JP2005275391A - Antireflection film and manufacturing method, polarizing plate, and liquid crystal display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film which has a hard coat layer combining correction in dot defects and interference unevenness with solving problems in handling such as curling and brittleness, and which has sufficient antireflective performance, abrasion resistance, and productivity, and to provided a polarizing plate using the antireflection film, and a display device. <P>SOLUTION: The antireflection film has, on a transparent support, the hard coat layer containing at least one layer of transparent resin and a low-refractive-index layer having a lower refractive index than the support and hard coat layer in this order, wherein the transparent resin contains, as a main component, a mixture of a multifunctional (meth)acrylate (A) and multifunctional (meth)acrylate (B) which has the same skeleton with the multifunctional (meth)acrylate and has a spacer group between the skeleton and a (meth)acryloyl group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antireflection film, and more particularly, to an antireflection film that is excellent in antireflection properties and scratch resistance, and has reduced point defects and hard coat interference unevenness.

  In general, the antireflection film is used in a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD), and a contrast reduction or image due to reflection of external light. In order to prevent reflection of light, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film is generally produced by forming a film with a low refractive index layer having an appropriate thickness on the transparent support and having a lower refractive index than that of the transparent support on the outermost layer of the film. ing. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface of the display, high scratch resistance is required. When the support is a plastic film having a thickness of several tens of μm to several mm, in order to realize high scratch resistance, in addition to the strength of the coating film itself of the low refractive index layer, adhesion to the lower layer, A hard coat layer for supplementing the low indentation elasticity of the support is essential. Particularly in recent years, in applications such as televisions and monitors, high scratch resistance has been demanded, and in addition to the strength of the outermost layer film, improvement of indentation elasticity by the hard coat layer is a major issue.

  Patent Documents 1 to 4 disclose a coating composition having abrasion resistance mainly composed of inorganic ultrafine particles such as silica and a polyfunctional (meth) acrylate monomer. It is described that these compositions can be used with a film thickness of about 1 to 50 μm. Inclusion of inorganic ultrafine particles has a great effect in improving the indentation elastic modulus of the hard coat layer and preventing curling deterioration when it is made thick, while such a hard coat layer is formed from a roll film state. There was a problem that the brittleness and flexibility of the film required in the process of punching into the leaves deteriorated. In order to avoid such a problem, the film thickness can be reduced within the range permitted by the indentation elasticity, but when the film thickness of the hard coat layer is 6 μm or less, the interface between the transparent support and the hard coat layer, the hard coat layer When the film is applied to a display device, the color unevenness (referred to as interference unevenness) due to the interference of reflected light at the interface between the surface and the upper layer or air deteriorates, or the point defect increases. There is a problem of degrading the quality.

In Patent Document 5, a (meth) acrylate monomer having a solid content of 60 to 80% by weight on a cellulose triacetate film, and a prepolymer and an oligomer such as urethane (meth) acrylate, polyester acrylate, and epoxy acrylate as necessary are added. By applying the hard coat coating composition thus formed, by providing a hard coat layer having a dry coating amount of 8 to 30 g / m ² , point defects can be eliminated, and the scratch resistance and chemical resistance are excellent. It is disclosed that a hard coat film can be obtained. However, in this patent document, it is described that when flexibility is required, the amount of monomer is reduced or the crosslinking density is reduced by using a monofunctional or bifunctional acrylate monomer, In the former, the effect of improving the elastic modulus is insufficient, and in the latter, the molecular weight of the monomer is reduced, so that the surface of the coated surface is deteriorated (whitening, etc.) due to excessive diffusibility to the support, and skin irritation is deteriorated. There was a problem of inviting.
Japanese Patent Publication No.62-21815 Japanese Patent No. 3035402 Japanese Patent No. 3096862 Japanese Patent No. 3164431 Japanese Patent Laid-Open No. 8-80472

In short, the present situation is that no antireflection film having a hard coat layer in which point defects, interference unevenness, curl and brittleness are sufficiently compatible has been proposed.
Accordingly, an object of the present invention is to provide an antireflection film that has both improvement of point defects and interference unevenness and improvement of curling and brittleness, and at the same time sufficient antireflection, scratch resistance and high productivity. There is to do.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the object can be achieved by adjusting the composition and film thickness of the transparent resin contained in the hard coat layer. The invention has been completed.
That is, the present invention achieves the object by the following configuration.
1. In an antireflection film having a hard coat layer containing at least one transparent resin on a transparent support, a low refractive index layer having a refractive index lower than that of any one of the support and the hard coat layer in this order,
The transparent resin has a polyfunctional (meth) acrylate (A) having two or more (meth) acryloyl groups, the same skeleton as the polyfunctional (meth) acrylate, and the skeleton and (meth) acryloyl An antireflection film comprising, as a main component, a mixture with a polyfunctional (meth) acrylate (B) having a spacer group between them.
2. The average molecular weight of the polyfunctional (meth) acrylate (A) is 200 to 600, and the average molecular weight of the polyfunctional (meth) acrylate (B) is 300 to 2000. Antireflection film.
3. The spacer group in the polyfunctional (meth) acrylate (B) has a structure introduced by any of lactone addition having 3 to 10 carbon atoms and alkylene glycol modification having 2 to 20 carbon atoms, The antireflection film according to claim 1 or 2.
4). The antireflection according to claim 1, wherein the hard coat layer contains inorganic oxide ultrafine particles having a refractive index of 1.20 to 1.50 and an average particle diameter of 1 to 500 nm. the film.
5). The hard coat layer contains an organosilane represented by the following general formula (1), a hydrolyzate thereof, and a partial condensate thereof, or a mixture thereof. 4. The antireflection film according to any one of 4 above.
Formula _{^{(1) :( R 10) m}} -Si (X) 4-m
(In the formula, R ¹⁰ represents at least one of a substituted and unsubstituted alkyl group and a substituted and unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3. Represents.)
6). 6. The antireflection film as described in any one of 1 to 5 above, wherein the hard coat layer has a thickness of 6 to 15 μm.
7). The antireflection film as described in any one of 1 to 6 above, wherein the number of point defects having a size of 50 μm or more is 5 or less per square meter on the surface of the hard coat layer.
8). 8. The antireflection film as described in any one of 1 to 7 above, wherein the transparent support is a cellulose acylate film having a thickness of 40 μm to 120 μm.
9. The low refractive index layer is a layer having a refractive index of 1.30 to 1.55, the low refractive index layer contains a fluorine atom in a range of 35 to 80% by mass, and has a crosslinkable or polymerizable functional group. A fluorine-containing polymer (C) containing a crosslinked or polymer as a main component, the fluorine-containing polymer (C) comprising a fluorine-containing vinyl monomer polymer unit and a polymer unit having a (meth) acryloyl group in the side chain. The antireflection film as described in any one of 1 to 8 above, which is a copolymer comprising a main chain composed only of carbon atoms.
10. The low refractive index layer is the fluoropolymer (C), the average particle size is 30% to 150% of the thickness of the low refractive index layer, and the refractive index comprising a hollow structure is 1.17 to 1.40. A certain curable composition containing at least one kind of inorganic fine particles (D), hydrolyzate of organosilane represented by the following general formula (1) and / or its partial condensate (E) is applied and cured. The antireflection film according to claim 1, wherein the antireflection film is a cured film formed as described above.
Formula (1); (R10) _m -Si (X) _4-m
(In the formula, R10 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)
11. A polarizing plate, wherein at least one of the surface protective films of the polarizing plate is the antireflection film according to any one of 1 to 9 above.
12 One of the two surface protective films of the polarizing plate is the antireflection film according to claim 1, and the other surface protective film is attached to the polarizing film of the surface protective film. An optical compensation film having an optical compensation layer comprising an optically anisotropic layer on a surface opposite to the surface to be combined, the optically anisotropic layer containing a compound having a discotic structural unit, and the discotic The disk surface of the structural unit is inclined with respect to the surface protective film surface, and the angle formed by the disk surface of the discotic structural unit and the surface protective film surface varies in the depth direction of the optically anisotropic layer. The polarizing plate according to claim 11, wherein:
13. 13. A liquid crystal display device having at least one polarizing plate as described in 11 or 12 above.
14 The hard coat layer is formed by reverse coating using a micro gravure method, subsequently drying the solvent with dry air, and further curing. A method for producing an antireflection film.
15. The reflection according to claim 1, wherein the hard coat layer is formed by coating using a microgravure method, subsequently drying the solvent with a drying wind, and further curing. The manufacturing method of a prevention film.
16. 11. The antireflection film as described in any one of 1 to 10 above, which is formed by applying the hard coat layer using a die coating method, subsequently drying the solvent with a dry air, and further curing. Manufacturing method.

  The antireflection film of the present invention is improved in point defects and interference unevenness, has no handling problems such as curling and brittleness, and has sufficient antireflection properties, scratch resistance and productivity. Therefore, a display device such as a liquid crystal display device having the antireflection film of the present invention directly or via a polarizing plate provided with the antireflection film is excellent in productivity, scratch resistance, and external light. There are few reflections and background reflections, and the visibility is extremely high.

A basic configuration of a preferred embodiment of the antireflection film of the present invention will be described with reference to the drawings.
Here, FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the antireflection film of the present invention. The present embodiment is a preferred example of a single-layer antireflection film having only a low refractive index layer as the antireflection layer, and is excellent in brittleness and curl characteristics while reducing point defects and interference unevenness.
The antireflection film 1 of this embodiment shown in FIG. 1 includes a transparent support 2, a hard coat layer 3 formed on the transparent support 2, and a low refractive index layer 4 formed on the hard coat layer 3. It consists of.
In the present embodiment, the hard coat layer may be provided directly on the transparent support, but may be provided via another layer such as an antistatic layer or a moisture-proof layer.
In this embodiment, the a ^* value of the color of the reflected light under the C light source is −2 to 2, the b ^* value is −3 to 3, and the reflectance in the range of 380 nm to 780 nm. A ratio between the minimum value and the maximum value is preferably 0.5 to 0.99, because the color of the reflected light becomes neutral. Further, when the b * value of the transmitted light under the C light source is 0 to 3, it is preferable because the yellow color of white display when applied to a display device is reduced.

