JP2005122147A - Antireflection film, its producing method, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film which has a high definition plotting performance, has superior antireflection performance and antidazzle performance and, moreover, has high durability, to provide a producing method of the antireflection film, to provide a polarizing plate which is provided with an antireflection layer having superior optical performances, physical strength and weatherability, and is inexpensive, and to provide an image display device which is subjected to antireflection treatment having satisfactory weatherability. <P>SOLUTION: The anti-reflection film contains the antireflection layer on a transparent substrate and has a ruggedness profile where the thickness of the antireflection layer is substantially uniform, the arithmetic average roughness Ra of the film outermost surface of the antireflection layer surface side is 0.02 to 1μm, the average interval Sm of ruggedness is 5 to 65μm and the ratio Rz/Ra between the ten points average roughness Rz and Ra is 10 or smaller. In the producing method of the antireflection film, the ruggedness profile is formed by embossing. In the polarizing film, the antireflection film is used as a surface-protecting film. The image display device is provided with the antireflection film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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

The antireflection film is provided in various image display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display device (CRT). Anti-reflection films are also provided on glasses and camera lenses. As the antireflection film, a multilayer film in which a transparent thin film of metal oxide is laminated has been conventionally used. The reason for using a plurality of transparent thin films is to prevent reflection of light in a wavelength range as wide as possible in the visible range. The transparent thin film of metal oxide is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method which is a kind of physical vapor deposition method.
A transparent thin film of metal oxide has excellent optical properties as an antireflection film, but a film formation method by vapor deposition or sputtering is low in productivity and is not suitable for mass production. The antireflection film by the PVD method may be formed on a support having an antiglare property due to surface unevenness depending on applications. Although the parallel light transmittance is lower than that formed on a smooth support, the reflection of the background is scattered and reduced by surface irregularities, so it exhibits anti-glare properties and, together with the antireflection effect, forms an image. When applied to an apparatus, the display quality is remarkably improved.

  Instead of vapor deposition, a method of forming an antireflection film having a multilayer structure by applying inorganic fine particles has been proposed. As a means for imparting antiglare properties to the antireflection film by coating, a method of applying an antireflection layer on a support having surface irregularities, or a coating for forming an antireflection layer with matte particles for forming surface irregularities In addition to the method of adding to the liquid, a method of forming a concavo-convex shape on the surface of the antireflection film (antireflection layer) by an embossing method or the like has been proposed. An anti-reflection layer and a method of embossing (for example, Patent Document 1, Patent Document 2, etc.) before the coating layer is completely cured after coating are disclosed. However, it is difficult to keep the film thickness of each layer of the antireflection film (antireflection layer) composed of a thin multi-layer structure, resulting in uneven antiglare and antireflection properties. There is a problem that will occur. On the other hand, the method of embossing after preparation of a smooth antireflection film is proposed (for example, patent documents 3, patent documents 4, etc.).

In recent years, the demand for high definition, that is, high image quality is extremely high along with the increase in viewing angle and response speed of liquid crystal displays. This high definition is realized by miniaturization of the liquid crystal cell size. However, as the cell size decreases, an antireflection film having an antiglare property is formed in an ultrahigh definition region of, for example, 133 ppi (133 pixels / inch) or more. There is a problem in that the light that is transmitted and reaches the eyes of the user has a luminance variation, that is, the problem of “glaring” occurs and the display quality deteriorates.
This “glare” is due to the presence of projections and depressions larger than the image display cell on the surface of the antireflection film, so that the transmitted light from a single cell is condensed by the lens effect, or RGB from several adjacent cells This is a drawing failure that occurs when transmitted light causes color mixing.

  On the other hand, an antiglare or antireflection film for an image display device is often mounted on the outermost surface of the device because of its function. In particular, when used in a television, a computer monitor, or a portable digital device, various external forces may be applied during use. Therefore, it has been desired to improve resistance to scratches and push-in and weather resistance.

JP 2000-206317 A JP 2000-214302 A JP 2000-275401 A JP 2000-275404 A

An object of the present invention is to provide an antireflection film excellent in high-definition drawing properties, antireflection properties and antiglare properties.
Another object of the present invention is to provide an antireflection film having excellent high durability in addition to the above excellent characteristics.
Another object of the present invention is to form a controlled fine structure on the film surface by facilitating pattern transfer of the plate by embossing in a transparent resin film having an antireflection layer, and to provide an antiglare effect. It is an object of the present invention to provide a method for producing an antireflection film having a long roll form and good productivity that does not cause defects such as “glare” even in recent high-definition image drawing apparatuses.
Another object of the present invention is to provide a polarizing plate with an antireflection layer excellent in optical performance, physical strength, and weather resistance at low cost and in large quantities.
Another object of the present invention is to provide an image display device that has been subjected to antireflection treatment with good weather resistance by appropriate means.

According to the present invention, an antireflection film having the following constitution, a production method thereof, a polarizing plate, and an image display device are provided, and the above object of the present invention is achieved.
1. In an antireflection film comprising an antireflection layer on a transparent support,
The thickness of the antireflection layer is substantially uniform, and the arithmetic average roughness Ra of the outermost surface of the film on the antireflection layer surface side is 0.02 to 1 μm, the average interval Sm between irregularities is 5 to 65 μm, and ten points. An antireflection film having an uneven shape having a ratio Rz / Ra of average roughness Rz to Ra of 10 or less.
2. The outermost surface of the antireflection film has a maximum unevenness height Ry of 2 μm or less, and the inclination angle of the uneven profile (inclination angle distribution with respect to the regular reflection surface) is distributed to 15 degrees or less. 1. The antireflection film as described in 1.
3. 3. The antireflection film as described in 1 or 2 above, wherein a fine uneven shape on the surface of the antireflection layer is formed by an embossing method after the antireflection layer is applied and dried.
4). 4. The antireflection film as described in any one of 1 to 3 above, wherein a hard coat layer is provided between the transparent support and the antireflection layer.
5). The hard coat layer is formed by applying and curing a hard coat layer curing composition containing at least one compound selected from a polymerizable compound cured by radical polymerization reaction and a polymerizable compound cured by cationic polymerization reaction. 5. The antireflection film as described in 4 above, which is a cured film.
6). The hard coat layer-curing composition comprises at least one each of a crosslinkable polymer containing a repeating unit represented by the following general formula (1) and a compound containing two or more ethylenically unsaturated groups in the same molecule. 6. The antireflection film as described in 5 above, which comprises

In general formula (1), a ¹ and a ² may be the same or different and each represents a hydrogen atom, an aliphatic group, —COOR ₁ , or —CH ₂ COOR ₁ . Here, R ₁ represents a hydrocarbon group.
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group.
L represents a single bond or a divalent linking group.
7). The antireflection layer is formed of a two-layer structure having a high refractive index layer having a higher refractive index than that of the support between the transparent support and a low refractive index layer having a lower refractive index than that of the transparent support. The antireflection film according to claim 1.
8). A high-refractive index layer in which the antireflection layer has a refractive index higher than that of the support in order from the low-refractive index layer side between the transparent support and the low-refractive index layer having a lower refractive index than the transparent support; It is formed from a three-layer structure having a medium refractive index layer having a refractive index intermediate between the support and the high refractive index layer, and the medium refractive index layer has the following formula (I) for the design wavelength λ (400 to 680 nm). The antireflective film as described in any one of 1 to 7 above, wherein the high refractive index layer satisfies the following formula (II) and the low refractive index layer satisfies the following formula (III):
lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)
mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)
nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III)
(Where, l is 1, n1 is the refractive index of the medium refractive index layer, and d1 is the layer thickness (nm) of the medium refractive index layer, m is 2, and n2 is high. The refractive index of the refractive index layer, and d2 is the thickness (nm) of the high refractive index layer, n is 1, n3 is the refractive index of the low refractive index layer, and d3 is the low refractive index. (Thickness layer thickness (nm))
9. The high refractive index layer having a higher refractive index than the support contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium, and has a refractive index of 1. The antireflection film as described in any one of 1 to 8 above, which is 55 to 2.40.
10. Forming an antireflection layer comprising at least one low refractive index layer having a refractive index lower than the refractive index of the transparent support on the transparent support in sequence or simultaneously, and embossing the outermost surface on the antireflection layer side The arithmetic average roughness Ra is 0.02 to 1 μm on the surface of the antireflection layer after processing, the average interval Sm between the irregularities is 5 to 65 μm, and the ratio of the ten-point average roughness Rz to Ra Rz / Ra The manufacturing method of the antireflection film characterized by including the process of forming the unevenness | corrugation of 15 or less.
11. A plate used for embossing is shaped by electric discharge machining, and the surface of the plate has a surface shape with an arithmetic average roughness Ra of 0.2 to 1.0 μm and an average interval Sm of unevenness of 5 to 30 μm. 11. The method for producing an antireflection film as described in 10 above.
12 A polarizing plate having at least one surface protective film on the surface of a polarizer, wherein the surface protective film is produced by the antireflection film according to any one of 1 to 9 or the method according to 10 or 11 above. A polarizing plate, which is an antireflection film.
13. The antireflection film according to any one of 1 to 9 or the antireflection film produced by the method according to 10 or 11 above is used for one of the two surface protection films, and the other surface protection film is used as the other surface protection film. An optical compensation film having an optical compensation layer comprising an optically anisotropic layer on the surface opposite to the surface to be bonded to the polarizing film of the surface protective film is used, and the optical anisotropic layer has a discotic structure. A layer formed of a compound having a unit, the disc surface of the discotic structural unit is inclined with respect to the surface protective film surface, and the disc surface of the discotic structural unit and the surface protective film surface 13. The polarizing plate as described in 12 above, wherein the average angle formed varies in the depth direction of the optically anisotropic layer.
14 14. An image display device having at least one polarizing plate as described in 12 or 13 above.
15. 14. A TN, STN, VA, IPS, or OCB mode transmissive, reflective, or transflective liquid crystal display device having at least one polarizing plate described in 12 or 13 above.

The antireflection film of the present invention is formed by coating an antireflection film on a flexible transparent support, and in particular, the antireflection film of the present invention having an antireflection film having a multilayer structure has the outermost surface specified. In the case of an anti-reflection film produced from a long roll transparent support, since the uneven shape aligned with the size and specific distribution is formed and the thickness of the anti-reflection layer is substantially uniformly controlled, Excellent uniform antireflection and antiglare properties on the entire film surface.
Further, the antireflection film of the present invention has a multilayer structure including a high refractive index layer, and by dispersing specific superparticulate titanium oxide as high refractive index particles for the high refractive index layer, the weather resistance is remarkably increased. Can be improved.
The polarizing plate using the antireflection film of the present invention as a protective film is a polarizing plate provided with an antireflection film excellent in optical performance, physical strength, and weather resistance, and can be provided in a large amount at a low cost. .
Furthermore, the image display device of the present invention includes an antireflection film or a polarizing plate excellent in the above characteristics, is excellent in antireflection performance, and is excellent in visibility and display quality.

In the present invention, the antireflection film obtained by coating an antireflection layer (antireflection film) on a flexible transparent support, particularly the antireflection film comprising an antireflection layer having a multilayer structure has a specific outermost surface. Concave and convex shapes having a uniform size and a specific distribution are formed, and the thickness of the antireflection layer is controlled substantially uniformly. Thereby, also in the antireflection film produced from a long roll transparent support body, it becomes what was excellent in the uniform antireflection property and anti-glare property in the whole film surface. This is achieved by applying a specific shape after forming a cured film by sequentially coating at least a high refractive index layer and a low refractive index layer on a transparent support. Furthermore, by applying a hard coat layer made of a cured resin with a specific structure between the antireflection layer and the transparent support, the shape of the antireflection film after curing can be changed to a fine uneven shape by an embossing method. It is possible to impart a fine structure stably without the need to do so.
The reason why the anti-reflection film having the surface irregularity and the anti-reflection layer having a substantially uniform thickness is thought to be mainly due to the following two factors. The heat and pressure generated by embossing cause the support to undergo plastic deformation and elastic deformation, and the hard coat resin layer and antireflection layer substantially elastically deform. Next, when the heat and pressure applied by embossing are released, the elastic deformation of the hard coat resin layer and the antireflection layer tends to return to the original state, but the support is plastically deformed. It is estimated that the state of deformation is maintained.
Furthermore, the antireflection film of the present invention can remarkably improve the optical properties and weather resistance by dispersing specific titanium oxide in the superparticles as high refractive index particles for the high refractive index layer.

The antireflection layer of the present invention will be described below. In the present specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.
[Layer structure of antireflection layer]
The antireflection layer according to the present invention is formed by providing at least a low refractive index layer having a lower refractive index than that of the transparent support on the transparent support, and preferably has a higher refractive index than that of the transparent support. One of the multilayer antireflection layers in which two or more layers of a refractive index layer (light transmission layer) and a low refractive index layer (light transmission layer) having a lower refractive index than the transparent support are laminated on the transparent support. Formed.
The antireflection layer composed of two layers has a layer structure in the order of a transparent support, a high refractive index layer, and a low refractive index layer (outermost layer). The transparent support, the high refractive index layer and the low refractive index layer have a refractive index satisfying the following relationship. Note that in this specification, the term “two-layer stack, three-layer stack, etc.” does not include the transparent support in the number of stacks.
Refractive index of high refractive index layer> refractive index of transparent support> refractive index of low refractive index layer A hard coat layer may be provided between the transparent support and the high refractive index layer. Further, the hard coat layer may be a high refractive index hard coat layer or an antiglare high refractive index hard coat layer.
The high refractive index, medium refractive index, and low refractive index described here refer to the relative refractive index between layers.

The antireflection layer comprising at least three layers has, for example, a three-layer structure in the order of a transparent support, a middle refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer). The transparent support, the middle refractive index layer, the high refractive index layer, and the low refractive index layer have a refractive index that satisfies the following relationship.
The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer Further, a hard coat layer is provided between the transparent support and the medium refractive index layer. Also good. Further, the medium refractive index layer may be a hard coat layer, that is, a medium refractive index hard coat layer.
Such an antireflection film having a three-layer structure has an optical film thickness of each of the medium refractive index layer, the high refractive index layer, and the low refractive index layer, that is, the product of the refractive index and the film thickness with respect to the design wavelength λ. JP-A-59-50401 describes that nλ / 4 is preferably around or a multiple thereof.
Further, particularly, the medium refractive index layer satisfies the following formula (I), the high refractive index layer satisfies the following formula (II), and the low refractive index layer satisfies the following formula (III) with respect to the design wavelength λ. preferable.
lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)
mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)
nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III)
(Where, l is 1, n1 is the refractive index of the medium refractive index layer, and d1 is the layer thickness (nm) of the medium refractive index layer, m is 2, and n2 is high. The refractive index of the refractive index layer, and d2 is the thickness (nm) of the high refractive index layer, n is 1, n3 is the refractive index of the low refractive index layer, and d3 is the low refractive index. The thickness of the rate layer (nm)). The design wavelength is in the range of 400 to 680 nm, preferably in the range of 450 to 600 nm, and more preferably in the range of 500 to 550 nm.

Further, for a transparent support having a refractive index of 1.45 to 1.55 made of, for example, triacetyl cellulose (refractive index: 1.49), n1 is 1.60 to 1.65, and n2 is 1. .85 to 1.95, n3 is particularly preferably a refractive index of 1.35 to 1.45, and a refractive index of 1.55 to 1.65 made of polyethylene terephthalate (refractive index: 1.66). It is particularly preferable that n1 is 1.65 to 1.75, n2 is 1.85 to 2.05, and n3 is 1.35 to 1.45.
When materials of medium refractive index layer and high refractive index layer having the above refractive index cannot be selected, it is better to combine a plurality of layers having a refractive index higher than the set refractive index and a layer having a low refractive index. In order to realize the reflectance characteristics of the present invention, it is possible to form a layer substantially optically equivalent to a medium refractive index layer or a high refractive index layer having a set refractive index by using a known equivalent film principle. Can also be used. The above-mentioned “antireflection layer comprising at least three layers” includes four or five layers of antireflection layers using such an equivalent film.
Thereby, the color of the reflected light of the antireflection film becomes neutral, and the visibility of the display image of the display device becomes excellent.

The “substantially uniform” thickness of the antireflection layer means that the uniformity, that is, the variation in the thickness of the antireflection layer is within ± 6% of the average thickness. Preferably it is within ± 5%, particularly preferably within ± 3%.
For example, a three-layer type in which a low-refractive index layer, a high-refractive index layer, and a medium-refractive index layer are stacked with a thickness of nλ / 4 (n is an integer of 1 to 3) in this order from the air interface side. In the case of the design, the upper limit of the uniformity of the film thickness of each layer is ± 6%.
The thickness of the antireflective layer can be used in the art, such as transmission electron microscope (TEM), scanning electron microscope (SEM), atomic force microscope (AFM) and X-ray photoelectron spectrometer (ESCA), if desired. Analysis can be performed by various known surface analysis techniques.

  In the antireflection layer of the present invention having the above layer structure, at least a hard coat layer improved in accordance with the present invention and a high refractive index layer are used.

[Surface shape of antireflection film]
The surface of the uppermost layer of the antireflection layer of the present invention has an arithmetic average roughness (Ra) of surface irregularities of the layer based on JIS B 0601-1994 of 0.02 to 1.0 μm and an average interval (Sm) of surface irregularities. The ratio (Rz / Ra) of 10-point average roughness (Rz) to arithmetic average roughness (Ra) is 10 or less. Further, it is preferable that the maximum height (Ry) of the surface unevenness is 2 μm or less, and further, the inclination angle of the uneven profile (inclination angle distribution with respect to the regular reflection surface) is 15 degrees or less.
Preferably, the arithmetic average roughness (Ra) is 0.02 to 0.8 μm, the average interval (Sm) of the surface irregularities is 5 to 50 μm, and the ratio (Rz / Ra) of (Rz) to (Ra) is 9 The maximum height (Ry) is 0.05 to 1.5 μm and the inclination angle is 0.25 to 15 degrees. Particularly preferably, the arithmetic average roughness (Ra) is 0.04 to 0.6 μm, the average interval (Sm) of the surface irregularities is 10 to 40 μm, and the ratio of (Rz) to (Ra) (Rz / Ra) Is 8 or less, the maximum height (Ry) is 0.1 to 1.0 μm, and the inclination angle is 0.25 to 10 degrees.
Here, the relationship between Ra and Rz indicates the uniformity of surface irregularities.
Further, it is preferable that the inclination angle of the uneven profile is small. The tilt angle of the irregular uneven profile is not unambiguous and has a distribution, but if the frequency of the small tilt angle increases, the anti-glare property cannot be obtained, and if the frequency of the large tilt angle increases, the anti-glare film becomes white. Sometimes come.
The concave and convex shapes on the film surface can be evaluated by a two-dimensional roughness meter SJ-400 manufactured by Mitutoyo Corporation or a “micromap” machine manufactured by RYOKA SYSTEM Co., Ltd.

