an average particle size of 0.55 μm Particle D: Average particle 3.5 μm diameter crosslinked poly ((meth) acrylate) particles Particle E: Silica fine particles having an average particle diameter of 1.0 μm Particle F: Crosslinked poly (acryl-styrene) particles having an average particle diameter of 0.55 μm Particle G: Average particle diameter 1 0.0 μm crosslinked poly ((meth) acrylate) particles << Evaluation >>
About the produced anti-glare anti-reflective films 1-11, after implementing the following durability test, it evaluated about the following items. The obtained results are shown in Table 1.

  Table 1 also shows the results of the scattering reflection ratio (scattering reflectance / integrated reflectance) of the antiglare layer measured before laminating the low refractive index layer of each antiglare antireflection film. The method for measuring the scattering reflection ratio is as follows.

(Measurement method of scattering reflectance ratio (scattering reflectance / integrated reflectance))
Using a spectrocolorimeter CM-2500d manufactured by Konica Minolta Sensing Co., Ltd., SCI (integral reflectance) and SCE (scattering reflectance) were measured under the conditions of a measurement diameter of 8 mm and an observation field of view of 2 °.

<Durability test>
From each roll of anti-glare antireflection film of 3500 m, a test sample was cut out to A4 size, and cycle thermostat (−40 ° C./30 minutes, then left at 85 ° C./30 minutes, alternately) Cycle), the xenon fade meter was used for light irradiation for 14 days to conduct a durability test. Next, the antiglare antireflection film subjected to the durability test was evaluated after conditioning for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 55%.

<Anti-glare properties>
Visual sensory evaluation was performed. Judgment criteria are as follows.

◎: The outline of the fluorescent lamp is blurred and the reflection is not noticeable at all. ○: The outline of the fluorescent lamp is slightly noticeable but not so much. △: The outline of the fluorescent lamp is recognized but acceptable. X: The outline of the fluorescent lamp. I can clearly see and I am worried about the reflection 《Contrast (High-Definition Sharpness)》
A sample was placed on the color filter, and observed with an optical microscope by transmitted light from the back surface (color filter side), and the clearness of the contour of the image was visually evaluated. FIG. 1 shows an outline of the apparatus, and FIG. 2 shows an actual observation example.

<Surface hardness: pencil hardness>
Using the test pencil specified by JIS-S6006, according to the pencil hardness evaluation method specified by JIS-K5400, the surface of the low refractive index layer was repeatedly scratched 5 times with a pencil of each hardness using a 500 g weight, and scratches were 1 The hardness up to the book was measured. The higher the number, the higher the hardness.

"chemical resistance"
Using the office cleaner (trade name Scotch Office Cleaner OC-100WG, manufactured by Sumitomo 3M), the same spot is applied to the surface of the low refractive index layer of the antiglare antireflection film subjected to the durability test, using a load of 1000 g / cm ^2. The state after rubbing 20 times and after rubbing was observed and evaluated according to the following criteria. The following apparatus was used for surface rubbing.

Surface rubbing device; Shinto Kagaku Co., Ltd. friction and wear testing machine (Tribo Station TYPE: 32, moving speed 4000 mm / min)
(Evaluation criteria)
◎: No peeling ○: Level where slight peeling is seen (no problem in practical use)
Δ: Peeling is observed ×: All rubbed parts are peeled off.

  As can be seen from the results in Table 1, the antiglare antireflection film of the present invention in which the antireflection layer has a scattering reflectance of 2 to 60% and a low refractive index layer containing a cationic polymerizable compound is laminated. 1 to 7 are excellent in optical characteristics such as antiglare property and sharpness, and excellent in film strength (pencil hardness) and chemical resistance after the durability test. In particular, it can be seen that the antiglare antireflection films 1 to 3, 5 and 6 of the present invention having a scattering reflectance of 20 to 60% or an antiglare layer containing fluoroacrylic fine particles have particularly excellent performance. Moreover, about the anti-glare anti-reflective films 1-11, a black acrylic board with an adhesive was affixed on the back coat surface, light absorption treatment was performed, and CM-3700d (manufactured by Konica Minolta Sensing Co., Ltd.) from the low refractive index layer surface. ) Was used to measure the reflectance. As a result, the average reflectance of the antiglare antireflection film of the present invention was 1.5% or less, and had a good external light antireflection function.