FIG. 2 is a cross-sectional view schematically showing another preferred embodiment of the antireflection film of the present invention. In the present embodiment, the refractive index is higher than that of the transparent support 6 and the hard coat layer 7 as the antireflection layer, the refractive index is lower than that of the high refractive index layer 9, and the refractive index is highest among all the layers. This is a preferred example of an antireflection film consisting of three layers of a high refractive index layer 9 and a low refractive index layer 10 having the lowest refractive index among all, and the average reflectance is reduced to 0.5% or less. It can be preferably used for TV and monitor applications.

  In the optical characteristics of the antireflection film of the present invention, it is preferable that the specular reflectance is 0.5% or less and the transmittance is 90% or more because reflection of external light can be suppressed and visibility is improved.

  The structure of the antireflection film of the present invention will be described in detail below. In the present specification, the description “numerical value A to numerical value B” representing the range of physical property values and characteristic values represents the meaning of “numerical value A to numerical value B”.

[Hard coat layer]
The hard coat layer is formed for the purpose of compensating the low indentation elasticity of the transparent support made of a plastic film and imparting scratch resistance to the film as evaluated by pencil scratching or the like.

  The hard coat layer has the same skeleton as the polyfunctional (meth) acrylate (A) having a transparent resin having two or more (meth) acryloyl groups and the polyfunctional (meth) acrylate (A), and The main component is a mixture of a polyfunctional (meth) acrylate (B) having a spacer group between the skeleton and the (meth) acryloyl group. 6-15 micrometers is preferable and, as for the film thickness of a hard-coat layer, 7-10 micrometers is more preferable. When the thickness of the hard coat layer is less than 6 μm, the effect of improving the indentation elasticity is reduced, the number of point defects on the surface of the hard coat layer due to foreign matters having a particle size of several μm is increased, interference unevenness is deteriorated, etc. Problems occur. From the viewpoint of the characteristic factor when applied to a polarizing plate and a liquid crystal display device, the number of point defects is preferably 5 or less per square meter on the hard coat layer surface. On the other hand, when the film thickness of the hard coat layer exceeds 15 μm, the curl of the antireflection film after forming the hard coat film or the antireflection layer increases, so that not only the handling suitability in the next step is deteriorated, Problems such as deterioration of flexibility and / or brittleness and deterioration of workability occur. In the present specification, the descriptions of “(meth) acryloyl”, “(meth) acrylate”, “(meth) acrylic acid”, etc. are “acryloyl and / or methacryloyl”, “acrylate and / or methacrylate”, respectively. The meaning of “acrylic acid and / or methacrylic acid” is expressed.

<Translucent resin>
The translucent resin contained in the hard coat layer is pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol rudi (meth) acrylate, 1,4-cyclohexanediol The polyfunctional (meth) acrylate monomer (A) such as rudi (meth) acrylate has the same molecular skeleton as the polyfunctional (meth) acrylate monomer (A), and the skeleton and the (meth) acrylate As a main component a mixture of a polyfunctional (meth) acrylate (B) having a spacer group between the Royle group. As the polyfunctional (meth) acrylate monomer (A), those having three or more (meth) acryloyl groups derived from pentaerythritol, dipentaerythritol and trimethylolpropane are preferable. In a mixture of monomers with different skeletons, depending on the combination of materials, surface failure occurs when the compatibility is low, or when the reaction rate difference is large, the cross-linked structure becomes non-uniform and surface failure (scattering, etc. May cause problems such as deterioration of transparency and uniformity at the surface) and deterioration of curl. In order to improve the curl when thickened, and to achieve both flexibility and / or brittleness improvement and indentation elasticity enhancement effect, the spacer group is added with a lactone having 3 to 10 carbon atoms, 2 to 2 carbon atoms Preferably it has a structure introduced by any of the 20 alkylene glycol modifications. The spacer is preferably modified by ethylene oxide or propylene oxide, introduced by lactone addition of 3 to 10 carbon atoms such as caprolactone, or modified by alkylene glycol modification of 2 to 20 carbon atoms.

A preferable structure as a spacer group is represented by the following general formula (a) or (b).
Formula (a) -CO- [C (R 41) (R 42)] j-O- *
Formula (b) - {[C ( R 41) (R 42)] k-O} q- *
In the general formula, R ⁴¹ and R ⁴² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, j and k is an integer of 2 to 6, q represents an integer of 1 to 5, a plurality of R ⁴¹ and / or R ⁴² may be the same or different, and * represents the position to which the (meth) acryloyl group is bonded. R ⁴¹ and R ⁴² are preferably a hydrogen atom or a methyl group, j is preferably 2 to 4, k is preferably 2 or 3, and q is preferably 1 to 3.

The molecular weight of the polyfunctional (meth) acrylate monomer (A) is preferably in the range of 200 to 600, and the molecular weight of the polyfunctional (meth) acrylate (B) is preferably in the range of 300 to 2000 in terms of average molecular weight. . The reason why the average molecular weight is used here is that it is difficult to obtain a compound having a uniform introduction ratio of spacer groups, and it is practical to use it as a mixture of compounds having different introduction ratios. If the molecular weight is lower than the above range, the diffusion (penetration) rate to the support is too fast, which may cause surface defects or increase skin permeability, resulting in skin irritation and sensitization. Such a safety problem may occur. On the other hand, when the molecular weight is higher than the above range, the diffusion (penetration) property to the support is too small, which causes a problem in adhesion or a problem that the coating property deteriorates because the coating solution viscosity increases. is there.
The polyfunctional (meth) acrylate monomer (A) has the same molecular skeleton as the polyfunctional (meth) acrylate monomer (A), and has a spacer group between the skeleton and the (meth) acryloyl group. If the mixing ratio of the polyfunctional (meth) acrylate (B) is in the range of 10 to 1 to 10 (weight ratio), a well-balanced mixing ratio such as curl, brittleness, and scratching strength in the design film thickness is selected. Good.
The polyfunctional (meth) acrylate monomer (A) has the same molecular skeleton as the polyfunctional (meth) acrylate monomer (A), and has a spacer group between the skeleton and the (meth) acryloyl group. The addition amount of the mixture of polyfunctional (meth) acrylate (B) is 50-99.8 mass% with respect to the total solid content of the hard coat layer, preferably 70-99.5 mass%, and 80-98 mass. % Is more preferable.

<Inorganic oxide ultrafine particles>
In particular, when triacetyl cellulose is used for the transparent support, inorganic oxide ultrafine particles having a refractive index of 1.20 to 1.50 and an average particle diameter of 1 to 500 nm are added to the hard coat layer of the present invention. preferable. By adding an optimal amount of such a material, the difference between the refractive index (1.49) of the transparent support and the refractive index of the hard coat layer is reduced, so that the interference unevenness of the hard coat layer is reduced.
The translucent resin used in the present invention has a polyfunctional (meth) acrylate (A) having two or more (meth) acryloyl groups, the same skeleton as the polyfunctional (meth) acrylate, and Since the main component is a mixture of a polyfunctional (meth) acrylate (B) having a spacer group between the skeleton and the (meth) acryloyl group, even if such a material is added, the punching suitability and the like are flexible. There is no major deterioration in sex.

<Organosilane, sol component>
The hard coat layer of the present invention includes an organosilane compound, a hydrolyzate thereof and a partial condensate thereof, or a mixture thereof (hereinafter referred to as an organosilane compound hydrolyzate) in the coating solution for forming the layer. And any of the partial condensates thereof or a mixture thereof are referred to as a sol component). Details of specific examples will be described later in the description of the low refractive index layer.

  The organosilane compound and the sol component are effective when added to either the hard coat layer or the low refractive index layer of the present invention, but in the case where the hard coat layer and the low refractive index layer are in direct contact, By adding to this layer, the effect of improving the scratch resistance is particularly remarkable. In this case, it is particularly preferable to use an organosilane for the hard coat layer and a sol component for the low refractive index layer.

<Photopolymerization initiator>
Polymerization of these translucent resins is started by irradiating ionizing radiation to the following photo radical polymerization initiator. Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide 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.
Latest UV curing technology (P.159, publisher: Kazuhiro Takasato, publisher) Technical Information Association, 1
(Published in 1999) also describes various examples and is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Nippon Ciba-Geigy Co., Ltd.
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.

The transparent resin has a polyfunctional (meth) acrylate (A) and the same skeleton as the polyfunctional (meth) acrylate, and a spacer group between the skeleton and the (meth) acryloyl group. In addition to the functional (meth) acrylate (B), a crosslinkable functional group is introduced into the polymer using a monomer having a crosslinkable functional group, and a crosslinked structure is introduced into the binder polymer by the reaction of the crosslinkable functional group. May be.
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 anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer 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.

<Surfactant>
The hard coat layer of the present invention has a hard coat layer formed of either a fluorine-based surfactant or a silicone-based surfactant, or both, in order to ensure surface uniformity such as coating unevenness, drying unevenness, and point defects. It may be contained in the coating composition for use. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film of the present invention appears in a smaller addition amount.
The purpose is to increase productivity by giving high-speed coating suitability while improving the surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a copolymer with a vinyl monomer copolymerizable therewith are useful, which include a corresponding repeating unit and a repeating unit corresponding to the monomer (ii) below.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula (2) General formula (2)

In the general formula (2), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1-6, and n is 1-6. Represents an integer. R ¹² 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 is preferably an oxygen atom. m is preferably an integer of 1 or more and 4 or less, and 2 is particularly preferable. n is preferably 1 to 4, and a mixture of 1 to 4 may be used.