A method for measuring the tilt angle will be described in detail. As shown in FIG. 1, perpendicular points are extended vertically from three points A, B, and C on the support, and points at which the three points intersect the surface are denoted as A ′, B ′, and C ′. An inclination angle is defined as an angle θ formed by a normal line D ′ of the triangle A′B′C ′ plane and a perpendicular line O ′ extending vertically upward from the support. The measurement area is preferably 0.25 square millimeters or more on the support, and this surface is divided into triangles on the support and measured, and the obtained inclination angles are averaged to obtain the average inclination angle of the surface.
There are several devices to measure, but an example will be described. A case will be described in which an SXM520-AS150 model manufactured by Micromap (USA) is used as the apparatus. For example, when the objective lens is 10 times, the measurement unit of the tilt angle is 0.85 square microns, and the measurement range is 0.48 square millimeters. If the magnification of the objective lens is increased, the measurement unit and the measurement range are reduced accordingly. The measurement data can be analyzed using software such as MAT-LAB, and the tilt angle distribution can be calculated. As a result, it is possible to easily obtain the ratio of the inclination angle of 10 ° or more.
In the present invention, the ratio of the inclination angle of 10 ° or more is 2% or less, more preferably 1% or less. Thereby, both anti-glare property and black can be seen black.

[Transparent support for antireflection film]
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7, more preferably 1.45 to 1.7, and particularly preferably 1.45 to 1.65.

  A plastic film is preferably used as the transparent support. Examples of plastic film materials include cellulose esters (eg, cellulose acetates, nitrocelluloses), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene). -1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethylpentene), polysulfone, polyether Sulfones, polyarylates, polyetherimides, polymethyl methacrylates and polyether ketones are included.

Those obtained by adding known additives (for example, antistatic agents, ultraviolet absorbers, plasticizers, slip agents, colorants, antioxidants, flame retardants, etc.) to the organic polymer constituting these organic substrates Can be used. For these details, materials described in detail on pages 16 to 22 of the invention association disclosure technique (public technical number 2001-1745, issued on March 15, 2001, invention association) are preferably used. The amount of these additives added is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, based on the base material.
In particular, when the antireflection film of the present invention is used as one side of a surface protective film of a polarizing plate for use in a liquid crystal display device, an organic EL display device or the like, a cellulose ester is preferably used.
Cellulose ester raw material cellulose used in the present invention includes cotton linter, kenaf, wood pulp (hardwood pulp, conifer pulp), etc., and any cellulose ester obtained from any raw material cellulose can be used, optionally mixed. May be.
In the present invention, cellulose acylate is produced by esterification from cellulose. However, the above-mentioned particularly preferable cellulose is not always usable as it is, and linter, kenaf and pulp are purified and used.
In the present invention, the cellulose acylate is a fatty acid ester of cellulose, but a lower fatty acid ester of cellulose is more preferable.
Here, the lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose acetate is preferred as the cellulose ester, and examples thereof include diacetyl cellulose and triacetyl cellulose. It is also preferable to use mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate.
As these cellulose acylate films, those described in the published technical report No. 2001-1745 are preferably used. In addition, polyethylene terephthalate or polyethylene naphthalate is preferable when it is used by being attached to a glass substrate or the like for use in a flat CRT or PDP.

  The film thickness of the transparent support is not particularly limited, but the film thickness is preferably 1 to 300 μm, preferably 30 to 150 μm, particularly preferably 40 to 120 μm, and most preferably 40 to 100 μm.

[High refractive index layer]
The high refractive index layer of the present invention is typically a curable film having a refractive index of 1.55 to 2.40, which is formed by coating a curable composition containing at least high refractive index inorganic compound fine particles and a matrix binder. Consists of. The refractive index is preferably 1.65 to 2.30, more preferably 1.80 to 2.00. The high refractive index layer of the present invention has a refractive index of 1.55 to 2.40, which is a so-called high refractive index layer or a medium refractive index layer. Sometimes referred to collectively as a high refractive index layer. The refractive index of the medium refractive index layer is 1.55 to 2.40, preferably 1.55 to 2.10, and particularly preferably 1.55 to 1.80.

[Composition for high refractive index layer]
[High refractive index particles]
The high refractive index inorganic fine particles contained in the high refractive index layer of the present invention preferably have a refractive index of 1.80 to 2.80 and an average primary particle size of 3 to 150 nm. Particles having a refractive index of less than 1.80 are not preferred because the effect of increasing the refractive index of the film is small, and particles having a refractive index of more than 2.80 are colored. Further, particles having an average primary particle diameter exceeding 150 nm are not preferable because the haze value when a film is formed is high and the transparency of the film is impaired, and if it is less than 3 nm, it is difficult to maintain a high refractive index. In the present invention, more preferred inorganic fine particles are those having a refractive index of 1.90 to 2.80 and an average primary particle size of 3 to 100 nm, and more preferably a refractive index of 1.90 to 2.80. And the average particle diameter of a primary particle is a particle | grain of 5-80 nm.
Specific examples of preferable high refractive index inorganic fine particles include Ti, Zr, Ta, In, Nd, Sn, Sb, Zn, LaW, Ce, Nb, V, Sm, Y and other oxides or composite oxides, sulfides. And particles containing as a main component. Here, the main component refers to a component having the largest content (mass%) among the components constituting the particles. In the present invention, particles mainly composed of an oxide or composite oxide containing at least one metal element selected from Ti, Zr, Ta, In, and Sn are preferred. The inorganic fine particles used in the present invention may contain various elements in the particles. Examples thereof include Li, Si, Al, B, Ba, Co, Fe, Hg, Ag, Pt, Au, Cr, Bi, P, and S. In the case of tin oxide and indium oxide, it is preferable to contain elements such as Sb, Nb, P, B, In, V, and halogen in order to increase the conductivity of the particles. What was contained is the most preferable.

Particularly preferred are inorganic fine particles (hereinafter sometimes referred to as “specific oxides”) mainly composed of titanium dioxide containing at least one element selected from Co, Zr, and AL. In particular, the preferred element is Co. The total content of Co, Al, and Zr with respect to Ti is preferably 0.05 to 30% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.2 to 7% by mass with respect to Ti. %, Particularly preferably 0.3 to 5% by mass, most preferably 0.5 to 3% by mass.
Co, Al, and Zr are present inside or on the surface of the inorganic fine particles mainly composed of titanium dioxide. It is more preferable that it exists inside the inorganic fine particles mainly composed of titanium dioxide, and most preferable that it exists both inside and on the surface. These specific metal elements may exist as oxides.

Further, as another preferable inorganic particle, a double oxide of titanium element and at least one metal element (hereinafter also abbreviated as “Met”) selected from metal elements whose oxide has a refractive index of 1.95 or more The particles and the double oxide include inorganic fine particles doped with at least one metal ion selected from Co ions, Zr ions, and Al ions (sometimes referred to as “specific double oxide”). It is done. Here, Ta, Zr, In, Nd, Sb, Sn, and Bi are preferable as the metal element of the metal oxide having a refractive index of 1.95 or more. In particular, Ta, Zr, Sn, and Bi are preferable. The content of the metal ions doped in the double oxide is preferably within a range not exceeding 25 mass% with respect to the total amount of metal [Ti + Met] constituting the double oxide from the viewpoint of maintaining the refractive index. More preferably, it is 0.05-10 mass%, More preferably, it is 0.1-5 mass%, Most preferably, it is 0.3-3 mass%.
The doped metal ion may exist as either a metal ion or a metal atom, and appropriately exists from the surface to the inside of the double oxide. It is preferably present both on the surface and inside.

  The inorganic fine particles used in the present invention preferably have a crystal structure or an amorphous structure. The crystal structure is preferably mainly composed of rutile, a mixed crystal of rutile / anatase, or anatase, and particularly preferably a rutile structure. As a result, the inorganic fine particles of the specific oxide or specific double oxide of the present invention are 1.90 to 2.80, preferably 2.10 to 2.80, more preferably 2.20 to 2. It is possible to have a refractive index of 80. Moreover, the photocatalytic activity of titanium dioxide can be suppressed, and the weather resistance of the high refractive index layer of the present invention can be remarkably improved.

  A conventionally known method can be used as a method of doping the specific metal element or metal ion described above. For example, methods described in JP-A-5-330825, JP-A-11-263620, JP-A-11-512336, European Patent No. 0335773, etc., ion implantation methods (for example, Shunichi Gonda, Jun Ishikawa) 3. Eiji Kamijo, “Ion beam applied technology” (CMC Co., Ltd., published in 1989, Yasushi Aoki, Surface Science, Vol.18, (5), pp.262, 1998, Shoichi Anbo, etc. Science, Vol. 20 (2), pp 60, 1999 and the like).

The inorganic fine particles used in the present invention may be surface treated. In the surface treatment, the surface of the particles is modified using an inorganic compound and / or an organic compound, the wettability of the surface of the inorganic particles is adjusted, and the particles are formed into fine particles in an organic solvent. Dispersibility and dispersion stability can be improved. Examples of the inorganic compound capable of modifying the particle surface by physicochemical adsorption on the particle surface include inorganic compounds containing silicon (such as SiO ₂ ) and inorganic compounds containing aluminum (Al ₂ O _3). , Al (OH) ₃ ), cobalt-containing inorganic compounds (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), zirconium-containing inorganic compounds (ZrO ₂ , Zr (OH) _4, etc.), iron And inorganic compounds containing Fe (such as Fe ₂ O ₃ ).

Moreover, the surface modifier of inorganic fillers, such as a conventionally well-known metal oxide and an inorganic pigment, can be used for the example of the organic compound used for surface treatment. For example, it is described in “Pigment Dispersion Stabilization and Surface Treatment Technology / Evaluation”, Chapter 1 (Technical Information Association, 2001).
Specifically, an organic compound having a polar group having an affinity for the surface of the inorganic particles can be used. Such organic compounds include compounds referred to as coupling compounds. Examples of the polar group having an affinity for the surface of the inorganic particles include a carboxyl group, a phosphono group, a hydroxy group, a mercapto group, a cyclic acid anhydride group, and an amino group, and a compound containing at least one kind in the molecule is preferable. . For example, long chain aliphatic carboxylic acids (eg, stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, etc.), polyol compounds (eg, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, ECH (epichlorohydrin) modified glycerol triacrylate Etc.), phosphono group-containing compounds (for example, EO (ethylene oxide) -modified phosphate triacrylate, etc.), alkanolamines (ethylenediamine EO adducts (5 mol), etc.).
As a coupling compound, a conventionally well-known organometallic compound is mentioned, A silane coupling agent, a titanate coupling agent, an aluminate coupling agent etc. are contained. Of these, a silane coupling agent is most preferable. Specific examples include compounds described in paragraph numbers “0011” to “0015” in JP-A-2002-9908 and 2001-310423.
Two or more kinds of these surface treatments can be used in combination.

  As the oxide fine particles used in the present invention, fine particles having a core / shell structure that forms a shell made of an inorganic compound using the fine particles as a core are also preferable. The shell is preferably an oxide composed of at least one element selected from Al, Si, and Zr. Specifically, for example, the contents described in JP-A-2001-166104 can be mentioned.

  The shape of the inorganic fine particles used in the present invention is not particularly limited, but is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape. The inorganic fine particles of the present invention may be used alone or in combination of two or more.

(Dispersant)
In order to use the inorganic particles used in the present invention as stable predetermined ultrafine particles, it is preferable to use a dispersant together. The dispersant is preferably a low molecular compound or a high molecular compound having a polar group having an affinity for the surface of the inorganic fine particles.
Examples of the polar group include a hydroxy group, a mercapto group, a carboxyl group, a sulfo group, a phosphono group, an oxyphosphono group, a —P (═O) (R ₁ ) (OH) group, and —O—P (═O) (R ₁ ) (OH) group, amide group (—CONHR ₂ , —SO ₂ NHR ₂ ), cyclic acid anhydride-containing group, amino group, quaternary ammonium group and the like.
Here, R ₁ represents a hydrocarbon group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxy group) Ethyl group, cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, cyclohexyl group, etc.). R ₂ represents a hydrogen atom or the same content as R ₁ .

In the polar group, the group having a dissociable proton may be a salt thereof. The amino group and quaternary ammonium group may be any of primary amino group, secondary amino group or tertiary amino group, and more preferably tertiary amino group or quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is an aliphatic group having 1 to 12 carbon atoms (such as those having the same contents as the above R group). Is preferred. The tertiary amino group may be a ring-forming amino group containing a nitrogen atom (for example, a piperidine ring, a morpholine ring, a piperazine ring, a pyridine ring, etc.), and the quaternary ammonium group is a cyclic amino group. Or a quaternary ammonium group. In particular, an alkyl group having 1 to 6 carbon atoms is more preferable.
The polar group of the dispersant according to the present invention is preferably an anionic group having a pKa of 7 or less or a salt of these dissociating groups. In particular, carboxyl groups, sulfo groups, phosphono groups, oxyphosphono groups, or salts of these dissociating groups are preferred.

The dispersant preferably further contains a crosslinkable or polymerizable functional group. As the crosslinkable or polymerizable functional group, an ethylenically unsaturated group (for example, (meth) acryloyl group, allyl group, styryl group, vinyloxy group carbonyl group, vinyloxy group, etc.) capable of addition reaction / polymerization reaction by radical species, And cationically polymerizable groups (epoxy groups, thioepoxy groups, oxetanyl groups, vinyloxy groups, spiroorthoester groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, preferably ethylene. An unsaturated group, an epoxy group, or a hydrolyzable silyl group.
Specifically, for example, compounds described in paragraphs [0013] to [0015] in JP-A No. 11-153703, Patent No. US6110858B1, JP-A No. 2002-27776069, and JP-A No. 2001-310423. Etc.

  The dispersant used in the present invention is also preferably a polymer dispersant. In particular, polymer dispersants containing an anionic group and a crosslinkable or polymerizable functional group are exemplified, and those functional groups are the same as those described above.

  The amount of the dispersant used relative to the inorganic fine particles is preferably in the range of 1 to 100% by mass, more preferably 3 to 50% by mass, and most preferably 5 to 40% by mass. Two or more dispersants may be used in combination.

(Dispersion medium)
In the present invention, the dispersion medium used for wet dispersion of inorganic fine particles can be appropriately selected from water and organic solvents, and is preferably a liquid having a boiling point of 50 ° C. or higher, and has a boiling point of 60 ° C. to 180 ° C. It is more preferable that the organic solvent be in the range.
The dispersion medium is preferably used at a ratio of 5 to 50% by mass of the total dispersion composition containing inorganic fine particles and a dispersant. More preferably, it is a ratio of 10 to 30% by mass. Within this range, dispersion proceeds easily, and the resulting dispersion is in a viscosity range with good workability.

  Examples of the dispersion medium include alcohols, ketones, ester amides, ethers, ether esters, hydrocarbons, halogenated hydrocarbons and the like. Specifically, alcohols (eg, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, etc.), ketones (eg, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, etc.), Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, Methyl chloroform, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ethers (eg, dioxane, tetra Dorofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ether alcohols (e.g., 1-methoxy-2-propanol, ethyl cellosolve, methyl carbinol and the like). Two or more of them may be mixed and used. Preferred dispersion media include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol. A coating solvent system mainly comprising a ketone solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is also preferably used.

(Inorganic fine particles)
The curable coating composition for forming the high refractive index layer of the present invention is a composition in which inorganic ultrafine particles having an average particle diameter of 100 nm or less are dispersed, whereby the stability of the liquid of the composition is improved, In the cured film formed from this curable coating composition, inorganic fine particles are uniformly dispersed in an ultrafine particle state in the matrix of the cured film, and a transparent film having a uniform optical property and a high refractive index is achieved. . The size of the ultrafine particles present in the matrix of the cured film is preferably in the range of an average particle size of 3 to 100 nm, more preferably 5 to 100 nm. In particular, 10 to 80 nm is most preferable.
Furthermore, it is preferable that large particles having an average particle diameter of 500 nm or more are not included, and it is particularly preferable that large particles having an average particle diameter of 300 nm or more are not included. Thereby, the specific uneven | corrugated shape mentioned above can form the cured film surface.
In order to disperse the high refractive index inorganic particles in the size of ultrafine particles not containing coarse particles in the above range, for example, a wet dispersion method using a medium having an average particle diameter of less than 0.8 mm together with the dispersant Achieved with a method of dispersing in

  Examples of the wet disperser include conventionally known ones such as a sand grinder mill (eg, a bead mill with pins), a dyno mill, a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. In particular, a sand grinder mill, a dyno mill, and a high-speed impeller mill are preferable for dispersing the oxide fine particles of the present invention in ultrafine particles.

As the media used together with the disperser, the average particle size is less than 0.8 mm, and when the average particle size is within this range, the inorganic fine particle size is 100 nm or less and the particle size is uniform. Fine particles can be obtained. The average particle diameter of the media is preferably 0.5 mm or less, more preferably 0.05 to 0.3 mm.
Moreover, as a medium used for wet dispersion, beads are preferable. Specifically, zirconia beads, glass beads, ceramic beads, steel beads, etc. are mentioned, and 0.05 to 0.2 mm from the viewpoint of durability and ultrafine particle formation that hardly cause breakage of beads during dispersion. The dispersion temperature in the dispersion step in which zirconia beads are particularly preferred is preferably 20 to 60 ° C, more preferably 25 to 45 ° C. When dispersed in ultrafine particles at a temperature in this range, re-aggregation and precipitation of the dispersed particles do not occur. This is presumably because adsorption of the dispersant to the inorganic compound particles is appropriately performed and dispersion stability is not deteriorated due to desorption of the dispersant from the particles at room temperature.

By using the dispersion method described above, a high refractive index film excellent in refractive index uniformity, film strength, adhesion to an adjacent layer, etc. without impairing transparency is preferably formed.
Moreover, you may implement a preliminary dispersion process before the said wet dispersion | distribution process. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.
Furthermore, in order to remove coarse aggregates in the dispersion, the dispersion particles in the dispersion satisfy the above-mentioned range of the average particle diameter and the monodispersibility of the particle diameter. It is also preferable to arrange the filter medium so as to be microfiltered. The filter medium for fine filtration preferably has a filtration particle size of 25 μm or less. The type of filter medium for microfiltration is not particularly limited as long as it has the above performance, and examples thereof include a filament type, a felt type, and a mesh type. The material of the filter medium for finely filtering the dispersion is not particularly limited as long as it has the above performance and does not adversely affect the coating solution, and examples thereof include stainless steel, polyethylene, polypropylene, and nylon.

