JP2006023350A - Antireflection film, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film which has excellent anti-dazzling property, high transparency, little coloring, high physical strength such as scratch resistance and excellent anti-sticking property of dirt (dust or the like), and to provide a polarizing plate subjected to anti-reflection treatment according to a proper means and an image display device. <P>SOLUTION: The antireflection film is made by applying at least a light diffusion layer, an antistatic layer and a low refractive index layer having a refractive index lower than that of an transparent substrate in this order on the transparent substrate. Therein, the antireflection film is constituted such that the value obtained by dividing a center line average roughness Ra2 on the antistatic layer surface after applying the antistatic layer with a center line average roughness Ra1 on the light diffusion layer surface before applying the antistatic layer falls into 0.5 to 1.0. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

In recent years, liquid crystal display devices (LCDs) have become larger in screen size, and liquid crystal display devices provided with antireflection films are increasing.
Antireflection films are used in various image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT) to reflect external light and In order to prevent a decrease in contrast due to reflection, it is arranged on the surface of the display. Therefore, the antireflection film is required to have high physical strength (such as scratch resistance), transparency, chemical resistance, and weather resistance (such as moisture and heat resistance). Furthermore, measures are required to prevent dust (such as dust) that reduces the visibility of the display from adhering to the surface of the antireflection film.

As an antireflection layer (a high refractive index layer, a medium refractive index layer, a low refractive index layer, etc.) used for an antireflection film, a multilayer film obtained by laminating a transparent thin film of metal oxide has been conventionally used. The metal oxide transparent thin film has been usually formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method which is a kind of physical vapor deposition method. However, the method of forming a transparent thin film of metal oxide by vapor deposition is not suitable for mass production because of low productivity, and a method of forming by high productivity coating has been proposed (for example, see Patent Documents 1 to 4). .
In order to improve the dust adhesion prevention property of the antireflection film produced by the coating method, it is effective to give conductivity to any of the coating layers. It is effective to contain a fluorine-containing compound.
In order to impart conductivity without impairing the transparency of the film, various methods for incorporating an antistatic layer into a layer located on the support side of the coating layer have been studied. (Patent Documents 5 and 6) In this layer arrangement, since various functional layers for controlling the optical characteristics can be installed on the antistatic layer, the optical characteristics are reduced by installing the antistatic layer on the surface side. However, there is a drawback that the conductivity is difficult to be expressed. In order to remedy this drawback, in a configuration in which the antistatic layer is located on the support side, a very small amount of highly conductive functional particles having a considerably large particle size are contained so as to be located between the antistatic layer and the surface. A method of making a conductive path between the antistatic layer and the surface has been proposed (Patent Document 7), but there are problems such as an increase in cost and an increase in haze.
Furthermore, in the antireflection film composed of three or more layers, a layer configuration in which the conductive layer is adjacent to the low refractive index layer on the surface is also disclosed (Patent Document 8), but a light diffusion layer having unevenness is not used. It was not a technology that achieved both antiglare and electrical conductivity.

On the other hand, a polarizing plate is an indispensable optical material in a liquid crystal display device, and generally has a structure in which a polarizing film is protected by two protective films.
If an antireflection function can be imparted to these protective films, significant cost reduction and thinning of the display device can be achieved.
The protective film used for the polarizing plate needs to have sufficient adhesion to be bonded to the polarizing film. As a method for improving the adhesion to the polarizing film, it is common practice to saponify the protective film to hydrophilize the surface of the protective film.

JP 2002-116323 A JP 2002-156508 A JP 2002-361769 A JP 2003-4903 A JP 2000-233467 A JP 2002-254573 A JP 2003-39586 A Japanese Patent Laid-Open No. 11-138777

  An object of the present invention is to provide an antireflection film that has excellent antiglare properties, high transparency, low coloration, high physical strength such as scratch resistance, and excellent dust and dust adhesion prevention properties. That is. It is another object of the present invention to provide a polarizing plate and an image display device that have been subjected to antireflection treatment by appropriate means.

  The above object has been achieved by an antireflection film, a polarizing plate and an image display device having the following constitution.

(1) An antireflection film in which at least a light diffusion layer, an antistatic layer, and a low refractive index layer having a lower refractive index than that of the transparent support are coated in this order on the transparent support, and the antistatic layer is applied. The value obtained by dividing the center line average roughness Ra2 on the surface of the antistatic layer after coating the antistatic layer by the centerline average roughness Ra1 on the surface of the light diffusing layer is 0.5 to 1.0. Antireflection film characterized by
(2) The center line average roughness Ra1 of the light diffusion layer surface before coating of the antistatic layer is 0.03 to 0.30 μm, and Ra2 of the surface of the antistatic layer after coating of the antistatic layer is 0. The antireflection film as described in (1), which has a thickness of 0.02 to 0.25 μm.
(3) The antireflection film as described in (1) or (2), wherein the antistatic layer and / or the low refractive index layer is formed by a process including at least coating and ionizing radiation curing.
(4) The antireflection according to any one of (1) to (3), wherein the low refractive index layer is formed by crosslinking or polymerization reaction of a fluorine-containing compound represented by the following general formula (1) the film.
General formula (1)

In General Formula (1), L represents a C1-C10 coupling group, m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit of any vinyl monomer, and may be a single component or a plurality of components. x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65.
(5) The antireflection film as described in any one of (1) to (4), wherein the low refractive index layer contains hollow silica fine particles.
(6) The antireflection film as described in any one of (1) to (5), wherein the surface resistance on the side having the low refractive index layer is 1 × 10 ¹² Ω / □ or less.
(7) The antireflection film as described in any one of (1) to (6), wherein the conductive material contained in the antistatic layer is a metal oxide.
(8) The antistatic film according to any one of (1) to (7), wherein the antistatic layer has a thickness of 60 to 200 nm.
(9) The antireflection film as described in any one of (1) to (8) above, wherein the conductive material contained in the antistatic layer is fine particles having a specific surface area of 10 to 400 m ² / g.
(10) The antireflection film as described in any one of (1) to (9) above, wherein the conductive material contained in the antistatic layer is fine particles having an average particle diameter of 1 to 200 nm.
(11) The antireflection film as described in any one of (1) to (10) above, wherein the conductive material contained in the antistatic layer is dispersed with a dispersant having an anionic group.
(12) The antireflection film as described in any one of (1) to (11) above, wherein the content of the conductive material in the antistatic layer is 20 to 60% by mass of the total solid content of the antistatic layer. .

(13) The antireflection film as described in any one of (1) to (12), wherein the light diffusion layer contains translucent particles having an average particle diameter of 0.5 to 8 μm.
(14) The refractive index of the binder matrix of the light diffusing layer is 1.45 to 1.90, and the refractive index difference between the binder matrix of the light diffusing layer and the translucent particles is 0.02 to 0.30. The antireflection film according to any one of (1) to (13).
(15) The antireflection film as described in any one of (1) to (14) above, wherein irregularities are formed on the surface having the low refractive index layer and have antiglare properties.

(16) The antireflection according to any one of (1) to (15) above, wherein the low refractive index layer contains a polysiloxane compound represented by the following general formula (A) and / or a derivative thereof: the film.
Formula (A)

In general formula (A), R ^{1 to} R ⁴ each independently represent a substituent having 1 to 20 carbon atoms, and when there are a plurality of each group, they may be the same or different from each other, R ¹ , R ³ , R ⁴
At least one of the groups represents a crosslinkable or polymerizable functional group. p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, r represents an integer satisfying 0 ≦ r ≦ 500, and may be a random copolymer or a block copolymer.
(17) Any one of the above (1) to (16), wherein any layer on the transparent support contains an organosilane compound represented by the following general formula (a) and / or a derivative thereof: An antireflection film according to claim 1.

Formula _{^{(a) (R 10) s}} -Si (Z) 4-s

In general formula (a), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Z represents a hydroxyl group or a hydrolyzable group. s represents an integer of 1 to 3.
(18) The antireflection film as described in any one of (1) to (17) above, wherein any layer on the transparent support is formed in an atmosphere having an oxygen concentration of 4% by volume or less. .
(19) A polarizing plate comprising the antireflection film according to any one of (1) to (18) on at least one of two protective films of a polarizing film.
(20) An image display device, wherein the antireflection film according to any one of (1) to (18) or the polarizing plate according to (19) is disposed on an image display surface.
(21) The image display apparatus according to (22), wherein the image display apparatus is a TN, STN, IPS, VA, or OCB mode transmissive, reflective, or transflective liquid crystal display apparatus.

The antireflection film of the present invention is characterized in that the antistatic layer is provided in contact with the low refractive index layer (directly below the low refractive index layer). With this layer structure, an unexpectedly large antistatic effect is maintained even when the antistatic layer is thinned, and the unevenness is reflected on the antireflection film surface even though the light diffusion layer is a lower layer. As a result, it was found that good light diffusibility can also be exhibited. Even if an antistatic layer or the like is coated on the light diffusing layer as a condition for exhibiting such an excellent effect, the surface roughness is the surface roughness of the light diffusing layer before the upper layer is coated. Is maintained within the range of 0.5 to 1.0, and this is due to the contribution of the thin layer and the high conductivity effect by the above layer configuration.
Further, in order for the surface roughness of the surface of the antistatic layer to fall within the above-mentioned roughness ratio range reflecting the surface roughness of the light diffusion layer, the contribution of uniformity of the upper layer thickness is large. The uniformity is such that the center line average roughness Ra1 on the surface of the light diffusion layer is 0.03 to 0.30 μm, and Ra2 on the surface of the antistatic layer after coating the antistatic layer is 0.02 to 0.25 μm. It was also found that sometimes secured.
The effects summarized in the next section are obtained by the above features of the present invention.

According to the present invention, it is possible to provide an antireflection film having high scratch resistance and excellent dust resistance and antifouling properties against dust such as dust.
Furthermore, the polarizing plate and image display apparatus which have the said characteristics can be provided by these.

Hereinafter, the present invention will be described in more detail.
(Antistatic layer)
The antistatic layer in the present invention will be described.
In the antireflection film of the present invention, by constructing an antistatic layer, it is possible to prevent dust (dust etc.) from adhering to the surface of the antireflection film, that is, to exhibit an excellent dustproof property. Dust resistance is expressed by lowering the surface resistance value of the antireflection film surface, and the higher the conductivity of the antistatic layer, the higher the effect. In the antireflection film of the present invention, the surface resistance value of the surface having the low refractive index layer containing the fluorine-containing compound is preferably 1 × 10 ¹³ Ω / □ or less, and preferably 1 × 10 ¹² Ω / □. □ or less is more preferable, 1 × 10 ¹⁰ Ω / □ or less is further preferable, and 1 × 10 ⁸ Ω / □ or less is particularly preferable.

  In the antireflection film of the present invention, setting a layer on a support by a coating (coating) method is called coating. At least one layer of the antistatic layer is coated on the transparent support. The antistatic layer is applied between the light diffusion layer and the low refractive index layer having a fluorine-containing compound.

In the case of coating the antistatic layer, it is preferable to prepare the antistatic layer by incorporating a conductive material (electroconductive particles, electron conductive organic compounds, etc.) in a binder (binder, etc.). . In particular, an electron conductive type conductive material is preferable in that it is less susceptible to environmental changes, has stable conductive performance, and exhibits excellent conductive performance even in a low-humidity environment.
Hereinafter, a preferable method for producing an antistatic layer by a coating method will be described.

<Conductive material>
As a preferable conductive material used for the antistatic layer, an electron conductive conductive material such as a π-conjugated conductive organic compound or conductive fine particles is preferable.
Examples of π-conjugated conductive organic compounds include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, heteroatom-containing polyaniline, and mixed conjugated systems. And poly (phenylene vinylene).

Examples of the conductive fine particles include carbon-based, metal-based, metal oxide-based, and conductive coating-based fine particles.
Examples of the carbon-based fine particles include carbon powders such as carbon black, ketjen black, and acetylene black, carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, and carbon flakes of pulverized expanded graphite.
Metal fine particles include metals such as aluminum, copper, gold, silver, nickel, chromium, iron, molybdenum, titanium, tungsten, tantalum, and powders of alloys containing these metals, metal flakes, iron, copper And metal fibers such as stainless steel, silver-plated copper and brass.
Metal oxide fine particles include tin oxide, antimony-doped tin oxide (ATO), indium oxide, tin-doped indium oxide (ITO), zinc oxide, aluminum-doped zinc oxide, zinc antimonate, pentoxide And antimony.
As the conductive coated fine particles, for example, the surface of various fine particles such as titanium oxide (spherical, needle-shaped), potassium titanate, aluminum borate, barium sulfate, mica, silica, etc. can be formed with a conductive material such as tin oxide, ATO, or ITO. Resin beads such as coated conductive fine particles, polystyrene, acrylic resin, epoxy resin, polyamide resin, polyurethane resin and the like surface-treated with a metal such as gold and / or nickel are preferable.

  As the conductive material of the antistatic layer, π-conjugated conductive organic compound (especially polythiophene-based conductive polymer), and as conductive fine particles, metal-based fine particles (especially gold, silver, silver / palladium alloy, copper, nickel, Aluminum) and metal oxide fine particles (in particular, tin oxide, ATO, ITO, zinc oxide, aluminum-doped zinc oxide) are preferable. In particular, an electroconductive conductive material such as a metal or metal oxide is preferable, and metal oxide fine particles are particularly preferable.

The mass average particle size of the primary particles of the conductive material is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm. The average particle diameter of the conductive material can be measured by a light scattering method or an electron micrograph.
The specific surface area of the conductive material is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.
The shape of the conductive material is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a scale shape, a needle shape, or an indefinite shape, and particularly preferably an indefinite shape, a needle shape, or a scale shape.

<Method for forming antistatic layer>
When the antistatic layer is produced by a coating method, the conductive material is preferably used for forming the antistatic layer in a dispersion state.
In dispersing the conductive material, it is preferable to disperse in the dispersion medium in the presence of a dispersant.
By dispersing using a dispersant, the conductive material can be dispersed extremely finely, making it possible to produce a transparent antistatic layer. In particular, when an antistatic layer is used as an optical interference layer and the layer also has an antireflection function, it is possible to improve the antireflection performance by improving the transparency of the layer by finely dispersing the conductive material. preferable.

For dispersing the conductive material according to the present invention, it is preferable to use a dispersant having an anionic group. As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo group), a phosphoric acid group (phosphono group), a sulfonamide group, or a salt thereof is effective. Group, phosphoric acid group or a salt thereof is preferable, and carboxyl group and phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersant per molecule may be one or more. For the purpose of further improving the dispersibility of the conductive material, the dispersion material may contain a plurality of anionic groups per molecule. The average number per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.
Examples of the dispersant having an anionic polar group include phosphanol (PE-510, PE-610, LB-400, EC-6103, RE-410, etc .; manufactured by Toho Chemical Industry Co., Ltd.), Disperbyk (-110, − 111, -116, -140, -161, -162, -163, -164, -164, -170, -171, etc .; manufactured by Big Chemie Japan), Aronix M5300, etc .; manufactured by Toagosei Co., Ltd., KAYAMER ( PM-21, PM-2, etc .; manufactured by Nippon Kayaku Co., Ltd.).