(Ii) Monomer general formula (3) represented by the following general formula (3) copolymerizable with the above (i)

In the general formula (3), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specifically, it represents 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 alkoxy groups, hydroxyl groups, alkylcarbonyl groups, arylcarbonyl groups, carboxyl groups, alkyl ether groups, aryl ether groups, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and nitro groups. , Cyano group, amino group and the like, but not limited thereto. The linear, branched or cyclic alkyl group having 2 to 20 carbon atoms may be a linear or branched ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group. Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc. A polycyclic cycloalkyl group such as a tricycloundecyl group, a tetracyclododecyl group, an adamantyl group, a norbornyl group, or a tetracyclodecyl group is preferably used. As ^{R 14, - (C2H4O) a} -R 141 or - (C ₃ H ₆ O) a polyalkyleneoxy group preferably represented by b-R ¹⁴¹ (a and b is an integer of 1 to 30, a- R ¹⁴¹ represents an alkyl group having 1 to 4 carbon atoms.), A mixed polyalkyleneoxy group having both a unit represented by (C ₂ H ₄ O) and a unit represented by (C ₃ H ₆ O) preferable.

  The amount of the fluoroaliphatic group-containing monomer represented by the following general formula (2) used in the fluoropolymer surfactant used in the present invention is 10 mol based on each monomer of the fluoropolymer. % Or more, preferably 15 to 70 mol%, more preferably 20 to 60 mol%.

The preferable mass average molecular weight of the fluoropolymer surfactant used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass, and more preferably, with respect to the coating solution. It is the range of 0.01-1 mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient. Adversely affect the scratch resistance).

  Examples of the specific structure of the fluoropolymer surfactant described above are shown below, but this is not restrictive. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  By selecting a fluoropolymer that can be extracted by the solvent that forms the upper layer when the upper layer is applied as a surfactant, there is no uneven distribution on the lower layer surface (interface with the lower layer), and the adhesion between the upper layer and the lower layer By providing this, it is possible to provide an antireflection film that maintains surface uniformity even during high-speed application and has high scratch resistance. Examples of such materials include a homopolymer having a repeating unit corresponding to the monomer (iv) below, or a repeating unit corresponding to the monomer (iii) below and a repeating unit corresponding to the monomer (iv) below. Copolymers containing are useful.

(Iii) Fluoroaliphatic group-containing monomer represented by the following general formula (4) General formula (4)

In the general formula (4), R ¹⁶ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ¹⁷ ) —, more preferably an oxygen atom or —N (R ¹⁷ ) —, and still more preferably an oxygen atom. In the general formula (4), m represents an integer of 1 to 6, and n represents an integer of 1 to 18. R ¹⁷ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. In the general formula (4), m is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. n is preferably from 2 to 12, and more preferably from 4 to 8.
(Iv) Monomer general formula (5) represented by the following general formula (5) copolymerizable with the above (iii)

In the general formula (5), R ¹⁸ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y represents an oxygen atom, a sulfur atom or —N (R ²⁰ ) —, more preferably an oxygen atom or —N (R ²⁰ ) —, and still more preferably an oxygen atom. R ¹⁹ is a C 1-20 linear, branched or cyclic alkyl group which may have a substituent, an alkyl group containing a poly (alkyleneoxy) group, and an aromatic group which may have a substituent. (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 is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferable. .
Examples of the specific structure of the fluoropolymer surfactant described above are shown below, but this is not restrictive. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

<Solvent>
Since there are cases where the hard coat layer of the present invention is wet-coated directly on a transparent support, the solvent used in the coating composition is an important factor. The requirements are to dissolve various solutes sufficiently, to avoid coating unevenness and drying unevenness in the coating to drying process, not to dissolve the support too much (necessary for preventing deterioration of flatness, whitening, etc.), Conversely, the minimum degree includes swelling the support (necessary for adhesion) and the like.
As specific examples, when triacetyl cellulose is used for the support, various ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.), various cellosolves (ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.), swelling property adjustment Therefore, a highly soluble material such as methyl acetate or ethyl acetate, or a material that is difficult to swell such as methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, or tert-butanol may be appropriately mixed and used. it can.

[Low refractive index layer]
The refractive index of the low refractive index layer in the antireflection film of the present invention is 1.30 to 1.55, preferably 1.35 to 1.45.
When the refractive index is less than 1.30, the antireflection performance is improved, but the mechanical strength of the film is lowered, and when it exceeds 1.55, the antireflection performance is remarkably deteriorated.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
Formula (I): (m / 4) × 0.7 <n1 × d1 <(m / 4) × 1.3
In the formula, m is a positive odd number, n1 is the refractive index of the low refractive index layer, and d1 is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

The material for forming the low refractive index layer will be described below.
The low refractive index layer of the antireflection film of the present invention comprises a binder component, a small amount of additives, and a solvent. The binder component preferably has a low refractive index, and examples thereof include a fluorine-containing polymer and inorganic fine particles described later. In order to improve the cohesive strength of the layer, an organosilane compound, a hydrolysis / condensation product thereof (referred to as a sol component), a curable compound, or the like can be contained as a part of the binder component. Examples of the small amount additive include an antifouling agent, a slip agent, a dustproof agent, an antistatic agent, and a polymerization initiator.

<Fluoropolymer>
As a preferable example of the low refractive index layer of the present invention, a fluorine-containing polymer is included as a low refractive index binder. The fluorine polymer is preferably a fluorine-containing polymer that is crosslinked by heat or ionizing radiation with a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less. In order to impart a decrease in refractive index, cohesive strength, and adhesion to the lower layer, a fluorine-containing polymer containing fluorine atoms in the range of 35 to 80% by mass is preferable. When the antireflection film of the present invention is mounted on an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, preferably 500 gf or less, more preferably 300 gf or less, 100 gf or less is most preferable. Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch, preferably 0.3 GPa or more, more preferably 0.5 GPa or more.

  Examples of the fluorine-containing polymer used in the low refractive index layer include hydrolysis and dehydration condensate of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). And a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as structural components.

  Other specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3. -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemical) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Of these, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerizing monomers having a self-crosslinkable functional group in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxyl groups, amino groups , A monomer having a sulfo group or the like (for example, obtained by polymerization of (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. Structural units, structural units in which a crosslinking reactive group such as a (meth) acryloyl group is introduced into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group) When the polymer structure has a carboxyl group, a hydroxyl group, an amino group, a sulfo group, etc., it is possible to impart thermal crosslinkability, and when it has a (meth) acryloyl group, etc., ionizing radiation crosslinking is possible. Sex can be imparted.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tertbutylacrylamide, N-silane) B hexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

  A preferred form of the fluorine-containing polymer used in the present invention is that of general formula 1.

In 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, It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred examples include *-(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 the linking site on the polymer main chain side, ** is the linking on the (meth) acryloyl group side) Represents a part). 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 the 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. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  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.

  A particularly preferred form of the copolymer used in the present invention is General Formula 2.

In general formula 2, X, x, and y have the same meaning as in general formula 1, and the preferred 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.

  Specific examples of the fluorine-containing polymer represented by General Formula 1 or General Formula 2 are shown below, but the present invention is not limited thereto.

For the copolymer represented by the general formula 1 or 2, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized. As the reprecipitation solvent, isopropanol, hexane, methanol and the like are preferable.
The low refractive index layer of the present invention is mainly composed of a crosslinked or polymer of a fluorine-containing polymer containing fluorine atoms in the range of 35 to 80% by mass in the fluorine-containing polymer and containing a crosslinkable or polymerizable functional group. It is preferable to contain as a main component here, and it indicates what has the largest content (mass) in the solid content which forms the low refractive index layer.

<Inorganic fine particles>
The low refractive index layer of the present invention may contain at least one kind of inorganic fine particles.
The coating amount of the inorganic fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.
Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost. The average particle diameter of the silica fine particles is preferably 30% or more and 150% or less of the thickness of the low refractive index layer, more preferably 35% or more and 80% or less, and further preferably 40% or more and 60% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the silica fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. What has been described above for silica fine particles also applies to other inorganic particles.
Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to further reduce the increase in the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles, and the hollow silica fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1. .35, more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle shell is b, the porosity X represented by the following formula (II) is preferably 10 to 60%, more preferably 20 to 60%. Most preferably, it is 30 to 60%.
Formula (II)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
If the hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the low refractive index is less than 1.17. Rate particles do not hold.
The refractive index of these hollow silica particles was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica fine particles having the above particle size (“large size particles”). May be used in combination with a silica fine particle having a diameter).
Since the fine silica particles having a small size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.
When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small size is preferably from 1 nm to 20 nm, more preferably from 5 nm to 15 nm, and particularly preferably from 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

Silica fine particles are treated with a physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to increase the affinity and binding to the binder component. Further, chemical surface treatment with a surfactant, a coupling agent or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, silane coupling treatment is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

<Curable compound>
A curable compound can be added to the low refractive index layer. As the curable compound, a (meth) acrylate monomer is preferably used. Examples of the (meth) acrylate monomer include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, 1,4 -Cyclohexane diacrylate, pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, Side modified products, vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide ( Examples include methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination. The addition amount may be adjusted by the content of the material having a low refractive index such as hollow particles, and is preferably 0 to 70% by weight with respect to the entire low refractive index layer. If it is added more than that, the refractive index of the layer increases, and a preferable antireflection layer cannot be designed.

<Organosilane, sol component>
The low refractive index layer constituting the antireflection film of the present invention comprises an organosilane compound and / or a hydrolyzate thereof and / or a partial condensate thereof, a so-called sol component (hereinafter referred to as such) in the coating liquid forming the layer. From the viewpoint of scratch resistance. This sol component is condensed by a drying and heating process after coating the coating solution to form a cured product, which becomes a binder for the layer. Moreover, when this hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.
The organosilane compound is preferably represented by the following general formula (1).
Formula _{^{(1) :( R 10) m}} -Si (X) 4-m
In the general formula (1), 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, 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.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I, etc.) And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO, C ₂ H ₅ COO, etc.), preferably alkoxy. A group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively.
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 (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.