(Matrix of high refractive index layer)
The high refractive index layer contains at least high refractive index inorganic ultrafine particles and a matrix.
According to a preferred embodiment of the present invention, the matrix of the high refractive index layer is at least one of (i) an organic binder, or (ii) a hydrolyzable functional group-containing organometallic compound and a partial condensate of this organometallic compound. It is formed by curing after applying a composition for forming a high refractive index layer containing.
(I) Organic binder As the organic binder,
(A) a conventionally known thermoplastic resin;
(B) a combination of a conventionally known reactive curable resin and a curing agent, or (c) a combination of a binder precursor (such as a curable polyfunctional monomer or polyfunctional oligomer described below) and a polymerization initiator,
The binder formed from is mentioned.
A coating composition for forming a high refractive index layer is prepared from a dispersion containing the binder forming component (a), (b) or (c) above, a high refractive index composite oxide fine particle and a dispersant. After apply | coating a coating composition on a transparent support body and forming a coating film, it is hardened | cured by the method according to the component for binder formation, and a high refractive index layer is formed. The curing method is appropriately selected depending on the type of the binder component. For example, a crosslinking reaction or a polymerization reaction of a curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer) is performed by at least one of heating and light irradiation. The method to make it occur is mentioned. Especially, the method of forming the binder which hardened | cured the crosslinking reaction or the polymerization reaction of the curable compound by irradiating light using the combination of said (c) is preferable.
Furthermore, it is preferable to carry out a crosslinking reaction or a polymerization reaction with the dispersant contained in the dispersion liquid of the high refractive index composite oxide fine particles simultaneously with or after the application of the coating composition for forming the high refractive index layer.
The binder in the cured film thus prepared is, for example, a crosslinking or polymerization reaction between the above-described dispersant and a curable polyfunctional monomer or polyfunctional oligomer that is a precursor of the binder, and the binder contains a dispersant. An anionic group is incorporated. Further, since the binder in the cured film has a function in which the anionic group maintains the dispersion state of the inorganic fine particles, the crosslinked or polymerized structure imparts a film forming ability to the binder and contains high refractive index inorganic compound fine particles. The physical strength, chemical resistance, and weather resistance in the cured film can be improved.

Examples of the thermoplastic resin include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, polyvinyl chloride copolymer resin, polyacrylic resin, polymethacrylic resin, and polyolefin resin. , Urethane resin, silicon resin, imide resin and the like.
Moreover, it is preferable to use the reaction curable resin, that is, a thermosetting resin and / or an ionizing radiation curable resin. Thermosetting resins include phenolic resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicon resin, polysiloxane Examples thereof include resins. Examples of ionizing radiation curable resins include radical polymerizable unsaturated groups ((meth) acryloyloxy groups, vinyloxy groups, styryl groups, vinyl groups, etc.) and / or cationic polymerizable groups (epoxy groups, thioepoxy groups, vinyloxy groups). , Oxetanyl group, etc.), for example, relatively low molecular weight polyester resin, polyether resin, (meth) acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol Examples include polyene resins.
As needed for these reaction curable resins, crosslinking agents (epoxy compounds, polyisocyanate compounds, polyol compounds, polyamine compounds, melamine compounds, etc.), polymerization initiators (azobis compounds, organic peroxide compounds, organic halogen compounds, oniums) Conventionally known compounds such as curing agents such as UV photoinitiators such as salt compounds and ketone compounds) and polymerization accelerators (organic metal compounds, acid compounds, basic compounds, etc.) are used. Specific examples include compounds described by Fuzo Yamashita and Tosuke Kaneko “Crosslinking Agent Handbook” (published by Taiseisha, 1981).

Hereinafter, a method for forming a cured binder by crosslinking or polymerizing a curable compound by light irradiation using the combination of (c), which is a preferable method for forming a cured binder, will be mainly described.
The functional group of the photocurable polyfunctional monomer or polyfunctional oligomer may be either radically polymerizable or cationically polymerizable.

Examples of the radical polymerizable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group is preferable.
It is preferable to contain a polyfunctional monomer containing two or more radically polymerizable groups in the molecule.
The radical polymerizable polyfunctional monomer is preferably selected from compounds having at least two terminal ethylenically unsaturated bonds. Preferably, it is a compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule. Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention. These can have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.
Examples of radically polymerizable monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Examples thereof include esters of saturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Also, addition reaction products of unsaturated carboxylic acid esters and amides having a nucleophilic substituent such as hydroxyl group, amino group and mercapto group with monofunctional or polyfunctional isocyanates and epoxies, polyfunctional carboxylic acids. A dehydration condensation reaction product with an acid or the like is also preferably used. A reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.

Examples of the aliphatic polyhydric alcohol compound include alkanediol, alkanetriol, cyclohexanediol, cyclohexanetriol, inositol, cyclohexanedimethanol, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin and the like. Polymerizable ester compounds (monoesters or polyesters) of these aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, for example, described in paragraph numbers [0026] to [0027] of JP-A-2001-139663, for example. The compound of this is mentioned.
Examples of other polymerizable esters include, for example, vinyl methacrylate, allyl methacrylate, allyl acrylate, aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231. Those having an aromatic skeleton as described in JP-A-2-226149 and those having an amino group as described in JP-A-1-165613 are also preferably used.

  Specific examples of polymerizable amides formed from an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis- (meth) acrylamide, 1,6-hexamethylene bis- (meth) acrylamide, diethylenetriamine tris ( Examples include meth) acrylamide, xylylene bis (meth) acrylamide, and those having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, it has a vinylurethane compound containing 2 or more polymerizable vinyl groups in one molecule (Japanese Examined Patent Publication No. 48-41708, etc.), urethane acrylate (Japanese Examined Patent Publication No. 2-16765, etc.), and an ethylene oxide skeleton. Urethane compounds (JP-B 62-39418, etc.), polyester acrylates (JP-B 52-30490, etc.)), and further described in Japan Adhesion Association Vol. 20, No. 7, pp. 300-308 (1984). These photocurable monomers and oligomers can also be used.
Two or more kinds of these radically polymerizable polyfunctional monomers may be used in combination.

Next, a cationically polymerizable group-containing compound (hereinafter, also referred to as “cationic polymerizable compound” or “cationic polymerizable organic compound”) that can be used for forming the binder of the high refractive index layer will be described.
As the cationically polymerizable compound used in the present invention, any compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator can be used. Examples thereof include an epoxy compound, a cyclic thioether compound, a cyclic ether compound, a spiro orthoester compound, and a vinyl ether compound. In the present invention, one or more of the above cationic polymerizable organic compounds may be used.

As the cationically polymerizable group-containing compound, the number of cationically polymerizable groups in one molecule is preferably 2 to 10, and particularly preferably 2 to 5. The molecular weight of the compound is 3000 or less, preferably in the range of 200 to 2000, particularly preferably in the range of 400 to 1500. If the molecular weight is too small, volatilization during the film formation process becomes a problem, and if it is too large, the compatibility with the composition for forming a high refractive index layer is deteriorated.
Examples of the epoxy compound include aliphatic epoxy compounds and aromatic epoxy compounds.
Examples of aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, and the like. Can do. In addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxystearate, octyl epoxide stearate, epoxidized linseed oil, epoxidized polybutadiene, etc. Can be mentioned. In addition, as the alicyclic epoxy compound, polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring, or unsaturated alicyclic ring (for example, cyclohexene, cyclopentene, dicyclooctene, tricyclodecene, etc.) ) Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing the containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid.
Examples of the aromatic epoxy compound include mono- or polyglycidyl ethers of mono- or polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts. Examples of these epoxy compounds include compounds described in paragraphs [0084] to [0086] of JP-A No. 11-242101, and paragraph numbers [0044] to [0046] of JP-A No. 10-158385. And the compounds described.
Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable in consideration of fast curability. In the present invention, one of the above epoxy compounds may be used alone, but two or more may be used in appropriate combination.

Examples of the cyclic thioether compound include compounds in which the epoxy ring is a thioepoxy ring.
Specific examples of the compound containing an oxetanyl group as a cyclic ether include the compounds described in paragraphs [0024] to [0025] in JP-A No. 2000-239309. These compounds are preferably used in combination with an epoxy group-containing compound.

Examples of the spiro orthoester compound include compounds described in JP 2000-506908 A.
Examples of vinyl hydrocarbon compounds include styrene compounds, vinyl group-substituted alicyclic hydrocarbon compounds (vinyl cyclohexane, vinyl bicycloheptene, etc.), and compounds described in the radical polysynthetic monomers (compounds whose V1 is equivalent to -O-) , Propenyl compounds (Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 32, 2895 (1994), etc.), alkoxy allene compounds (Journal of Polymer Science: Part A, Polymer A: Polymer 93, Polymer A, Polymer, 24, A. Description, etc.), vinyl compounds (Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 34, 1015 (199). 6), JP-A-2002-29162, etc.), isopropenyl compounds (Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 34, 2051 (1996), etc.) and the like.
Two or more kinds may be used in appropriate combination.

  Moreover, it is preferable to use the compound which contains at least 1 each in the molecule | numerator chosen from said radical polymerizable group and cationic polymerizable group for the polyfunctional compound of this invention. Examples thereof include compounds described in paragraphs [0031] to [0052] in JP-A-8-277320, compounds described in paragraph No. [0015] in JP-A-2000-191737, and the like. The compounds used in the present invention are not limited to these.

  The radical polymerizable compound and the cationic polymerizable compound described above are preferably contained in a mass ratio of radical polymerizable compound: cation polymerizable compound in a ratio of 90:10 to 20:80, and 80:20 to More preferably, it is contained at a ratio of 30:70.

Next, the polymerization initiator used in combination with the binder precursor in the combination (c) will be described in detail.
Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
The polymerization initiator (L) of the present invention is a compound that generates radicals or acids by light and / or heat irradiation. The photopolymerization initiator (L) used in the present invention preferably has a maximum absorption wavelength of 400 nm or less. Thus, the handling can be performed under a white light by setting the absorption wavelength to the ultraviolet region. A compound having a maximum absorption wavelength in the near infrared region can also be used.

First, the compound (L1) that generates radicals will be described in detail.
The compound (L1) that generates radicals preferably used in the present invention refers to a compound that generates radicals by irradiation with light and / or heat and initiates and accelerates the polymerization of a compound having a polymerizable unsaturated group.
A known polymerization initiator or a compound having a bond with a small bond dissociation energy can be appropriately selected and used. Moreover, the compound which generate | occur | produces a radical can be used individually or in combination of 2 or more types.
Examples of the compound that generates radicals include conventionally known organic peroxide compounds, thermal radical polymerization initiators such as azo polymerization initiators, amine compounds (described in Japanese Patent Publication No. 44-20189), organic halogenated compounds, carbonyls, and the like. Examples include photo radical polymerization initiators such as compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, and disulfone compounds.

Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A 63-298339, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, an oxazole compound substituted with a trihalomethyl group: an S-triazine compound.
More preferred are s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring.

  Examples of other organic halogen compounds include ketones, sulfides, sulfones and nitrogen-containing heterocycles described in paragraphs [0039] to [0048] of JP-A-5-27830.

  Examples of the carbonyl compound include, for example, “Latest UV Curing Technology”, pages 60 to 62 (published by Technical Information Association, 1991), paragraph numbers [0015] to [0016] of JP-A-8-134404, And the compounds described in paragraph Nos. [0029] to [0031] of the specification of No. 11-217518, and benzoin compounds such as acetophenone, hydroxyacetophenone, benzophenone, thioxan, benzoin ethyl ether, benzoin isobutyl ether Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, benzyldimethyl ketal, and acylphosphine oxide.

Examples of the organic peroxide compound include compounds described in paragraph [0019] of JP-A No. 2001-139663.
Examples of the metallocene compound include various titanocene compounds described in JP-A-2-4705 and JP-A-5-83588, iron-arene complexes described in JP-A-1-304453, JP-A-1-152109, and the like. Is mentioned.

  Examples of the hexaarylbiimidazole compound described in JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, 4,622,286, and the like. And various compounds.

Examples of the organic borate compound include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. Examples of the organic borate described are the compounds described. For example, the compounds described in paragraphs [0022] to [0027] of JP-A-2002-116539 can be mentioned.
As other organic boron compounds, organic boron such as JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, etc. Specific examples include transition metal coordination complexes and the like.

Examples of the sulfone compound include compounds described in JP-A-5-239015, and examples of the disulfone compound include those represented by general formulas (II) and (III) described in JP-A 61-166544. Compounds and the like.
These radical generating compounds may be used alone or in combination of two or more. As addition amount, it is 0.1-30 mass% with respect to the whole quantity of a radically polymerizable monomer, Preferably it is 0.5-25 mass%, Most preferably, it can add at 1-20 mass%. Within this range, the temporal stability of the composition for a high refractive index layer is highly polymerizable without problems.

Next, the photoacid generator (L2) that can be used as the photopolymerization initiator (L) will be described in detail.
Examples of the acid generator (L2) include photoinitiators for photocationic polymerization, photodecolorants for dyes, photochromic agents, known compounds such as known acid generators used in microresists, and the like, and A mixture thereof may be mentioned.
Examples of the acid generator (L2) include organic halogenated compounds and disulfone compounds. Specific examples of these organic halogen compounds and disulfone compounds are the same as those described for the compound generating a radical.
Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like, for example, paragraph numbers [0058] to [0059] of JP-A-2002-29162. And the like.

  In the present invention, the acid generator (L2) that is particularly preferably used includes onium salts. Among them, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are used for photosensitivity at the start of photopolymerization, and material stability of the compound. From the point of property etc., it is preferable.

  Specific examples of onium salts that can be suitably used in the present invention include, for example, an amylated sulfonium salt described in paragraph [0035] of JP-A-9-268205, and JP-A-2000-71366. Diaryl iodonium salt or triaryl sulfonium salt described in paragraph numbers [0010] to [0011] of the book, sulfonium salt of thiobenzoic acid S-phenyl ester described in paragraph number [0017] of JP-A-2001-288205, Examples include onium salts described in paragraph numbers [0030] to [0033] of JP-A-2001-133696.

Other examples of the acid generator include organic metal / organic halides described in paragraphs [0059] to [0062] of JP-A-2002-29162, and a photoacid generator having an o-nitrobenzyl type protecting group. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.).
These acid generators may be used alone or in combination of two or more. These acid generators are added in a proportion of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight, based on 100 parts by weight of the total weight of the cationically polymerizable monomer. can do. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the composition for high refractive index, polymerization reactivity and the like.

In the composition for high refractive index of the present invention, the radical polymerization initiator is 0.5 to 10% by mass and the cationic polymerization initiator is 1 to 10% by mass with respect to the total mass of the radical polymerizable compound and the cationic polymerizable compound. It is preferable to contain in the ratio of%. More preferably, it contains 1 to 5% by mass of radical polymerization initiator and 2 to 6% by mass of cationic polymerization initiator.
In the composition for high refractive index of the present invention, when a polymerization reaction is carried out by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination. Examples include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

Moreover, when performing a polymerization reaction by near infrared irradiation, it is preferable to use a near infrared spectral sensitizer together.
The near-infrared spectral sensitizer used in combination may be a light-absorbing substance having an absorption band in at least a part of the wavelength range of 700 nm or more, and a compound having a molecular extinction coefficient of 10,000 or more is preferable. Furthermore, a value having absorption in the region of 750 to 1400 nm and a molecular extinction coefficient of 20000 or more is preferable. Moreover, it is more preferable that there is a trough of absorption in the visible light wavelength region of 420 nm to 700 nm, and it is optically transparent. As the near-infrared spectral sensitizer, various pigments and dyes known as near-infrared absorbing pigments and near-infrared absorbing dyes can be used. Among these, it is preferable to use a conventionally known near-infrared absorber.
Commercially available dyes and literature (for example, “Chemical Industry”, May 1986, p. 45-51, “Near Infrared Absorbing Dye”, “Development and Market Trends of Functional Dyes in the 90s”, Chapter 2.3. (1990) CMC), “special function pigments” (edited by Ikemori and Piladani, 1986, issued by CMC Corporation), J. Am. FABIAN, Chem. Rev., 92, pp. 1197 to 1226 (1992), a catalog published in 1995 by Nippon Sensitive Dye Research Institute, Exciton Inc. Known dyes described in the laser dye catalog or patent issued in 1989.

(Ii) Organometallic compound containing a hydrolyzable functional group Curing after formation of a coating film by sol-gel reaction using an organometallic compound containing a hydrolyzable functional group as the matrix of the high refractive index layer used in the present invention It is also preferable to form a formed film. Examples of the organometallic compound include compounds composed of Si, Ti, Zr, Al and the like. Examples of the hydrolyzable functional group include an alkoxy group, an alkoxycarbonyl group, a halogen atom, and a hydroxyl group, and an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group is particularly preferable.
Preferred organometallic compounds are organosilicon compounds represented by the following general formula (1 ′) and partial hydrolysates (partial condensates) thereof. In addition, it is a well-known fact that the organosilicon compound represented by the general formula (1 ′) is easily hydrolyzed and subsequently undergoes a dehydration condensation reaction.

General formula (1 ′): (R ^a ) m-Si (X) n
In General Formula (1 ′), R ^a represents a substituted or unsubstituted aliphatic group having 1 to 30 carbon atoms or an aryl group having 6 to 14 carbon atoms. X represents a halogen atom (a chlorine atom, a bromine atom or the like), an OH group, an OR ² group, or an OCOR ² group. Here, R ² represents a substituted or unsubstituted alkyl group. m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. However, when m is 0, X represents an OR ² group or an OCOR ² group.
In the general formula (1 ′), the aliphatic group represented by ^Ra preferably has 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, benzyl). Group, phenethyl group, cyclohexyl group, cyclohexylmethyl, hexenyl group, decenyl group, dodecenyl group, etc.). More preferably, it has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms.
Examples of the aryl group for R ¹ include phenyl, naphthyl, anthranyl, and the like, and a phenyl group is preferable.

  Although there is no restriction | limiting in particular as a substituent, Halogen (fluorine, chlorine, bromine, etc.), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an 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 group (phenylthio etc.), alkenyl group (vinyl, 1-propenyl etc.), alkoxysilyl group (trimethoxysilyl, triethoxysilyl etc.), acyloxy group (acetoxy, (meth) acryloyl etc.), alkoxy Carbonyl group (methoxycarbonyl, ethoxycarbonyl) Bonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl etc.), acylamino group (acetylamino, benzoylamino) , Acrylicamino, methacrylamino and the like).