  The dispersant preferably further contains a crosslinkable or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include an ethylenically unsaturated group (for example, a (meth) acryloyl group, an allyl group, a styryl group, a vinyloxy group, etc.), a cationic polymerizable group ( Epoxy group, oxatanyl group, vinyloxy group, etc.), polycondensation reactive groups (hydrolyzable silyl group, etc., N-methylol group), etc., and the like, preferably a functional group having an ethylenically unsaturated group.

  The dispersant used for dispersing the conductive material used in the antistatic layer according to the present invention has an anionic group and a crosslinkable or polymerizable functional group, and has the crosslinkable or polymerizable functional group in the side chain. A dispersant is particularly preferred.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is 1000 or more. Preferably there is. The dispersant preferably has a mass average molecular weight (Mw) of 2,000 to 1,000,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000.

The amount of the dispersant used relative to the conductive material is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass, and most preferably 5 to 20% by mass. Two or more dispersants may be used in combination.
The conductive material is preferably dispersed in a dispersion medium in the presence of a dispersant.

As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (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 Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-meth Shi-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred.
Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

The conductive material is preferably dispersed using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a dyno mill, a high-speed impeller mill, an Eiger mill, a pebble mill, a roller mill, an attritor and a colloid mill. A media disperser such as a sand grinder mill or a dyno mill is particularly preferable. 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.
The conductive material is preferably made as fine as possible in the dispersion medium, and the mass average particle diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm.
By miniaturizing the conductive material to 200 nm or less, an antistatic layer that does not impair the transparency can be produced.

In the present invention, the antistatic layer preferably contains an organic compound binder in addition to the conductive material, and it is preferable to form a matrix of the layer with the binder and disperse the conductive material. Therefore, the antistatic layer is preferably prepared by adding a binder or a binder precursor to a dispersion liquid in which a conductive material is dispersed in a dispersion medium. As the binder or binder precursor, a non-curable thermoplastic resin, or a curable resin such as a thermosetting resin or an ionizing radiation curable resin can be used.
The softening temperature or glass transition point of the binder or binder precursor is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 100 ° C. or higher.

In the present invention, the antistatic layer is prepared by adding a photopolymerization initiator or the like to a binder precursor (compound having a crosslinkable or polymerizable functional group) in a dispersion to form a coating for forming an antistatic layer. It is particularly preferable that the antistatic layer-forming coating material is applied to the substrate and cured by crosslinking or polymerization reaction of the binder precursor. As the compound having a crosslinkable or polymerizable functional group as the binder precursor, an ionizing radiation curable compound is preferable. For example, an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer described later is preferable.
In the above production method, the binder of the antistatic layer is formed as a cured product of a compound having a crosslinkable or polymerizable functional group. Furthermore, it is preferable to form the binder of the antistatic layer by curing it by crosslinking reaction or polymerization reaction with the dispersing agent at the same time or after coating of the layer.
The binder of the antistatic layer produced in this way is, for example, the above-mentioned dispersant and an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer cross-linked or polymerized, and the binder has an anionic group of the dispersant. The physical strength of the antistatic layer containing the conductive material, in which the anionic group has the function of maintaining the dispersed state of the conductive material, and the crosslinked or polymerized structure imparts a film-forming ability to the binder. It is preferable because chemical resistance and weather resistance can be improved.

The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include (meth) alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate. (Meth) acrylic acid of polyoxyalkylene glycols such as acrylic acid diesters, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Diesters, (meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate, 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane, 2--2-bi {4- (acryloxy · polypropoxy) phenyl} (meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as propane, and the like.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like.
Two or more polyfunctional monomers may be used in combination.

It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  Commercially available radical photopolymerization initiators include Kayacure (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals Co., Ltd., Esacure (KIP100F, KB1, EB3, BP, manufactured by Sartomer) X33, KT046, KT37, KIP150, TZT) and the like.

In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in Kazuhiro Takasashi “Latest UV Curing Technology” (Technical Information Association, Inc., page 159, 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.

It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Examples of commercially available photosensitizers include Kayacure (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.
The photopolymerization reaction is preferably performed by ultraviolet irradiation after the antistatic layer is applied and dried.
For ultraviolet irradiation, ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, and the like can be used.

  The binder in which the antistatic layer is crosslinked or polymerized preferably has a structure in which the main chain of the polymer is crosslinked or polymerized. Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

  The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked or polymerized structure.

The anionic group is preferably bonded to the main chain as a side chain of the binder via a linking group.
The linking group that binds the anionic group and the main chain of the binder is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked or polymerized structure chemically bonds (preferably covalently bonds) two or more main chains. In the crosslinked or polymerized structure, it is preferable to covalently bond three or more main chains. The crosslinked or polymerized structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof. .

  The binder is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked or polymerized structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96 mol%, more preferably 4 to 94 mol%, and most preferably 6 to 92 mol%. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked or polymerized structure in the copolymer is preferably 4 to 98 mol%, more preferably 6 to 96 mol%, and most preferably 8 to 94 mol%.

The repeating unit of the binder may have both an anionic group and a crosslinked or polymerized structure. The binder may contain other repeating units (repeating units having neither an anionic group nor a crosslinked or polymerized structure).
The crosslinked or polymerized binder is preferably prepared by applying a coating for forming an antistatic layer on a transparent support, and simultaneously with or after application, by a crosslinking or polymerization reaction.

  The content of the conductive material in the antistatic layer is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass with respect to the mass of the antistatic layer. Two or more kinds of conductive materials may be used in combination in the antistatic layer.

Preferred coating solvents for the antistatic layer include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (Methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.
Particularly preferred coating solvents are ketones, aromatic hydrocarbons, or esters, and the most preferred solvents are ketones. Of the ketones, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable.
The coating solvent may contain other solvents. For example, aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, , Diethyl ether, dioxane, tetrahydrofuran) and ether alcohol (eg, 1-methoxy-2-propanol).

  The coating solvent preferably has a ketone solvent content of 10% by mass or more of the total solvent contained in the paint. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

Formation of the antistatic layer is preferably carried out in an atmosphere having an oxygen concentration of 4% by volume or less, particularly when the antistatic layer is formed by crosslinking or polymerization reaction of an ionizing radiation curable compound.
By preparing the antistatic layer in an atmosphere having an oxygen concentration of 4% by volume or less, the physical strength (such as scratch resistance), chemical resistance and weather resistance of the antistatic layer, as well as the antistatic layer and the antistatic layer, Adhesion between adjacent layers can be improved.
Preferably, it is prepared by crosslinking or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 3% by volume or less, more preferably 2% by volume or less, particularly preferably 1% by volume or less. Most preferably, it is 0.5 volume% or less.
As a method for reducing the oxygen concentration to 4% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

  The film thickness of the antistatic layer can be appropriately designed depending on the application. When producing an antistatic layer having excellent transparency, the film thickness is preferably 20 to 1000 nm, more preferably 40 to 300 nm, and still more preferably 60 to 200 nm.

The haze of the antistatic layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. The haze in this case is a value obtained by coating and curing only an antistatic layer on a smooth transparent support.
The antistatic layer is coated on the light diffusing layer, and the centerline average roughness Ra2 of the surface after coating (in order to distinguish it from Ra of other layers, Ra after coating of the antistatic layer is expressed as Ra2. ) Is preferably 0.02 to 0.25 μm, more preferably 0.04 to 0.20 μm, and most preferably 0.06 to 0.17 μm.
The strength of the antistatic layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.
Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better. For this reason, it is also preferable that the antistatic layer is hard-coated.

  In the antistatic layer, in addition to the above components (conductive material, polymerization initiator, photosensitizer, binder, etc.), resin, surfactant, coupling agent, thickener, anti-coloring agent, coloring agent (pigment) Dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like.

(Light diffusion layer)
The light diffusion layer is formed from a binder made of a light-transmitting polymer, light-transmitting particles, and a fine inorganic filler for increasing the refractive index or decreasing the refractive index, preventing crosslinking shrinkage, and increasing the strength.
The thickness of the light diffusion layer is usually about 0.5 μm to 30 μm, preferably 1 μm to 15 μm, and more preferably 1.5 μm to 10 μm. If it is too thick, there are disadvantages such as curl, haze value, and high cost. Conversely, if it is too thin, it becomes difficult to adjust the antiglare property and the light diffusion effect.

<binder>
The binder is preferably a translucent polymer having a saturated hydrocarbon chain or a polyether chain as the main chain, and more preferably a polymer having a saturated hydrocarbon chain as the main chain. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer (binder precursor) is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom.

Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester poly Acrylate), vinylbenzene and derivatives thereof (eg, 1,4-vinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-vinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide.
Furthermore, resins having two or more ethylenically unsaturated groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins And oligomers or prepolymers of polyfunctional compounds such as polyhydric alcohols. Two or more of these monomers may be used in combination, and the resin having two or more ethylenically unsaturated groups is preferably contained in an amount of 10 to 70% based on the total amount of the binder.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. It can be cured by a polymerization reaction to form an antireflection film.
The refractive index of the binder is preferably 1.45 to 2.00, more preferably 1.48 to 1.90, still more preferably 1.50 to 1.85, and particularly preferably 1.51. ~ 1.80. In addition, the refractive index of a binder is the value measured by remove | excluding translucent particle | grains from the component of the light-diffusion layer.
It is preferable to add the binder of a light-diffusion layer in 20-95 mass% with respect to the solid content of the coating composition of this layer.

As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasagi, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as ammonium sulfate, potassium persulfate and the like, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. And diazoaminobenzene, p-nitrobenzenediazonium and the like.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Therefore, a coating solution containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, translucent particles and an inorganic filler is prepared, and the coating solution is applied onto a transparent support and then polymerized by ionizing radiation or heat. It can be cured by reaction to form an antireflection film.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydrides, cyanoacrylate derivatives, melamine, etherified methylol, esters and urethanes, and metal alkoxides such as tetramethoxysilane can also be used as monomers for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

<Translucent particles>
The light diffusion layer contains translucent particles having a particle size larger than that of the fine inorganic filler particles described later and an average particle size of 0.5 to 8 μm, preferably 1 to 6 μm, such as inorganic compound particles or resin particles. The This is because the external light reflected on the display surface is scattered and weakened, or the viewing angle of the liquid crystal display device (especially the downward viewing angle) is enlarged, so that the contrast decreases, black / white inversion or hue changes even if the viewing angle in the viewing direction changes. It is used for the purpose of making it difficult to occur. If the average particle size is less than 0.5 μm, the light diffusing effect is weak, and if it is 8 μm or more, the rough feeling is noticeably undesirable.
The centerline average roughness Ra1 of the surface after coating the light diffusion layer is preferably 0.03 to 0.30 μm, more preferably 0.05 to 0.25 μm, and most preferably 0.07 to 0.20 μm. . (The centerline average roughness of the surface after coating of the light diffusion layer refers to the centerline average roughness of the surface before coating of the antistatic layer in the present invention.)
The difference in refractive index between the translucent particles and the translucent resin is 0.02 to 0.30, and particularly preferably 0.04 to 0.20. If the difference exceeds 0.30, the film becomes cloudy, and if it is less than 0.02, a sufficient light diffusion effect cannot be obtained. Similarly to the refractive index, the amount of the translucent particles added to the translucent resin is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusion effect cannot be obtained. It is 3-40 mass% in a light-diffusion layer total solid, and it is especially preferable that it is 5-25%.
The coating amount of the light-transmitting particle is preferably a particle content in the light diffusion layer formed in 10~10000mg / m ^2, more preferably 50~4000mg / m ^2, and most preferably a 100~1500mg / m ² So as to be contained in the diffusion layer.
The particle size distribution of the particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

The translucent particles may be used in combination of two or more different translucent particles. When two or more kinds of translucent particles are used, the translucent particles having the highest refractive index and the translucent particles having the lowest refractive index are used to effectively exert the refractive index control by mixing a plurality of types of particles. The difference in refractive index with the active particles is preferably 0.02 or more and 0.10 or less, and particularly preferably 0.03 or more and 0.07 or less. Further, it is possible to impart an antiglare property with a light-transmitting particle having a larger particle diameter and to impart another optical characteristic with a light-transmitting particle having a smaller particle diameter. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the translucent resin.
Specific examples of the translucent particles include particles of inorganic compounds such as silica particles, hollow silica particles, alumina particles, and TiO ₂ particles; polymethyl methacrylate particles, crosslinked polymethyl methacrylate particles, methyl methacrylate-styrene. Preferred examples include resin particles such as copolymer particles, polystyrene particles, crosslinked polystyrene particles, melamine resin particles, benzoguanamine resin particles, polycarbonate particles, and polyvinyl chloride particles. Of these, crosslinked styrene particles, crosslinked polymethyl methacrylate particles, and silica particles are preferred.
As the shape of the translucent particle, either a true sphere or an indeterminate shape can be used, but monodisperse particles are preferable from the viewpoint of controllability of haze value and diffusibility, and uniformity of the coated surface. For example, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less of the total number of particles, more preferably 0.1% or less. Yes, more preferably 0.01% or less. Particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and particles having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

The light diffusion layer has an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in addition to the above light-transmitting particles in order to increase the refractive index of the layer. It is preferable that a fine inorganic filler having an average primary particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less is contained.
Conversely, in a light diffusion layer using translucent particles having a high refractive index, the refractive index of the binder must be lowered in order to increase the difference in refractive index from the translucent particles. For this purpose, it is also preferable to use silica fine particles and hollow silica fine particles. The preferred particle size is the same as that of the high refractive index fine inorganic filler.
Specific examples of the fine inorganic filler used for the light diffusion layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The addition amount of these fine inorganic fillers is preferably 10 to 90%, more preferably 20 to 80%, and particularly preferably 30 to 75% of the total mass of the light diffusion layer.
The fine inorganic filler does not scatter because the particle size is sufficiently shorter than the wavelength of light, and the dispersion in which the filler is dispersed in the binder polymer has the property of an optically uniform substance.

<Unevenness on the surface before and after coating the antistatic layer>
In the antireflection film of the present invention, in order to exhibit effective dust resistance, an antistatic layer is further formed on the light diffusion layer at the center line average roughness Ra1 of the surface of the layer after coating the light diffusion layer. The value obtained by dividing the center line average roughness Ra2 on the surface of the layer after coating is required to be 0.5 to 1.0, preferably 0.55 to 0.95, more preferably 0.8. 6-0.9. If this value is greater than 1.0, the antiglare property and haze are too high, and the image contrast is lowered. On the other hand, if it is less than 0.5, the antiglare property is too low and surface reflection increases.
Regarding the preferred value of the center line average roughness Ra1 after coating of the light diffusion layer and the centerline average roughness Ra2 after coating of the antistatic layer thereon, it is as described in the section of each layer. Ra is described in Jiro Nara, Techno Compact Series (6) “Measurement and Evaluation Method of Surface Roughness” (General Technology Center, Inc.).
Such an uneven shape on the surface of each layer of the antireflection film of the present invention can be evaluated by an atomic force microscope (AFM).