Example 2
In the production of the antiglare antireflection film 1 of Example 1, the same procedure except that the cellulose ester film 1 as a film base material was changed to a commercially available Konica Minolta Tack KC4UY (manufactured by Konica Minolta Opto). An antiglare antireflection film 12 was produced. About the produced anti-glare anti-reflective film 12, it processed and evaluated similarly to Example 1. FIG. As a result, the antiglare antireflection film 1 of Example 1 had excellent performance.

Example 3
In the production of the antiglare antireflection film 1, antireflection films 13 and 14 were produced in the same manner except that the film base material was changed to the following film base material 2 and film base material 3.

<Preparation of film substrate 2>
<Production of Cellulose Ester Resin / Acrylic Resin Film 1>
(Dope solution composition 2)
Acrylic resin Dianal BR80 (Mitsubishi Rayon Co., Ltd.) 70 parts by mass (Mw 95000)
CAP482-20 (acyl group total substitution degree 2.75, acetyl group substitution degree 0.19, propionyl group substitution degree 2.56, Mw = 200000 manufactured by Eastman Chemical Co., Ltd.)
30 parts by weight Tinuvin 109 (manufactured by Ciba Japan) 1 part by weight Tinuvin 171 (manufactured by Ciba Japan) 1 part by weight Methylene chloride 300 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight While heating the above composition, It melt | dissolved and produced dope solution. In addition, CAP is a cellulose acetate propionate resin.

(Film formation of cellulose ester resin / acrylic resin film 1)
The produced dope solution was uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the film was peeled off from the stainless steel band support with a peeling tension of 162 N / m. The peeled acrylic resin web was evaporated at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while stretching 1.1 times in the width direction with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 10%.

  After stretching with a tenter and relaxing at 130 ° C for 5 minutes, drying is completed while transporting the drying zone at 120 ° C and 130 ° C with a number of rolls, slitting to a width of 1.5 m, and 20 mm wide at both ends of the film. A knurling process of 25 μm was performed, and the film was wound on a core with a winding tension of 220 N / m and a taper of 40%. The draw ratio in the film transport direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.

  The wound core had a diameter of 152 mm, an outer diameter of 165 to 180 mm, and a length of 1550 mm. A prepreg resin obtained by impregnating glass fibers and carbon fibers with an epoxy resin was used as the core material for the core. The surface of the core was coated with an epoxy conductive resin, the surface was polished, and the surface roughness Ra was finished to 0.3 μm. The film thickness was 40 μm, the winding length was 3500 m, and a cellulose ester resin / acrylic resin film 1 having a refractive index of 1.50 was produced.

<Production of Film Base 3>
A film substrate 3 (acrylic particle-containing cellulose ester resin / acrylic resin film 1) was prepared in the same manner except that the film substrate 2 was changed to the following dope solution composition 3 in the production of the film substrate 2.

(Preparation of acrylic particles)
A reactor with a reflux condenser with an internal volume of 60 liters was charged with 38.2 liters of ion-exchanged water and 111.6 g of sodium dioctylsulfosuccinate, and the temperature was raised to 75 ° C. under a nitrogen atmosphere while stirring at a rotational speed of 250 rpm. The effect of oxygen was virtually eliminated. 0.36 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of MMA 1657 g, BA 21.6 g, and ALMA 1.68 g was added all at once, and after the exothermic peak was detected, the mixture was held for another 20 minutes to polymerize the innermost hard layer. Completed. Next, 3.48 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of BA 8105 g, PEGDA (200) 31.9 g, and ALMA 264.0 g was continuously added over 120 minutes. Hold for a minute to complete the soft layer polymerization.