  Among these substituents, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group ((meta ) Acryloyl), a polymerizable acylamino group (acrylamino, methacrylamino). These substituents may be further substituted.

R ² represents substituted or unsubstituted alkyl. The explanation of the substituent in the alkyl group is the same as R ¹ .
m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. m is preferably 0, 1, 2 and particularly preferably 1. When m is 0, X represents an OR ² group or an OCOR ² group.
The content of the compound of the general formula (1 ′) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, particularly preferably 30 to 50% by mass, based on the total solid content of the high refractive index layer.

  Specific examples of the compound of the general formula (1 ′) include compounds described in paragraph numbers [0054] to [0056] of JP-A No. 2001-166104.

In the high refractive index layer, the organic binder preferably has a silanol group. When the binder has a silanol group, the physical strength, chemical resistance, and weather resistance of the high refractive index layer are further improved.
A silanol group is, for example, a binder precursor (such as a curable polyfunctional monomer or polyfunctional oligomer), a polymerization initiator, a high refractive index inorganic fine particle as a binder forming component constituting a coating composition for forming a high refractive index layer. An organosilicon compound represented by the general formula (1 ′) having a crosslinkable or polymerizable functional group is blended in the coating composition together with a dispersant contained in the dispersion of the coating composition, and the coating composition is placed on the transparent support. It can be introduced into the binder by applying a crosslinking reaction or a polymerization reaction to the dispersant, the polyfunctional monomer or polyfunctional oligomer, and the organosilicon compound represented by the general formula (1 ′).

  The hydrolysis / condensation reaction for curing the organometallic compound is preferably 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, trifluoroacetic acid, methanesulfonic acid and toluenesulfonic acid, inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia , Organic bases such as triethylamine and pyridine, metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium and tetrabutoxytitanate, metal chelate compounds of β-diketones and β-ketoesters, and the like. Specifically, for example, compounds described in paragraph numbers [0071] to [0083] in JP-A No. 2000-275403 are exemplified.

  The ratio of these catalyst compounds in the composition is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, and more preferably 0.5 to 10% by mass with respect to the organometallic compound. The reaction conditions are preferably adjusted as appropriate depending on the reactivity of the organometallic compound.

In the high refractive index layer, the matrix preferably has a specific polar group.
Specific polar groups include anionic groups, amino groups, and quaternary ammonium groups. Specific examples of the anionic group, amino group and quaternary ammonium group are the same as those described for the dispersant.

  The matrix of the high refractive index layer having a specific polar group, for example, by blending a coating composition for forming a high refractive index layer with a dispersion containing high refractive index inorganic fine particles and a dispersant, as a cured film forming component, A combination of a binder precursor having a specific polar group (such as a curable polyfunctional monomer or polyfunctional oligomer having a specific polar group) and a polymerization initiator, a specific polar group, and a crosslinked or polymerizable functional group At least one of the organosilicon compounds represented by the general formula (1 ′) having the formula: and, if desired, a monofunctional monomer having a specific polar group and a crosslinkable or polymerizable functional group. The composition is applied onto a transparent support to crosslink or disperse the dispersant, monofunctional monomer, polyfunctional monomer or polyfunctional oligomer and / or the organosilicon compound represented by the general formula (1 ′). Obtained by polymerization reaction.

The monofunctional monomer having a specific polar group functions as a dispersion aid for inorganic fine particles in the coating composition. Furthermore, after coating, a uniform dispersion of inorganic fine particles in the high refractive index layer is maintained by using a binder, a crosslinking reaction or a polymerization reaction with a dispersant, a polyfunctional monomer or polyfunctional oligomer, and a physical reaction. A high refractive index layer excellent in strength, chemical resistance and weather resistance can be produced.
It is preferable that the usage-amount with respect to the dispersing agent of the monofunctional monomer which has an amino group or a quaternary ammonium group is 0.5-50 mass%, More preferably, it is 1-30 mass%. If the binder is formed by crosslinking or polymerization reaction simultaneously with or after the application of the high refractive index layer, the monofunctional monomer can function effectively before the application of the high refractive index layer.

Further, the matrix of the high refractive index layer of the present invention includes those which are cured and formed from a conventionally known organic polymer containing a cross-linked or polymerizable functional group, which corresponds to (b) of the organic binder described above. The polymer after the formation of the high refractive index layer preferably has a structure that is further crosslinked or polymerized. Examples of polymers include polyolefins (consisting of saturated hydrocarbons), polyethers, polyureas, polyurethanes, polyesters, polyamines, polyamides and melamine resins. Among these, polyolefin, polyether and polyurea are preferable, and polyolefin and polyether are more preferable. The mass average molecular weight of the organic polymer before curing is preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 3 × 10 ³ to 1 × 10 ⁵ .

The organic polymer before curing is preferably a copolymer having a repeating unit having a specific polar group as described above and a repeating unit having a crosslinked or polymerized structure. The ratio of the repeating unit having an anionic group in the polymer is preferably 0.5 to 99% by mass, more preferably 3 to 95% by mass, and 6 to 90% by mass in all repeating units. Most preferred. The repeating unit may have two or more anionic groups which may be the same or different.
When the repeating unit having a silanol group is included, the ratio is preferably 2 to 98 mol%, more preferably 4 to 96 mol%, and most preferably 6 to 94 mol%.
When the repeating unit having an amino group or a quaternary ammonium group is included, the proportion is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass.

The silanol group, amino group, and quaternary ammonium group can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked or polymerized structure.
The proportion of the repeating unit having a crosslinked or polymerized structure in the polymer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and most preferably 8 to 60% by mass.

The matrix formed by crosslinking or polymerizing the binder is preferably formed by applying a coating composition for forming a high refractive index layer on a transparent support and performing crosslinking or polymerization reaction simultaneously with or after application.
In the high refractive index layer of the present invention, other compounds can be appropriately added depending on applications and purposes. For example, 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, and the high refractive index layer includes an aromatic ring and a halogen other than fluorine. When an element such as a chemical element (for example, Br, I, Cl, etc.), S, N, P or the like is contained, the refractive index of the organic compound is increased. Binders that can be used are also preferably used.
In the total solid content of the high refractive index layer, the addition amount of the binder is 20 to 80% by mass and the addition amount of the high refractive particles is 20 to 80% by mass, preferably the addition amount of the binder is 25 to 75% by mass and high. The addition amount of the refractive particles is 25 to 75% by mass.

(Other composition of high refractive index layer)
In the high refractive index layer of the present invention, other compounds can be appropriately added depending on applications and purposes. For example, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support. Binders obtained by crosslinking or polymerization reaction of curable compounds containing atoms such as N and P can also be preferably used.

  In addition to the above-mentioned components (inorganic fine particles, polymerization initiators, sensitizers, etc.), the high refractive index layer includes resins, surfactants, antistatic agents, coupling agents, thickeners, anti-coloring agents, and coloring agents. (Pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, conductive metal fine particles, etc. are added. You can also

[Formation of high refractive index layer]
The high refractive index layer is preferably formed by applying the above-described coating solution for the high refractive index layer directly or via another layer on the transparent support described later.
The coating solution for the high refractive index layer of the present invention is obtained by mixing and diluting a specific inorganic compound ultrafine particle dispersion, a matrix binder solution, and additives used as necessary in a coating dispersion medium to a predetermined concentration. Prepared. As the dispersion medium for coating, the same dispersion solvent as that for the ultrafine particle dispersion of the inorganic compound described above is used. Two or more of them may be mixed and used. Preferred dispersion media include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol. A coating solvent system mainly comprising a ketone solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is also preferably used, and the ketone solvent content is 10% by mass of the total solvent contained in the high refractive index layer coating composition. The above is preferable. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For the filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 5 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 15 kgf / cm ² or less, more preferably 10 kgf / cm ² or less, and further preferably 2 kgf / cm ² or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

In the present invention, the high refractive index layer comprises a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating, and the composition for forming a high refractive index layer of the present invention on a transparent substrate film to be described later. It can be produced by applying a known thin film forming method such as a method, a gravure coating method, a micro gravure coating method or an extrusion coating method, followed by drying, light and / or heat irradiation. Preferably, curing by light irradiation is advantageous from rapid curing. Furthermore, it is also preferable to perform heat treatment in the latter half of the photocuring treatment.
The light source for light irradiation may be any ultraviolet light region or near-infrared light. Ultraviolet, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halide lamps may be used as ultraviolet light sources. Xenon lamps, sunlight, etc. Various available laser light sources having a wavelength of 350 to 420 nm may be irradiated as a multi-beam. Further, examples of the near-infrared light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp. Various available laser light sources having a wavelength of 750 to 1400 nm may be irradiated in a multi-beam form.
When using a near-infrared light source, it may be used in combination with an ultraviolet light source, or may be irradiated from the substrate surface side opposite to the high refractive index layer coating side. Film curing in the depth direction within the coating layer proceeds without delay with the vicinity of the surface, and a cured film with a uniform curing state can be obtained In the case of photo radical polymerization by light irradiation, it can be performed in air or an inert gas However, it is preferable to reduce the oxygen concentration as much as possible in order to shorten the induction period of the polymerization of the radical polymerizable monomer or to sufficiently increase the polymerization rate. The irradiation intensity of the irradiated ultraviolet rays is preferably about 0.1 to 100 mW / cm ² , and the light irradiation amount on the coating film surface is preferably 100 to 1000 mJ / cm ² . Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

In the pencil hardness test according to JIS K 5400 of the high refractive index layer, it is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher.
Further, in the Taber test according to JIS K 5400, it is preferable that the wear amount of the test piece coated with the high refractive index layer before and after the test is smaller.
The haze of the high refractive index layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

[Medium refractive index layer]
The antireflection film of the present invention preferably has a two-layer structure in which the high refractive index layers are composed of different refractive indexes. That is, a low refractive index layer formed by applying the composition by the above method is formed on a high refractive index layer having a higher refractive index, adjacent to the high refractive index layer, and having a low refractive index. A three-layer structure in which an intermediate refractive index layer having a refractive index intermediate between the refractive index of the support and the refractive index of the high refractive index layer is formed on the opposite side of the layer is preferable. As described above, the refractive index of each refractive index layer is relative.
The material constituting the middle refractive index layer of the present invention may be any conventionally known material, but the same material as the high refractive index layer is preferable. The refractive index is easily adjusted by the type and amount of inorganic fine particles, and a thin layer having a film thickness of 30 to 500 nm is formed in the same manner as described in the high refractive index layer. More preferably, the film thickness is 50 to 300 nm.
In the total solid content of the medium refractive index layer, the addition amount of the binder is 20 to 80% by mass and the addition amount of the high refractive particles is 20 to 80% by mass, preferably the addition amount of the binder is 25 to 75% by mass and high. The addition amount of refractive particles is 25 to 75% by mass.

[Low refractive index layer]
The material for forming the low refractive index layer of the present invention will be described below.
The antireflection film of the present invention is formed by sequentially laminating a low refractive index layer on a high refractive index layer provided on a transparent substrate. The refractive index of the low refractive index layer is in the range of 1.20 or more and less than 1.55. The range is preferably 1.30 to 1.50, particularly preferably 1.35 to 1.48.
The low refractive index layer of the present invention is preferably constructed as an outermost layer having scratch resistance and antifouling properties. As means for greatly improving the scratch resistance, it is effective to impart slipperiness to the surface, and means including introduction of a conventionally known silicone-containing compound or introduction of a fluorine-containing compound can be applied. For the low refractive index layer of the present invention, a cured fluorine-containing resin mainly composed of a thermosetting or ionizing radiation-curable crosslinkable fluorine-containing compound is preferably used.

In the present invention, “mainly comprising a fluorine-containing compound” means that the fluorine-containing compound contained in the outermost layer occupies 50% by mass or more with respect to the total mass of the outermost layer, and occupies 60% by mass or more. Is more preferable.
The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47. Moreover, it is preferable that a fluorine-containing compound contains a fluorine atom in 35-80 mass%.
Examples of the fluorine-containing compound include a fluorine-containing polymer, a fluorine-containing surfactant, a fluorine-containing ether, and a fluorine-containing silane compound. Specifically, for example, paragraph numbers [0018] to [0026] of JP-A-9-222503, paragraph numbers [0019] to [0030] of JP-A-11-38202, paragraph number [0027] of JP-A-2001-40284. ] To [0028] and the like.

As the fluorine-containing polymer, a copolymer comprising a repeating structural unit containing a fluorine atom, a repeating structural unit containing a crosslinkable or polymerizable functional group, and a repeating structural unit composed of other substituents is preferred.
Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.), (meta ) A part of acrylic acid or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical Co., Ltd.) or M-2020 (manufactured by Daikin)), a complete or partially fluorinated vinyl ether, and the like. From the viewpoint of refractive index, solubility, transparency, availability, etc., hexafluoropropylene is particularly preferable.
Examples of the crosslinkable or polymerizable functional group are the same as those of the material for a high refractive index layer.

  As commercially available fluorine-containing compounds, TEFRON AF1600 (refractive index n = 1.30 manufactured by DuPont), CYTOP (n = 1.34 manufactured by Asahi Glass Co., Ltd.), 17FM (manufactured by Mitsubishi Rayon Co., Ltd. n = 1.35) ), Opstar JN-7212 (JSR Corporation n = 1.40), Opstar JN-7228 (JSR Corporation n = 1.42), LR201 (Nissan Chemical Industries Ltd. n = 1.38) (all trade names) can also be used.

As other repeating structural units, a hydrocarbon-based copolymer component is preferable for solubilizing the coating solvent, and a fluorine-based polymer introduced with about 50% is preferable. In this case, it is preferable that a polysiloxane structure is introduced because the antifouling property is improved.
There is no limitation on the method for introducing the polysiloxane structure, but for example, as described in JP-A-11-189621, JP-A-11-228631, and JP-A-2000-313709, a polysiloxane block is used using a silicone macroazo initiator. Examples thereof include a method for introducing a copolymer component, and a method for introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. In these cases, the polysiloxane component is preferably 0.5 to 10% by mass, particularly preferably 1 to 5% by mass in the polymer.

For addition of antifouling properties, polysiloxanes containing reactive groups other than the above (for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22- 164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30 AK-32 (trade name, manufactured by Toagosei Co., Ltd.), Silaplane FM0275, Silaplane FM0721 (manufactured by Chisso), etc.), silanol groups at both ends of the polysiloxane structure described in JP-A-11-258403 A means for adding a compound or the like is also preferred. In this case, these polysiloxanes are preferably added in the range of 0.5 to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1 to 5% by mass.
The low refractive index layer may be composed of the cured polymer itself or may contain other compositions. In the case of a cured film combined with another composition, the amount of the polymer added is preferably 10 to 95% by mass based on the total solid content of the low refractive index layer. More preferably, it is 30-90 mass%.

The crosslinking or polymerization reaction of the fluorine-containing polymer having a crosslinking or polymerizable group is preferably carried out by irradiating or heating the coating composition for forming the outermost layer simultaneously with or after coating. Examples of the polymerization initiator and the sensitizer include those similar to those used in the high refractive index layer.
Also preferred is a sol-gel cured film in which a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.
For example, polyfluoroalkyl group-containing silane compounds or partially hydrolyzed condensates thereof (compounds described in JP-A-58-142958, JP-A-58-147483, JP-A-58-147484, etc.), JP-A-9-157582 Perfluoroalkyl group-containing silane coupling agents described in Japanese Patent Publication No. JP-A-2000-117902, JP-A-2000-117902, JP-A-2000-48590, And the like described in JP-A-2002-53804).
The low refractive index layer may contain fillers (for example, inorganic fine particles and organic fine particles, silane coupling agents, slip agents (silicon compounds such as dimethyl silicon), surfactants and the like as additives other than the above. In particular, it is preferable to contain inorganic fine particles, a silane coupling agent, and a slip agent.

  As the inorganic fine particles, low refractive index compounds such as silicon dioxide (silica) and fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride) are preferable. Particularly preferred is silicon dioxide (silica). The mass average diameter of the primary particles of the inorganic fine particles is preferably 1 to 150 nm, more preferably 3 to 100 nm, and most preferably 1 to 80 nm. The inorganic fine particles are preferably more finely dispersed. The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape.

(Inorganic fine particles with hollow structure)
The low refractive index layer preferably uses hollow inorganic fine particles (hereinafter sometimes referred to as hollow particles) in order to further reduce the increase in the refractive index. The hollow particles preferably have a refractive index of usually 1.17 to 1.40, preferably 1.17 to 1.37, and more preferably 1.17 to 1.35. Here, the refractive index represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell forming the hollow particle. The refractive index of the hollow particles is preferably 1.17 or more from the viewpoint of the strength of the particles and the scratch resistance of the low refractive index layer containing the hollow particles.
The refractive index of these hollow particles can be measured with an Abbe refractometer [manufactured by Atago Co., Ltd.].

When the radius of the cavity in the hollow particle is r _i and the radius of the particle outer shell is r _o , the void ratio w (%) of the hollow particle is calculated according to the following formula (6).
Formula (6): w = (r _i / r _o ) ³ × 100
The void ratio of the hollow particles is preferably 10 to 60%, more preferably 20 to 60%.

The average particle diameter of the hollow particles is preferably 30 to 100%, more preferably 35 to 80%, and particularly preferably 40 to 60% of the thickness of the low refractive index layer. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow particles is preferably 30 to 100 nm, more preferably 35 to 80 nm, and particularly preferably 40 to 60 nm. When the average particle size is in the above range, the strength of the film is sufficiently expressed, which is preferable.
(Dispersion of inorganic fine particles)
In order to stabilize dispersion in the dispersion liquid or the curable composition for forming a low refractive index layer, or to improve the affinity and binding properties with the binder component, any of the inorganic fine particles described above may be used. A physical surface treatment such as a plasma discharge treatment or a corona discharge treatment, or a chemical surface treatment with a surfactant or a coupling agent may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (for example, a titanium coupling agent or a silane coupling agent) is preferably used. Of these, treatment with a silane coupling agent is particularly preferred. Examples of the silane coupling agent include those represented by the general formula (2).

Formula _{^{(2) :( R 21) q}} -Si (Y 21) 4-q
(In the formula, R ²¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Y ²¹ represents a hydroxyl group or a hydrolyzable group. Q represents an integer of 1 to 3)

The above-mentioned coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in order to perform surface treatment in advance before the preparation of the coating liquid for forming the curable low refractive index layer. It is preferable to add it as an additive at the time of preparation to be contained in the layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

(Organosilane compound)
Next, the hydrolyzate and / or partial condensate of organosilane represented by the general formula (2) will be described.
Formula _{^{(2) :( R 21) q}} -Si (Y 21) 4-q

In the general formula (2), R ²¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. 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, and examples thereof include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. . Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

Y ²¹ 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 And R ²² COO (R ²² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and examples thereof include CH ₃ COO, C ₂ H ₅ COO, etc.), preferably Is an alkoxy group, particularly preferably a methoxy group or an ethoxy group.
q represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ²¹ or the Y ²¹ there are a plurality, a plurality of R ²¹ or Y ²¹ may be different even in the same, respectively.