A well-known method is used as a method of forming surface irregularities. In the present invention, a method of forming by pressing a plate having a concavo-convex shape with high pressure on the surface of the film (for example, embossing), or a method of incorporating particles in a specific coating layer of the antireflection film is preferable. . In particular, the latter method is preferable because surface irregularities can be easily formed.
In the method of forming irregularities on the surface by embossing, a known method can be applied, but it is particularly preferable to form irregularities by the method described in Japanese Patent Application Laid-Open No. 2000-329905.

(Low refractive index layer)
The low refractive index layer used in the present invention contains a fluorine-containing compound. In particular, it is preferable to construct a low refractive index layer mainly composed of a fluorine-containing compound. The low refractive index layer mainly composed of a fluorine-containing compound is usually positioned as the outermost layer of the antireflection film and also has a function as an antifouling layer. Here, “mainly containing a fluorine-containing compound” means that the mass ratio of the fluorine-containing compound is the largest among the components contained in the low refractive index layer, and the content of the fluorine-containing compound is It is preferable that it is 50 mass% or more with respect to the total mass of a low refractive index layer, and it is more preferable that 60 mass% or more is contained.

  The fluorine-containing compound of the low refractive index layer is preferably formed by a crosslinking or polymerization reaction of a fluorine-containing compound having a crosslinking or polymerizable functional group, and the crosslinking or polymerizable functional group is an ionizing radiation curable functional group. It is preferable that Hereinafter, the fluorine-containing compound contained in the low refractive index layer will be described.

<Fluorine-containing compounds>
The refractive index of the fluorine-containing compound contained in the low refractive index layer is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47, More preferably, it is 1.38-1.45.
Examples of the fluorine-containing compound include a fluorine-containing polymer, a fluorine-containing silane compound, a fluorine-containing surfactant, and a fluorine-containing ether.
Examples of the fluorine-containing polymer include those synthesized by crosslinking or polymerization reaction of ethylenically unsaturated monomers containing fluorine atoms. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Fluorinated vinyl ethers and esters of fluorine-substituted alcohols with acrylic acid or methacrylic acid are included.

As the fluorine-containing polymer, a copolymer comprising a repeating structural unit containing a fluorine atom and a repeating structural unit not containing a fluorine atom can also be used.
The copolymer can be obtained by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom and an ethylenically unsaturated monomer not containing a fluorine atom.
Examples of ethylenically unsaturated monomers not containing fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylate esters (eg, methyl acrylate, ethyl acrylate, acrylic acid-2- Ethyl hexyl, etc.), methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene and its derivatives (eg, styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.) , Vinyl ether (eg, methyl vinyl ether), vinyl ester (eg, vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamide (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide, etc.), Ruamido and acrylonitrile, and the like.

  Examples of the fluorine-containing silane compound include silane compounds containing a perfluoroalkyl group.

  Fluorine-containing surfactants are those in which part or all of the hydrocarbon hydrogen atoms constituting the hydrophobic part are replaced by fluorine atoms, and the hydrophilic part is anionic, cationic, nonionic and amphoteric. Any of these may be used.

  The fluorine-containing ether is a compound generally used as a lubricant. Examples of the fluorinated ether include perfluoropolyether.

  As the fluorine-containing compound of the low refractive index layer, a fluorine-containing polymer into which a crosslinked or polymerized structure is introduced is particularly preferable. The fluorine-containing polymer into which a crosslinked or polymerized structure is introduced can be obtained by crosslinking or polymerizing a fluorine-containing compound having a crosslinked or polymerizable functional group.

  The fluorine-containing compound having a crosslinkable or polymerizable functional group can be obtained by introducing a crosslinkable or polymerizable functional group as a side chain into a fluorine-containing compound having no crosslinkable or polymerizable functional group. The crosslinkable or polymerizable functional group is a functional group that reacts with light (preferably ultraviolet irradiation), electron beam (EB) irradiation or heating to cause the fluorinated polymer to have a crosslinked or polymerized structure. preferable. Examples of the crosslinkable or polymerizable functional group include groups such as (meth) acryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene. A commercially available product may be used as the fluorine-containing compound having a crosslinkable or polymerizable functional group.

  The fluorine-containing compound of the low refractive index layer preferably contains as a main component a copolymer comprising a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain. The component derived from the copolymer is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the outermost layer. Below, the said copolymer preferable to be used for a low refractive index layer is demonstrated.

Fluorine-containing vinyl monomers include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (eg, biscoat) 6FM (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), M-2020 (trade name, manufactured by Daikin Industries, Ltd.) and the like, and fully or partially fluorinated vinyl ethers, etc. are preferable. From the viewpoints of refractive index, solubility, transparency, availability, etc., hexafluoropropylene is particularly preferred.
The fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass.

  The copolymer has a repeating unit having a (meth) acryloyl group. The method for introducing the (meth) acryloyl group is not particularly limited. For example, (i) after synthesizing a polymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid chloride, (meth) (Ii) a method in which acrylic acid anhydride, a mixed acid anhydride of (meth) acrylic acid and methanesulfonic acid, etc. are allowed to act, (ii) (meth) acrylic acid is added to the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid. (Iii) a method of allowing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and a (meth) acryloyl group to act on the polymer having the nucleophilic group, and (iv) after synthesizing a polymer having an epoxy group ( (V) a method of allowing meth) acrylic acid to act; (v) an epoxy group such as glycidyl methacrylate and (meth) acryloyl on a polymer having a carboxyl group Examples thereof include a method of allowing a compound having a group to act, and (vi) a method of dehydrochlorination after polymerizing a vinyl monomer having a 3-chloropropionic acid ester moiety. Among these, in the present invention, it is particularly preferable to introduce a (meth) acryloyl group by the method (i) or (ii) to a polymer containing a hydroxyl group.

  The repeating unit having a (meth) acryloyl group in the side chain preferably occupies 5 to 90% by mass, more preferably 30 to 70% by mass, and 40 to 60% by mass in the copolymer. It is particularly preferred.

  In addition to the repeating unit derived from the fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, the copolymer includes adhesion to a lower layer such as a transparent support, polymer Tg (for coating hardness). Other vinyl monomers can be suitably copolymerized from various viewpoints such as solubility in solvents, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer, more preferably 0 to 40 mol%, particularly preferably 0. ˜30 mol%.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethyl styrene, p-methoxy styrene, etc.) ), Vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate) , Vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide) Etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile derivatives and the like.

As a preferred form of a copolymer composed of a repeating unit derived from the fluorine-containing vinyl monomer used in the present invention and a repeating unit having a (meth) acryloyl group in the side chain, one represented by the following general formula (1) is exemplified. It is done.
General formula (1)

In the general formula (1), L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, linear or branched. , May have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred _{examples, * - (CH 2) 2} -O - **, * - (CH 2) 2 -NH - **, * - (CH 2) 4 -O - **, * - (CH 2) ₆ −O − **, * − (CH ₂ ) ₂ −O− (CH ₂ ) ₂ −O − **, −CONH− (CH ₂ ) ₃ −O − **, * −CH ₂ CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side) And the like. m represents 0 or 1;

  In general formula (1), X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In general formula (1), A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. It can be appropriately selected from various viewpoints such as adhesion, Tg of polymer (contributing to film hardness), solubility in solvent, transparency, slipperiness, dustproof / antifouling property, and can be selected according to the purpose. You may be comprised by the some vinyl monomer.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

Furthermore, what is represented by General formula (2) is mentioned as an especially preferable form of the said copolymer.
General formula (2)

In general formula (2), X, x, and y are each synonymous with general formula (1), and their preferable ranges are also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula (1) is applicable.
z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.
As the copolymer represented by the general formula (2), those satisfying 40 ≦ x ≦ 60, 30 ≦ y ≦ 60, and z2 = 0 are particularly preferable.

  Preferable specific examples of the copolymer represented by the general formula (1) or the general formula (2) include those described in [0043] to [0047] of JP-A-2004-45462. Further, the method for synthesizing the copolymer represented by the general formula (1) or the general formula (2) is also described in detail in the publication.

  In the present invention, the composition used for producing the low refractive index layer is preferably in the form of a paint, and a fluorine-containing compound is an essential constituent, and various additives and radical polymerization initiators are added as necessary. It is prepared by dissolving in an appropriate solvent. At this time, the concentration of the solid content is appropriately selected depending on the use, but is preferably 0.01 to 60% by mass, more preferably 0.5 to 50% by mass, and particularly preferably about 1% to 20% by mass. .

The low refractive index layer is made up of fillers (for example, inorganic fine particles and organic fine particles), slip agents (polysiloxane compounds such as dimethyl silicone), organosilane compounds and derivatives thereof, binders, surfactants, etc. Additives can be included. In particular, it is preferable to add a filler (for example, inorganic fine particles and organic fine particles) and a slipping agent (polysiloxane compound such as dimethyl silicone).
Hereinafter, preferred fillers, slip agents and the like used for the low refractive index layer will be described.

<Preferable filler for low refractive index layer>
It is preferable to add a filler (for example, inorganic fine particles or organic fine particles) in terms of improving the physical strength (such as scratch resistance) of the low refractive index layer. As the filler added to the low refractive index layer, inorganic fine particles are preferable. Among them, silicon dioxide (silica) having a low refractive index, hollow silica, silica having pores, fluorine-containing particles (magnesium fluoride, calcium fluoride, fluorine). Barium fluoride) and the like are preferable. Particularly preferred are silicon dioxide (silica) and hollow silica.

  The mass average particle diameter of the primary particles of the filler is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. It is preferable that the filler is more finely dispersed in the low refractive index layer. The shape of the filler is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape, and has a structure having hollow, fine pores or fine voids as a particle structure. Is more preferable. Particularly preferable shapes are a spherical shape and an indefinite shape. The filler may be crystalline or amorphous.

  The filler is used in plasma dispersion or corona discharge treatment in order to stabilize the dispersion in the dispersion or paint, or to increase the affinity and binding properties with the components of the low refractive index layer. Physical surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. A surface treatment with a coupling agent is particularly preferred. As the coupling agent, an alkoxy compound (eg, titanate coupling agent, silane coupling agent) is preferably used. In particular, silane coupling agent treatment is effective.

As for the surface treatment of the filler, it is preferable to carry out the surface treatment in advance before preparing the paint for the low refractive index layer, but in the case of surface treatment with a coupling agent, a coupling agent is added to the paint at the time of preparation of the paint. It is also preferable to carry out the addition.
The filler is preferably dispersed in advance in a medium (such as a solvent).

  The addition amount of the filler is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass with respect to the total mass of the low refractive index layer. If the amount is too small, the effect of improving the physical strength (such as scratch resistance) decreases, and if it is too large, the low refractive index layer may become cloudy.

  The average particle diameter of the filler is preferably 20 to 100%, more preferably 30 to 80%, and particularly preferably 30% to 50% with respect to the film thickness of the low refractive index layer.

  When the filler added to the low refractive index layer is silicon dioxide fine particles, it is particularly preferable to use hollow silicon dioxide fine particles. The hollow silicon dioxide fine particles preferably have a refractive index of 1.17 to 1.45, more preferably 1.17 to 1.40, and still more preferably 1.17 to 1.37. Here, the refractive index of the hollow silicon dioxide fine particles represents the refractive index of the entire particles, and does not represent the refractive index of only the outer silicon dioxide forming the hollow silicon dioxide fine particles. The refractive index of the low refractive index layer can be lowered by using hollow silicon dioxide fine particles.

  At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is expressed by the following formula (1).

Equation ^{(1) x = (4πa 3} /3) / (4πb 3/3) × 100

The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.

  It is also preferable to use two or more fillers in combination. Further, particles having different average particle diameters can be used in combination.

<Preferable slip agent for low refractive index layer>
The slip agent is preferably added from the viewpoint of improving the physical strength (such as scratch resistance) and antifouling property of the low refractive index layer.
Examples of the slip agent include fluorine-containing ether compounds (perfluoropolyether and derivatives thereof), polysiloxane compounds (dimethylpolysiloxane and derivatives thereof), and the like. Polysiloxane compounds are preferred.

Preferable examples of the polysiloxane compound include those having a substituent at the terminal and / or side chain of a compound containing a plurality of dimethylsilyloxy units as repeating units.
The compound containing a dimethylsilyloxy unit as a repeating unit may contain a structural unit (substituent) other than the dimethylsilyloxy unit. The substituents may be the same or different, and a plurality of substituents are preferable.

  Examples of preferred substituents include groups containing (meth) acryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done.

  Although there is no restriction | limiting in particular in the molecular weight of a slip agent, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular in Si atom content of a siloxane compound, it is preferable that it is 5 mass% or more, it is especially preferable that it is 10-60 mass%, and it is most preferable that it is 15-50 mass%.

  A particularly preferred slip agent is a polysiloxane compound having a crosslinkable or polymerizable functional group represented by the following general formula (A) and a derivative thereof (for example, a crosslink of a polysiloxane compound represented by the general formula (A)) Or a polymer, a reaction product of a polysiloxane compound represented by formula (A) and a compound having a crosslinkable or polymerizable functional group other than the polysiloxane compound).

Formula (A)

In general formula (A), R ^{1 to} R ⁴ each independently represent a substituent having 1 to 20 carbon atoms, and when there are a plurality of each group, they may be the same or different from each other, R ¹ , R ³ and R ⁴ represent a cross-linkable or polymerizable functional group.
p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, r represents an integer satisfying 0 ≦ r ≦ 500, and the polysiloxane portion surrounded by {} is a block copolymer even if it is a random copolymer. There may be.

  The low refractive index layer used in the present invention may contain a cured product containing a polysiloxane compound having a crosslinkable or polymerizable functional group represented by the general formula (A) and / or a derivative thereof and a fluorine-containing compound. preferable.

  The content of the polysiloxane compound and / or derivative thereof is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass with respect to the fluorine-containing compound. %.

  In the polysiloxane compound and / or derivative thereof, a preferable crosslinkable or polymerizable functional group can form a bond by crosslinking or polymerizing with other constituent components (fluorine-containing compound, binder, etc.) of the outermost layer. Any functional group may be used, for example, a group having an active hydrogen atom (for example, a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group, a hydrosilyl group, a silanol group, etc.), a group capable of cationic polymerization ( Epoxy groups, oxetanyl groups, oxazolyl groups, vinyl groups, vinyloxy groups, etc.), groups having unsaturated double bonds that can be crosslinked or polymerized by radical species (such as (meth) acryloyl groups, allyl groups), hydrolyzable silyls Groups (eg alkoxysilyl groups, acyloxysilyl groups, etc.), acid anhydrides, isocyanate groups, Group (active halogen atom, a sulfonic acid ester, etc.) which may be substituted by agents.