When there are a plurality of R ¹⁰ , at least one is preferably a substituted alkyl group or a substituted aryl group, and among them, an organosilane compound having a vinyl polymerizable substituent represented by the following general formula (1a) is preferable.
General formula (1a)

In formula (1a), R ¹⁰ and X represents a group having the same meaning as R ¹⁰ and X in the general formula (1). Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferred, and * -COO-** is particularly preferred. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

  L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and a substituent having a linking group (for example, ether, ester, amide, etc.) inside. Or an unsubstituted alkylene group, a substituted or unsubstituted arylene group having a linking group inside, and a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and an alkylene group having a linking group inside are preferable. Further, an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether or ester linking group inside are more preferred, and an unsubstituted alkylene group and an alkylene group having an ether or ester linking group inside are 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.

  n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.

  Two or more kinds of the compounds represented by the general formula (1) or the general formula (1a) may be used in combination. Although the specific example of a compound represented by General formula (1) or General formula (1a) below is shown, it is not limited.

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

  The hydrolysis reaction and / or condensation reaction of organosilane 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, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, oxalic acid is particularly preferable, and metal chelate compounds are also preferable.

The metal chelate compound can be suitably used without particular limitation as long as it has a metal selected from Zr, Ti or Al as a central metal. Within this category, two or more metal chelate compounds may be used in combination. Specific examples of the metal chelate compound used in the present invention include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n Zirconium chelate compounds such as -propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium , Titanium chelate compounds such as diisopropoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diiso Ropoxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis ( Examples include aluminum chelate compounds such as ethyl acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) 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 hydrolysis / condensation reaction is usually performed by adding 0.3 to 2 mol, preferably 0.5 to 1 mol of water to 1 mol of the hydrolyzable group of organosilane, and in the presence or absence of the solvent. Under stirring and preferably in the presence of a catalyst at 25-100 ° C.
When the hydrolyzable group is an alkoxide and the catalyst is an organic acid, the carboxyl group or sulfo group of the organic acid supplies protons, so the amount of water added can be reduced, and the amount of the alkoxide group of the organosilane can be reduced to 1 mol. The amount of water added is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. When alcohol is used as the solvent, it is also preferred that substantially no water is added.

The catalyst is used in an amount of 0.01 to 10 mol%, preferably 0.1 to 5 mol% based on the hydrolyzable group when the catalyst is an inorganic acid, and when the catalyst is an organic acid, The optimum amount used varies depending on the amount of water added, but in the case of adding water, it is 0.01 to 10 mol%, preferably 0.1 to 5 mol% with respect to the hydrolyzable group. When water is not added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50 to 150 mol%, based on the hydrolyzable group. And particularly preferably 50 to 120 mol%.
Although the reaction is carried out by stirring at 25 to 100 ° C., it is preferably adjusted as appropriate depending on the reactivity of the organosilane.

  The metal chelate compound of the present invention is preferably 0.01 to 50% by mass, more preferably 0.1 to 50%, based on the organosilane, from the viewpoint of the speed of the condensation reaction and the film strength when formed into a coating film. It is used at a ratio of 0.5% by mass, more preferably 0.5-10% by mass.

  In addition to the composition containing the hydrolyzate and / or partial condensate of the organosilane compound and the metal chelate compound, the coating solution for the low refractive index layer used in the present invention includes a β-diketone compound and / or a β-ketoester. Preferably a compound is added. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention and acts as a stability improver for the composition used in the present invention. Is. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ 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 content of the hydrolyzate and / or partial condensate of the organosilane compound is preferably small for a surface layer that is a relatively thin film and large for a lower layer that is a thick film. In the case of a surface layer such as a low refractive index layer, 0.1 to 50% by mass of the total solid content of the containing layer (addition layer) is preferable, 0.5 to 20% by mass is more preferable, and 1 to 10% by mass is preferable. Most preferred.
The amount added to the layers other than the low refractive index layer is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and more preferably 0.05 to 10 mass% of the total solid content of the containing layer (addition layer). More preferably, it is 0.1 to 5% by mass.
In the present invention, first, a composition containing a hydrolyzate and / or partial condensate of the organosilane compound and a metal chelate compound is prepared, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto is prepared. It is preferable to coat by coating it in at least one coating solution of a hard coat or a low refractive index layer.

  5-100 mass% is preferable, the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer has more preferable 5-40 mass%, 8-35 mass% is still more preferable, 10-30 mass % Is particularly preferred. If the amount used is small, it is difficult to obtain the effect of the present invention, and if the amount used is too large, the refractive index increases or the shape / surface shape of the film deteriorates.

<Anti-fouling agent, slip agent>
For the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, known silicone-based or fluorine-based antifouling agents, slipping agents, and the like can be appropriately added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass of the total solid content of the low n layer. Particularly preferably 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl 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 molecular weight, 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 silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferable silicone compounds include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), Chisso Corporation, FM-0725, FM-7725, DMS-U22, RMS-033, RMS-083, UMS-182 (named above), etc. It is not limited to.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₆ H, etc.), and alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl groups, per A fluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ (CF _{2) 4 H, -CH 2 CH} 2 OCH 2 CH 2 C 8 F 17, -CH 2 C H ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.
It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink, Megafac F-171. , F-172, F-179A, Defender MCF-300 (named above), but not limited thereto.

<Dustproofing agent, antistatic agent>
For the purpose of imparting properties such as dust resistance and antistatic property, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like may be added as appropriate. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass of the total solid content of the low n layer. Particularly preferably 0.1 to 5% by mass. Examples of preferable compounds include, but are not limited to, Dainippon Ink Co., Ltd., MegaFuck F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean.

<Polymerization initiator>
Polymerization initiators that generate radicals by ionizing radiation include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide 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.
Latest UV curing technology (P.159, publisher: Kazuhiro Takasato, publisher) Technical Information Association, 1
(Published in 1999) also describes various examples and is useful for the present invention.
Preferable examples of the commercially available ionizing radiation cleavage type ionizing radiation radical polymerization initiator include Irgacure (651, 184, 907) manufactured by Ciba Geigy Japan.
The ionizing radiation polymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.
In addition to the ionizing radiation polymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Further, the exemplified compounds (I-1 to 21) described as the compounds (1 to 21) described in JP-A No. 2000-80068 are remarkably effective in improving the scratch resistance and can be preferably used.

As the polymerization initiator that generates radicals by 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 Etc.

<Solvent>
As a solvent used in the coating composition for forming the low refractive index layer of the present invention, it is possible to dissolve or disperse each component, to easily form a uniform surface in the coating process and the drying process, and liquid storage stability. Can be used, and various solvents selected from the viewpoint of having an appropriate saturated vapor pressure can be used. From the viewpoint of the drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of a solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.
Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C) and other ethers, ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as ketone (79.6 ° C.), methanol (64.5 ° C.), ethanol (78.3 ° C.), 2-propanol (82.4 ° C.), 1-propanol (97.2 ° C.), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.) and propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.) and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.
Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.) 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

[High refractive index layer, middle refractive index layer]
In the antireflection film of the present invention, a high refractive index layer or a medium refractive index layer can be provided in order to impart better antireflection performance.
The refractive index of the high refractive index layer is 1.55 to 2.40, and if there is a layer within this range, it can be said that the high refractive index layer in the present invention exists. The range of this refractive index is a range called a so-called high refractive index layer or medium refractive index layer, but in the following specification, these layers may be collectively referred to as a high refractive index layer.
When a high refractive index layer and a medium refractive index layer are mixed, a layer having a refractive index higher than that of the support, hard coat layer, and medium refractive index layer is referred to as a high refractive index layer. A layer higher than the coat layer and the medium refractive index layer and lower than the high refractive index layer is referred to as a medium refractive index layer. The refractive index can be adjusted as appropriate by adjusting the amount of inorganic fine particles to be added and the amount of binder used.

The refractive index of the medium refractive index layer in the antireflection film of the present invention is 1.55-1.85, preferably 1.60-1.75.
The refractive index of the high refractive index layer in the antireflection film of the present invention is 1.65 to 2.20, preferably 1.80 to 1.95.
Furthermore, it is preferable in terms of low reflectivity that the medium refractive index layer satisfies the following mathematical formula (III) and the high refractive index layer satisfies the following mathematical formula (IV).
Formula (III) (l / 4) × 0.7 <n2 × d2 <(l / 4) × 1.3
Formula (IV) (p / 4) × 0.7 <n3 × d3 <(p / 4) × 1.3
In the formula, p is 1 or 2, n3 is the refractive index of the high refractive index layer, and d3 is the film thickness (nm) of the high refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (III) and (IV) means that l and p which satisfy | fill numerical formula (III) and (IV) exist in the said wavelength range.

<Inorganic fine particles mainly composed of titanium dioxide>
The high refractive index layer and / or the medium refractive index layer contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium. The main component means a component having the largest content (mass%) among the components constituting the particles.
The inorganic fine particles mainly composed of titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, and most preferably 2.20 to 2.80. The mass average diameter of the primary particles is preferably 1 to 200 nm, more preferably 2 to 100 nm, and particularly preferably 2 to 80 nm.

By containing at least one element selected from Co, Al, and Zr in inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, and a high refractive index layer and / or medium refraction. The weather resistance of the rate layer can be improved.
The inorganic fine particles mainly composed of titanium dioxide used in the present invention may be surface-treated. The surface treatment is performed using an inorganic compound containing cobalt, an inorganic compound such as Al (OH) ₃ or Zr (OH) ₄ , or an organic compound such as a silane coupling agent. The inorganic fine particles mainly composed of titanium dioxide of the present invention may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.
The shape of the inorganic fine particles mainly composed of titanium dioxide contained in the high refractive index layer and / or the medium refractive index layer is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape, and particularly preferably. Are indefinite shape and spindle shape.