There are no particular limitations on the substituents contained in R ^21, a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group (methyl, ethyl, i- propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino) , Arylamino, methacrylamino etc.), and the like. These substituents may be further substituted.

When there are a plurality of R ^{21 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.

  Among the organosilane compounds represented by the general formula (2), an organosilane compound having a vinyl polymerizable substituent such as a methacryloyloxy group or an acryloyloxy group is particularly preferable. Specific examples include those described in paragraph numbers [0026] to [0028] of JP-A-2004-42278.

  The hydrolyzate and / or partial condensate of an organosilane compound is generally produced by treating the organosilane compound in the presence of a catalyst. Examples of the catalyst include acids, bases, organometallic compounds, and the like, and specific examples include the same as described in the high refractive index layer sol-gel reaction.

The low refractive index layer of the present invention preferably has a surface dynamic friction coefficient of 0.25 or less. The dynamic friction coefficient described here refers to a dynamic friction coefficient between a surface and a stainless steel hard sphere having a diameter of 5 mm when a load of 0.98 N is applied to a stainless steel hard sphere having a diameter of 5 mm and the surface is moved at a speed of 60 cm / min. Preferably it is 0.17 or less, Most preferably, it is 0.15 or less.
Further, the contact angle of water on the outermost surface is preferably 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.
When the low refractive index layer is located below the outermost layer, the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.). The coating method is preferable because it can be manufactured at a low cost.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.
The addition amount of the inorganic fine particles is preferably 5 to 95% by mass with respect to the total solid content. More preferably, it is 10-70 mass%, Most preferably, it is 10-50 mass%.
The haze of the low refractive index layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K 5400.
Further, the wear amount, the surface dynamic friction coefficient, and the contact angle with water in the Taber test according to JIS K 5400 are preferably the same as those of the uppermost layer.

[Hard coat layer]
The hard coat layer is provided on the surface of the transparent support in order to impart physical strength to the antireflection film. In particular, it is preferably provided between the transparent support and the high refractive index layer.
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. For example, a coating composition containing a polyester (meth) acrylate, a polyurethane (meth) acrylate, a polyfunctional monomer, a polyfunctional oligomer, or a hydrolyzable functional group-containing organometallic compound is coated on a transparent support, and a curable compound is applied. It can be formed by a crosslinking reaction or a polymerization reaction.
The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound. Specifically, those having the same contents as the matrix binder of the high refractive index layer can be mentioned.

A more preferred embodiment is to use a polymerizable compound that cures by radical polymerization reaction and cationic polymerization reaction. The polymerizable compound may contain a radical polymerizable group and a cationic polymerizable group in the same molecule, or may be a compound contained in different molecules and a mixture of both.
A multilayer antireflection film composed of a curable film formed mainly from a curable composition mainly containing these polymerizable compounds can uniformly and stably form surface irregularities by embossing described later. These are presumed to be due to appropriate action of thermoelastic deformation of the hard coat layer.

  As a preferable specific curable composition embodiment, both a crosslinkable polymer containing a repeating unit represented by the following general formula (1) and a compound containing two or more ethylenically unsaturated groups in the same molecule are used. And a curable composition that contains and cures by polymerizing both the ring-opening polymerizable group and the ethylenically unsaturated group in the crosslinkable polymer.

In general formula (1), a ¹ and a ² may be the same or different and each represents a hydrogen atom, an aliphatic group, —COOR ₁ , or —CH ₂ COOR ₁ . R ₁ represents a hydrocarbon group.
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group.
L represents a single bond or a divalent linking group.

The crosslinkable polymer containing the repeating unit represented by the general formula (1) will be described in detail. In the general formula (1), a ¹ and a ² represent a hydrogen atom, an aliphatic group, preferably an alkyl group having 1 to 4 carbon atoms, —COOR ₁ , or —CH ₂ COOR ₁ . R ₁ represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.
L is a single bond or a divalent linking group, preferably a single bond, -O-, an alkylene group, an arylene group, * -COO-, * -CONH-, * -OCO-, or * -NHCO-. (Here, * means linking to the main chain on the * side).
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group. The monovalent group containing a ring-opening polymerizable group is a monovalent group having a ring structure in which ring-opening polymerization proceeds by the action of a cation, anion, radical, etc. Among them, cationic ring-opening polymerization of a heterocyclic compound Is preferred. Preferred monovalent groups containing a ring-opening polymerizable group include vinyloxy groups or monovalent groups containing an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring, an oxazoline ring and the like. Among them, a monovalent group including an epoxy ring, an oxetane ring and an oxazoline ring is particularly preferable, and a monovalent group including an epoxy ring is most preferable.
When P represents an ethylenically unsaturated group, preferred ethylenically unsaturated groups include acryloyl group, methacryloyl group, styryl group, and vinyloxycarbonyl group.

The crosslinkable polymer containing the repeating unit represented by the general formula (1) of the present invention is preferably synthesized simply by polymerizing a corresponding monomer. In this case, radical polymerization is the simplest and preferable as the polymerization reaction.
Although the preferable specific example of the repeating unit represented by General formula (1) below is shown, this invention is not limited to these.

Among the repeating units represented by the general formula (1) of the present invention, more preferable examples are repeating units derived from methacrylates or acrylates having an epoxy ring. Among them, glycidyl methacrylate and glycidyl acrylate are particularly preferable examples. E-1 and E-3 derived from the above.
Moreover, the crosslinkable polymer containing the repeating unit represented by the general formula (1) of the present invention may be a copolymer composed of a plurality of types of repeating units represented by the general formula (1). Curing shrinkage can be more effectively reduced by using either E-1 or E-3 copolymer.

  The crosslinkable polymer containing a repeating unit represented by the general formula (1) of the present invention may be a copolymer containing a repeating unit other than the general formula (1). In particular, when it is desired to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or to control the content of the ring-opening polymerizable group of the crosslinkable polymer, it can be a copolymer containing a repeating unit other than the general formula (1). . As a method for introducing the repeating unit other than the general formula (1), a method of introducing the corresponding monomer by copolymerization is preferable.

When the repeating unit other than the general formula (1) is introduced by copolymerizing a corresponding vinyl monomer, the monomer preferably used is derived from acrylic acid or α-alkyl acrylic acid (for example, methacrylic acid). Esters or amides (for example, Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, acrylamide, 2-acrylamide-2) -Methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetone acrylamide, acryloylmorpholine, N-methylol acrylamide, N-methylol methacrylamide, alkyl ester (Meth) acrylate (alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, etc.), 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, octafluoropentyl (meth) acrylate, cyclohexyl (Meth) acrylate, cyclopentyl (meth) acrylate, 2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-ylmethyl (meth) acrylate 3-methyl-2-norborn Nylmethyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.), acrylic acid or α-alkyl acrylic acid (acrylic acid, Methacrylic acid, itaconic acid, etc.), vinyl esters (eg vinyl acetate), esters derived from maleic acid or fumaric acid (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), maleimides (N-phenylmale) Mi Etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (eg butadiene, cyclopentadiene, isoprene), aromatic vinyl compounds (eg styrene, p-chlorostyrene, t -Butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate, vinylidene chloride, vinyl Ruki ethers (e.g. methyl vinyl ether), ethylene, propylene, 1-butene, isobutene and the like. Two or more of these vinyl monomers may be used in combination. Vinyl monomers other than these are listed in Research Disclosure No. Those described in 19551 (1980, July) can be used.
In the present invention, esters derived from acrylic acid or methacrylic acid, amides, and aromatic vinyl compounds are particularly preferably used vinyl monomers.

  As the repeating unit other than the general formula (1), a repeating unit having a ring-opening polymerizable group or a reactive group other than the ethylenically unsaturated group can also be introduced. In particular, if you want to increase the hardness of the hard coat layer, or if you want to improve the adhesion between layers when using another functional layer on the substrate or hard coat, a copolymer containing reactive groups other than ring-opening polymerizable groups The method is preferable. As a method for introducing a repeating unit having a reactive group other than the ring-opening polymerizable group, a method of copolymerizing a corresponding vinyl monomer (hereinafter referred to as “reactive monomer”) is simple and preferable.

  Although the preferable specific example of a reactive monomer is shown below, this invention is not limited to these.

<Preferable specific example of reactive monomer>
Hydroxyl group-containing vinyl monomers (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomers (eg, isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N -Methylol group-containing vinyl monomers (for example, N-methylolacrylamide, N-methylolmethacrylamide, etc.), carboxyl group-containing vinyl monomers (for example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate), alkyl halides Vinyl monomers (eg chloromethylstyrene, 2-hydroxy-3-chloropropyl methacrylate), acids Water-containing vinyl monomers (eg maleic anhydride), formyl group-containing vinyl monomers (eg acrolein, methacrolein), sulfinic acid group-containing vinyl monomers (eg potassium styrenesulfinate), active methylene-containing vinyl monomers (eg acetoacetoxyethyl) Methacrylate), amino group-containing monomers (for example, allylamine), alkoxysilyl group-containing monomers (for example, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltrimethoxysilane), and the like.

  In the crosslinkable polymer containing the repeating unit represented by the general formula (1) of the present invention, the proportion of the repeating unit represented by the general formula (1) is 30% by mass or more and 100% by mass or less, preferably 50%. It is 70 mass% or more and 100 mass% or less especially preferably. When the repeating unit other than the general formula (1) does not have a crosslinking reactive group, the hardness decreases if the content is too large, and when it has a crosslinking reactive group, the hardness may be maintained, but curing shrinkage may occur. May become large and brittleness may deteriorate. In particular, when using a copolymer of an alkoxysilyl group-containing monomer (for example, methacryloyloxypropyltrimethoxysilane) and a repeating unit represented by the general formula (1), the molecular weight decreases such as dehydration and dealcoholization during the crosslinking reaction. When accompanied, curing shrinkage tends to increase. General formula (1) in the case of introducing a repeating unit having a crosslinking reactive group that undergoes a crosslinking reaction with a decrease in molecular weight into a crosslinkable polymer containing a repeating unit represented by the general formula (1) of the present invention. ) Is preferably 70% by mass or more and 99% by mass or less, more preferably 80% by mass or more and 99% by mass or less, and particularly preferably 90% by mass or more and 99% by mass or less.

  A preferred molecular weight range of the crosslinkable polymer containing the repeating unit represented by the general formula (1) is from 1,000 to 1,000,000, more preferably from 3,000 to 200,000 in terms of mass average molecular weight. Most preferably, it is 5000 or more and 100,000 or less. In addition, the said mass mean molecular weight is measured by GPC method and is a polystyrene conversion value.

A compound containing two or more ethylenically unsaturated groups in the same molecule that can be used in the present invention will be described. Preferred types of ethylenically unsaturated groups are allyloyl group, methacryloyl group, styryl group, and vinyl ether group, particularly preferably methacryloyl group or acryloyl group, and particularly preferably acryloyl group. Although the compound containing an ethylenically unsaturated group should just have two or more ethylenically unsaturated groups in a molecule | numerator, More preferably, it is three or more. Among them, a compound having an acryloyl group is preferable, a compound called a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule, a molecule called urethane acrylate, polyester acrylate, or epoxy acrylate. An oligomer having several acrylate groups and having a molecular weight of several hundred to several thousand can be preferably used. Specifically, the same thing as the polyfunctional monomer of an above described high refractive index layer is mentioned.
These polymerizable compounds are preferably used in combination with a polymerization initiator, and specific examples thereof include those described in the high refractive index layer.
The hard coat layer is composed of the cured polymer itself or may contain other compositions. In the case of a cured film combined with another composition, the addition amount of the cured polymer is preferably 10 to 95% by mass with respect to the total solid mass of the hard coat layer. More preferably, it is 30-90 mass%.

The hard coat layer preferably contains inorganic fine particles having an average primary particle size of 300 nm or less. More preferably, it is 10-150 nm, More preferably, it is 20-100 nm. The average particle diameter here is a mass average diameter. By setting the average particle size of the primary particles to 200 nm or less, a hard coat layer that does not impair the transparency can be formed.
The inorganic fine particles have functions of increasing the hardness of the hard coat layer and suppressing curing shrinkage of the coating layer. It is also added for the purpose of controlling the refractive index of the hard coat layer.
Specific examples of the composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO 00/46617.

The content of the inorganic fine particles in the hard coat layer is preferably 10 to 90% by mass and more preferably 15 to 80% by mass with respect to the total mass of the hard coat layer.
As described above, the high refractive index layer can also serve as the hard coat layer. When the high refractive index layer also serves as the hard coat layer, it is preferably formed by finely dispersing inorganic fine particles and using the technique described in the high refractive index layer to be contained in the hard coat layer.
The film thickness of the hard coat layer can be appropriately designed depending on the application. The thickness of the hard coat layer is preferably 0.2 to 15 μm, more preferably 0.5 to 12 μm, and particularly preferably 0.7 to 10 μm.

The strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K 5400.
Further, in the Taber test according to JIS K 5400, the smaller the wear amount of the test piece before and after the test, the better.

[Other layers]
The laminated antireflection film may further be provided with a moisture proof layer, an antistatic layer, a primer layer, an undercoat layer, a protective layer, a shield layer, and a sliding layer. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Formation of antireflection film]
[Formation of antireflection film]
Each layer of the antireflection film having a multilayer structure is formed by 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 or an extrusion coating method (described in US Pat. No. 2,681,294). , Can be formed by coating. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).
In the antireflection film of the present invention, at least the high refractive index layer and the low refractive index layer are laminated, so that bright spot defects are easily noticeable when foreign matters such as dust and dust are present. The bright spot defect in the present invention is a defect that can be seen by reflection on the coating film as described above, and can be detected by an operation such as black coating on the back surface of the antireflection film after coating. The bright spot defects that can be visually observed are generally 50 μm or more. When there are many bright spot defects, the yield at the time of manufacture falls, and a large-area antireflection film cannot be manufactured.
In the antireflection film of the present invention, the number of bright spot defects is 20 or less per square meter, preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.

In order to continuously produce the antireflection film of the present invention, a process of continuously feeding a roll-shaped support film, a process of applying and drying a coating liquid, a process of curing a coating film, and a support having a cured layer A step of winding the body film is performed.
The film support is continuously sent from the roll-shaped film support to the clean room, and the static electricity charged on the film support is removed by the electrostatic charge-off device in the clean room, and then the film support adheres on the film support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating solution is applied onto the film support in the application section installed in the clean room, and the applied film support is sent to the drying chamber and dried.
The film support having the dried coating layer is sent from the drying chamber to the radiation curing chamber, irradiated with radiation, and the monomer contained in the coating layer is polymerized and cured. Furthermore, the film support having a layer cured by radiation is sent to the thermosetting portion and heated to complete the curing, and the film support having the layer that has been completely cured is wound up into a roll shape.

The above steps may be performed every time each layer is formed, or a plurality of coating units-drying chambers-radiation curing units-thermosetting chambers may be provided to continuously form each layer.
In order to produce an antireflection film with few bright spot defects in the present invention, as described above, the degree of dispersion of the high refractive index ultrafine particles in the high refractive index layer coating is precisely controlled, and the coating liquid Examples include microfiltration operation. At the same time, each layer forming the antireflection layer is subjected to a dusting process on the film before the coating process in the coating unit and the drying process performed in the drying chamber are performed in a clean air atmosphere and before the coating is performed. It is preferable that dust is sufficiently removed. The air cleanliness of the coating process and the drying process is preferably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably, it is preferably class 1 (particles of 0.5 μm or more are 35.5 particles / (cubic meter) or less) or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

As a dust removal method used in a dust removal step as a pre-process for coating, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571, described in JP-A-10-309553 Highly clean air is blown at a high speed to peel off the deposit from the film surface, and suction is performed at a suction port adjacent to the film. Ultrasonic-vibrated compressed air described in JP-A-7-333613 is sprayed onto the deposit. And a dry dust removal method such as a method of peeling and suctioning (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with a liquid and then washed by spraying the liquid onto the rubbed surface is used. Can do. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable from the viewpoint of dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the film support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

[Formation of surface shape of antireflection film]
In the antireflection film of the present invention, it is preferable to form the specific surface irregularities of the present invention by embossing an antireflection film having a multilayer structure produced as described above.

[Embossed surface shape]
The shape of the embossed plate in the present invention is not preferred if the irregularity arrangement has a high regularity because light interference occurs. The following uneven parameters are preferable. The average irregularity period (RSm) is preferably 5 μm to 100 μm, more preferably 5 μm to 50 μm, and most preferably 5 μm to 30 μm. The arithmetic average roughness (Ra) is preferably 0.05 μm to 20 μm, more preferably 0.3 to 5 μm, and most preferably 0.3 μm to 1 μm. The inclination angle of the concavo-convex profile is preferably distributed from 0.5 degrees to 10 degrees, and more preferably from 0.5 degrees to 5 degrees.

  Average irregularity period (RSm), arithmetic average roughness (Ra), and average inclination angle are two-dimensional roughness meter SJ-400 type manufactured by Mitutoyo Corporation or “Micromap” machine manufactured by RYOKA SYSTEM Co., Ltd. Can be measured.

[Embossed version]
The embossed plate used in the present invention has the above-mentioned irregularities formed on the metal surface, and is used as a method for forming irregular irregular patterns on the metal surface by shot processing, electric discharge machining, etching processing, laser processing, etc. it can. Of these, shot machining and electric discharge machining are preferable in that an irregular irregular pattern can be automatically formed. Even in etching and laser processing, random patterning is possible by a resist pattern creation method or a laser beam operation method.

The metal preferably used as the embossed plate may be any iron alloy containing carbon and chromium having a Vickers hardness of 500 or more, and examples thereof include high carbon steel, chromium-molybdenum steel, and stainless steel.
As a method for increasing the surface hardness, a nitriding treatment in which an iron alloy typified by stainless steel is reacted under a high temperature by introducing a nitrogen compound such as ammonia under vacuum is widely known. In addition, plating treatment represented by hard chrome plating is also effective. Nickel plating in which phosphorus or phosphorus and boron is introduced (Kanizen plating, Kaniboro plating of Nippon Kanisen Co., Ltd.), TiC, WC, SiC, B ₄ C, Chromium and nickel plating with eutectoid ceramic particles such as TiB ₂ can also be used effectively.
The coating thickness of these hard layers is preferably 5 μm to 300 μm, more preferably 20 μm to 100 μm.