  Next, 1.32 g of APS was added, and after stirring for 5 minutes, a monomer mixture consisting of 2106 g of MMA and 201.6 g of BA was continuously added over 20 minutes. The polymerization of was completed.

  Next, 1.32 g of APS was added, and after 5 minutes, a monomer mixture consisting of 3148 g of MMA, 201.6 g of BA and 10.1 g of n-OM was continuously added over 20 minutes. Next, the temperature was raised to 95 ° C. and held for 60 minutes to complete the polymerization of the outermost hard layer 2.

  A small amount of the polymer latex thus obtained was collected, and the flat particle size was determined by the absorbance method, which was 0.10 μm. The remaining latex was poured into a 3% by mass sodium sulfate warm aqueous solution, salted out and coagulated, and then dried after repeated dehydration and washing to obtain acrylic particles having a three-layer structure.

  The above abbreviations are the following materials.

MMA; methyl methacrylate MA; methyl acrylate BA; n-butyl acrylate ALMA; allyl methacrylate PEGDA; polyethylene glycol diacrylate (molecular weight 200)
n-OM; n-octyl mercaptan APS; ammonium persulfate (production of acrylic ester-containing cellulose ester resin / acrylic resin film 1)
(Dope solution composition 3)
Dianar BR80 (manufactured by Mitsubishi Rayon Co., Ltd.) 70 parts by mass CAP482-20 30 parts by mass The prepared acrylic particles 20 parts by mass Tinuvin 109 (manufactured by Ciba Japan) 1 part by mass Tinuvin 171 (manufactured by Ciba Japan) 1 Part by mass Methylene chloride 300 parts by mass Ethanol 40 parts by mass Butanol 5 parts by mass The above composition was sufficiently dissolved while heating to prepare a dope solution.

  The antiglare antireflection films 13 and 14 and the antiglare antireflection film 1 produced above were evaluated in the same manner as in Example 1 except that the durability test was changed to the following conditions. The obtained results are shown in Table 2.

<Durability test>
From each roll of anti-glare antireflection film of 3500 m, a test sample was cut out to A4 size and cycled thermometer (−40 ° C. · 30 minutes, then left at 85 ° C. · 30 minutes alternately) 500 Cycle), the xenon fade meter was used for light irradiation for 21 days to conduct a durability test.

  As can be seen from the results in Table 2, the performance after the more severe durability test is that the film substrate is a cellulose ester resin and an acrylic resin than the antiglare antireflection film 1 in which the film substrate is a cellulose ester resin. The antiglare antireflection film 13 and the film base material made of cellulose ester resin, acrylic resin and acrylic particles have better performance, particularly from acrylic resin and acrylic particles. The resulting antiglare antireflection film 14 was also excellent in surface hardness (pencil hardness).

Example 4
According to the following method, each of the antiglare antireflection films 1 to 11 and the retardation film Konica Minolta Tack KC4FR-2 (manufactured by Konica Minolta Opto Co., Ltd.), each using a polarizing plate as a polarizing plate protective film. Produced.

(A) Production of Polarizing Film A long polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water for 60 seconds, and then immersed in an aqueous solution at 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water. . This was washed with water and dried to obtain a long polarizing film.

(B) Production of Polarizing Plate Next, according to the following steps 1 to 5, the polarizing film and the polarizing plate protective film were bonded together to produce a polarizing plate.

  Step 1: Each of the antiglare antireflection films and KC4FR-2 were immersed in a 2 mol / L potassium hydroxide solution at 50 ° C. for 80 seconds, then washed with water and dried. In addition, about the anti-glare anti-reflective film, the peelable protective film (product made from PET) was affixed on the surface in which the low-refractive-index layer was provided previously, and was protected.