<Dispersant>
A dispersant can be used for dispersing the inorganic fine particles. For dispersion, it is particularly 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 (and a sulfo group), a phosphoric acid group (and a phosphono group), or a sulfonamide group, or a salt thereof is effective. A sulfonic acid group, a phosphoric acid group and a salt thereof are preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersant per molecule may be one or more, but it is preferably 2 or more on average, more preferably 5 or more, and particularly preferably 10 It is more than one. Multiple types of anionic groups may be contained in one molecule. Furthermore, the dispersant preferably contains a cross-linkable or polymerizable functional group.

<High refractive index layer and / or medium refractive index layer, formation method thereof>
The inorganic fine particles mainly composed of titanium dioxide used for the high refractive index layer and / or the medium refractive index layer are used for forming the high refractive index layer in a dispersion state.
In the dispersion of the inorganic fine particles, it is dispersed in a dispersion medium in the presence of the dispersant.
As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of the dispersion medium include water, alcohol, ketone, ester, aliphatic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, amide, ether, ether alcohol. 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 inorganic fine particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pin bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.
The inorganic fine particle dispersion is preferably made as fine as possible in the dispersion medium, and has a mass average diameter of 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 refining the inorganic fine particles to 200 nm or less, a high refractive index layer that does not impair the transparency can be formed.

The high-refractive index layer and / or medium-refractive index layer used in the present invention is preferably a binder precursor (ionizing radiation) necessary for forming a matrix in a dispersion liquid in which inorganic fine particles are dispersed in a dispersion medium as described above. Curable compound, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer, and the coating composition for forming a high refractive index layer is applied on a transparent support to form ionizing radiation curable. It is formed by curing by a crosslinking reaction or a polymerization reaction of a compound (for example, a polyfunctional monomer or polyfunctional oligomer, and the polyfunctional (meth) acrylates (A) and (B) described in the hard coat layer are preferable)). Is preferred.

  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. As the radical photopolymerization initiator, the same hard coat layer as described above is used.

In the high refractive index layer and / or the medium refractive index layer, the binder preferably further has a silanol group. When the binder further has a silanol group, the physical strength, chemical resistance, and weather resistance of the high refractive index layer are further improved.
For example, a silanol group may be formed by adding a compound having a cross-linkable or polymerizable functional group to the coating composition for forming the high refractive index layer, and coating the coating composition on a transparent support. Monomers, polyfunctional oligomers, and the like can be introduced into the binder by a crosslinking reaction or a polymerization reaction.

  In the high refractive index layer and / or the medium refractive index layer, the binder preferably has an amino group or a quaternary ammonium group. A monomer having an amino group or a quaternary ammonium group maintains good dispersibility of the inorganic fine particles in the high refractive index layer, and can produce a high refractive index layer excellent in physical strength, chemical resistance, and weather resistance. .

  The crosslinked or polymerized binder 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 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 high refractive index layer and / or the medium refractive index layer can contain fine inorganic fine particles in addition to the inorganic fine particles mainly composed of titanium dioxide.
The content of the inorganic fine particles in the high refractive index layer and / or the medium refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, particularly preferably the mass of the high refractive index layer. It is 15 to 75% by mass. Two or more inorganic fine particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
An ionizing radiation curable compound containing an aromatic ring in a high refractive index layer and / or a medium refractive index layer, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), S, N Binders obtained by crosslinking or polymerization reactions such as ionizing radiation curable compounds containing atoms such as, P can also be preferably used.
In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

For the high refractive index layer and / or medium refractive index layer, in addition to the above components (inorganic fine particles, polymerization initiator, photosensitizer, etc.), resin, surfactant, antistatic agent, coupling agent, thickening agent Agents, anti-coloring agents, coloring agents (pigments, dyes), anti-glare particles, antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, A surface modifier, conductive metal fine particles, and the like can also be added.
The film thickness of the high refractive index layer and / or the medium refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

  In the formation of the high refractive index layer and / or the medium refractive index layer, the crosslinking reaction or polymerization reaction of the ionizing radiation curable compound is preferably an oxygen concentration of 10% by volume or less, preferably an oxygen concentration of 6% by volume or less. Is preferably carried out in an atmosphere having an oxygen concentration of 2% by volume or less, most preferably 1% by volume or less.

[Transparent support]
As the transparent support of the antireflection film of the present invention, a plastic film is preferably used. As the polymer forming the plastic film, cellulose acylate (eg, triacetylcellulose, diacetylcellulose, cellulose acetate propionate, cellulose acetate butyrate, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film Co., Ltd.), Polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON Corporation), Etc. Among these, triacetyl cellulose, polyethylene terephthalate, norbornene resin, and amorphous polyolefin are preferable, and triacetyl cellulose is particularly preferable.
Cellulose acylate consists of a single layer or a plurality of layers. Single-layer triacetyl cellulose is prepared by drum casting or band casting disclosed in JP-A-7-11055, and the latter triacetyl cellulose is a special feature of the published patent publication. It is prepared by the so-called co-casting method disclosed in Japanese Utility Model Publication Nos. 61-94725 and 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose acylate dope, and the film is dried to some extent on the support and peeled off from the support. A process comprising passed through a drying unit to remove the solvent by various transport means.

A typical solvent for dissolving cellulose acylate as described above is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass).

  As for the above-mentioned various cellulose acylates (films made of triacetyl cellulose and the like) and methods for producing the same, the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, the following public technical bulletin 2001) -1745).

  The thickness of the cellulose acylate is preferably 40 μm to 120 μm. In consideration of handling suitability, coating suitability, etc., about 80 μm is preferable, but from the recent trend of thinning display devices, there is a great need for thinning the polarizing plate. From the viewpoint of thinning the polarizing plate, about 40 μm to 60 μm is preferable. When such a thin cellulose acylate is used as the transparent support of the antireflection film of the present invention, the solvent, film thickness, crosslinking shrinkage ratio, etc. of the layer directly applied to the cellulose acylate are optimized. It is preferable to avoid problems such as handling and application suitability.

<About other layers>
As another layer that may be provided between the transparent support and the hard coat layer of the present invention, an antistatic layer (when there is a request to reduce the surface resistance value from the display side, there is a problem of dust on the surface, etc. A moisture-proof layer, an adhesion improving layer, a rainbow unevenness (interference unevenness) preventing layer, and the like.
These layers can be formed by a known method.

The antireflection film of the present invention can be formed by the following method, but is not limited to this method.
[Adjustment of coating solution]

  First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating, or before and behind that.

  In the coating solution for forming the hard coat layer etc., almost all foreign matters corresponding to the dry film thickness (about 50 nm to 120 nm) of the layer (low refractive index layer, medium refractive index layer, etc.) directly formed thereon are obtained. It is preferable to perform filtration that can be removed (points to 90% or more). Since the translucent particles for imparting light diffusivity are equal to or greater than the film thickness of the low refractive index layer or the middle refractive index layer, the filtration is an intermediate solution to which all materials other than the translucent particles are added. It is preferable to carry out with respect to. In addition, when a filter capable of removing foreign substances having a small particle diameter as described above is not available, almost all foreign substances corresponding to the wet film thickness (about 1 to 10 μm) of the layer directly formed thereon are removed. It is preferable to perform filtration. By such means, the point defects of the layer formed directly thereon can be reduced.

[Coating / Drying]
Next, a coating solution for directly forming a layer to be applied on a support such as a hard coat layer, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method They are coated on a transparent support by a micro gravure coating method or an extrusion coating method (see US Pat. No. 2,681,294), and heated and dried with a drying air or the like. Thereafter, it is cured by light irradiation and / or heating. Thereby, a hard coat layer or the like is formed.
Here, a plurality of hard coat layers can be formed if necessary.
Next, in the same manner, a coating liquid for forming a low refractive index layer is applied onto the hard coat layer, and after drying the solvent, light irradiation and / or heating is performed to form the low refractive index layer. In this way, the antireflection film of the present invention is obtained.

  When forming the hard coat layer, it is preferable to apply the coating solution on the base film directly or via another layer in the range of 6 to 30 μm as the wet coating thickness. When forming a low refractive index layer, a medium refractive index layer, or a high refractive index layer, the coating composition is in the range of 1 to 10 μm as the wet coating thickness directly on the hard coat layer or via another layer. It is preferable to apply | coat a thing, and it is more preferable to apply | coat in the range of 2-5 micrometers.

  The hard coat layer and the low refractive index layer are applied directly on the base film or via other layers, and then conveyed by a web to a heated zone to dry the solvent. In this case, the temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is relatively low temperature, and the second half is preferably relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some of the commercially available photo radical generators used in combination with ultraviolet curable resins volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in warm air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the dry wind after apply | coating the coating composition of each layer on a base film is 0.1-2 m / sec on the surface of a coating film, when the solid content concentration of the said coating composition is 1 to 50%. It is preferable to be in the range in order to prevent drying unevenness.
Moreover, after apply | coating the coating composition of each layer on a base film, the temperature difference of the conveyance roll and base film which contacts the surface opposite to the coating surface of a base film in a drying zone is 0 degreeC-20. Within the range of ° C., drying unevenness due to heat transfer unevenness on the transport roll can be prevented, which is preferable.

[Curing]
Next, the hard coat layer, the low refractive index layer, the medium refractive index layer and the high refractive index layer that are formed as necessary will be described.
The hard coat layer, the low refractive index layer, the intermediate refractive index layer and the high refractive index layer which are formed according to the present invention are cured by ionizing radiation and / or heat on the web after the solvent drying zone. Pass through the zone to be cured and cure the coating. For example, when curing by ultraviolet rays, it is preferable to cure each layer by irradiating an irradiation amount of ultraviolet rays of 10mJ / cm ² ~1000mJ / cm ² by an ultraviolet lamp. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation. In the present invention, ionizing radiation is used in the commonly used meaning, and refers to radiation that causes excitation and ionization when passing through a substance, that is, particle radiation and electromagnetic waves that are also simply called radiation, Specifically, α rays, β rays, γ rays, high energy particles, neutrons, electron beams, light rays (ultraviolet rays and visible rays), and the like. Particularly preferred ionizing radiation for the present invention is ultraviolet rays and visible rays.