  These crosslinkable or polymerizable functional groups are appropriately selected according to the constituent components of the low refractive index layer. Preferably, it is an ionizing radiation curable functional group.

  The crosslinkable or polymerizable functional group of the general formula (A) is preferably crosslinked or polymerized with the crosslinkable or polymerizable functional group of the fluorine-containing compound, and the particularly preferred functional group is a cationic ring-opening polymerization reaction. A reactive group (in particular, an epoxy group, an oxetanyl group, etc.) and a radical polymerization reactive group (in particular, a (meth) acryloyl group).

The substituent represented by R ^{2 in the} general formula (A) is a substituted or unsubstituted organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a hexyl group). Etc.), a fluorinated alkyl group (trifluoromethyl group, pentafluoroethyl group, etc.) or an aryl group having 6 to 20 carbon atoms (for example, a phenyl group, a naphthyl group, etc.), more preferably an alkyl having 1 to 5 carbon atoms. Group, a fluorinated alkyl group or a phenyl group, particularly preferably a methyl group. These may be further substituted with these groups.
When R ¹ , R ³ , and R ^{4 in the} general formula (A) are not cross-linked or polymerizable functional groups, the above organic groups can be taken.

  p represents an integer satisfying 1 ≦ p ≦ 4. q represents an integer satisfying 10 ≦ q ≦ 500, preferably 50 ≦ q ≦ 400, and particularly preferably 100 ≦ q ≦ 300. r represents an integer satisfying 0 ≦ r ≦ 500, preferably 0 ≦ r ≦ q, and particularly preferably 0 ≦ r ≦ 0.5q.

The polysiloxane structure of the compound represented by the general formula (A) may be a homopolymer in which the repeating unit (—OSi (R ² ) ₂ —) is composed of only a single substituent (R ² ). A random copolymer constituted by a combination of repeating units having different substituents or a block copolymer may be used.

The compound represented by the general formula (A) preferably has a mass average molecular weight of 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ , and particularly preferably 10 ⁴ to 10 ⁵ . is there.

  The polysiloxane compound represented by the general formula (A) is commercially available, for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22 -164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS, X-22-174DX, X-22-2426, X-22-170DX , X-22-176D, X-22-1821 (manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (manufactured by Toa Gosei Chemical Co., Ltd.), Silaplane FM-0275, FM -0721, FM-0725, FM-7725, DMS-U22, RMS-033, RMS-083, UMS-182 (manufactured by Chisso Corporation) and the like can also be used. Moreover, it can also produce by introduce | transducing a crosslinking or polymerizable functional group into the hydroxyl group, amino group, mercapto group, etc. which a commercially available polysiloxane compound contains.

  Specific examples of preferable polysiloxane compounds represented by the general formula (A) include those described in JP-A 2003-329804 [0041] to [0045], but are not limited thereto. Is not to be done.

  The addition amount of the polysiloxane compound represented by the general formula (A) and / or its derivative is preferably 0.05 to 30% by mass, more preferably 0.1 to 30% by mass with respect to the total solid content of the outermost layer. 20 mass%, More preferably, it is 0.5-15 mass%, Most preferably, it is 1-10 mass%.

<Low refractive index layer and formation method thereof>
The low refractive index layer can be prepared by applying a paint in which the above-mentioned fluorine-containing compound and, if necessary, the above-mentioned filler, the above-mentioned polysiloxane compound and / or a derivative thereof are dissolved or dispersed in a solvent. preferable.
Preferred solvents include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, etc.) Isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.
Particularly preferred solvents are ketones, aromatic hydrocarbons and esters, and most preferred solvents are ketones. Of the ketones, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable. The solvent preferably has a ketone solvent content of 10% by mass or more based on the total solvent contained in the paint. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.
Two or more kinds of solvents can be used in combination.

In the case of a fluorine-containing compound having a crosslinkable or polymerizable functional group, it is preferable to produce a low refractive index layer by crosslinking or polymerizing the fluorine-containing compound simultaneously with or after the application of the low refractive index layer.
If the fluorine-containing compound has a functional group that crosslinks or polymerizes with a radical, it is preferable to perform a crosslinking or polymerization reaction using a radical polymerization initiator, particularly a photoradical polymerization initiator. Moreover, if it has a functional group which crosslinks or polymerizes with a cation, it is preferable to carry out a crosslinking or polymerization reaction using a cationic polymerization initiator, particularly a photocationic polymerization initiator.

  As the radical polymerization initiator, those that generate radicals by the action of heat or those that generate radicals by the action of light are preferable. Particularly preferred are radical photopolymerization initiators.

As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p- Nitrobenzenediazonium and the like can be mentioned.

In the case of using a compound that initiates radical polymerization by the action of light, for example, it can be cured by irradiation with light according to the compound to be used such as ultraviolet rays to produce a low refractive index layer.
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides There are compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in Kazuhiro Takasashi “Latest UV Curing Technology” (Technical Information Association, Inc., page 159, 1991).
A commercially available radical photopolymerization initiator can also be preferably used, and examples include the initiator described in the antistatic layer.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of fluorine-containing compounds, More preferably, it is the range of 1-10 mass parts. Furthermore, a photosensitizer can be preferably used in combination with these photopolymerization initiators, and examples thereof include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Commercially available photosensitizers can also be preferably used, and examples include sensitizers described in the antistatic layer.

The binder is preferably added in terms of improving the physical strength (such as scratch resistance) of the low refractive index layer and the adhesion between the outermost layer and the adjacent layer.
If the fluorine-containing compound is a compound having a crosslinkable or polymerizable functional group, the binder is preferably a binder having a functional group that crosslinks or polymerizes with the fluorine containing compound.
In particular, if the fluorine-containing compound is a compound having a photocrosslinkable or photopolymerizable functional group, the binder is preferably a polyfunctional monomer having a photocrosslinkable or photopolymerizable functional group. Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those described for the antistatic layer. Two or more polyfunctional monomers may be used in combination.
The fluorine-containing compound of the low refractive index layer includes a fluorine-containing compound having a crosslinking or polymerizable functional group, a polysiloxane compound represented by the general formula (A) and / or a derivative thereof, and / or the crosslinking or polymerization. It is preferably a cured product formed from a fluorine-containing compound having a functional group and a binder that crosslinks or polymerizes.

The low-refractive index layer is formed by dissolving or dispersing a fluorine-containing compound and other constituents of the outermost layer at the same time as or after application, and then performing light irradiation, electron beam irradiation, heat treatment, etc. It is preferable to carry out a polymerization reaction.
In the case of ultraviolet irradiation, ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, and the like can be used.

The production of the low refractive index layer is preferably carried out in an atmosphere having an oxygen concentration of 4% by volume or less, particularly when the outermost layer is formed by the crosslinking or polymerization reaction of an ionizing radiation curable compound.
By producing the low refractive index layer in an atmosphere having an oxygen concentration of 4% by volume or less, the physical strength (scratch resistance, etc.), chemical resistance and weather resistance of the low refractive index layer, and the outermost and outermost layers Adhesion between adjacent layers can be improved.
Preferably, it is produced by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 3% by volume or less, more preferably an oxygen concentration of 2% by volume or less, particularly preferably an oxygen concentration. Is 1% by volume or less, most preferably 0.5% by volume or less.
As a method for reducing the oxygen concentration to 4% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

  The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and particularly preferably 60 to 120 nm. When the low refractive index layer is used as an antifouling layer, the film thickness is preferably 3 to 50 nm, more preferably 5 to 35 nm, and particularly preferably 7 to 25 nm.

  The low refractive index layer preferably has a surface dynamic friction coefficient of 0.25 or less in order to improve the physical strength of the antireflection film. The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless steel hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless steel hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.

Further, in order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with respect to water is 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.
Further, the contact angle of the surface of the low refractive index layer with water is preferably not changed before and after the saponification treatment, which will be described later. It is.

  The haze of the low refractive index layer is preferably as low as possible. It is preferably 3% or less, more preferably 2% or less, and particularly preferably 1% or less.

  The strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  In addition to the above components (fluorine-containing compounds, polymerization initiators, photosensitizers, fillers, slip agents, binders, etc.), the low refractive index layer contains surfactants, antistatic agents, coupling agents, and thickeners. Agents, anti-coloring agents, coloring agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, etc. Can also be added.

The refractive index of the low refractive index layer is preferably 1.20 to 1.55. More preferably, it is 1.30-1.50, More preferably, it is 1.35-1.48, Most preferably, it is 1.37-1.45.
The low refractive index layer is composed of an organosilane compound represented by the following general formula (a) and a derivative thereof (hydrolyzate and a crosslinked silicon compound formed by condensation of the hydrolyzate). It is also preferable to contain the compound chosen from these.

(Hard coat layer)
The antireflection film of the present invention can be provided with a hard coat layer in order to impart physical strength. In particular, it is preferably provided between the transparent support and the outermost layer.
The hard coat layer is preferably formed by a crosslinking or polymerization reaction of an ionizing radiation curable compound. For example, it can be formed by applying a coating containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and crosslinking or polymerizing the polyfunctional monomer or polyfunctional oligomer.
The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those exemplified for the antistatic layer, and it is preferable to polymerize using a photopolymerization initiator and a photosensitizer. The photopolymerization reaction is preferably performed by ultraviolet irradiation after the hard coat layer is applied and dried.
The hard coat layer is preferably constructed by applying a paint for forming a hard coat layer on the surface of the transparent support.

As the coating solvent, ketones, esters, and aromatic hydrocarbons exemplified in the antistatic layer are preferable. In particular, by using a ketone solvent, for example, the adhesion between the surface of a transparent support (particularly, a triacetyl cellulose support) and the hard coat layer is further improved.
Particularly preferred coating solvents are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
The coating solvent may contain a solvent other than the ketone solvent exemplified for the antistatic layer.
The coating solvent preferably has a ketone solvent content of 10% by mass or more of the total solvent contained in the coating composition. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

When the hard coat layer is prepared by crosslinking or polymerization reaction of an ionizing radiation curable compound, the crosslinking or polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 4% by volume or less. By producing in an atmosphere having an oxygen concentration of 4% by volume or less, a hard coat layer excellent in physical strength (such as scratch resistance) and chemical resistance can be produced.
Preferably, it is prepared by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 3% by volume or less, more preferably an oxygen concentration of 2% by volume or less, particularly preferably an oxygen concentration of 1 Volume% or less, most preferably 0.5 volume% or less.
As a method for reducing the oxygen concentration to 4% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm, and particularly preferably 3 to 5 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

Resin, dispersant, surfactant, antistatic agent, silane coupling agent, thickener, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, UV Absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added. In addition, for the purpose of increasing the hardness of the hard coat layer, suppressing curing shrinkage, controlling the refractive index, and the like, inorganic fine particles having an average primary particle diameter of 1 to 200 nm described later can be added.
Furthermore, particles having an average particle size of 0.2 to 10 μm, which will be described later, may be contained for the purpose of imparting an antiglare function and a function of expanding the viewing angle of a liquid crystal display device.

(Transparent support)
The transparent support is preferably a plastic film. As the plastic film, cellulose ester (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, poly-1, 4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, poly Methylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate And polyether ketones. Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred, and triacetyl cellulose is particularly preferred when used in a liquid crystal display device.

  When the transparent support is a triacetyl cellulose film, a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent is prepared by a single layer casting method or a multi-layer co-casting method. A cellulose film is preferred.

In particular, from the viewpoint of environmental conservation, a triacetyl cellulose film prepared using a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a low temperature dissolution method or a high temperature dissolution method is preferable. .
The triacetylcellulose film preferably used in the present invention is exemplified in the Japan Society for Invention and Innovation (public technical number 2001-1745).

The film thickness of the transparent support is not particularly limited, but the film thickness is preferably 1 to 300 μm, preferably 30 to 150 μm, particularly preferably 40 to 120 μm, and most preferably 40 to 100 μm.
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.
The haze of the transparent support is preferably low. It is preferably 2.0% or less, and more preferably 1.0% or less.
The refractive index of the transparent support is preferably 1.40 to 1.70.

An infrared absorber or an ultraviolet absorber may be added to the transparent support. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass.
In addition, an inert inorganic compound particle may be added to the transparent support as a slipping agent. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin.

  A surface treatment may be performed on the transparent support. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and corona discharge treatment are particularly preferred.

(Organosilane compound)
In the present invention, an organosilane compound that can be particularly preferably used for each layer of the antireflection film will be described.
It is preferable to add an organosilane compound and / or a derivative thereof to any layer on the transparent support from the viewpoint of improving the physical strength of the film (such as scratch resistance) and the adhesion between the film and the layer adjacent to the film. .

  As the organosilane compound and / or a derivative thereof, a compound represented by the following general formula (a) and / or a derivative thereof can be used. Preferred are organosilane compounds containing a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group (( (Meth) acryloyl, etc.) and a polymerizable acylamino group (acrylamino, methacrylamino, etc.).

Formula _{^{(a) (R 10) s}} -Si (Z) 4-s

In general formula (a), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
Z represents a hydroxyl group or a hydrolyzable group. For example, an alkoxy group (an alkoxy group having 1 to 5 carbon atoms is preferable. Examples thereof include a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and R ¹² COO (R ¹² is a hydrogen atom or An alkyl group having 1 to 5 carbon atoms is preferred, and examples thereof include CH ₃ COO, C ₂ H ₅ COO, etc., preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. It is.
s represents an integer of 1 to 3. 1 or 2 is preferable, and 1 is particularly preferable.
When R ¹⁰ or Z there is a plurality, the plurality of R ¹⁰ or Z may be different.

The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy groups (phenoxy) Etc.), alkylthio groups (such as methylthio and ethylthio), arylthio groups (such as phenylthio), alkenyl groups (such as vinyl and 1-propenyl), alkoxysilyl groups (such as trimethoxysilyl and triethoxysilyl), acyloxy groups (acetoxy, acryloyl) Oxy, methacryloyloxy, etc.), alkoxycal Nyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino Groups (acetylamino, benzoylamino, acrylamino, methacrylamino and the like) and the like, and these substituents may be further substituted with these substituents.

  Of these, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group. In particular, a crosslinked or polymerizable functional group is preferable, and an epoxy group, a polymerizable acyloxy group ((meth) acryloyl), and a polymerizable acylamino group (acrylamino, methacrylamino) are preferable. These substituents may be further substituted with the above-described substituents.

When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group. Among the organosilane compounds represented by the general formula (a) and derivatives thereof, organosilane compounds having a vinyl polymerizable substituent represented by the following general formula (b) and / or derivatives thereof are preferable.
General formula (b)

In the general formula (b), R ¹¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond, * -COO-**, * -CONH-**, * -O-**, or * -NH-CO-NH-**, and represents a single bond, * -COO-**, * -CONH-** is preferred, single bond, * -COO-** is more preferred, and * -COO-** is particularly preferred. Here, * represents a position bonded to ═C (R ¹¹ ) —, and ** represents a position bonded to L.