The shot processing can be carried out by spraying particles such as glass, zirconia, tungsten, etc., having a diameter of 50 μm or less and a bulk specific gravity of 1.5 kg / L or more at a pressure of 1 kg / cm ² or more. The average irregularity period can be controlled by particle diameter, and the average roughness can be controlled by particle bulk density, spraying pressure, and shot time.

As the surface processing method of the embossed plate used in the present invention, the electric discharge processing method is most preferable because the surface unevenness can be precisely controlled.
When forming irregularities on the plate surface by electrical discharge machining, important parameters of the plate material are hardness, melting point, and thermal conductivity coefficient. These affect the shape and speed at which the surface is carved by the heat generated by the discharge. That is, when the hardness and melting point are different, the amount and shape of the carved by melting differ even if the same amount of heat is generated by the discharge. In addition, the thermal conductivity coefficient affects the speed at which the locally heated heat is diffused by the discharge spark, and is therefore reflected in the uneven period and depth.
When the above-mentioned various surface hardening treatments are performed, the plate obtained by the same electric discharge machining has not only the arithmetic average roughness and the average uneven period, but also the composite waveform and randomness of the uneven arrangement as a result of overlapping large and small unevenness. Change. From the above, by combining the electrical discharge machining conditions and the surface material of the plate, the film after embossed transfer has excellent anti-glare and anti-reflective properties without whiteness or roughness in the drawn image. Is expressed.

  For electric discharge machining, a general-purpose sculpture electric discharge machine (for example, manufactured by Mitsubishi Electric Corporation, manufactured by Sodick Corporation) can be used. In order to obtain a fine concavo-convex shape, a model equipped with a CAD / CAM function capable of position control in units of microns is preferable.

Electrical discharge machining includes positive discharge that applies a positive potential to an electrode and negative discharge that applies a negative potential. In the case of positive discharge, the amount of heat generated on the surface of the workpiece is high, so the processing speed is fast, but uneven uneven shapes often occur. In the negative discharge, the electrode is heavily consumed, but the uneven shape on the workpiece surface becomes more uniform, which is preferable as an embossed plate used in the present invention.
The electrode is preferably made of copper having a low electrical resistance and a high thermal conductivity coefficient. In order to make each local discharge minute and reduce the discharge energy to obtain a fine uneven shape, the thickness of the plate electrode is preferably 5 mm or less, more preferably 3 mm or less, and most preferably 2 mm or less. However, if sufficient rigidity cannot be obtained with copper, it is also preferable to use brass.
Control of the discharge voltage includes a method of generating a pulse on the power supply side and a capacitor discharge using an RC circuit formed by the power supply circuit and the electric discharge machine. In the formation of the embossed plate in the present invention, the capacitor discharge is preferable because a uniform uneven shape is obtained with a larger area. A higher applied voltage is preferable because discharge can be performed in a state where the distance between the electrode and the workpiece is large, and thus heat and molten pieces are released efficiently. 100 to 500 V corresponding to the upper limit of the semiconductor power source is used.

[Embossing]
As an embossing method, any of a flat plate press, a continuous belt plate press, and a roll plate press can be adopted. Among these, continuous belt plate press and roll plate press are most preferable as continuous processing of the belt-like material, and roll plate press is most preferable from the viewpoint of the degree of freedom of press pressure and press temperature.

The material of the roll used for the roll plate press can be used without limitation, such as metal, ceramic, synthetic resin, composite of synthetic resin and metal or glass, as long as it has rigidity that can withstand the pressing pressure. From this viewpoint, the plate surface preferably has a Vickers hardness of 500 or more, and practically 500 to 1000.
As a method for increasing the surface hardness, a nitriding treatment in which an iron alloy typified by stainless steel is reacted under a high temperature by introducing a nitrogen compound such as ammonia under vacuum is widely known. In addition, plating treatment represented by hard chrome plating is also effective, such as nickel plating (Kanizen's Kanigen plating, crab boron plating) or TiC, WC, SiC, B ₄ C, TiB ₂ in which phosphorus or phosphorus and boron are introduced. Chromium and nickel plating with eutectoid ceramic particles such as can also be used effectively.
The coating thickness of these hard layers is preferably 5 μm to 300 μm, more preferably 20 μm to 100 μm.
The embossing operation according to the present invention is a method of pattern transfer while pressing a heated plate called a “hot emboss” on a resin film, and is a plate having a temperature not higher than that of a preheated resin film. This is different from “cold embossing” in which the pattern is transferred by pressing. The means for heating the plate is not limited as long as the plate surface can be heated to 80 ° C. or higher and the temperature distribution on the plate surface is small. However, heating wire heater, electromagnetic induction heating, infrared heater, the inside of the plate has a hollow structure, hot water, oil, steam, etc. A jacket heater that circulates the heat medium can be preferably used. Of these, heating wire heaters, electromagnetic induction heating (for example, heat rolls manufactured by Tokuden Co., Ltd.), and jacket type heaters are preferable as methods that can be used for roll plate presses. Electromagnetic induction heating and jacketing are preferable because the temperature distribution on the plate surface is small. A type heater is more preferable.

There is no particular limitation on the diameter of the embossing roll used in the roll plate press. Although φ50 mm to φ3000 mm that can be manufactured as a roll can be applied, it is substantially φ50 mm to φ2000 mm due to the fact that it can be accurately processed to a straightness of several μm / m width and the mass is enlarged.
As long as the material of the backup roll installed opposite to the embossing roll has rigidity enough to withstand the pressing pressure, it can be used without limitation, such as metal, ceramic, synthetic resin, synthetic resin and metal, and glass composite. From the viewpoint of durability, it is preferable that the steel is coated with an iron alloy containing carbon and chromium having a Vickers hardness of 500 or more. The coating thickness is 10 μm to 50 mm, preferably 50 μm to 50 mm. Hard chrome plating having high Vickers hardness, excellent corrosion resistance, and easy surface polishing can also be preferably used. The surface roughness of the backup roll is preferably as small as possible in order to keep the back surface of the resin film smooth. Specifically, the arithmetic average roughness (Ra) obtained as a mirror finish of the metal surface is preferably 0.01 μm or less.

  There is no particular limitation on the diameter of the backup roll used in the roll plate press. Although φ50 mm to φ3000 mm that can be manufactured as a roll can be applied, it is practically φ50 mm to φ2000 mm due to the fact that it can be accurately processed to a straightness of several μm / m width and the mass is enlarged.

  The backup roll may be cooled. A jacket structure in which the inside of the roll has a hollow structure and a coolant such as cold water is circulated and cold air blowing can be preferably used. The advantage of cooling the backup roll is that, when the resin film contains an additive such as a plasticizer, crying and evaporation from the inside of the film can be reduced, and the resin film is brought into contact with the backup roll immediately after passing through the press section. As a result, the transfer pattern can be fixed by cooling immediately.

The pressing conditions are the pressure applied to the film surface, the surface temperature of the plate, and the pressing time. The pressing pressure is preferably 1 × 10 ⁵ Pa or more, more preferably 1 × 10 ^{5 to} 100 × 10 ⁵ Pa, and most preferably 5 × 10 ^{5 to} 50 × 10 ⁵ Pa. In the diameter range of the roll plate and the backup roll used in the present invention, the linear pressure corresponding to these pressure ranges is preferably 1000 N / cm or more, more preferably 1000 to 50000 N / cm, and most preferably 5000 to 30000 N / cm. .
The surface temperature of the plate in hot embossing is preferably 80 ° C. or higher. More preferably, it is 80 to 220 ° C, and most preferably 100 to 200 ° C.
The press time can be strictly defined in the flat plate press and the continuous belt press. The pressing time is preferably 1 second to 600 seconds, more preferably 10 seconds to 600 seconds, and most preferably 10 seconds to 300 seconds. In the case of a roll press, the effective press time is determined by the contact length between the embossed loose and the nip portion of the backup roll by the press pressure and the transport speed of the resin film. Since the contact length of the nip portion varies depending on the physical properties (diameter, elastic modulus, etc.) and pressing conditions (pressure, temperature) of the embossing roll and the backup roll, it cannot be specified unconditionally. The conveyance speed is preferably 1 to 50 m / min, more preferably 1 to 30 m / min, and most preferably 5 to 30 m / min.

  In the case of a roll plate press, when a pressing pressure is applied through a rotating shaft, the roll is bent and a uniform pressure does not act in the width direction. In order to reduce this, a crown roll method in which a deflection amount corresponding to the press pressure is predicted in advance and a roll diameter is corrected, or a bend correction method in which a pressure is applied to the rotating shaft opposite to the press direction can be applied. The center diameter in the width direction of the roll is preferably increased to a taper shape of 5 μm to 50 μm per 1 m of roll width, more preferably increased to a taper shape of 5 μm to 30 μm, and most preferably increased to a taper shape of 10 μm to 30 μm. The bend correction pressure varies depending on the physical properties (diameter, elastic modulus, etc.) of the embossing roll and the backup roll and pressing conditions (pressure, temperature), but preferably reacts at 3 to 20% of the pressing pressure. It is more preferable that the reaction occurs at 3% to 15%, and it is most preferable that the reaction occurs at 5% to 10% of the press pressure.

In the embossing of the optical film incorporated in the image display device according to the present invention, it is necessary to strictly control the dust. The process from sending out the film coated with the antireflection layer to embossing and winding it again is performed in a clean room environment of class 100 or higher, preferably class 10 or higher.
It is also preferable to send out a film coated with an antireflection layer and use a dust remover before the embossing process. A known dry or wet dust removing method can be used. Specifically, the same as described in the preparation of the antireflection film can be given.

Thus preferably 10μm or more foreign substances is less than 10 U / m ² on the film surface after dust removal treatment in a clean room, more preferably less than 1 U / m ^2, 0.1 U / m ² Most preferably, it is less than.

It is also preferable to provide a step of preheating the transparent resin film before the embossing step. When a room temperature film is introduced into an embossed plate of 80 ° C. or higher in the present invention, rapid softening and volume change, and further, frictional resistance between the film and the plate may be entangled to generate wrinkles. In order to avoid this, a method of gradually heating to the embossing temperature can be adopted.
In the step of heating the polymer film to room temperature or higher in advance, collision of hot air, contact heat transfer using a heating roll, induction heating using microwaves, radiant heat heating using an infrared heater, or the like can be preferably used. In particular, contact heat transfer using a heating roll is preferable in terms of high heat transfer efficiency and a small installation area, and fast rise in film temperature at the start of conveyance. A general double jacket roll or electromagnetic induction roll (manufactured by Tokuden) can be used. The film temperature after heating is preferably 25 to 220 ° C, more preferably 25 to 150 ° C, and most preferably 40 to 100 ° C. Moreover, in order to control to the said temperature range, you may perform feedback control with respect to a heating means.

It is also preferable to provide a step of cooling the film after the embossing step. The film after hot embossing is in a heated state, and the surface shape transferred by embossing may be deformed or relaxed if it receives contact with the tension or roller associated with conveyance without sufficiently reducing the compression elastic modulus due to temperature drop. It often happens. In order to avoid this, a method of forcibly cooling the film immediately after hot embossing can be adopted.
As means for lowering the temperature of the polymer film, collision of cold air with the polymer film or contact heat transfer with a cooling roll can be preferably employed. The film temperature after cooling is preferably 80 ° C. or lower, more preferably 10 ° C. to 80 ° C., and most preferably 15 ° C. to 70 ° C. The film temperature is preferably measured with a non-contact infrared thermometer. It is also possible to adjust the cooling temperature by performing feedback control on the cooling means.

  In roll embossing for continuous conveyance, a drying step can be performed before the winding step. Before the transparent resin film is wound into a roll, it may be dried by heating in order to adjust the water content to a preferable level. Conversely, the humidity can be adjusted with a wind having a set humidity.

[Characteristics of antireflection film]
The lower the reflectance of the antireflection film, the better. Specifically, the average reflectance in the wavelength region of 450 to 650 nm is preferably 2% or less, more preferably 1% or less, and most preferably 0.7% or less. The haze of the antireflection film is preferably 40% or less. Furthermore, 0.5 to 30% is preferable, and 1 to 20% is particularly preferable.

In the antireflection film of the present invention, the number of bright spot defects is 20 or less per square meter, preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.
The strength of the antireflection film is preferably as low as possible in the Taber abrasion test based on JISK-6902.
Further, the pencil hardness with a 1 kg load is preferably H or more, more preferably 2H or more, and most preferably 3H or more.

[Weather resistance of antireflection film]
JIS K 5600-7-7 of the antireflective film of the present invention comprising a high refractive index layer containing an inorganic compound selected from the above-mentioned “specific oxide” and “specific double oxide” as high refractive index particles. : The weather resistance by the accelerated weather resistance test based on 1999 is demonstrated. Specifically, the performance after 150 hours of treatment is excellent as shown below.
That is, the haze after the accelerated weather resistance test is such that the increase is within 10% and the maximum haze does not exceed 3% with respect to the haze before the weather resistance test. Further, the increase in the amount of wear in the Taber abrasion test based on JIS K 6902 was within 10%.
Furthermore, the number of luminance defects having a size of 50 μm or more is 20 or less, preferably 10 or less per square meter.

[Protective film for polarizing plate]
When the antireflection film of the present invention is used as a protective film for a polarizing film (protective film for polarizing plate), the surface of the transparent support opposite to the side having the high refractive index layer, that is, the surface to be bonded to the polarizing film It is preferable that the contact angle with respect to water be 40 ° or less to ensure sufficient adhesion to the polarizing film.
As the transparent support, it is particularly preferable to use a cellulose acylate film.
The following two methods are mentioned as a method of producing the protective film for polarizing plates in this invention.
(1) A method of coating each of the above layers (eg, hard coat layer, high refractive index layer, low refractive index layer, etc.) on one surface of a saponified transparent support.
(2) A method in which the above layers (eg, hard coat layer, high refractive index layer, low refractive index layer, etc.) are coated on one surface of the transparent support, and then the side to be bonded to the polarizing film is saponified.

  Furthermore, a saponification treatment solution can be applied to the surface of the transparent support on the side to be bonded to the polarizing film of the antireflection film, and the side to be bonded to the polarizing film can be saponified.

  Protective films for polarizing plates have optical performance (antireflection performance, antiglare performance, etc.), physical performance (such as scratch resistance), chemical resistance, antifouling performance (contamination resistance, etc.), weather resistance (moisture and heat resistance, light resistance) In terms of properties, it is preferable to satisfy the performance described in the antireflection film of the present invention.

[surface treatment]
The hydrophilic treatment of the surface of the transparent support can be performed by a known method. Examples thereof include a method of modifying the film surface by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali treatment, and the like. Details of these are described in detail on pages 30 to 32 of the aforementioned public technical number 2001-1745. Among these, an alkali saponification treatment is particularly preferable, and it is extremely effective as a surface treatment of a cellulose acylate film.
It is preferable to saponify the transparent support or the antireflection film in an alkali solution by immersing it for an appropriate time or by applying an alkali solution. Examples of the alkaline solution and treatment include those described in JP-A No. 2002-82226 and WO 02/46809. The saponification treatment is preferably carried out so that the contact angle with water on the film surface is 45 ° or less.
The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.

[Polarizer]
The preferable polarizing plate of this invention has the antireflection film of this invention in 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 water contact angle of 40 ° or less on the surface of the transparent support opposite to the side having the high refractive index layer, that is, the surface to be bonded to the polarizing film. It is preferable.
By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function can be produced, and the cost can be greatly reduced and the display device can be thinned.
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 film]
The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
As the optical compensation film, a known film can be used. However, in terms of widening the viewing angle, an optical compensation layer made of a compound having a discotic structural unit described in JP-A-2001-100042 is provided. In addition, an optical compensation film characterized in that an average angle formed by the discotic compound and the support varies in the depth direction of the layer is preferable.
The angle has fluctuation in each part, but the average angle is preferably increased as the distance from the support surface side of the optically anisotropic layer increases.
When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

[Image display device]
The antireflection film can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). The antireflection film adheres the transparent support side of the antireflection film to the image display surface of the image display device.

The antireflection film and polarizing plate used in the present invention are twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell ( It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device in a mode such as OCB).
When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained.
Further, by combining with a λ / 4 plate, it can be used to reduce the reflected light from the surface and inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

[Example 1-1]
(Preparation of coating liquid for hard coat layer (HCL-1))
1296 g of tetramethylolmethane tetraacrylate and 809 g of a methyl ethyl ketone 53.2 mass% solution of polyglycidyl methacrylate (mass average molecular weight: 1.5 × 10 ⁴ ) were dissolved in a mixed solution of 943 g of methyl ethyl ketone and 880 g of cyclohexanone, and then Irgacure with stirring. 184, 48.1 g and 24 g of di (t-butylphenyl) iodonium hexafluorophosphate (Di (t-butylphenyl) iodonium hexafluorophosphate) were added and stirred for 10 minutes. The mixture was filtered through a polypropylene filter having a pore size of 0.5 μm to prepare a composition for hard coat layer (HCL-1).

(Preparation of oxide fine particle dispersion (PL-1))
100 g of titanium dioxide fine particles surface-treated with aluminum oxide and stearic acid (TTO-55B: titanium oxide content 79-85%: manufactured by Ishihara Sangyo Co., Ltd.), 22 g of dispersant (D-1) having the following structure, and 285 g of cyclohexanone And zirconia beads having a particle diameter of 0.1 mm (YTZ ball, manufactured by Nikkato Co., Ltd.) and dispersed by a dyno mill. The dispersion temperature was 35 to 40 ° C. for 8 hours. The beads were separated with a 200 mesh nylon cloth to prepare an oxide fine particle dispersion (PL-1).
The dispersion particle diameter of the obtained dispersion was a particle having an average particle diameter of 75 nm with good monodispersity as measured by a transmission electron microscope.
Moreover, as a result of measuring the particle size distribution of the dispersion (Laser analysis / scattered particle size distribution measuring apparatus LA-920, manufactured by HORIBA, Ltd.), the particle size of 300 nm or more was 0%.

(Preparation of Medium Refractive Index Layer Coating Solution (ML-1))
To 88.9 g of the above oxide fine particle dispersion (PL-1), a mixed solvent of 452.4 g of methyl ethyl ketone and 1753.7 g of cyclohexanone was added with stirring. Next, DPHA (polyfunctional acrylate monomer, Nippon Kayaku Co., Ltd.), 58.4 g, Irgacure 907, 3.1 g, photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 1.1 g, methyl ethyl ketone A mixed solvent of 30.0 g and 116.1 g of cyclohexanone was added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (ML-1) for a medium refractive index layer.