The oxygen concentration at the time of curing is preferably 15% by volume or less, more preferably 1% by volume or less, and still more preferably 0.3% by volume or less. When the oxygen concentration at the time of curing exceeds 15% by volume, the film thickness after solvent drying of each layer of the present invention is as thin as about 0.1 μm to several tens μm (the surface area per volume is large). Inactivation of radicals becomes prominent, and as a result, the scratch resistance of the cured film, specifically, the scratch resistance described later is fatally inferior, the surface partially swells when the upper layer is applied, or Since it dissolves, interfacial mixing occurs, causing problems such as deterioration in reflection characteristics.
In order to control the oxygen concentration at the time of curing as described above, it is preferable to reduce the oxygen concentration by purging nitrogen gas or the like.

  Further, when the hard coat layer has a curing rate (100-residual functional group content) of a value of less than 100%, the low refractive index layer of the present invention is provided on the hard coat layer to reduce it by ionizing radiation and / or heat. When the refractive index layer is cured, it is preferable that the lower hard coat layer has a higher curing rate than before the low refractive index layer is provided, because the adhesion between the hard coat layer and the low refractive index layer is improved.

  The antireflection film of the present invention produced as described above can be used for a liquid crystal display device by making a polarizing plate using the antireflection film. In this case, it arrange | positions on the outermost surface of a display by providing an adhesive layer on one side. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film in the polarizing plate from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

  When producing a polarizing plate using the antireflection film of the present invention as one of the surface protective films of two polarizing films, the antireflection film is on the side opposite to the side having the antireflection structure. It is preferable to improve the adhesion on the adhesive surface by hydrophilizing the surface of the transparent support, that is, the surface to be bonded to the polarizing film.

[Saponification]
(1) Method of immersing in alkaline solution This is a technique in which an antireflection film is immersed in an alkaline solution under appropriate conditions to saponify all surfaces reactive with alkali on the entire surface of the film. Is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 N, particularly preferably 1 to 2 N. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set depending on the material and configuration of the antireflection film and the target contact angle.
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 opposite to the surface having the antireflection layer 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 adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle with water on the surface of the transparent support opposite to the side having the low refractive index layer, the better from the viewpoint of adhesion to the polarizing film, while the dipping method simultaneously reduces the low refractive index. Since it is damaged by alkali from the surface having the rate layer to the internal hard coat layer, it is important to set the reaction conditions to the minimum necessary. As an index of the damage received by the antireflection layer due to alkali, when the contact angle to water of the transparent support on the opposite surface is used, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, More preferably, it is 30 to 50 degrees, and further preferably 40 to 50 degrees. If it is 50 degrees or more, a problem arises in the adhesion to the polarizing film, which is not preferable. On the other hand, if the angle is less than 10 degrees, the damage received by the antireflection film is too large, so that the physical strength is impaired, which is not preferable.

(2) Method of applying alkaline solution As a means for avoiding damage to the antireflection film in the above immersion method, the alkaline solution is applied only to the surface opposite to the surface having the antireflection film under appropriate conditions, heated, An alkaline solution coating method of washing with water and drying is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, peeling, etc. caused by alkaline liquids. Is possible.

  In any of the saponification methods (1) and (2), since each layer can be formed by unwinding from a roll-shaped support, a series of operations can be performed in addition to the above-described antireflection film manufacturing process. You can go. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

(3) Method of saponification by protecting the antireflection film with a laminate film As in the case of (2) above, when the hard coat layer and / or the low refractive index layer has insufficient resistance to an alkaline solution, the low refractive index After laminating the laminated film on the surface on which the low refractive index layer is formed after forming the layer, the cellulose acylate surface opposite to the surface on which the low refractive index layer is formed is hydrophilized by immersing in an alkali solution, Thereafter, the laminate film can be peeled off. Even in this method, only the surface opposite to the surface on which the cellulose acylate antireflection layer is formed is subjected to the hydrophilic treatment necessary as a polarizing plate protective film without damaging the hard coat layer and the low refractive index layer. Can do. Compared with the method (2), there is an advantage that a laminate film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

(4) Method of immersing in alkali solution after forming up to hard coat layer Up to hard coat layer is resistant to alkaline solution, but if the low refractive index layer is insufficient in resistance to alkaline solution, after forming up to hard coat layer It is also possible to soak both surfaces in an alkali solution to hydrophilize both surfaces, and then form a low refractive index layer on the hard coat layer. Although the manufacturing process is complicated, there is an advantage that the interlayer adhesion between the hard coat layer and the low refractive index layer is improved particularly when the low refractive index layer has a hydrophilic group such as a fluorine-containing sol-gel film.

(5) Method of forming an antireflection film on cellulose acylate that has been saponified in advance Cellulose acylate has been saponified, for example, by immersing it in an alkali solution in advance, and either one of the surfaces is hard-coated directly or via another layer A layer or a low refractive index layer may be formed. When saponifying by immersing in an alkaline solution, interlayer adhesion between the hard coat layer or other layers and the cellulose acylate surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the hard coat layer or other layer is formed is treated with corona discharge, glow discharge or the like to remove the hydrophilic surface, and then the hard coat layer or other layer. It can be dealt with by forming. Further, when the hard coat layer or other layer has a hydrophilic group, the interlayer adhesion may be good.

Below, the polarizing plate using the antireflection film of this invention and the liquid crystal display device using this polarizing plate are demonstrated.
[Polarizer]
The preferable polarizing plate of this invention has the antireflection film of this invention as at least one of the protective film (protective film for polarizing plates) of a polarizing film. As described above, the polarizing plate protective film has a contact angle with water of 10 to 50 degrees on the surface of the transparent support opposite to the side having the antireflection structure, that is, the surface to be bonded to the polarizing film. It is preferable to be in the range.
By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function excellent in physical strength and light resistance can be produced, and the cost can be greatly reduced and the display device can be thinned. .
Further, by preparing a polarizing plate using the antireflection film of the present invention as one of the protective films for polarizing plates and an optical compensation film having optical anisotropy described later as the other protective film of the polarizing film, Thus, a polarizing plate capable of improving the contrast in the bright room of the liquid crystal display device and greatly widening the vertical and horizontal viewing angles can be produced.

[Optical compensation layer]
By providing the polarizing plate with an optical compensation layer (retardation layer), the viewing angle characteristics of the liquid crystal display screen can be improved.
A known layer can be used as the optical compensation layer, but it has optical anisotropy made of a compound having a discotic structural unit described in JP-A-2001-100042 in terms of widening the viewing angle. An optical compensation layer having a layer, wherein the angle formed by the discotic compound and the transparent support varies with the distance from the transparent support, is preferable.
The angle preferably increases as the distance from the transparent support surface side of the optically anisotropic layer increases.
When the optical compensation layer is used as a protective film for a 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.
Further, an aspect in which the optically anisotropic layer further contains a cellulose ester, an aspect in which an alignment layer is formed between the optically anisotropic layer and the transparent support, and an optical compensation layer having the optically anisotropic layer It is also preferable that the transparent support has an optically negative uniaxial property, has an optical axis in the normal direction of the transparent support surface, and further satisfies the following conditions.

      20 <[{(nx + ny) / 2} -nz] × d <400

  In the above conditional expression, nx is the refractive index in the slow axis direction (direction in which the refractive index is maximum) in the layer surface, and ny is the refraction in the fast axis direction (direction in which the refractive index is minimum) in the layer surface. The ratio, nz, is the refractive index in the thickness direction of the layer, and d represents the thickness of the optical compensation layer.

[Polarizing film]
As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, with a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed between the moving direction of the film at the exit of the process of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. It can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

  The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

[Liquid Crystal Display]
The antireflection film of the present invention 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). Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

  The antireflection film of the present invention, when used as one side of the surface protective film of the polarizing film, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of a mode such as a curry compensate bend cell (OCB).

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) In addition to (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Collection) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for viewing angle expansion ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 45882525 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

  In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having a viewing angle widening effect is included in the two protective films on the back and front of the polarizing film. By using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle expansion effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis of perfluoroolefin copolymer (1))

Into a stainless steel autoclave with a stirrer of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² , 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 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1). The resulting polymer had a refractive index of 1.421.

(Synthesis of perfluoroolefin copolymer (2))
In the synthesis of the perfluoroolefin copolymer (1), a perfluoroolefin copolymer (2) was prepared in the same manner as the synthesis of the perfluoroolefin copolymer (1) except that acrylic acid chloride was changed to methacrylic acid chloride. ) Was synthesized.

(Preparation of organosilane sol solution)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. After that, 30 parts of ion exchange water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain an organosilane sol solution. 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, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating liquid A for hard coat layer)
・ KAYARAD DPCA-30, manufactured by Nippon Kayaku Co., Ltd. (mixture of partially caprolactone-modified dipentaerythritol hexaacrylate, including unmodified product, average 3 (units per molecule) added) 100 parts by mass ・ KAYARAD DPHA, Nippon Kayaku 20 parts by mass, manufactured by Yakuhin Co., Ltd. • 100 parts by mass of methyl ethyl ketone • 20 parts by mass of cyclohexanone • Irgacure 907, manufactured by Ciba Specialty Chemicals
3 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 µm.

(Preparation of coating liquid B for hard coat layer)
・ KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd. (mixture of partially caprolactone-modified dipentaerythritol hexaacrylate, including unmodified product, average 2 (unit / molecule) addition) 100 parts by mass 10 parts by mass of cyclohexanone ・ Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.
3 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 µm.

(Preparation of coating liquid C for hard coat layer)
-Biscoat 295, Osaka Organic Chemical Co., Ltd. (trimethylolpropane triacrylate) 100 parts by mass-Biscote 360, Osaka Organic Chemicals Co., Ltd. (partial ethylene oxide modified trimethylolpropane triacrylate,
Average 3 (unit / 1 molecule) modification) 20 parts by mass • 90 parts by weight of methyl ethyl ketone • 10 parts by weight of cyclohexanone • Irgacure 907, manufactured by Ciba Specialty Chemicals
5 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 μm.