L ¹ represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and an alkylene group having a linking group therein are preferred. An unsubstituted alkylene group and an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferred, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

t represents 0 or 1; t is preferably 0.
R ¹⁰ has the same meaning as in formula (a), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
Z has the same meaning as in formula (a), preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred. When a plurality of Z are present, the plurality of Z may be the same or different.

Two or more kinds of the compounds represented by the general formula (a) and the general formula (b) and their derivatives may be used in combination.
Although the specific example of the organosilane compound represented by general formula (a) and general formula (b) below is shown, this invention is not limited to these.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable.

In the present invention, the derivative of the organosilane compound represented by the general formula (a) and the general formula (b) is a hydrolyzate of the organosilane compound represented by the general formula (a) and the general formula (b), It means a partial condensate. Hereinafter, preferred derivatives (hydrolyzate and / or partial condensate) of the organosilane compound used in the present invention will be described.
The hydrolysis reaction and / or condensation reaction of the organosilane compound is generally performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferred is an organic acid having an acid dissociation constant of 2.5 or less in water, and methanesulfonic acid. Of these, oxalic acid, phthalic acid and malonic acid are more preferred, and oxalic acid is particularly preferred.

The organosilane hydrolysis / condensation reaction can be carried out in the absence of a solvent or in a solvent, but an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, Ketones and esters are preferred.
The solvent preferably dissolves the organosilane and the catalyst. Moreover, it is preferable to use an organic solvent as a paint or a part of the paint, and it is preferable that the solvent does not impair the solubility or dispersibility when mixed with other materials.

Among these, examples of alcohols include monohydric alcohols and dihydric alcohols, and among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms.
Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the reaction is not particularly limited, but is usually in the range of 1% to 90%, preferably in the range of 20% to 70%.

0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane compound, in the presence or absence of the above solvent, and in the presence of a catalyst. And by stirring at 25 to 100 ° C.
In the present invention, (wherein, R ¹³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ¹³ OH alcohol of the general formula R ¹⁴ COCH ₂ COR ¹⁵ (wherein represented by, R ¹⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms) and selected from Zr, Ti and Al. It is preferable to perform the hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a metal as a central metal.

The metal chelate compound includes an alcohol represented by a general formula R ¹³ OH (wherein R ¹³ represents an alkyl group having 1 to 10 carbon atoms) and a general formula R ¹⁴ COCH ₂ COR ¹⁵ (wherein R ¹⁴ is carbon. From Zr, Ti, and Al having a ligand represented by a compound represented by an alkyl group having 1 to 10 carbon atoms, R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) Any metal having a selected metal as a central metal can be suitably used without particular limitation. Two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ¹³ ) _p1 (R ¹⁴ COCHCOR ¹⁵ ) _p2 , Ti (OR ¹³ ) _q1 (R ¹⁴ COCHCOR ¹⁵ ) _q2 , and Al (OR ¹³ ) _r1 (R ¹⁴ Those selected from the group of compounds represented by COCHCOR ¹⁵ ) _r2 are preferred, and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ¹³ and R ¹⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ¹⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. If it is less than 0.01% by mass, the condensation reaction of the organosilane compound is slow, and the durability of the coating film may be reduced. On the other hand, if it exceeds 50% by mass, the hydrolyzate and / or partial condensate of the organosilane compound And the storage stability of the composition containing the metal chelate compound may decrease, which is not preferable.

  A β-diketone compound and / or a β-ketoester compound is added to the composition containing the organosilane compound and / or derivative thereof (hydrolyzate, partial condensate) and a metal chelate compound added as necessary. It is preferable to do.

In the present invention, a β-diketone compound and / or a β-ketoester compound represented by the general formula R ¹⁴ COCH ₂ COR ¹⁵ is preferably used, and acts as a stability improver for the composition. That is, by coordinating to metal atoms in the metal chelate compounds (zirconium, titanium and / or aluminum compounds), organosilane compound derivatives (hydrolysates, partial condensates, etc.) by these metal chelate compounds It is considered that the action of accelerating the condensation reaction is suppressed and the action of improving the storage stability of the resulting composition is achieved. R ¹⁴ and R ¹⁵ constitute a β- diketone compound and / or β- ketoester compound are the same as R ¹⁴ and R ¹⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition may be inferior, which is not preferable.

  The amount of the organosilane compound and / or derivative thereof added is appropriately adjusted depending on the layer to be added. The addition amount is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, further preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass with respect to the total solid content of the layer. It is.

Organosilane compounds and / or derivatives thereof are preferred because crosslinking or polymerization reaction with other components of the layer containing them can greatly improve the physical strength (scratch resistance, etc.) of the film. . For this reason, it is preferable that the organosilane compound has a functional group that crosslinks or polymerizes, or a compound having a functional group that crosslinks or polymerizes with the organosilane compound in an inorganic fine particle or a binder.
For example, an organosilane compound having an ionizing radiation-curable crosslinking or polymerizable functional group and / or a derivative thereof is further crosslinked with another compound having an ionizing radiation-curable crosslinking or polymerizable functional group in the film. Alternatively, a cured product is produced by a polymerization reaction.

  Preferred layers for adding the organosilane compound are an antistatic layer, a hard coat layer, an antiglare layer, a light diffusion layer, a high refractive index layer, a low refractive index layer, and an outermost layer, more preferably a hard coat layer, It is an antiglare layer, a light diffusion layer, a low refractive index layer, or an outermost layer, and particularly preferably an outermost layer and / or a layer adjacent to the outermost layer.

(Anti-reflection film formation method, etc.)
In the present invention, each layer constituting the antireflection film is preferably prepared by a coating method. When formed by coating, each layer is formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating or extrusion coating (US Pat. No. 2,681, 294 specification). Two or more layers may be applied simultaneously. For the simultaneous application method, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, “Coating Engineering ", page 253, Asakura Shoten (1973). Wire bar coating, gravure coating, and micro gravure coating are preferred. In particular, the micro gravure coating method is preferable.
The micro gravure coating method is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and having a gravure pattern engraved on the entire circumference, below the support and in the transport direction of the support. , Reversely rotating, scraping off excess coating liquid from the surface of the gravure roll with a doctor blade, and transferring a fixed amount of coating liquid onto a support and coating.

  In the micro gravure coating method, the number of gravure patterns engraved on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch. The depth of the gravure pattern is preferably 1 to 600 μm, more preferably 5 to 200 μm. The rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm. It is preferable that the conveyance speed of a support body is 0.5-100 m / min, More preferably, it is 1-50 m / min.

  When each layer of the antireflection film is prepared by a coating method, it is preferable to add a surface conditioner to the coating material used for preparing the layer. Hereinafter, the surface conditioner will be described.

(Surface improver)
In order to improve surface defects (coating irregularities, drying irregularities, point defects, etc.), the paint used for producing any layer on the transparent support of the present invention is a fluorine-based and / or silicone-based coating. It is preferable to add a surface improver.

The surface improver preferably changes the surface tension of the paint by 1 mN / m or more. Here, the surface tension of the paint changes by 1 mN / m or more when the surface tension of the paint after the addition of the surface conditioner is added, including the concentration process during coating / drying. It means that it changes by 1 mN / m or more as compared with the surface tension of the paint.
Preferably, it is a surface improver that has the effect of lowering the surface tension of the paint by 1 mN / m or more, more preferably a surface improver that lowers by 2 mN / m or more, and particularly preferably a surface improver that lowers by 3 mN / m or more.

Preferable examples of the fluorine-based surface improving agent include compounds containing a fluoroaliphatic group (abbreviated as “fluorine surface improving agent”). In particular, an acrylic resin, a methacrylic resin, and a copolymer thereof, including a repeating unit corresponding to the monomer of the following general formula (i) and a repeating unit corresponding to the monomer of the following general formula (ii) Copolymers with possible vinyl monomers are preferred.
Such monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley Interscience (1975) Chapter 2, Pages 1-483 are preferably used.
For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can give you.
Formula (i)

In the general formula (i), R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and particularly preferably an oxygen atom. R ²² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group. a represents an integer of 1 to 6, more preferably 1 to 3, and particularly preferably 1. b represents an integer of 1 to 18, more preferably 4 to 12, and particularly preferably 6 to 8.
Two or more types of fluoroaliphatic group-containing monomers represented by the general formula (i) may be contained in the fluorine-based surface improver as a constituent component.
General formula (ii)

In the general formula (ii), R ²³ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. Y ² represents an oxygen atom, a sulfur atom or —N (R ²⁵ ) —, more preferably an oxygen atom or —N (R ²⁵ ) —, and particularly preferably an oxygen atom. R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group.
R ²⁴ represents a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group, or a substituted or unsubstituted aromatic group (for example, A phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms in total is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is still more preferable. The poly (alkyleneoxy) group will be described below.

Poly (alkyleneoxy) group, - (OR) - a group in which a repeating unit, R represents an alkylene group having 2 to 4 carbon atoms, such as _{-CH 2 CH 2 -, - CH} 2 CH 2 CH _2- , -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-.
The oxyalkylene units (-OR-) in the poly (oxyalkylene) group may be the same as in poly (oxypropylene), and two or more different oxyalkylenes are randomly distributed. It may be a linear or branched oxypropylene or oxyethylene unit, or a linear or branched oxypropylene unit block or an oxyethylene unit block. May be.
The poly (oxyalkylene) chain may also include those linked by one or more chain bonds (for example, —CONH—Ph—NHCO—, —S—, etc .: Ph represents a phenylene group). If the chain bond has a valence of 3 or more, this provides a means for obtaining branched oxyalkylene units. When this copolymer is used in the present invention, the molecular weight of the poly (oxyalkylene) group is suitably from 250 to 3,000.
Poly (oxyalkylene) acrylates and methacrylates are commercially available hydroxypoly (oxyalkylene) materials, for example, trade name “Pluronic” [Pluronic (Asahi Denka Kogyo Co., Ltd.), Adeka Polyether (Asahi Denka Kogyo Co., Ltd.) "Carbowax" [Carbowax (Glico Product)], "Triton" (Toriton (Rohm and Haas)) and PEG (Daiichi Kogyo Seiyaku Co., Ltd.) It can be produced by reacting with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride by a known method. Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

In the fluorine-based surface improver comprising the fluoroaliphatic group-containing monomer represented by the general formula (i), the fluoroaliphatic represented by the general formula (i) with respect to the total amount of monomers used for forming the fluorine-based surface improver The amount of the group-containing monomer is preferably 50 mol% or more, more preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol%.
Moreover, it is preferable that the quantity of the monomer shown by general formula (ii) is 0-50 mol%, and it is more preferable that it is 0-30 mol%.

The preferred weight average molecular weight of the fluorine-based planar improver comprising the fluoroaliphatic group-containing monomer represented by the general formula (i) is preferably 3000 to 100,000, more preferably 6,000 to 80,000, and 8, 000 to 60,000 is more preferable.
Here, the mass average molecular weight is expressed in terms of polystyrene by GTH analyzer using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) by solvent THF and differential refractometer detection. The content is the area% of the peak in the molecular weight range when the peak area of a component having a molecular weight of 300 or more is defined as 100%.

  The preferred amount of addition of the fluorine-based surface improver comprising the fluoroaliphatic group-containing monomer represented by the general formula (i) is in the range of 0.001 to 5% by mass with respect to the coating material of the layer to be added, preferably The range is 0.005 to 3% by mass, and more preferably 0.01 to 1% by mass.

  Hereinafter, examples of the specific structure of the fluorine-based surface improver composed of the fluoroaliphatic group-containing monomer represented by the general formula (i) will be shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

From the viewpoint of adjusting the surface tension, a fluorine-based surface improver containing a monomer having a structure different from the above is also preferable. In particular, an acrylic resin, a methacrylic resin, and a copolymer thereof, containing a repeating unit corresponding to the monomer of the following general formula (iii) and a repeating unit corresponding to the monomer of the following general formula (iv) Copolymers with possible vinyl monomers are preferred.
General formula (iii)

In the general formula (iii), R ³¹ represents a hydrogen atom or a methyl group, X ³ represents an oxygen atom, a sulfur atom or —N (R ³² ) —, m is an integer of 1 to 6, and n is 2 or An integer of 3 is represented. R ³² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. X ³ is preferably an oxygen atom. M in the general formula 2 is preferably an integer of 1 to 6, and 2 is particularly preferable. N in the general formula 2 is 1 to 3, and a mixture of 1 to 3 may be used.

As the monomer copolymerizable with the monomer represented by the general formula (iii), a monomer represented by the following general formula (iv) is preferable.
Formula (iv)

In the general formula (iv), R ¹³ represents a hydrogen atom or a methyl group, Y ¹ represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, and R ¹⁵ represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Group, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - it is preferred. R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula (iii) used for the synthesis of the fluorine-based planarity improver comprising the fluoroaliphatic group-containing monomer represented by the general formula (iii) It is 10 mol% or more based on the total amount of each monomer of an improving agent, Preferably it is 15-70 mol%, More preferably, it is the range of 20-60 mol%.

  The preferred weight average molecular weight of the fluorine-based surface improver comprising the fluoroaliphatic group-containing monomer represented by the general formula (iii) is preferably 3000 to 100,000, and more preferably 5,000 to 80,000. The preferred amount of addition of the fluorine-based surface improver comprising the fluoroaliphatic group-containing monomer represented by the general formula (iii) is the effect, the drying property of the coating film, and the performance of the coating film (for example, reflectance, scratch resistance). Etc.) is preferably in the range of 0.001 to 5% by mass, more preferably in the range of 0.005 to 3% by mass, and still more preferably 0.01 to 1%. It is the range of mass%.

  Hereinafter, examples of the specific structure of the fluorine-based surface improver composed of the fluoroaliphatic group-containing monomer represented by the general formula (iii) are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

The surface conditioner of the present invention includes ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), It is preferable to use it for a paint containing an aromatic hydrocarbon solvent (toluene, xylene, etc.). In particular, a ketone solvent is preferable. Among the ketone solvents, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable.
Moreover, it is preferable that it is especially a coating material containing 10 mass% or more of a ketone solvent of all the solvents. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

  The solvent of the paint may contain a solvent other than the ketone solvent. For example, water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ester (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), fat Aromatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethyl) Examples include acetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol) and the like.

  A planarity improving agent may worsen the adhesiveness of the interface of a layer. Accordingly, it is preferable to elute the surface improver present on the surface of the layer into the coating material forming the adjacent layer of the layer so that the surface improver does not remain in the vicinity of the interface between the layers. Therefore, it is preferable to contain a solvent that dissolves the surface improver in the paint of the adjacent layer. As such a solvent, the above ketone solvents are preferable.

  In order to form a hard coat layer, an antiglare layer, a light scattering layer, an antistatic layer, and a high refractive index layer, it is particularly preferable to add a surface state improver to the coating of the layer formed on the transparent support. Particularly preferred are paints for forming a hard coat layer, an antiglare layer, and a light scattering layer.