(Preparation of coating solution for high refractive index layer (HL-1))
A mixed solvent of 198.1 g of methyl ethyl ketone and 792.4 g of cyclohexanone was added to 400 g of the above oxide fine particle dispersion (PL-1) with stirring. Next, a mixed solution of DPHA, 37.5 g, Irgacure 907, 2.0 g, photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 0.5 g, methyl ethyl ketone 18.7 g, and cyclohexanone 74.6 g is added. Then, ultrasonic dispersion was performed for 10 minutes. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (HL-1) for a high refractive index layer.

(Preparation of coating solution for low refractive index layer (LL-1))
A heat-crosslinkable fluorine-containing polymer having a refractive index of 1.42 (OPSTAR JN7228, solid content concentration of 6% by mass, manufactured by JSR Corporation) is solvent-substituted, and the heat-crosslinkable fluoropolymer has a solid content concentration of 10% by mass of methyl isobutyl. A ketone solution was obtained. In the above heat-crosslinkable fluoropolymer solution 56.0 g, silica fine particle methyl ethyl ketone dispersion (MEK-ST, solid content concentration 30 mass%, manufactured by Nissan Chemical Co., Ltd.) 8.0 g, the following silane compound 1.75 g, and 73.0 g of methyl isobutyl ketone and 33.0 g of cyclohexanone were added and stirred. A low refractive index layer coating solution (LL-1) was prepared by filtration through a polypropylene filter having a pore size of 0.4 μm.

(Preparation of silane compound)
A reactor equipped with a stirrer and a reflux condenser, 161 g of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 123 g of oxalic acid, and 415 g of ethanol were added and mixed. After making it react for time, it cooled to room temperature and obtained the transparent silane compound as a curable composition.

(Preparation of antireflection film)
With an ultrasonic dust remover, the surface of the application side of a triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) with a film thickness of 80 μm is subjected to charge removal treatment, and then the hard coat layer coating liquid (HCL-1) is applied. It apply | coated using the gravure coater. After drying at 80 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^{2. The} coating layer was cured by irradiating with an irradiation amount of 500 mJ / cm ² to form a hard coat layer having a thickness of 8 μm. On the hard coat layer, a medium refractive index layer coating solution (ML-1) was applied using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ^2. An ultraviolet ray with an irradiation amount of 550 mJ / cm ² was irradiated to cure the coating layer to form a medium refractive index layer (refractive index 1.63, film thickness 70 nm).
On the middle refractive index layer, a coating solution for high refractive index layer (HL-1) was applied using a gravure coater. After drying at 100 ° C., using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol% or less, an illuminance of 550 mW / cm ^2, an irradiation dose of 550 mJ / cm ^2, to form a high refractive index layer (refractive index 1.90, film thickness 107 nm).
On the high refractive index layer, the low refractive index layer coating solution (LL-1) was applied using a gravure coater. After drying at 80 ° C. and using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less, the illuminance is 550 mW / cm ^2, an irradiation dose of 600 mJ / cm ^2, and heated at 140 ° C. 20 minutes to form a low refractive index layer (refractive index 1.43, film thickness 86 nm). In this way, an antireflection film was produced.
In the above, the coating and drying steps are performed in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 is just before the coating. High air was blown at a high speed to separate the deposits from the film surface, and coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

(Formation of surface irregularities)
An embossing calendar machine (manufactured by Yuri Roll Co., Ltd.) is equipped with an embossing plate (H-1) with the following contents, under conditions of a linear pressure of 500 kgf / cm, a preheating temperature of 90 ° C., and an embossing roll temperature of 160 ° C. Then, a press operation was performed on one side of the antireflection film to produce an antiglare film.
The backup roll was carried out at room temperature and a conveyance speed of 1 m / min.
[Embossed version (H-1)]
Heat-cured S45C cored metal roll with a diameter of 20 cm and a width of 12 cm is added with 3 g / L of graphite particles with an average particle size of 1.5 μm in the kerosene processing liquid, and the electric discharge machine EA8 type manufactured by Mitsubishi Electric Corporation is used. Then, a negative capacitor discharge machining was performed with a copper electrode having a thickness of 0.5 mm, and the embossed plate (H-1) shown in Table 1 having an arithmetic average roughness (Ra) of 0.3 μm and an average unevenness period (RSm) of 25 μm was obtained. Obtained.

(Evaluation of surface shape)
The shape of each obtained film surface is based on JIS B 0601-1994, and the arithmetic average roughness (Ra), ten-point average roughness (Rz), maximum height (Ry), and surface unevenness of the surface unevenness. The average interval (Sm) was evaluated with a two-dimensional roughness meter SJ-400 manufactured by Mitutoyo Corporation. However, Ra, Rz, and Ry were measured with a length of 4 μm, and Sm with a measured length of 20 μm. The uniformity of the surface irregularities was calculated by the ratio (Ra / Rz). The inclination angle distribution of the concavo-convex profile is as follows: Surface Explorer SX-520 system (manufactured by Ryoka System Co., Ltd., interference microscope (Nikon MM-40 / 60 series) Objective lens: Two-beam interference objective lens, using halogen lamp, CCD camera: 640 × 480)), and measured using the micromap software. Table 2 shows the physical properties related to the surface shape.

[Example 1-2]
Except for changing the embossed plate to H-2 described in Table 1 below, embossing was performed in the same manner as in Example 1 to produce an antiglare film. Table 2 shows the physical properties related to the surface shape.
[Example 1-3]
Except that the embossed plate was changed to H-3 described in Table 1 below, embossing was performed in the same manner as in Example 1 to produce an antiglare film. Table 2 shows the physical properties related to the surface shape.

[Comparative Example 1-1]
Except that the embossed plate was changed to H-4 described in Table 1 below, embossing was performed in the same manner as in Example 1 to produce an antiglare film. Table 2 shows the physical properties related to the surface shape.
[Comparative Example 1-2]
Except that the embossed plate was changed to H-5 described in Table 1 below, embossing was performed in the same manner as in Example 1 to produce an antiglare film. Table 2 shows the physical properties related to the surface shape.
[Comparative Example 1-3]
Except having changed the embossing plate into H-6 described in Table 1 below, embossing was performed in the same manner as in Example 1 to produce an antiglare film. Table 2 shows the physical properties related to the surface shape.

[Evaluation of anti-glare film performance]
The antiglare-stopping film was evaluated by the following method, and the results are shown in Table 3.
(Evaluation of haze)
The haze of the high refractive index layer film was evaluated using a haze meter (NHD-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.).
(Evaluation of reflectance)
Using a spectrophotometer (V-550, ARV-474, manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in the wavelength region of 380 to 780 nm. The average reflectance in the wavelength range of 450 to 650 nm was determined.
(Anti-glare evaluation)
A bare fluorescent lamp (8000 cd / m 2) without a louver was projected on the produced antiglare film, and the degree of blur of the reflected image was evaluated according to the following criteria.
◎: The outline of the fluorescent lamp is not understood at all. ○: The outline of the fluorescent lamp is slightly known. △: The fluorescent lamp is blurred, but the outline can be identified. ×: The fluorescent lamp is hardly blurred (evaluation of glare)
The produced antiglare film is placed on a cell imitated by 133 ppi (133 pixels / inch) at a distance of 1 mm, and the degree of glare (brightness variation due to surface unevenness of the antiglare film) is as follows. Visual evaluation was performed based on the standard.
◎: Very little glare seen ○: Slight glare △: Slightly glaring ×: Glare can be clearly recognized

(Evaluation of bright spot foreign matter)
The back surface of the film after all layers were applied was black-coated with magic ink or the like, and the number of bright spot defects on the coating film was visually determined. The size of the bright spot defect that can be visually observed is 50 μm or more. Bright spot defects were counted by number per square meter.
(Evaluation of adhesion)
Each antireflection film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. On the surface of each antireflection film having the antireflection layer, 11 squares and 11 horizontal cuts are made in a grid pattern with a cutter knife to make a total of 100 square squares, made by Nitto Denko Corporation. The adhesion test on the polyester adhesive tape (NO.31B) was repeated 3 times at the same place. The presence or absence of peeling was visually observed, and the following four-stage evaluation was performed.
A: No peeling at 100 mm was observed. ○: No peeling was observed at 100 mm within 2 mm. Δ: 10-100 mm was observed at 100 mm. Thing that has been peeled off at 100 mm exceeds 10 mm

(Evaluation of scratch resistance)
In the antireflection film, a load of 200 g / cm ² was applied to # 0000 still wool, and the state of scratches after 10 reciprocations was observed and evaluated according to the following criteria.
◎: Scratches are not found at all ○: Scratches are slightly visible but not noticeable △: Scratches are clearly visible ×: Scratches are clearly visible (evaluation of pencil hardness)
The high refractive index layer film was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%, and then visually evaluated using a 3H test pencil specified by JIS S6006 under a load of 1 kg with the following contents. .
○: No scratches are observed in the evaluation of n = 5 Δ: One or two scratches in the evaluation of n = 5 ×: Three or more scratches in the evaluation of n = 5 (texture)
A polarizing film was bonded to both sides of a 10 cm square glass plate in a crossed Nicol arrangement, and an antiglare film was further bonded to one side with the embossed surface facing up. The embossed surface was observed at a position 2 m away from a 100 W white light bulb, and the following rankings were performed on the texture.
Rank 5: The reflected light intensity is visually uniform and moist texture Rank 1: The intensity of the reflected light is visually dispersed, and the extremes of ranks 5 and 1 are determined in advance. The relative rank was evaluated.

The variation widths of the film thicknesses of the antireflection layers of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3 were within ± 2.5% for all the samples.
In Examples 1-1 to 1-3, all of optical properties, film adhesion, and strength were good. Furthermore, the antiglare property, glare and texture were good. On the other hand, Comparative Examples 1-1 to 1-3 could not improve both the antiglare property and the glare.
As described above, the antireflection film of the present invention exhibited good performance.

Example 2-1 and Example 2-2
(Preparation of hard coat layer coating solution (HCL-2))
After dissolving 1296 g of trimethylolpropane triacrylate and 809 g of methyl ethyl ketone 53.2 mass% solution of a polymerizable compound having the following structure in a mixed solution of 943 g of methyl ethyl ketone and 880 g of cyclohexanone, Irgacure 184, 48.1 g, and 24 g of the structure initiator (I-2) was added and stirred for 10 minutes. The mixture was filtered through a polypropylene filter having a pore size of 0.5 μm to prepare a composition for hard coat layer (HCL-2).

(Preparation of hard coat layer coating solution (HCL-3))
250 g of urethane acrylate oligomer UV-6300B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), polymerizable compound having the following structure, 75 g, Irgacure 907, 7.5 g, Kayacure DETX, 5.0 g, and initiator having the following structure (I- 3) 3 g was dissolved in a mixed solution of 192.5 g of methyl ethyl ketone and 128.3 g of cyclohexanone. After the mixture was stirred, it was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution (HCL-3).

(Preparation of hard coat layer coating solution (HCL-4))
436.9 g of polyfunctional acrylate monomer (DPHA, Nippon Kayaku Co., Ltd.) and 13.1 g of Irgacure 907 (Nihon Kayaku Co., Ltd.) were dissolved in a mixed solution of 330 g of methyl ethyl ketone and 220 g of cyclohexanone. After the mixture was stirred, it was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution (HCL-4).

(Preparation of oxide fine particle dispersion (PL-2))
Production of titanium dioxide particles: Based on the example of JP-A-5-330825 (paragraph number [0014], lines 3 to 17), except that iron (Fe) was changed to cobalt (III) chloride Similarly, cobalt-containing titanium dioxide fine particles (P-2) in which cobalt was doped into titanium dioxide particles were prepared. The amount of cobalt doped was 98.5 / 1.5 in terms of Ti / Co (mass ratio).
The produced titanium dioxide particles had a rutile-type crystal structure, and the average particle size of primary particles was 40 nm, the specific surface area was 38 nm, and the specific surface area was 44 m ² / g.
Preparation of oxide fine particle dispersion: 100 g of the above oxide fine particles (P-2), 20 g of polymer dispersant (D-2) having the following structure, and 360 g of cyclohexanone are added together with zirconia beads having a particle diameter of 0.1 mm. Dispersed by dynomill. The dispersion temperature was 35 to 40 ° C. for 5 hours. An oxide fine particle dispersion (PL-2) having an average diameter of 55 nm with a particle diameter of 300 nm or more being 0% was prepared.

(Preparation of oxide fine particle dispersion (PL-3))
Production of titanium dioxide particles: iron (Fe) was changed to zirconyl nitrate (ZrO (NO ₃ ) ₂ ) based on the example of JP-A-5-330825 (paragraph number [0014], lines 3 to 17). In the same manner, zirconium-containing titanium dioxide fine particles (P-3) in which zirconium was doped into titanium dioxide particles were produced. The doped amount of zirconium was 97.5 / 2.5 in terms of Ti / Zr (mass ratio).
The produced titanium dioxide particles had a rutile crystal structure, the average primary particle size was 40 nm, and the specific surface area was 39 m ² / g.
Preparation of oxide fine particle dispersion: To 100 g of the above oxide fine particles (P-3), 18 g of the following dispersant (D-3) and 303 g of cyclohexanone are added, and dynomill is used using zirconia beads having a particle diameter of 0.1 mm. Dispersed by. The dispersion temperature was 40 to 45 ° C. and the dispersion time was 6 hours to prepare an oxide fine particle dispersion (PL-3). The average diameter of the dispersed particles of the obtained dispersion was 55 nm, and the particle size of 300 nm or more was 0%.

(Preparation of oxide fine particle dispersion (PL-4))
Preparation of titanium dioxide particles: Cobalt doped with cobalt (III) chloride and aluminum chloride and aluminum-containing titanium dioxide based on the example of JP-A-5-330825 (paragraph [0014], lines 3 to 17) Fine particles (P-4) were produced. The doping amount of cobalt and aluminum was Ti / Co / Al (mass ratio), and was 97.5 / 1.25 / 1.25.
The produced titanium dioxide particles had a rutile crystal structure, the average primary particle size was 40 nm, and the specific surface area was 39 m ² / g.
Preparation of oxide fine particle dispersion: Dinomill using zirconia beads having a particle diameter of 0.1 mm by adding 22 g of the following dispersant (D-4) and 366 g of cyclohexanone to 100 g of the oxide fine particles (P-4). Dispersed by. The dispersion temperature was 40 to 45 ° C. and the dispersion time was 6 hours to prepare an oxide fine particle dispersion (PL-4). The average diameter of the dispersed particles of the obtained dispersion was 55 nm, and the particle size of 300 nm or more was 0%.

(Preparation of oxide fine particle dispersion (PL-5))
Preparation of titanium dioxide particles: Based on an example of JP-A-5-330825 (paragraph number [0014], lines 3 to 17), titanium dioxide particles are doped with cobalt to produce aluminum hydroxide and zirconium hydroxide. Titanium dioxide fine particles (P-5) that had been surface-treated using the above were prepared.
The amount of cobalt doped was 98.5 / 1.5 in terms of Ti / Co (mass ratio).
The produced titanium dioxide particles had a rutile-type crystal structure, and the average particle size of primary particles was 40 nm, the specific surface area was 38 nm, and the specific surface area was 44 m ² / g.
Preparation of oxide fine particle dispersion: Similar to PL-2, except that the oxide fine particle P-2 is changed to P-5, an oxide fine particle dispersion (PL) having an average particle size of 300 nm or more and an average diameter of 55 nm (PL -5) was prepared.

(Preparation of oxide fine particle dispersion (PL-6))
A mixture of 92 g of composite oxide [Ti / Ti + Ta = 0.8 molar ratio] fine particles (P-6) composed of Ti and Ta doped with cobalt ions (doping amount 4 mass%), 31 g of silyl compound having the following structure and 337 g of cyclohexano Was finely dispersed in a sand mill (1/4 G sand mill) for 6 hours. The media used was 1400 g of 0.2 mmφ zirconia beads. 1N hydrochloric acid 0.1g was added here, and it heated up at 80 degreeC by nitrogen atmosphere, and also stirred for 4 hours. The obtained surface-treated doped composite oxide fine particles (PL-6) had a particle size of 60 nm, and the particle size of 300 nm or more was 0%.

(Preparation of oxide fine particle dispersion (PL-7))
Compound oxide composed of titanium, bismuth and zirconium [Bi / Bi + Ti + Zr = 0.08 molar ratio, Zr / Bi + Ti + Zr = 0.05 molar ratio] (P-7) 100 g, the following dispersing agent (D-7) 25 g, and 375 g of cyclohexanone was added and dispersed by dynomill using zirconia beads having a particle diameter of 0.1 mm. The dispersion temperature was 40 to 45 ° C. and the dispersion time was 6 hours to prepare a composite oxide fine particle dispersion (PL-7). The average diameter of the dispersed particles of the obtained dispersion was 75 nm, and the particle size of 300 nm or more was 0%.

(Preparation of coating solution for low refractive index layer (LL-2))
In 193 g of cyclohexanone and 623 g of methyl ethyl ketone, 1.7 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 1.7 g of reactive silicone (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved. Further, 182 g of a 18.4 mass percent methyl isobutyl ketone solution of the following fluorine-containing copolymer was added, and after stirring, filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm to apply for a low refractive index layer. A liquid (LL-2) was prepared.

(Preparation of coating solution for low refractive index layer (LL-3))
To 193 g of cyclohexanone and 623 g of methyl ethyl ketone, 1.7 g of a polyfunctional acrylate monomer (DPHA, manufactured by Nippon Kayaku Co., Ltd.), 1.7 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and reactive silicone (X-22) -164C, 1.7% from Shin-Etsu Chemical Co., Ltd.) was dissolved. Further, 182 g of a 18.4 mass percent methyl isobutyl ketone solution of a fluorinated copolymer (Chemical Formula 14) was added, and after stirring, the mixture was filtered with a polypropylene filter (PPE-03) having a pore size of 3 μm to obtain a low refractive index layer. Coating solution (LL-2) was prepared.

(Preparation of coating solution for low refractive index layer (LL-4))
[Preparation of Sol Solution a]
A stirrer, a reactor equipped with a reflux condenser, 119 parts of methyl ethyl ketone, 101 parts of acryloyloxypropyltrimethoxysilane (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

[Preparation of hollow silica dispersion a]
Hollow silica fine particle sol (Isopropyl alcohol silica sol, manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20 mass%, silica particle refractive index 1.31, Preparation Example 4 of JP-A-2002-79616 500 parts by weight, 30 parts of acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 parts of diisopropoxyaluminum ethyl acetate, and after mixing, 9 parts 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. While adding cyclohexanone to 500 g of this dispersion so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. No foreign matter was generated in the dispersion, and the viscosity when the solid content concentration was adjusted to 20% by mass with cyclohexanone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion A-1 was analyzed by gas chromatography, it was 1.5%.