  Process 2: The above-mentioned polarizing film was immersed for 1 to 2 seconds in the polyvinyl alcohol adhesive tank of 2 mass% of solid content.

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and KC4FR-2 and antiglare antireflection film that had been subjected to alkali treatment in Step 1 were sandwiched and laminated.

Process 4: It bonded together by the speed of about 2 m / min with the pressure of 20-30 N / cm < ² > with the two rotating rollers. At this time, care was taken to prevent bubbles from entering.

  Step 5: The sample prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare a polarizing plate.

  Carefully peel off the polarizing plate on the outermost surface of a commercially available liquid crystal display panel (NEC color liquid crystal display MultiSync LCD1525J: model name LA-1529HM). A liquid crystal display device was prepared so as to be on the surface side. The liquid crystal panels 101 to 111 thus obtained were placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S · D / MX Matsushita Electric) was placed on the ceiling 3 m high from the floor. Sangyo Co., Ltd.) 40W × 2 were set as one set, and 10 sets were arranged at intervals of 1.5 m. In this case, when the evaluator is in front of the display surface of the liquid crystal display panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling portion from the evaluator's overhead to the rear. Each liquid crystal panel was tilted by 25 ° from the vertical direction with respect to the desk, and the visibility of the screen (visibility) was evaluated by dividing it into the following ranks so that a fluorescent lamp was reflected. Further, the bright spot foreign matter of the liquid crystal panels 101 to 111 produced above was also evaluated in the following rank. The obtained results are shown in Table 3.

<Evaluation>
(Visibility)
A: I don't care about the reflection of the nearest fluorescent lamp, and I can clearly read characters with a font size of 8 or less. B: The reflection of a nearby fluorescent lamp is somewhat anxious, but I don't care about the distance. Can manage to read characters with font size of 8 or less C: It is difficult to read characters with font size of 8 or less due to the reflection of distant fluorescent lights.
The display of the liquid crystal panels 101 to 111 was displayed in black on the entire surface, and the diameter and number of bright spot foreign materials were counted with a loupe, and evaluated according to the following criteria. At this time, the magnification of the loupe was 50 times.

○: Foreign matter having a size of 100 μm or more is not recognized. X: Foreign matter having a size of 100 μm or more is recognized. This is a practically problematic level.

  As a result of the evaluation, the liquid crystal display device using the antireflection films 1 to 7 of the present invention is good in both visibility and bright spot foreign matter as compared with the antiglare antireflection films 8 to 11 of the comparative example. there were.

It is the schematic of the apparatus which measures high-definition definition. It is an example of the sample photograph observed with the high-definition definition apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transmission optical microscope 2 Sample 3 Color filter 4 Light source

Claims (8)

The film base has an antiglare layer, the ratio of the scattering reflectance to the integrated reflectance of the antiglare layer is 2 to 60%, and the antiglare layer has a direct or other layer on it. An antiglare antireflection film, wherein a low refractive index layer is laminated, and the low refractive index layer forming material contains at least one cationic polymerizable compound. The anti-glare antireflection film according to claim 1, wherein the scattering reflectance ratio is 20 to 60%. The antiglare antireflection film according to claim 1 or 2, wherein the antiglare layer contains fine particles, and the fine particles are fluorine-containing acrylic resin particles. The antiglare antireflection film according to any one of claims 1 to 3, wherein the film substrate contains a cellulose ester resin. The antiglare antireflection film according to any one of claims 1 to 4, wherein the film substrate contains a cellulose ester resin and an acrylic resin. The antiglare antireflection film according to any one of claims 1 to 4, wherein the film substrate contains a cellulose ester resin, an acrylic resin, and acrylic particles. A polarizing plate characterized by using the antiglare antireflection film according to any one of claims 1 to 6 on at least one surface. An image display device comprising the antiglare antireflection film according to claim 1 or the polarizing plate according to claim 7.