(Antireflection film)
In the antireflection film of the present invention, in order to improve physical strength (such as scratch resistance), the dynamic friction coefficient of the surface having the outermost layer is preferably 0.25 or less. The dynamic friction coefficient described here is the same as the surface and diameter on the side having the outermost layer when a load of 0.98 N is applied to a stainless hard sphere having a diameter of 5 mm and the surface on the side having the outermost layer is moved at a speed of 60 cm / min. The coefficient of dynamic friction between 5 mm stainless hard spheres. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
Further, the antireflection film preferably has a contact angle with water of 80 ° or more on the surface having the outermost layer in order to improve the antifouling performance. More preferably, it is 90 ° or more, and particularly preferably 100 ° or more.

  The haze of the antireflection film according to the present invention is preferably 0.5 to 60%, more preferably 1 to 50%, and most preferably 1 to 40%.

  The reflectance of the antireflection film of the present invention is preferably as low as possible, preferably 3.0% or less, more preferably 2.5% or less, still more preferably 2.0% or less, and particularly preferably 1.5% or less. .

(Structure of antireflection film)
A configuration example of the antireflection film of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view schematically showing a layer structure of an antireflection film having excellent antireflection performance.

The embodiment shown in FIG. 1 has a layer structure in the order of a transparent support 1, an antiglare layer 2, an antistatic layer 4, and a low refractive index layer (outermost layer) 5. The particles 3 contained in the antiglare layer 2 are particles having an average particle size of 0.2 to 10 μm.
In the embodiment shown in FIG. 1, the transparent support 1, the antistatic layer 4, and the low refractive index layer 5 have a refractive index that satisfies the following relationship. That is, the refractive index of the antistatic layer> the refractive index of the transparent support> the refractive index of the low refractive index layer.

  1, the antistatic layer satisfies the following formula (11) and the low refractive index layer satisfies the following formula (12), as described in JP-A-59-50401. Is preferable in that it can be an antireflection film having further excellent antireflection performance.

Formula (11) (m ₈ λ / 4) × 0.7 <n ₈ d ₈ <(m ₈ λ / 4) × 1.3

In formula (11), m ₈ is a positive integer (generally 1, 2 or 3), n ₈ is the refractive index of the antistatic layer, and d ₈ is the layer thickness (nm) of the antistatic layer. is there. λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).

Formula (12) (m ₉ λ / 4) × 0.7 <n ₉ d ₉ <(m ₉ λ / 4) × 1.3

In Equation (12), m ₉ is a positive odd number (generally 1), n ₉ is the refractive index of the low refractive index layer, and d ₉ is the layer thickness (nm) of the low refractive index layer. λ is the wavelength of visible light, and is a value in the range of 380 to 680 (nm).
In addition, the aspect shown in FIG. 1 is an antireflection film excellent in antiglare property.

(Protective film for polarizing plate)
The antireflection film of the present invention can be used as a protective film for a polarizing film (protective film for polarizing plate). In this case, the contact angle with respect to water of the surface of the transparent support opposite to the side having the outermost layer, that is, the surface to be bonded to the polarizing film is preferably 40 ° or less. More preferably, it is 30 ° or less, and particularly preferably 25 ° or less. Setting the contact angle to 40 ° or less is effective in improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. This contact angle can be adjusted by the following saponification treatment conditions.

  As the transparent support of the antireflection film used as the protective film for polarizing plate, it is particularly preferable to use a triacetyl cellulose film.

The following two methods are mentioned as a method of producing the protective film for polarizing plates in this invention.
(1) A method of coating each of the above layers (eg, antistatic layer, hard coat layer, low refractive index layer, high refractive index layer, outermost layer, etc.) on one surface of a saponified transparent support.
(2) After coating each of the above layers (eg, antistatic layer, hard coat layer, low refractive index layer, outermost layer, etc.) on one surface of the transparent support, the side to be bonded to the polarizing film is saponified. Technique.

In the method (1), when only one surface of the transparent support is saponified, each layer is coated on the side not saponified. When both surfaces of the transparent support are saponified, the surface of the saponified transparent support on the side where each layer is applied is surface-treated by a technique such as corona discharge treatment, glow discharge treatment, flame treatment, etc. It is preferable to coat each layer.
In said (2), it is preferable to immerse the whole antireflection film in a saponification liquid. In this case, the antireflection film can also be saponified on the surface of the transparent support to be bonded to the polarizing film by protecting the surface having each layer with a protective film and immersing it in a saponification solution.
Furthermore, a saponification treatment solution can be applied to the surface of the transparent support on the side to be bonded to the polarizing film of the antireflection film, and the side to be bonded to the polarizing film can be saponified.
The saponification treatment is carried out after antireflection performance is imparted on the protective film, whereby the cost can be further reduced, and the method (2) is particularly preferable in that the protective film for polarizing plate can be produced at a low cost.

Protective films for polarizing plates have optical performance (antireflection performance, antiglare performance, etc.), physical performance (such as scratch resistance), chemical resistance, antifouling performance (contamination resistance, etc.), weather resistance (moisture and heat resistance, light resistance) Property) and dustproof performance, it is preferable to satisfy the performance described in the antireflection film of the present invention.
Accordingly, the surface resistance value of the surface having the outermost layer is preferably 1 × 10 ¹³ Ω / □ or less, more preferably 1 × 10 ¹² Ω / □ or less, and more preferably 1 × 10 ¹⁰ Ω / □. More preferably, it is more preferably 1 × 10 ⁸ Ω / □ or less.
The coefficient of dynamic friction on the surface having the outermost layer is preferably 0.25 or less. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
Further, the contact angle with respect to water on the surface having the outermost layer is preferably 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.

(Saponification treatment)
The saponification treatment is preferably carried out by a known method, for example, by immersing a transparent support or an antireflection film in an alkali solution for an appropriate time.
The alkaline liquid is preferably a potassium hydroxide aqueous solution and / or a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / l, particularly preferably 1 to 2 mol / l. The liquid temperature of a preferable alkali liquid is 30-70 degreeC, Most preferably, it is 40-60 degreeC.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface of the transparent support is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 25 ° or less.

(Polarizer)
The polarizing plate of the present invention has the antireflection film of the present invention on at least one of the polarizing film protective film (polarizing plate protective film). As described above, the polarizing plate protective film has a water contact angle of 40 ° or less on the surface of the transparent support opposite to the side having the outermost layer, that is, the surface to be bonded to the polarizing film. preferable.

By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function can be produced, and the cost can be greatly reduced and the display device can be thinned.
The polarizing plate using the antireflection film of the present invention as one of the two protective films and the optical compensation film having optical anisotropy described later as the other is further provided with a contrast in a bright room of a liquid crystal display device. This is preferable because the viewing angle in the vertical and horizontal directions can be greatly widened.

(Optical compensation film)
The optical compensation film (retardation film) can improve viewing angle characteristics of a liquid crystal display screen.
As the optical compensation film, a known film can be used, but in terms of widening the viewing angle, the optical compensation film has an optically anisotropic layer made of a compound having a discotic structural unit, and the discotic compound and the film surface The optical compensation film is preferably characterized in that the angle formed by is changed in the depth direction of the optically anisotropic layer. That is, the orientation state of the compound having a discotic structural unit is preferably, for example, a hybrid orientation, a bent orientation, a twist orientation, a homogeneous orientation, a homeotropic orientation, or the like, and particularly preferably a hybrid orientation. The angle is preferably increased as the distance from the support surface side of the optical compensation film increases in the optically anisotropic layer.
When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

  Also, an embodiment in which the optically anisotropic layer further contains a cellulose ester, an embodiment in which an alignment layer is formed between the optically anisotropic layer and the transparent support of the optical compensation film, and the optically anisotropic layer An embodiment in which the transparent support of the optical compensation film has an optically negative uniaxial property and an optical axis in the normal direction of the surface of the transparent support, and an embodiment satisfying the following conditions are also preferable.

  20 ≦ {(nx + ny) / 2−nz} × d ≦ 400

In the equation, nx is a refractive index in the slow axis direction in the plane (maximum refractive index in the plane), ny is a refractive index in the direction perpendicular to the slow axis in the plane, and nz is a refractive index in the direction perpendicular to the plane. Rate. D is the thickness (nm) of the optically anisotropic layer.

(Image display device)
The antireflection film can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). The antireflection film adheres the transparent support side of the antireflection film to the image display surface of the image display device.
The antireflection film and polarizing plate used in the present invention are twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB). It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of the mode. In particular, for a TN mode or IPS mode liquid crystal display device, as described in JP-A-2001-100043, a polarizing plate having the above optical compensation film and antireflection film as a protective film is used. Thus, viewing angle characteristics and antireflection characteristics can be greatly improved.
Further, by using in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selection layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.), in a transmissive or transflective liquid crystal display device, Furthermore, a display device with high visibility can be obtained.
Further, by combining with a λ / 4 plate, it can be used to reduce reflected light from the surface and the inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto.
(Synthesis of perfluoroolefin copolymer PF-1)

A stainless steel autoclave equipped with a stirrer was charged with 40 parts by mass of ethyl acetate, 14.7 parts by mass of hydroxyethyl vinyl ether, and 0.55 parts by mass of dilauroyl peroxide, and the system was deaerated and replaced with nitrogen gas. Further, 25 parts by mass 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 (529 kPa). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² (314 kPa), the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out.
The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 parts by mass of the polymer product was obtained.
Next, 20 parts by mass of the polymer product was dissolved in 100 parts by mass of N, N-dimethylacetamide, and 11.4 parts by mass 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 and washed with water. The organic layer was extracted and concentrated, and the obtained polymer was reprecipitated with hexane to obtain 19 parts by mass of the perfluoroolefin copolymer PF-1. The obtained perfluoroolefin copolymer had a refractive index of 1.421.
The perfluoroolefin copolymer PF-1 was dissolved in methyl ethyl ketone to obtain a solution having a solid content concentration of 30%.

(Preparation of organosilane compound A solution)
A reactor equipped with a stirrer and a reflux condenser, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (product) Name: Kerope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) 3 parts by mass was added and mixed, and then 30 parts by mass of ion-exchanged water was added and reacted at 60 ° C. for 4 hours. The solution was cooled to room temperature to obtain a solution of organosilane compound A. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, when analyzed by gas chromatography, the raw material 3-acryloxypropyltrimethoxysilane hardly remained.

(Preparation of light diffusion layer paint H-1)
50.0 parts by mass of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.) and a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2 0.0 part by mass, 0.75 part by mass of fluorine-based surface improver (P-7), 10.0 parts by mass of organosilane compound (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 38.5 parts by mass of toluene Was added and stirred. After applying this solution, the refractive index of the coating film obtained by ultraviolet curing was 1.51.
Further, a 30% toluene dispersion 1.7 of crosslinked polystyrene particles having an average particle diameter of 3.5 μm (refractive index 1.61, SX-350, manufactured by Soken Chemical Co., Ltd.) dispersed in this solution at 10,000 rpm with a Polytron disperser. 13.3 parts by mass of a 30% toluene dispersion of a mass part and crosslinked acrylic-styrene particles having an average particle size of 3.5 μm (refractive index: 1.55, manufactured by Soken Chemical Co., Ltd.) dispersed at 10,000 rpm with a polytron disperser. Part was added and stirred.
A light diffusion layer coating material H-1 was prepared by filtration through a polypropylene filter having a pore size of 30 μm. The refractive index of the coating film made of this paint was 1.51.
The surface tension of the light diffusion layer coating material H-1 was 32 mN / m.

(Preparation of light diffusion layer paint H-2)
In the light diffusing layer coating H-1, the amount of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.) was reduced to 47.0 parts by mass, and the average particle size 3 Average particle obtained by dispersing 2.6% by mass of 30% toluene dispersion of 0.5 μm cross-linked polystyrene particles (refractive index 1.60, SX-350, manufactured by Soken Chemical Co., Ltd.) and 10,000 rpm with a polytron disperser. A coating material for light diffusion layer H-1 except that the 30% toluene dispersion of crosslinked acrylic-styrene particles having a diameter of 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.) was increased to 20.0 parts by mass. In the same manner, the mixture was added, stirred and filtered to prepare a light diffusion layer coating material H-2.

(Preparation of light diffusing layer coating H-3)
In the light diffusion layer coating H-2, the average particle size of the crosslinked polystyrene particles was changed to 2.5 μm, and the average particle size of the crosslinked acrylic-styrene particles was changed to 2.5 μm. In the same manner as in No. 2, the mixture was added, stirred and filtered to prepare a light diffusion layer coating material H-3.

(Preparation of light diffusing layer coating H-4)
In the light diffusion layer coating H-2, the average particle size of the crosslinked polystyrene particles was changed to 4.5 μm, and the average particle size of the crosslinked acrylic-styrene particles was also changed to 4.5 μm. In the same manner as in No. 2, the mixture was added, stirred and filtered to prepare a light diffusing layer coating H-4.

(Preparation of light diffusion layer paint H-5)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku (DPHA), 285.0 parts by mass of a transparent high-refractive-index hard coat material containing fine particles of zirconium oxide (Desolite Z7404, manufactured by JSR Corporation) Ltd.) 85.0 parts by mass, organosilane compound (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) 28.0 parts by mass, methyl isobutyl ketone 60.0 parts by mass, methyl ethyl ketone 17.0 parts by mass were added. And stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.
Further, 30% methyl isobutyl of cross-linked PMMA particles (refractive index 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) with enhanced classification with an average particle size of 3.0 μm dispersed in this solution at 10,000 rpm with a polytron disperser. 30% methyl ethyl ketone of 35.0 parts by mass of a ketone dispersion, silica particles having an average particle diameter of 1.5 μm (refractive index: 1.46, Seahosta KE-P150, manufactured by Nippon Shokubai Co., Ltd.) dispersed at 10,000 rpm with a Polytron disperser 90.0 parts by mass of the dispersion was added and stirred. A hard coat layer coating material (II) was prepared by filtering through a polypropylene filter having a pore size of 30 μm. The refractive index of the coating film formed from this paint was 1.61.
In the hard coat layer coating (II), the surface tension of the coating was 25 mN / m.

(Preparation of light diffusion layer paint H-6)
The light diffusing layer coating H-5 is the same as the light diffusing layer coating H-5 except that the average particle diameter of the crosslinked PMMA particles strengthened in the classification of the light diffusing layer coating H-5 is changed to 3.5 μm. -6 was prepared.

(Antistatic layer coating AS-1)
A commercially available coating for transparent antistatic layer "Pertron C-4456S-7" (solid content concentration 45%, manufactured by Nippon Pernox Co., Ltd.) was used as antistatic layer coating A. C-4456S-7 is a coating for transparent antistatic layer containing conductive fine particles ATO dispersed using a dispersant. The refractive index of the coating film made of this paint was 1.55.

(Antistatic layer coating AS-2)
Dispersant (B-) having an anionic group and a methacryloyl group on 20.0 parts by mass of commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g, manufactured by Mitsubishi Materials Corporation) 1) 5.0 parts by mass and 75 parts by mass of methyl ethyl ketone were added and stirred.