(Preparation of coating liquid D for hard coat layer)
・ KAYARAD DPHA, Nippon Kayaku Co., Ltd. 100 mass parts ・ Methyl ethyl ketone 90 mass parts ・ Cyclohexanone 10 mass parts ・ Irgacure 907, Ciba Specialty Chemicals Co., Ltd.
3 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 µm.

(Preparation of coating solution E for hard coat layer)
-KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd. (addition of partial caprolactone-modified dipentaerythritol hexaacrylate, including unmodified product, average 2 (units per molecule) addition) 100 parts by mass Cyclohexanone 15 parts by mass ・ Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.
8 parts by mass-MEK-ST (refractive index: 1.47, silica ultrafine particles with an average particle size of 15 nm, manufactured by Nissan Chemical Industries, Ltd.)
103 parts by mass-KBM-5103 (acryloyl group-containing organosilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
15 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 μm.

(Preparation of titanium dioxide fine particle dispersion)
MPT-129C, manufactured by Ishihara Sangyo Co., Ltd. (TiO ₂ : Co ₃ O ₄ : Al ₂ O ₃ :
ZrO ₂ = 90.5: 3.0: 4.0: 0.5 mass ratio) 257.1 parts by mass • The following dispersant: 38.6 parts by mass • Cyclohexanone 704.3 parts by mass The above mixture was massed by dynomill. Dispersion was performed until the average diameter reached 70 nm.

(Preparation of coating solution for medium refractive index layer)
-Titanium dioxide dispersion 88.9 parts by mass-KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd. 58.4 parts by mass-Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.
3.1 parts by mass-Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd. 1.1 parts by mass-Methyl ethyl ketone 482.4 parts by mass-Cyclohexanone 1869.8 parts by mass After stirring the above mixture, polypropylene having a pore size of 0.4 µm It filtered with the filter made from.

(Preparation of coating solution for high refractive index layer)
・ 586.8 parts by mass of the above titanium dioxide dispersion ・ KAYARAD DPHA, 47.9 parts by mass manufactured by Nippon Kayaku Co., Ltd. ・ Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.
4.0 parts by mass ・ Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd. 1.3 parts by mass ・ Methyl ethyl ketone 455.8 parts by mass ・ Cyclohexanone 1427.8 parts by mass It filtered with the filter made from a polypropylene.

(Preparation of hollow silica dispersion)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, CS60-IPA manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica particle refractive index 1.31) in 500 parts, acryloyloxypropyl After adding 30 parts of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) and 1.5 parts of diisopropoxyaluminum ethyl acetate, 9 parts of ion-exchanged water were added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added to obtain a hollow silica dispersion. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

(Adjustment of coating solution A for low refractive index layer)
-KAYARAD DPHA, Nippon Kayaku Co., Ltd. 1.4 mass parts-Perfluoroolefin copolymer (1) 5.6 mass parts-Hollow silica dispersion 20.0 mass parts-RMS-033 (reactive silicone, (Gelest Co., Ltd.)
0.7 parts by mass ・ Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.
0.2 parts by mass-Organosilane sol solution 6.2 parts by mass-MEK 305.9 parts by mass-Cyclohexanone 10.0 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 µm.

(Adjustment of coating liquid B for low refractive index layer)
-KAYARAD DPHA, Nippon Kayaku Co., Ltd. 1.4 mass parts-Perfluoroolefin copolymer (2) 5.6 mass parts-Hollow silica dispersion 20.0 mass parts-RMS-033 (reactive silicone, (Gelest Co., Ltd.)
0.7 parts by mass ・ Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.
0.2 parts by mass-Organosilane sol solution 6.2 parts by mass-MEK 305.9 parts by mass-Cyclohexanone 10.0 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 µm.

(Adjustment of coating liquid C for low refractive index layer)
-KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd. 3.6 parts by mass-Hollow silica dispersion 40.0 parts by mass-RMS-033 (reactive silicone, manufactured by Gelest Co., Ltd.)
0.7 parts by mass ・ Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.
0.2 parts by mass-Organosilane sol solution 8.0 parts by mass-MEK 276.0 parts by mass-Cyclohexanone 8.2 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 µm.

(Adjustment of coating liquid D for low refractive index layer)
-Perfluoroolefin copolymer (1) 10.0 parts by mass-X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 parts by mass-Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.
0.5 parts by mass-MEK 232.8 parts by mass-Cyclohexanone 7.2 parts by mass The above mixture was stirred and then filtered through a polypropylene filter having a pore size of 0.4 µm.

(Adjustment of coating liquid E for low refractive index layer)
Irgacure 907, the same as the coating solution A for low refractive index layer, except that 0.2 parts by mass of Ciba Specialty Chemicals Co., Ltd. was replaced with 0.2 parts by mass of the exemplified compound (I-21, the following structural formula). Thus, a coating solution E for a low refractive index layer was prepared.

[Example 1]
(1) Coating of hard coat (HC) layer A triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unwound in a roll form, and coating liquid A for hard coat layer is obtained. Using a micro gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern of 80 lines / inch and a depth of 40 μm, a gravure roll is applied at a rotational speed of 60 rpm and a conveying speed of 20 m / min. An air-cooled metal halide lamp (air graphics Co., Ltd.) with a wind speed of 0.1 m / sec to 2 m / sec. Ltd.) using illuminance 200 mW / cm ^2, and an irradiation dose of 120 mJ / cm ² to cure the coating layer, Oriritsu 1.51, to form a hard coat layer having a thickness of 8.5 .mu.m, was wound.

(2) Coating of low refractive index layer The triacetyl cellulose film coated with the hard coat layer is unwound again, and the coating liquid A for low refractive index layer is 180 lines / inch and a gravure pattern with a depth of 40 μm. Using a micro gravure roll having a diameter of 50 mm and a doctor blade, the coating was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 15 m / min, dried at 90 ° C. for 150 seconds, and an oxygen concentration of 0.1 under a nitrogen purge. Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) in a volume% atmosphere, the composition is cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ^2. A low refractive index layer having a thickness of 100 nm was formed and wound up.
(3) Saponification treatment of antireflection film The following treatment was performed on the film coated with the low refractive index layer.
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
In this way, a saponified antireflection film was produced. This is designated as Example 1 Sample 1.

(Evaluation of antireflection film)
About the obtained film, the following items were evaluated. The results are shown in Table 1.

(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.

(2) Evaluation of steel wool scratch resistance A rubbing test was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., grade No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
Even if you look very carefully, you can not see any scratches ◎
If you look very carefully, you can see slightly weak scratches.
I see weak scratches ○ △
I see moderate scratches △
There are scratches that can be seen at first glance △ × 〜 ×

(3) Pencil scratch test Pencil hardness was evaluated according to JIS K-5600-5-4.
(4) Eraser rubbing resistance evaluation An eraser (MONO, manufactured by Dragonfly Pencil Co., Ltd.) is fixed to the rubbing tip of a rubbing tester, and the sample is fixed with clips on the top and bottom of a smooth dish. Was applied (surface pressure: 500 g / cm ² ), and the rubbing test was performed by changing the number of rubbing. The rubbing conditions are as follows.
Rubbing distance (one way): 1 cm, rubbing speed: about 1 reciprocation / second The sample after rubbing was observed, and the rubbing resistance was evaluated as follows by the number of film peeling.
0-10 round trip film peeling ×
Film peeling after 10 to 30 round trips
30-50 reciprocating film peeling
50-100 reciprocating film peeling
100-150 round trip film peeling ○
No film peeling even after 200 round trips ◎
(5) Interference unevenness From the antireflection layer side in a state where a black film is pasted on the surface opposite to the antireflection layer of the antireflection film and the back surface reflection is eliminated under a scattering light source with a three-wavelength fluorescent tube covered with a scattering cover. Visual observation was made and the evaluation was as follows.
Strong interference unevenness is visible ×
Slightly strong interference unevenness is visible △ ×
Slightly visible but not bothering △
Almost invisible ○
Invisible at all ◎
(6) Curling The antireflection film was sampled in the longitudinal direction: 500 mm and the width direction: 1340 mm (same as the original fabric), and the curl state when the antireflection layer side was placed on a smooth table was visually observed. The evaluation was as follows.
Strong curl and concerns about handling ×
Strong curl but no problem with handling △
The curl is weak and there is no problem in handling ○
(7) Brittleness A mandrel test was performed according to JIS K-5600-5-1 and evaluated as follows.
No crack at 5mm ◎
No crack up to 8mm ○
No crack to ~ 20mm △
Cracking occurs between 25mm and 32mm ×
(8) Point defect Under a point light source, 100 hard coat layer coated films with a length of 1 m were sampled, and each was hard with a black film pasted on the opposite side of the hard coat layer to eliminate back reflection. Counting was performed by visual observation from the coat layer side, and the number of point defects per square meter was calculated as an average value thereof. When the point defects visually counted were observed with an optical microscope, they were all 50 μm or more in size.

[Example 1 Samples 2, 3, 6-14 (present invention) 4, 5 (comparative example)]
As described in Table 1, a sample was prepared in the same manner as in Example 1 Sample 1 except that the hard coat layer coating solution and / or the low refractive index layer coating solution of Example 1 Sample 1 were changed. evaluated. The results are shown in Table 1.

From the results shown in Table 1, the following is clear.
In the sample using the hard coat layer of the present invention, an antireflection film having a balance between scratch resistance, curl and brittleness after application of the antireflection layer is obtained in a thick region (7 to 10 μm). Moreover, a point defect is also favorable. Further, the samples of Examples 12, 13, and 14 were particularly excellent in scratch resistance due to steel wool rubbing and eraser rubbing. Further, when the polymerization initiator was replaced with Exemplified compounds (I-1) to (I-20) from Example 14, scratch resistance was particularly good as in Example 14. On the other hand, the sample of the comparative example is not preferable because a problem of curling and brittleness occurs in the thick region, and point defects increase in the thin region.
As described above, an antireflection film having excellent antireflection properties and high scratch resistance can be obtained by the present invention.