[Preparation of LL-4]
In 3.3 g of cyclohexanone and 593.9 g of methyl ethyl ketone, 933.3 g of JTA-113 (solid content 6%, manufactured by JSR Corporation), which is a thermally crosslinkable fluorine-containing silicone polymer composition solution, was dissolved. Furthermore, after adding the hollow silica dispersion liquid a195g and the sol liquid a12.7g in this order and stirring, the mixture is filtered through a polypropylene filter (PPE-03) having a pore size of 3 μm, and the coating liquid for low refractive index layer (LL-4) Was prepared.

[Example 2-1]
(Preparation of medium refractive index layer coating solution (ML-2))
To 88.9 g of the above oxide fine particle dispersion (PL-2), polyfunctional acrylate DPHA, 58.4 g, Irgacure 907, 3.1 g, Kayacure DETX, 1.1 g, methyl ethyl ketone 482.4 g, and cyclohexanone 1869. 8 g was added and stirred. After ultrasonic dispersion for 10 minutes, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a medium refractive index layer (ML-2).
(Preparation of coating solution for high refractive index layer (HL-2))
To 500 g of the above oxide fine particle dispersion (PL-2), a mixed solvent of 204.4 g of methyl ethyl ketone and 817.6 g of cyclohexanone was added with stirring. Next, a mixed solution of DPHA, 37.5 g, Irgacure 907, 2.5 g, photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 0.8 g, methyl ethyl ketone 19 g, and cyclohexanone 76.2 g was added. After stirring, ultrasonic dispersion was performed for 10 minutes. The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (HL-2) for a high refractive index layer.

(Preparation of antireflection film)
On the triacetyl cellulose film (TD-80UF), a hard coat layer coating solution (HCL-2) was applied using a gravure coater. After drying at 100 ° C., it was dried at 120 ° C. Next, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol% or less, an illuminance of 400 mW / cm ² and an irradiation amount of 500 mJ The coating layer was cured by irradiating UV light of / cm ² to form a hard coat layer having a thickness of 8 μm.
On the hard coat layer, an intermediate refractive index layer coating solution (ML-2) was applied using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ^2. An ultraviolet ray with an irradiation amount of 600 mJ / cm ² was irradiated to cure the coating layer to form a medium refractive index layer (refractive index 1.67, film thickness 70 nm).
On the middle refractive index layer, a high refractive index layer coating solution (HL-2) was coated using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ^2. An ultraviolet ray with an irradiation amount of 600 mJ / cm ² was irradiated to cure the coating layer to form a high refractive index layer (refractive index 1.95, film thickness 105 nm). On top of this, a coating solution for low refractive index layer (LL-2) was applied using a gravure coater. After drying at 80 ° C., an ultraviolet ray with an illuminance of 550 mW / cm ² and an irradiation amount of 600 mJ / cm ^{2 is} irradiated while purging with nitrogen so that the oxygen concentration becomes 1.0 volume% or less, and a low refractive index layer ( A refractive index of 1.43 and a film thickness of 86 nm) were formed.
(Formation of film surface shape)
The embossing calender machine (manufactured by Yuri Roll Co., Ltd.) is equipped with the embossed plate H-2 listed in Table 1, linear pressure 500Kgf / cm, preheating temperature 70 ° C, embossing roll temperature 140 ° C, backup roll normal temperature, transport A press operation was performed on one side of the antireflection film at a speed of 5 m / min to produce an antiglare film.

Example 2-2
Instead of the oxide fine particle dispersion (PL-2) for the high refractive index layer of Example 2-1, the same amount of the oxide fine particle dispersion (PL-1) used in Example 1-1 was used. Produced an antireflection film in the same manner as in Example 1. Next, this film was embossed under the same conditions as in Example 2-1, to produce an antiglare film.

(Evaluation of antireflection film)
Each sample was evaluated in the same manner as in Example 1 for each sample. As a result, both the high refractive index layer film and the antireflection film exhibited good performance equivalent to or better than that of Example 1.
Further, the following weather resistance test was conducted.
(Conditions for weather resistance test)
Using a sunshine weather meter (SX-75, manufactured by Suga Test Instruments Co., Ltd.), a weather resistance test was conducted under the conditions of sunshine carbon arc lamp, irradiance 150 W / m ² , relative humidity 50%, 100, 150 hours.
Each sample after the test was evaluated in the same manner as the evaluation method of Example 1. The results are shown in Tables 4 and 5.

  The optical properties and mechanical properties of the films of Examples 2-1 and 2-2 exhibited good performance equivalent to that of Example 1. Furthermore, when the performance after the weather resistance test of both films was examined, Example 2-2 showed a good result even for a longer time.

[Example 2-3 to Example 2-10] and Comparative Example 2
[Example 2-3 to Example 2-10]
(Preparation of Medium Refractive Index Layer Coating Liquid (ML-3-7) / High Refractive Index Layer Coating Liquid (HL-3-7))
In Example 2-1, in place of the oxide fine particle dispersion (PL-2), each oxide fine particle dispersion (PL-3 to 7) was used in the same manner as in Example 2-1, Medium refractive index layer coating solution (ML-3 to 7) / high refractive index layer coating solution (HL-3 to 7) was prepared.
As shown in Table 6, the coating liquid for hard coat layer / the coating liquid for medium refractive index layer / the coating liquid for high refractive index layer / the coating liquid for low refractive index layer was used in the same manner as in Example 2-1. An antiglare film was produced.

[Comparative Example 2]
In Example 2-3, an antiglare film was prepared in the same manner as in Example 2-3 except that the hard coat layer coating solution (HCL-4) was used instead of the hard coat layer coating solution (HCL-2). Was made.
About each sample, the surface shape and each evaluation item of the anti-glare film obtained by carrying out similarly to Example 2-1 were measured and evaluated. The results are shown in Tables 6 and 7.

  From the results shown in Table 7, all of the antiglare and antireflection films showed as good performance as that of Example 2-1. It turns out that Examples 2-5, 2-9, and 2-10 are excellent in weather resistance due to the cobalt-containing titanium dioxide particles subjected to surface treatment. On the other hand, Comparative Example 2 lacked antiglare properties and was not practically usable.

[Example 3]
(Preparation of hard coat layer dispersion (HCL-5))
Multifunctional acrylate monomer DPHA, 125 g, polymerizable compound having the following structure, 75 g, urethane acrylate oligomer UV-6300B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 125 g, Irgacure 907, 7.5 g, Kayacure DETX, 5.0 g, And 3 g of initiator (I-4) having the following structure was dissolved in a mixed solution of 192.5 g of methyl ethyl ketone and 128.3 g of cyclohexanone. After the mixture was stirred, it was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution (HCL-5).

(Preparation of oxide fine particle dispersion (PL-8))
A double oxide of Ti and Zr containing 3 mass% of Co ions by doping [Ti / Ti + Zr = 0.80 mass ratio (as oxide)] fine particles (P-8) 218 g with a dispersant (D- 8) 38.6 g, polymerization inhibitor t-butylhydroquinone 0.5 g, and methyl isobutyl ketone 702 g were added and dispersed by dynomill, and a high refractive index double oxide fine particle dispersion liquid (PL-8) having a mass average diameter of 65 nm Was prepared. The surface-treated oxide fine particles obtained had a particle size of 35 nm. Further, the particle size of 100 nm or more was 0%.

(Preparation of coating solution for high refractive index layer (HL-8))
65 g of methyl cellosolve, 20 g of tetraethoxysilane, 26 g of methyltrimethoxysilane and 54 g of 3-acryloyloxypropylmethyldimethoxysilane were added, the liquid temperature was kept at 5 to 10 ° C., and 36.8 g of 0.01 N hydrochloric acid was added while stirring. It was dripped in 3 hours. After completion of dropping, the mixture was stirred for 0.5 hours to obtain a partial hydrolyzate of the silyl compound. Next, 374.5 g of the oxide fine particle dispersion (PL-8) (concentration: 26.7% by mass), 11.8 g of pentaerythritol tetraacrylate, 2.2 g of zirconium acetylacetonate as a curing agent, and 0.5 g of oxalic acid , Irgacure 907, 0.6 g, and Kayacure-DETX 0.4 g were added to 57.1 g of the partial hydrolyzate of the above silyl compound, sufficiently stirred, and then filtered to obtain a coating solution for high refractive index layer (HL- 8) was prepared.

(Preparation of antireflection film)
A cellulose acylate film having a thickness of 80 μm was produced by the method described in Example 1 of JP-A No. 2001-151936. The above-mentioned hard coat layer coating solution was applied onto this transparent support and dried, and then the medium refractive index layer described in Example 2-1 was formed. On the middle refractive index layer, a coating solution for high refractive index layer (HL-8) was applied using a gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ^2. Irradiation with an irradiation amount of 600 mJ / cm ² , followed by heating at a temperature of 100 ° C. for 20 minutes to cure the coating layer to form a high refractive index layer (refractive index 1.94, film thickness 100 nm). The coating liquid for the low refractive index layer is coated on this using a # 3 wire bar, dried at 120 ° C. for 1 hour, and the coating liquid for the overcoat layer is coated on the antireflective film low refractive index layer. The coating was applied using a # 3 wire bar and dried at 120 ° C. for 1 hour to prepare an antireflection film.
(Formation of surface shape)
An embossing calender machine (manufactured by Yuri Roll Co., Ltd.) is equipped with an embossed plate H-3 with the following contents, linear pressure 500Kgf / cm, preheating temperature 70 ° C, embossing roll temperature 140 ° C, backup roll normal temperature, conveyance speed 3m The anti-glare film was produced by performing a pressing operation on one side of the antireflection film under the conditions of / min. The surface shape of the obtained antiglare film was as shown in Table 8. Further, the results of evaluating the performance of the film in the same manner as in Example 2 are shown in Table 9. From the results shown in Table 9, it can be seen that the same good performance as in Example 2 is exhibited.

[Example 4]
(Evaluation of image display device)
The image display device equipped with the anti-glare antireflection film of each of the present invention thus produced is excellent in anti-glare property and anti-reflective performance, and exhibits extremely excellent visibility without glare or white blurring. It was.

[Example 5]
(Preparation of protective film for polarizing plate)
In the antiglare antireflection film produced in Example 1, Examples 2-1 to 2-7, 9, 10 and Example 3, the transparent support on the side opposite to the side having the antireflection layer of the present invention was used. The surface was saponified by applying a saponification solution in which an alkaline solution composed of 57 parts by mass of potassium hydroxide, 120 parts by mass of propylene glycol, 535 parts by mass of isopropyl alcohol, and 288 parts by mass of water was kept at 40 ° C.
The alkaline solution on the surface of the saponified transparent support was thoroughly washed with water and then sufficiently dried at 100 ° C. Thus, the protective film for polarizing plates was produced.
(Preparation of polarizing plate)
A polyvinyl alcohol film having a thickness of 75 μm (manufactured by Kuraray Co., Ltd.) was immersed in an aqueous solution consisting of 1000 g of water, 7 g of iodine and 10.5 g of potassium iodide to adsorb iodine. Subsequently, this film was uniaxially stretched 4.4 times in the longitudinal direction in a 4% by mass boric acid aqueous solution, and then dried in a tension state to produce a polarizing film.
A saponified triacetyl cellulose surface of the antireflection film of the present invention (protective film for polarizing plate) was bonded to one surface of the polarizing film using a polyvinyl alcohol adhesive as the adhesive. Furthermore, a cellulose acylate film TD-80UF saponified in the same manner as above was bonded to the other surface of the polarizing film using the same polyvinyl alcohol-based adhesive.
(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmissive, reflective, or transflective liquid crystal display device equipped with the polarizing plate of the present invention thus fabricated has excellent antireflection performance and is extremely Visibility was excellent.

[Example 6]
(Preparation of polarizing plate)
In the optical compensation film (Wide View Film A 12B, manufactured by Fuji Photo Film Co., Ltd.), the surface opposite to the side having the optical compensation layer was saponified under the same conditions as in Example 4.
The polarizing film produced in Example 4 was saponified with the antireflection film (protective film for polarizing plate) produced in Example 4 on one surface of the polarizing film using a polyvinyl alcohol-based adhesive as an adhesive. The triacetyl cellulose surface was bonded. Further, the triacetyl cellulose surface of the saponified optical compensation film was bonded to the other surface of the polarizing film using the same polyvinyl alcohol adhesive.
(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmissive, reflective, or transflective liquid crystal display device equipped with the polarizing plate of the present invention thus fabricated does not use an optical compensation film. Compared with a liquid crystal display device equipped with a polarizing plate, the contrast in a bright room was excellent, the viewing angles of the top, bottom, left and right were very wide, and the antireflection performance was excellent, and the visibility and display quality were extremely excellent.
Producing a high-refractive-index layer containing composite oxide fine particles composed of specific elements, detailed in this specification, to provide a large number of inexpensive antireflection films with excellent weather resistance (especially light resistance) can do.
Furthermore, the polarizing plate and image display apparatus which hold | maintained the said characteristic by these can be provided.

It is explanatory drawing for demonstrating the method to measure the inclination | tilt angle of the uneven | corrugated profile of the antireflection film outermost surface.

Claims (15)

In an antireflection film comprising an antireflection layer on a transparent support,
The thickness of the antireflection layer is substantially uniform, and the arithmetic average roughness Ra of the outermost surface of the film on the antireflection layer surface side is 0.02 to 1 μm, the average interval Sm between irregularities is 5 to 65 μm, and ten points. An antireflection film having an uneven shape having a ratio Rz / Ra of average roughness Rz to Ra of 10 or less.   The top surface of the antireflection film has a maximum unevenness height Ry of 2 μm or less, and an inclination angle of the uneven profile (inclination angle distribution with respect to the regular reflection surface) is distributed to 15 degrees or less. Item 2. The antireflection film according to Item 1.   The antireflection film according to claim 1 or 2, wherein a fine uneven shape on the surface of the antireflection layer is formed by an embossing method after the antireflection layer is applied and dried.   The antireflection film according to claim 1, further comprising a hard coat layer between the transparent support and the antireflection layer.   The hard coat layer is formed by applying and curing a hard coat layer curing composition containing at least one compound selected from a polymerizable compound that is cured by a radical polymerization reaction and a polymerizable compound that is cured by a cationic polymerization reaction. The antireflection film according to claim 4, which is a cured film. The hard coat layer-curing composition comprises at least one each of a crosslinkable polymer containing a repeating unit represented by the following general formula (1) and a compound containing two or more ethylenically unsaturated groups in the same molecule. The antireflection film according to claim 5, comprising:

In general formula (1), a ¹ and a ² may be the same or different and each represents a hydrogen atom, an aliphatic group, —COOR ₁ , or —CH ₂ COOR ₁ . Here, R ₁ represents a hydrocarbon group.
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group.
L represents a single bond or a divalent linking group.   The antireflection layer is formed of a two-layer structure having a high refractive index layer having a higher refractive index than that of the support between the transparent support and a low refractive index layer having a lower refractive index than that of the transparent support. The antireflection film according to claim 1. A high-refractive index layer in which the antireflection layer has a refractive index higher than that of the support in order from the low-refractive index layer side between the transparent support and the low-refractive index layer having a lower refractive index than the transparent support; and The medium refractive index layer is formed of a three-layer structure having a medium refractive index layer having an intermediate refractive index between the support and the high refractive index layer, and the medium refractive index layer has the following formula (I) with respect to the design wavelength λ (400 to 680 nm). The antireflective film according to any one of claims 1 to 7, wherein the high refractive index layer satisfies the following formula (II) and the low refractive index layer satisfies the following formula (III).
(Lλ / 4) × 0.80 <n1d1 <(lλ / 4) × 1.00 (I)
(Mλ / 4) × 0.75 <n2d2 <(mλ / 4) × 0.95 (II)
(Nλ / 4) × 0.95 <n3d3 <(nλ / 4) × 1.05 (III)
(Where, l is 1, n1 is the refractive index of the medium refractive index layer, and d1 is the layer thickness (nm) of the medium refractive index layer, m is 2, and n2 is high. The refractive index of the refractive index layer, and d2 is the thickness (nm) of the high refractive index layer, n is 1, n3 is the refractive index of the low refractive index layer, and d3 is the low refractive index. (Thickness layer thickness (nm))   The high refractive index layer having a higher refractive index than the above support contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium, and has a refractive index. It is 1.55-2.40, The antireflection film in any one of the Claims 1 thru | or 8 characterized by the above-mentioned.   Forming an antireflection layer comprising at least one low refractive index layer having a refractive index lower than the refractive index of the transparent support on the transparent support in sequence or simultaneously, and embossing the outermost surface on the antireflection layer side The arithmetic average roughness Ra is 0.02 to 1 μm on the surface of the antireflection layer after processing, the average interval Sm between the irregularities is 5 to 65 μm, and the ratio of the ten-point average roughness Rz to Ra Rz / Ra The manufacturing method of the antireflection film characterized by including the process of forming the unevenness | corrugation of 15 or less.   A plate used for embossing is shaped by electric discharge machining, and the surface of the plate has a surface shape with an arithmetic average roughness Ra of 0.2 to 1.0 μm and an average interval Sm of unevenness of 5 to 30 μm. The method for producing an antireflection film according to claim 10.   A polarizing plate having at least one surface protective film on the surface of a polarizer, wherein the surface protective film is produced by the antireflection film according to any one of claims 1 to 9 or the method according to claim 10 or 11. A polarizing plate characterized by being an antireflection film.   The antireflection film according to any one of claims 1 to 9 or the antireflection film produced by the method according to claim 10 or 11 is used for one of the two surface protection films, and the other surface protection film is used as the other surface protection film. An optical compensation film having an optical compensation layer comprising an optically anisotropic layer on the surface opposite to the surface to be bonded to the polarizing film of the surface protective film is used, and the optically anisotropic layer is discotic. A layer formed of a compound having a structural unit, the disc surface of the discotic structural unit is inclined with respect to the surface protective film surface, and the disc surface of the discotic structural unit, the surface protective film surface, The polarizing plate according to claim 12, wherein the average angle formed by is changed in the depth direction of the optically anisotropic layer.   An image display device comprising at least one polarizing plate according to claim 12 or 13.   A TN, STN, VA, IPS, or OCB mode transmissive, reflective, or transflective liquid crystal display device comprising at least one polarizing plate according to claim 12 or 13.

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