The ATO particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.5 mm). It was 58 nm as a result of evaluating the mass mean particle diameter of the ATO particle | grains in a dispersion liquid by the light-scattering method.
To 100 parts by mass of the ATO dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), 14.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba Specialty) -0.9 mass part of Chemicals Co., Ltd. was added and stirred. In this way, antistatic layer coating material AS-2 was prepared. The refractive index of the coating film formed from this paint was 1.61.

(Antistatic layer coating AS-3)
Commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g,
3.0 parts by mass of the dispersant (B-1) having an anionic group and a methacryloyl group and 77 parts by mass of cyclohexanone were added to 20.0 parts by mass of Mitsubishi Materials Corporation and stirred.
The ATO particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.5 mm). It was 62 nm as a result of evaluating the mass mean particle diameter of the ATO particle | grains in a dispersion liquid by the light-scattering method.
To 100 parts by mass of the ATO dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), 16.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba Specialty) -0.8 part by mass of Chemicals Co., Ltd. was added and stirred. Thus, antistatic layer coating material AS-3 was prepared. The refractive index of the coating film made of this paint was 1.62.

(Antistatic layer coating AS-4)
Dispersant (B) having an anionic group and a methacryloyl group in 20.0 parts by mass of commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g, manufactured by Mitsubishi Materials Corporation) -1) 0.8 parts by mass and 79.2 parts by mass of cyclohexanone were added and stirred.
The ATO particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.5 mm). It was 102 nm as a result of evaluating the mass mean particle diameter of the ATO particle | grains in a dispersion liquid by the light-scattering method.
To 100 parts by mass of the ATO dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), 18.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba Specialty) -0.9 mass part of Chemicals Co., Ltd. was added and stirred. In this way, antistatic layer coating material AS-4 was prepared. The refractive index of the coating film formed from this paint was 1.63.

(Antistatic layer coating AS-5)
80 parts by mass of cyclohexanone was added to 20.0 parts by mass of commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g, manufactured by Mitsubishi Materials Corporation) and stirred. No dispersant was used.
The ATO particles in the liquid were dispersed in the same manner as described in the antistatic layer coating material C using a media disperser (using zirconia beads having a diameter of 0.5 mm). As a result of evaluating the mass average particle diameter of the ATO particles in the dispersion by the light scattering method, it was 250 nm, and the ATO fine particles could not be finely dispersed. In this way, an ATO dispersion was prepared.
To 100 parts by mass of the ATO dispersion, 19 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a polymerization initiator (Irgacure 907, Ciba Specialty Chemicals ( Co., Ltd.) 0.8 parts by mass was added and stirred to prepare antistatic layer coating material AS-5. The refractive index was 1.64.

(Antistatic layer coating AS-6)
The antistatic layer coating material AS-6 was prepared by adding 60 parts by weight of methyl ethyl ketone to 100 parts by weight of the antistatic layer coating material AS-3 coating material and stirring the mixture.

(Antistatic layer coating AS-7)
Dispersant (B) having an anionic group and a methacryloyl group in 20.0 parts by mass of commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g, manufactured by Mitsubishi Materials Corporation) -1) 3.0 parts by mass and 43.7 parts by mass of cyclohexanone were added and stirred.
The ATO particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.5 mm). It was 67 nm as a result of evaluating the mass mean particle diameter of the ATO particle | grains in a dispersion liquid by the light-scattering method.
To 66.7 parts by mass of the ATO dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), 16.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba -0.9 mass part of Specialty Chemicals Co., Ltd.) was added and stirred. In this way, antistatic layer coating material AS-7 was prepared. The refractive index of the coating film made of this paint was 1.62.

(Antistatic layer coating AS-8)
Dispersant (B) having an anionic group and a methacryloyl group in 20.0 parts by mass of commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g, manufactured by Mitsubishi Materials Corporation) -1) 3.0 parts by mass and 27.0 parts by mass of cyclohexanone were added and stirred.
The ATO particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.5 mm). It was 72 nm as a result of evaluating the mass mean particle diameter of the ATO particle | grains in a dispersion liquid by the light-scattering method.
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), 16.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba) was added to 50.0 parts by mass of the ATO dispersion. -0.9 mass part of Specialty Chemicals Co., Ltd.) was added and stirred. In this way, antistatic layer coating material AS-8 was prepared. The refractive index of the coating film made of this paint was 1.62.

(Antistatic layer coating AS-9)
Dispersant (B) having an anionic group and a methacryloyl group in 20.0 parts by mass of commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g, manufactured by Mitsubishi Materials Corporation) -1) 3.0 parts by mass and 48 parts by mass of cyclohexanone were added and stirred.
The ATO particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.5 mm). It was 62 nm as a result of evaluating the mass mean particle diameter of the ATO particle | grains in a dispersion liquid by the light-scattering method.
To 71 parts by mass of the ATO dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), 3.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba Specialty) -0.5 mass part of Chemicals Co., Ltd.) was added and stirred. In this way, antistatic layer coating material AS-9 was prepared. The refractive index of the coating film formed from this paint was 1.68.

(Antistatic layer coating AS-10)
The antistatic layer coating material AS-3, except that the dispersant B-1 of the antistatic layer coating material AS-3 was replaced with an equivalent amount of Aronics M5300 (carboxylic acid group-containing monomer, manufactured by Toagosei Co., Ltd.). Dispersion was carried out in exactly the same manner as above to prepare antistatic layer coating material AS-10. The particle diameter of the conductive material after dispersion was 65 nm, and the refractive index of the coating film formed from this paint was 1.62.

(Preparation of coating material L-1 for low refractive index layer)
13.0 parts by mass of heat-crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228A, solid content concentration 6%, manufactured by JSR Corporation), MEK dispersion of silica fine particles (MEK-ST-L, average particle diameter) 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Industries, Ltd.) 1.3 parts by mass, the above organosilane compound A solution 0.6 parts by mass, methyl ethyl ketone 5.0 parts by mass and cyclohexanone 0.6 parts by mass were added. And stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating L-1 for a low refractive index layer. The refractive index of the coating film formed from this paint was 1.42.

(Preparation of paint L-2 for low refractive index layer)
In 15.0 parts by mass of a heat-crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228A, solid content concentration 6%, manufactured by JSR Corporation), a MEK dispersion of silica fine particles (MEK-ST, average particle size 15 nm, Solid content concentration 30%, manufactured by Nissan Chemical Industries, Ltd.) 0.6 parts by mass, silica fine particle MEK dispersion (MEK-ST-L, average particle size 45 nm, solid content concentration 30%, Nissan Chemical Industries, Ltd.) (Product) 0.8 parts by mass, 0.4 parts by mass of the organosilane compound A solution, 3.0 parts by mass of methyl ethyl ketone, and 0.6 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating L-2 for a low refractive index layer. The refractive index of the coating film formed from this paint was 1.42.

(Preparation of MEK dispersion of hollow silica fine particles)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20% by mass, silica particle refractive index 1.31, prepared by changing the size according to Preparation Example 4 of JP-A-2002-79616 ) 500 parts, 30 parts of acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and 1.5 parts of diisopropoxyaluminum ethyl acetate (trade name: Kerope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) After addition and mixing, 9 parts of ion exchange water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. While adding methyl ethyl ketone so that the content of silica was almost constant in 500 g of this dispersion, solvent substitution by vacuum distillation was performed at a pressure of 20 kPa. No foreign matter was generated in the dispersion, and the viscosity when the solid content was adjusted to 20% by mass with methyl ethyl ketone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion A-1 was analyzed by gas chromatography, it was 1.5%.

(Preparation of paint L-3 for low refractive index layer)
13.0 parts by mass of a heat-crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228A, solid content concentration 6%, manufactured by JSR Corporation) was added to the MEK dispersion of the above-described hollow silica fine particles (refractive index 1.31, 1.95 parts by mass (average particle size 60 nm, solid content concentration 20%), 0.6 parts by mass of the organosilane compound A solution, 4.35 parts by mass of methyl ethyl ketone, and 0.6 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a low refractive index layer coating material L-3. The refractive index of the coating film formed from this paint was 1.40.

(Preparation of paint L-4 for low refractive index layer)
To a mixed solvent of isopropyl alcohol / methyl ethyl ketone = 1/1 (mass ratio), 1 mol of tetramethoxysilane and 2 mol of 0.1 mol / l hydrochloric acid were added. A hydrolysis reaction was performed by stirring at room temperature for 2 hours to prepare a hydrolyzate solution of tetramethoxysilane.
Isopropyl alcohol / methyl ethyl ketone = 1/1 (mass ratio), tetramethoxysilane hydrolyzate 9.0 parts by mass, pentaerythritol triacrylate 1.0 part by mass, polymerization initiator (Irgacure 907, Ciba Specialty Chemicals ( Co., Ltd.) 0.5 parts by mass, and the solid content concentration was added to 4.5% by mass and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a low refractive index layer coating material L-4. The refractive index of the coating film made of this paint was 1.45.

(Preparation of coating material L-5 for low refractive index layer)
A polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 15.0 parts by mass of the above-mentioned perfluoroolefin copolymer PF-1 (solid content concentration: 30%). 15 parts by mass, 0.23 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.), 81.8 parts by mass of methyl ethyl ketone and 2.8 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a low refractive index layer coating material L-6. The refractive index of the coating film formed from this paint was 1.43.

(Preparation of coating material L-6 for low refractive index layer)
In 10.5 parts by mass of the above-mentioned perfluoroolefin copolymer PF-1 (solid content concentration 30%), MEK dispersion of silica fine particles (MEK-ST-L, average particle size 45 nm, solid content concentration 30%, Nissan Chemical Industries, Ltd.) 4.5 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, Shin-Etsu Chemical Co., Ltd.) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd.) 0.23 parts by mass, 2.0 parts by mass of the organosilane compound A solution, 81.2 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a low refractive index layer coating material L-6. The refractive index of the coating film formed from this paint was 1.44.

(Preparation of coating material L-7 for low refractive index layer)
In 10.5 parts by mass of the above-mentioned perfluoroolefin copolymer PF-1 (solid content concentration 30%), hollow silica fine particle MEK dispersion (refractive index 1.31, average particle size 60 nm, solid content concentration 20). %) 6.75 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals ( 0.23 parts by mass, 0.2 parts by mass of the organosilane compound A solution, 81.2 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a low refractive index layer coating material L-7. The refractive index of the coating film made of this paint was 1.41.

(Preparation of coating material L-8 for low refractive index layer)
A mixture (DPHA, Nippon Kayaku Co., Ltd.) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate was added to 13.5 parts by mass of the above-mentioned perfluoroolefin copolymer PF-1 (solid content concentration 30%). 0.45 parts by mass, polysiloxane compound having an acryloyl group (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.15 parts by mass, photopolymerization initiator (Irgacure 907, Ciba Specialty Chemicals Co., Ltd.) 0.23 parts by mass, 81.2 parts by mass of methyl ethyl ketone, and 2.8 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a low refractive index layer coating material L-8. The refractive index of the coating film formed from this paint was 1.44.

[Example 1]

On a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm and a width of 1340 mm, a light diffusion layer coating material (H-1 to H-6) is applied by a microgravure coating method, and a conveyance speed. It apply | coated on the conditions of 30 m / min.
After it dried for 150 seconds at 60 ° C., with a nitrogen purge (hereinafter oxygen concentration of 0.5%), using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co.), illuminance 400 mW / cm ^2, irradiation The coating layer was cured by irradiating an ultraviolet ray having a quantity of 250 mJ / cm ² to produce a film with a light diffusion layer.

On the light diffusion layer coated as described above, the antistatic layer coating material (AS-1 to AS-10) was applied by a microgravure coating method under a transport speed of 15 m / min.
After drying at 100 ° C. for 150 seconds, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with nitrogen purge (oxygen concentration 0.5% or less), irradiation is 400 mW / cm ² . The coating layer was cured by irradiating an ultraviolet ray in an amount of 500 mJ / cm ² to produce a film having an antistatic layer.

On the antistatic layer, the low refractive index layer coating materials (L-1 to L-8) were applied by a microgravure coating method under the condition of a conveyance speed of 15 m / min.
Thereafter, the drying and curing conditions for L-1 to L-3 were as follows.
After drying at 120 ° C. for 150 seconds and further drying at 140 ° C. for 8 minutes, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) is used while purging with nitrogen (oxygen concentration 0.5% or less). Then, the coating layer was cured by irradiating ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² to form a low refractive index layer (outermost layer).
The drying and curing conditions for L-4 were as follows.
After drying at 120 ° C. for 150 seconds, the coating layer was cured by heat treatment at 140 ° C. for 20 minutes to form a low refractive index layer (outermost layer).
The drying and curing conditions for L-5 to L-8 were performed as follows.
After drying at 90 ° C. for 30 seconds, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with a nitrogen purge (oxygen concentration of 0.5% or less), an illuminance of 600 mW / cm ² and an irradiation amount The coating layer was cured by irradiating 600 mJ / cm ² of ultraviolet rays to form a low refractive index layer (outermost layer).

  The coating combination of the light diffusion layer, the antistatic layer and the low refractive index layer in the antireflection film was performed as described in Table 1. Furthermore, the average surface roughness Ra1 on the side having the light diffusion layer of the film coated up to the light diffusion layer of each antireflection film sample, and the average surface roughness on the side of the film coated up to the antistatic layer having the antistatic layer The results of measuring Ra2 using an atomic force microscope (AFM) are also shown in Table 1. (Table 1)

(Evaluation of antireflection film)
About the obtained antireflection film, the following items were evaluated. The results are shown in Table 2.

(1) Evaluation of surface resistance The surface resistance of the surface having the low refractive index layer (outermost layer) of the antireflection film was measured at 25 ° C. using a super insulation resistance / microammeter TR8601 (manufactured by Advantest). , And measured under conditions of relative humidity 60%.

(2) Evaluation of dust removability An antireflection film was attached to the monitor, and dust (futon, fiber waste from clothes) was sprinkled on the monitor surface. The dust was wiped off with a cleaning cloth, the dust removal property was examined, and the following three grades were evaluated.
○: Dust completely removed.
Δ: Some dust remained (within tolerance).
×: Dust remains considerably.

(3) Evaluation of anti-glare property An exposed fluorescent lamp (8000 cd / cm ² ) without a louver was projected on the produced anti-reflection film, and the degree of blur of the reflected image was evaluated according to the following criteria.
A: The outline of the fluorescent lamp is completely unknown.
○: The outline of the fluorescent lamp is slightly understood.
Δ: The periphery of the fluorescent lamp looks whitish, but the outline can be identified (within an allowable range).
X: Fluorescent lamp is hardly blurred.
(4) Evaluation of average reflectance Using a spectrophotometer (manufactured by JASCO Corporation; V-550), in the wavelength region of 380 to 780 nm, using a integrating sphere, the spectral reflectance at an incident angle of 5 ° is calculated. It was measured. In the evaluation of the spectral reflectance, an average reflectance of 450 to 650 nm was used.