[Example 2]
(1) Coating of hard coat layer / 3-layer antireflection layer, saponification treatment HC similar to sample 1 of Example 1 on a triacetyl cellulose film (TDY80UF, manufactured by Fuji Opto Materials Co., Ltd.) having a thickness of 80 μm Then, the medium refractive index layer coating solution, the high refractive index layer coating solution, and the low refractive index layer coating solution A are applied thereon under the same coating conditions as those of the low refractive index layer. After coating, the medium refractive index layer, the high refractive index layer, and the low refractive index layer are formed in this order by drying the solvent under the conditions described in Table 2 below and curing by UV irradiation. Example 2 Sample 1 was prepared by obtaining a film on which an antireflection layer was formed and subjecting it to a saponification treatment in the same manner as in Example 1.

  In addition, Example 2 Samples 2, 3, 6 were the same as Example 2 Sample 1 except that the coating liquid for the hard coat layer, the layer thickness, and the coating liquid for the low refractive index layer were as shown in Table 3. To 11 (invention) and Samples 4 and 5 (comparative examples) were prepared.

From the results shown in Table 3, the following is clear.
In the sample using the hard coat layer of the present invention, an antireflection film having a balance between scratch resistance, curl and brittleness after application of the antireflection layer is obtained in a thick region (7 to 10 μm). Moreover, a point defect is also favorable. On the other hand, the sample of the comparative example is not preferable because a problem of curling and brittleness occurs in the thick region, and point defects increase in the thin region.

[Example 3]
The PVA film was immersed in an aqueous solution of 2.0 g / l iodine and 4.0 g / l potassium iodide at 25 ° C. for 240 seconds, and further immersed in an aqueous solution of boric acid 10 g / l at 25 ° C. for 60 seconds. It introduced into the tenter drawing machine of the form of FIG. 2 described in 2002-86554, it extended | stretched 5.3 time, the tenter was bent like FIG. 2 with respect to the extending | stretching direction, and the width | variety was kept constant hereafter. After drying in an atmosphere of 80 ° C., it was detached from the tenter. The difference in transport speed between the left and right tenter clips was less than 0.05%, and the angle between the center line of the introduced film and the center line of the film sent to the next process was 46 °. Here, | L1-L2 | is 0.7 m, W is 0.7 m, and | L1-L2 | = W. The substantial stretching direction Ax-Cx at the tenter outlet was inclined by 45 ° with respect to the center line 22 of the film sent to the next process. Wrinkles and film deformation at the tenter exit were not observed.
Furthermore, it was bonded to a cellulose triacetate film (TD80UL, retardation value 3.0 nm) manufactured by Fuji Photo Film Co., Ltd., which had been saponified with an aqueous solution of PVA (manufactured by Kuraray Co., Ltd., PVA-117H) 3%, and further 80 A polarizing plate having an effective width of 650 mm was obtained by drying at ° C. The absorption axis direction of the obtained polarizing plate was inclined 45 ° with respect to the longitudinal direction. The polarizing plate had a transmittance at 550 nm of 43.7% and a polarization degree of 99.97%. Further, as shown in FIG. 2, when the substrate was cut into a size of 310 × 233 mm, a polarizing plate having an absorption efficiency of 91.5% and a 45 ° absorption axis inclined with respect to the side was obtained.
Next, the film of Example 1 Sample 1 and Example 2 Sample 1 (both saponified) was bonded to the polarizing plate to produce a polarizing plate with antireflection. When a liquid crystal display device having an antireflection layer disposed on the outermost layer using this polarizing plate was produced, excellent contrast was obtained because there was no reflection of external light, and excellent visibility was obtained. In particular, when the film of Sample 2 of Example 2 was used, a display device excellent in contrast was obtained because of the low reflectance.

[Example 4]
An 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.), immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes, neutralized and washed with water, and Examples 1 Sample 1 and Example 2 A saponified triacetyl cellulose film of Sample 1 was bonded to and protected on both sides of a known polarizer prepared by adsorbing iodine on polyvinyl alcohol and stretching to prepare a polarizing plate. A liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the anti-reflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF made of the product between the backlight and the liquid crystal cell was replaced, a display device with very high display quality was obtained with very little background reflection.

[Example 5]
Example 1 Protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmissive TN liquid crystal cell to which the film of Sample 1 and Example 2 Sample 1 was attached, and the protective film on the liquid crystal cell side of the polarizing plate on the backlight side The disc surface of the discotic structural unit is inclined with respect to the transparent support surface, and the angle formed by the disc surface of the discotic structural unit and the transparent support surface changes in the depth direction of the optical anisotropic layer. When the viewing angle widening film (wide view film SA 12B, manufactured by Fuji Photo Film Co., Ltd.) having an optical compensation layer is used, the contrast in the bright room is excellent, and the viewing angles in the vertical and horizontal directions are very wide. A liquid crystal display device having excellent visibility and high display quality was obtained. In particular, when the film of Example 2 Sample 1 was used, a display device having excellent contrast was obtained because of the low reflectance.

[Example 6]
Example 2 A polarizing plate with a single-sided antireflection film was prepared using Sample 1, and a λ / 4 plate was bonded to the opposite surface of the polarizing plate on the side having the antireflection film to display a display surface of an organic EL display device. When applied to the outermost surface on the side, surface reflection and reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

FIG. 1 is a cross-sectional view schematically showing the layer structure of the antireflection film of the present invention. FIG. 2 is a cross-sectional view schematically showing the layer structure of the multilayer antireflection film of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Hard coat layer 4 Low refractive index layer 5 Multilayer antireflection film 6 Transparent support 7 Hard coat layer 8 Medium refractive index layer 9 High refractive index layer 10 Low refractive index layer

Claims (16)

In an antireflection film having a hard coat layer containing at least one transparent resin on a transparent support, a low refractive index layer having a refractive index lower than that of any one of the support and the hard coat layer in this order,
The transparent resin has a polyfunctional (meth) acrylate (A) having two or more (meth) acryloyl groups, the same skeleton as the polyfunctional (meth) acrylate, and the skeleton and (meth) acryloyl An antireflection film comprising, as a main component, a mixture with a polyfunctional (meth) acrylate (B) having a spacer group between them.   The average molecular weight of the polyfunctional (meth) acrylate (A) is 200 to 600, and the average molecular weight of the polyfunctional (meth) acrylate (B) is 300 to 2000. Antireflection film.   The spacer group in the polyfunctional (meth) acrylate (B) has a structure introduced by either a lactone addition having 3 to 10 carbon atoms or an alkylene glycol modification having 2 to 20 carbon atoms, The antireflection film according to claim 1 or 2.   The antireflection according to claim 1, wherein the hard coat layer contains inorganic oxide ultrafine particles having a refractive index of 1.20 to 1.50 and an average particle diameter of 1 to 500 nm. the film. The hard coat layer contains an organosilane represented by the following general formula (1), a hydrolyzate thereof, and a partial condensate thereof, or a mixture thereof. 4. The antireflection film according to any one of 4 above.
Formula _{^{(1) :( R 10) m}} -Si (X) 4-m
(In the formula, R ¹⁰ represents at least one of a substituted and unsubstituted alkyl group and a substituted and unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3. Represents.)   The thickness of the said hard-coat layer is 6-15 micrometers, The antireflection film in any one of Claims 1-5 characterized by the above-mentioned.   The antireflection film according to claim 1, wherein the number of point defects having a size of 50 μm or more is 5 or less per square meter on the surface of the hard coat layer.   The antireflection film according to claim 1, wherein the transparent support is a cellulose acylate film having a thickness of 40 μm to 120 μm.   The low refractive index layer is a layer having a refractive index of 1.30 to 1.55, the low refractive index layer contains a fluorine atom in a range of 35 to 80% by mass, and has a crosslinkable or polymerizable functional group. A fluorine-containing polymer (C) containing a crosslinked or polymer as a main component, the fluorine-containing polymer (C) comprising a fluorine-containing vinyl monomer polymer unit and a polymer unit having a (meth) acryloyl group in the side chain. The antireflection film according to claim 1, wherein the antireflection film contains a main chain consisting of only carbon atoms. The low refractive index layer is the fluoropolymer (C), the average particle size is 30% to 150% of the thickness of the low refractive index layer, and the refractive index comprising a hollow structure is 1.17 to 1.40. A certain curable composition containing at least one kind of inorganic fine particles (D), hydrolyzate of organosilane represented by the following general formula (1) and / or its partial condensate (E) is applied and cured. The antireflection film according to claim 1, wherein the antireflection film is a cured film formed as described above.
Formula ^{(1); (R 10)} m -Si (X) 4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)   A polarizing plate, wherein at least one of the surface protective films of the polarizing plate is the antireflection film according to claim 1. One of the two surface protective films of the polarizing plate is the antireflection film according to claim 1, and the other surface protective film is attached to the polarizing film of the surface protective film. An optical compensation film having an optical compensation layer comprising an optically anisotropic layer on a surface opposite to the surface to be combined, the optically anisotropic layer containing a compound having a discotic structural unit, and the discotic The disk surface of the structural unit is inclined with respect to the surface protective film surface, and the angle formed by the disk surface of the discotic structural unit and the surface protective film surface varies in the depth direction of the optically anisotropic layer. The polarizing plate according to claim 11, wherein:   A liquid crystal display device comprising at least one polarizing plate according to claim 11.   The hard coat layer is formed by reverse coating using a micro gravure method, subsequently drying the solvent with dry air, and further curing. A method for producing an antireflection film.   The reflection according to claim 1, wherein the hard coat layer is formed by coating using a microgravure method, subsequently drying the solvent with a drying wind, and further curing. The manufacturing method of a prevention film.   The antireflection according to any one of claims 1 to 10, wherein the hard coat layer is formed by applying a die coat method, subsequently drying the solvent with a dry air, and further curing. A method for producing a film.

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