(5) Evaluation of dynamic friction coefficient The dynamic friction coefficient was evaluated as an index of the slipperiness of the surface of the antireflection film having the low refractive index layer (outermost layer). The dynamic friction coefficient was adjusted for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%, and then a dynamic friction measuring machine (HEIDON-14) was used with a stainless hard ball having a diameter of 5 mm, a load of 0.98 N, and a speed of 60 cm / min. Measured with

(6) Evaluation of scratch resistance On the surface of the antireflection film having the low refractive index layer (outermost layer), a rubbing test using steel wool was performed using a rubbing tester.
Steel wool (Grade No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was used as the scraping material, moving distance (one way) 13 cm, rubbing speed 13 cm / sec, load 4.9 N / cm ² , tip contact area: 1 cm × It was carried out under the conditions of 1 cm and the number of rubbing times of 10 reciprocations. The scratches on the surface of the outermost layer were visually observed and evaluated in the following four stages.
A: Even if you look carefully, no scratches are visible.
○: If you look carefully, you can see slightly weak scratches.
Δ: Weak scratches are visible (within tolerance).
×: A conspicuous scratch can be seen at a glance.

(7) Evaluation of contact angle The antireflection film was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. The contact angle of water on the surface of the antireflection film having the low refractive index layer (outermost layer) was evaluated.

(8) Evaluation of antifouling property An oily magic (ZEBRA Mackey, red) was attached to the surface of the antireflective film having the low refractive index layer (outermost layer), allowed to age for 30 minutes, and then wiped off with a cleaning cloth. The state of time was observed and evaluated in the following three stages.
○: The magic has been completely wiped off.
Δ: A part of the magic remains without being wiped off (within an allowable range).
X: Most of the magic remained without being wiped off.
(9) Evaluation of haze Haze was measured using a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.).
Five points were measured per sample, and the average value was adopted.

  From the results in Table 2, the samples 101 to 109, 111, 112, and 114 to 122 of the present invention in which the value obtained by dividing the antistatic layer Ra2 value by the light diffusion layer Ra1 value is in the range of 0.5 to 1.0 are compared. Compared to Samples 110, 113, and 123, the performance satisfies all the items of dust removal property, antiglare property, scratch resistance, and haze, and this is clearly due to the effect of the present invention.

[Comparative Example A]
On a triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm and a width of 1340 mm, an antistatic layer coating material (AS-3) is applied by a microgravure coating method at a conveyance speed of 15 m / It was applied under the condition of minutes.
After drying at 100 ° C. for 150 seconds, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with nitrogen purge (oxygen concentration 0.5% or less), irradiation is 400 mW / cm ² . The coating layer was cured by irradiating with an amount of 500 mJ / cm ² of ultraviolet rays to produce a film having an antistatic layer with a thickness of 0.1 μm.
On the antistatic layer coated as described above, the light diffusion layer coating material (H-1) was applied by a microgravure coating method at a transport speed of 30 m / min.
After it dried for 150 seconds at 60 ° C., with a nitrogen purge (hereinafter oxygen concentration of 0.5%), using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co.), illuminance 400 mW / cm ^2, irradiation The coating layer was cured by irradiating an amount of 250 mJ / cm ² of ultraviolet rays to produce a film having a light diffusion layer with a thickness of 4 μm.

On the light diffusion layer coated as described above, the coating material for low refractive index layer (L-1) was applied by a microgravure coating method under the condition of a conveyance speed of 15 m / min.
Then, after drying at 120 ° C. for 150 seconds and further drying at 140 ° C. for 8 minutes, a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.5% or less) Is used to cure the coating layer by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² to form a low refractive index layer (outermost layer) having a film thickness of 0.09 μm. Comparative sample A] was prepared. Table 3 shows the results of the same evaluation as in Example 1 performed on this sample.

[Comparative Example B]
The antistatic layer coating (AS-3) was applied to the above-prepared [Comparative Sample A] under the microgravure coating conditions in which the amount of coating liquid was 4 times, and the antistatic layer having a thickness of 0.41 μm after curing. A layer was made. On the antistatic layer, a light diffusion layer and a low refractive index layer were sequentially formed under the same conditions as in the above [Comparative Sample A] to prepare an antireflection film [Comparative Sample B]. Table 3 shows the results of the same evaluation as in Example 1 performed on this sample.

[Comparative Example C]
(Antistatic layer coating AS-11)
Dispersant (B) having an anionic group and a methacryloyl group in 20.0 parts by mass of commercially available conductive fine particles ATO (antimony-doped tin oxide T-1, specific surface area 80 m ² / g, manufactured by Mitsubishi Materials Corporation) -1) 2.0 parts by mass and 28 parts by mass of cyclohexanone were added and stirred.
The ATO particles in the liquid were dispersed using a media disperser (using zirconia beads having a diameter of 0.5 mm). It was 69 nm as a result of evaluating the mass mean particle diameter of the ATO particle | grains in a dispersion liquid by the light-scattering method.
To 50 parts by mass of the ATO dispersion, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), 2.0 parts by mass, a polymerization initiator (Irgacure 907, Ciba Specialty) -0.3 mass part of Chemicals Co., Ltd.) was added and stirred. Thus, antistatic layer coating material AS-11 was prepared. The refractive index of the coating film formed from this paint was 1.72.
This antistatic layer coating AS-11 is made the same as the layer arrangement of [Comparative Sample A], and the amount of coating liquid of the antistatic layer coating (AS-11) is quadrupled compared to [Comparative Sample A]. Coating was performed under microgravure coating conditions to produce an antistatic layer having a thickness of 0.60 μm after curing. On the antistatic layer, a light diffusion layer and a low refractive index layer were sequentially formed under the same conditions as in [Comparative Sample A] to prepare an antireflection film [Comparative Sample C]. Table 3 shows the results of the same evaluation as in Example 1 performed on this sample.

[Comparative Example D]
In the production of the low refractive index layer of the sample 101 of Example 1, the sample was completely the same as the sample 101 except that the low refractive index layer was cured in an air atmosphere (oxygen concentration of about 21%) without performing nitrogen purge. Similarly, an antireflection film [Comparative Sample D] was prepared and evaluated in the same manner as in Example 1. Table 3 shows the results of the same evaluation as in Example 1 performed on this sample.

The results of Table 3 will be described. From the comparison of the evaluation results of the comparative example A sample and the inventive sample 101 of Example 1, when the antistatic layer is applied to the lower side of the light diffusion layer, the surface resistance value increases and the dust removability is improved. You can see that it is inferior.
Next, from the comparison of the evaluation results of the comparative example B sample, the comparative example C sample, and the comparative example A sample, when the coating thickness of the antistatic layer is increased in the layer arrangement of the comparative example A sample (0 for 0.09 μm). .41 μm, 0.60 μm) It can be seen that the surface resistance value decreases, but the haze increases. Furthermore, the comparative example B sample and the comparative example C sample are darker in color than the sample 101 of the present invention 101 in the color evaluation in which the antireflection film is placed on white paper and visually observed. Was observed. Furthermore, it was confirmed that the cost would be increased by cost estimation.
From the comparison of the evaluation results of the comparative example D sample and the inventive sample 101 of Example 1, it can be seen that the scratch resistance deteriorates when the atmosphere during UV curing is performed in the air without purging with nitrogen.
About the said invention sample 101 and Comparative Example A sample-D sample, the adhesiveness evaluation by a postscript evaluation method was performed. As a result, the inventive sample 101, the comparative example A sample and the comparative example D sample were evaluated as ◎, the comparative sample B was evaluated as Δ, and the comparative sample C was evaluated as x.
It can be seen that, when an attempt is made to compensate for the decrease in conductivity caused by disposing the antistatic layer on the side close to the support as in Comparative Example Sample C by increasing the density of the conductive material in the antistatic layer, the adhesion is broken.

(10) Evaluation of adhesion The antireflection film sample was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. On the surface of each sample having the antistatic layer, 11 vertical and 11 horizontal cuts were made with a cutter knife in a grid pattern, and a total of 100 square squares were engraved, and Nitto Denko Corporation ) Made of polyester adhesive tape (No. 31B). After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken.
A: No peeling was observed at 100 mm.
○: peeling of 1 to 2 mm was observed at 100 mm.
Δ: Peeling of 3 to 10 mm was observed at 100 mm (within tolerance).
X: Peeling of 11 mm or more was observed at 100 mm.

[Example 2]
(Evaluation of image display device)
The antireflection films of the samples 101 to 109, 111, 112, and 114 to 122 of Example 1 are transferred to the image display device (TN, STN, IPS, VA, or OCB mode, transmissive type, reflective type, or transflective type). The liquid crystal display device was mounted on the display surface of a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode tube display device (CRT). The image display device using the antireflection film of the present invention was excellent in antireflection properties, dustproof properties, scratch resistance, and antifouling properties.
Furthermore, there is no occurrence of glare failure in the image display device in which the area of the cut surface is not more than 100 μm ² and the pixel size is 100 ppi (100 pixels / inch: 100 pixels per inch length). It was.

[Example 3]
(Preparation of protective film for polarizing plate)
A saponification solution in which a 1.5 mol / l sodium hydroxide aqueous solution was kept at 50 ° C. was prepared. Further, a 0.005 mol / l dilute sulfuric acid aqueous solution was prepared.
In the antireflection films of Samples 101 to 109, 111, 112, and 114 to 122 of Example 1, the surface of the transparent support opposite to the side having the low refractive index layer (outermost layer) was used for the saponification solution. And saponified.
The sodium hydroxide aqueous solution on the surface of the saponified transparent support is thoroughly washed with water, then washed with the above diluted sulfuric acid aqueous solution, and further, the diluted sulfuric acid aqueous solution is thoroughly washed with water and sufficiently dried at 100 ° C. I let you.
When the contact angle of the surface of the saponified transparent support on the side opposite to the side having the low refractive index layer (outermost layer) of the antireflection film was evaluated, it was 40 ° or less. Thus, the protective film for polarizing plates was produced.

(Preparation of polarizing plate)
An antireflection film of the present invention (protection for polarizing plate) is applied to one surface of a deflection film described in JP-A-2002-86554 using a 3% aqueous solution of PVA (PVA-117H manufactured by Kuraray Co., Ltd.) as an adhesive. The saponified triacetyl cellulose surface of the film) was bonded together. Further, a triacetyl cellulose film (Fuji Photo Film Co., Ltd., Fujitac, retardation value 3.0 nm) saponified in the same manner as above was bonded to the other surface of the polarizing film using the same adhesive. . Thus, the polarizing plate of this invention was produced.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or semi-transmission type liquid crystal display device equipped with the polarizing plate of the present invention thus produced has antireflection properties, dustproof properties, Excellent scratch resistance and antifouling properties.
Similar results were obtained with polarizing plates produced in the same manner as described above using various known deflection films.

[Example 4]
(Preparation of polarizing plate)
The surface of the optical compensation film (Wide View Film SA 12B, manufactured by Fuji Photo Film Co., Ltd.) opposite to the side having the optically anisotropic layer was saponified under the same conditions as in Example 3.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmissive, reflective, or transflective liquid crystal display device equipped with the polarizing plate of the present invention thus manufactured does not use an optical compensation film. Compared with a liquid crystal display device equipped with a polarizing plate, the contrast in a bright room was excellent, the viewing angles of the top, bottom, left and right were wide, and the antireflection property, dust resistance, scratch resistance, and antifouling property were excellent.
In particular, due to the light scattering effect of transmitted light by the cross-linked polystyrene particles, cross-linked acrylic-polystyrene particles, cross-linked PMMA particles, and silica particles, the downward viewing angle was remarkably widened, and the yellowness in the left-right direction was improved.
Similar results were obtained with polarizing plates produced in the same manner as described above using various known deflection films.

[Example 5]
(Evaluation of image display device)
When the antireflection films of Samples 101 to 109, 111, 112, and 114 to 122 of Example 1 were mounted on an organic EL display device, they were excellent in antireflection, dustproof, scratch resistance, and antifouling properties.
Further, a polarizing plate protective film prepared in Example 3 on one side of the polarizing film and a polarizing plate having a λ / 4 plate on the other side were prepared in the same manner as in Example 3. When the above polarizing plate was mounted on an organic EL display device, reflection of light from the glass surface on which the polarizing plate was attached was also cut, and a display device with extremely high visibility was obtained.

It is the schematic which shows the aspect which applies an antireflection film to an image display apparatus typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent support 2 Light-diffusion layer 3 Translucent particle | grains 4 Antistatic layer 5 Low refractive index layer

Claims (14)

  An antireflection film in which at least a light diffusion layer, an antistatic layer, and a low refractive index layer having a lower refractive index than that of the transparent support are coated in this order on the transparent support, and before the antistatic layer is applied The value obtained by dividing the center line average roughness Ra2 of the antistatic layer surface after coating the antistatic layer by the centerline average roughness Ra1 of the light diffusion layer is 0.5 to 1.0. Anti-reflection film.   The center line average roughness Ra1 of the surface of the light diffusion layer before coating of the antistatic layer is 0.03 to 0.30 μm, and Ra2 of the surface of the antistatic layer after coating of the antistatic layer is 0.02 to 0.02. The antireflection film according to claim 1, wherein the film has a thickness of 0.25 μm.   3. The antireflection film according to claim 1, wherein the antistatic layer and / or the low refractive index layer is formed by a process including at least coating and ionizing radiation curing. The antireflective film according to claim 1, wherein the low refractive index layer is formed by a crosslinking or polymerization reaction of a fluorine-containing compound represented by the following general formula (1).
General formula (1)

In General Formula (1), L represents a C1-C10 coupling group, m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit of any vinyl monomer, and may be a single component or a plurality of components. x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65.   The antireflective film according to any one of claims 1 to 4, wherein the low refractive index layer contains hollow silica fine particles. The antireflection film according to claim 1, wherein the surface resistance on the side having the low refractive index layer is 1 × 10 ¹² Ω / □ or less.   The antireflection film according to claim 1, wherein the conductive material contained in the antistatic layer is a metal oxide.   The antistatic film according to claim 1, wherein the antistatic layer has a thickness of 60 to 200 nm.   9. The antireflection film according to claim 1, wherein the content of the conductive material in the antistatic layer is 20 to 60% by mass of the total solid content of the antistatic layer.   The antireflection film according to claim 1, wherein the light diffusion layer contains translucent particles having an average particle diameter of 0.5 to 8 μm.   The refractive index of the binder matrix of the light diffusing layer is 1.45 to 1.90, and the refractive index difference between the binder matrix of the light diffusing layer and the translucent particles is 0.02 to 0.30. The antireflection film according to claim 1.   A polarizing plate comprising the antireflection film according to claim 1 on at least one of two protective films of a polarizing film.   An image display device, wherein the antireflection film according to claim 1 or the polarizing plate according to claim 12 is disposed on an image display surface.   14. The image display device according to claim 13, wherein the image display device is a TN, STN, IPS, VA, or OCB mode transmissive, reflective, or transflective liquid crystal display device.

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