JP2007065635A - Optical film, particularly antireflection film and method of manufacturing the same, and polarizer and liquid crystal display device using antireflection film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film, which is reduced in white blur, and which is superior in front contrast and the contrast in an oblique direction, and to provide a polarizer and display device using the same. <P>SOLUTION: An optical film comprises a layer with at least internal scattering properties on a transparent support, and has image sharpness, as measured in an optical comb width of 0.5 mm in conformity to JIS K7105, of 30.0% to 99.9%. Also, a haze value caused by surface scattering is less than 3%, and the haze value caused by internal scattering is 15-40%. Specifically, the antireflection film includes at least the internal scattering layer and a low index refraction layer that are laminated on the transparent support in this order, and has a specified integral reflectivity, a difference between the integral reflectivity and mirror reflectivity, the light quantity I<SP>45°</SP>reflected in the direction slanted at +45° with respect to the light quantity I<SB>0</SB>incident slanting at -60°, and the surface and interior haze values. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection film, a polarizing plate, and an image display device. More specifically, there is almost no white blur in a bright room, which will be described later, the contrast is good in a bright room, and it is used on the surface of a liquid crystal display device. In addition, an antireflection film having an internal scattering property and a low refractive index layer that can improve contrast in an oblique direction without reducing front contrast, a polarizing plate using the antireflection film as a surface protective film, The present invention relates to an image display device using an antireflection film polarizing plate.

  Anti-reflection films are generally used in display devices such as CRT, plasma display (PDP), electroluminescence display (ELD) and liquid crystal display (LCD) to prevent image reflection due to reflection of external light. It is arranged on the outermost surface. The antireflection film forms a low refractive index layer on the surface of the film, thereby reducing the reflectance of the surface and reducing the reflection of an image on the surface. Furthermore, in order to reduce the reflection of the surface, an anti-glare antireflection film that uses unevenness on the surface and blurs the image reflected on the surface using surface scattering at the unevenness. There is. Antireflection films include films having internal scattering properties in addition to surface scattering properties. In particular, when an anti-reflection film with strong anti-glare property is used to reduce the reflection, a fine unevenness of brightness (referred to as glare) due to surface irregularities of the anti-glare film has been accompanied by the recent increase in definition of display devices. As a means for improving the problem, a technique relating to an antiglare film having high internal scattering in addition to surface scattering has been disclosed (Patent Document 1).

  Further, as disclosed in Patent Document 2 and the like, when a light scattering film is used on the outermost surface of a display device, the antireflection function has an effect of suppressing surface reflection of external light in a bright room. It is known that a film having both of these is preferable.

  In recent years, the market for applications to display devices having a large screen, such as a liquid crystal television, has been rapidly expanding. In such an application, the display device is frequently used in a bright room, and when a film having a conventional anti-glare layer is applied to the surface of the display device, the entire surface glows white under the bright room. (Hereinafter referred to as white blur) has become a problem.

  Recently, an anti-glare film having a high internal scattering property with improved glare as described above is also used in this application. However, the high internal scattering property causes a problem that the contrast inherent in the display device is lowered. Therefore, it is not necessarily optimal for this application. Patent Document 3 discloses a technique for improving the color reproducibility of a liquid crystal display device by providing an anti-glare layer having a specific haze value on the viewer side of a liquid crystal display device having a polarizer and a phase difference compensation element. However, there is no description about the front contrast and the diagonal contrast of the display device, and the description of the surface reflectance of the film, the surface haze and the classification of the internal haze and the surface haze are not sufficient, There is no sufficient description regarding improvement of image display performance.

Japanese Patent No. 3507719 JP 2003-270409 A Japanese Patent No. 3602438

As shown in the background art above, while reducing the reflection of images and preventing white blur, bright room contrast, and lowering the front contrast when used in an image display device to a level where there is no problem, At present, no antireflection film satisfying the contrast improvement has been proposed.
Accordingly, an object of the present invention is to provide an antireflection film having high antireflection properties and white blurring prevention properties, and having good front contrast and oblique contrast when used in an image display device. . Another object of the present invention is to provide a production method capable of producing the above antireflection film with high productivity.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problems can be solved and the object can be achieved by the following (1) to (20). It came to complete.
That is, the present invention achieves the object by the following configuration.
(1) It has a layer having at least internal scattering on the transparent support, and the image clarity according to JIS K7105 is 30.0% to 99.9% when measured with an optical comb width of 0.5 mm. An optical film having a haze value attributable to surface scattering of less than 3% and a haze value attributable to internal scattering of 15 to 40%.
(2) An antireflective film in which at least an internal scattering layer and a low refractive index layer are laminated in this order on a transparent support, and the refractive index of the low refractive index layer is less than that of the internal scattering layer. 0.04 or more, the integrated reflectance of the antireflection film is 3.5% or less, and the image clarity according to JIS K7105 is 30.0% to 99.9% when measured with an optical comb width of 0.5 mm. A haze value due to surface scattering is less than 3%, and a haze value due to internal scattering is 15 to 40%.
(3) The antireflection film as described in item (2), wherein the specular reflectance is 0.5% or more and 3.3% or less.
(4) The center line average roughness Ra of the optical film or antireflection film is 0.01 to 0.25 μm, and the ten-point average roughness Rz is 5 or more times Ra. Item 6. An optical film according to item (1) or an antireflection film according to item (2) or (3).
(5) The centerline average roughness Ra of the antireflection film is 0.01 to 0.12 μm, and the image clarity according to JIS K7105 is 45.0% when measured with an optical comb width of 0.5 mm. The amount of light I ⁴⁵ ° reflected in the direction inclined by + 45 ° with respect to the amount of light I ₀ incident with an inclination of −60 ° with respect to the vertical direction from the low refractive index layer side is 90.0%. The antireflection film according to any one of Items (2) to (4), wherein:
Formula (1) -LOG ₁₀ (I ⁴⁵ ° / I ₀ ) ≧ 4.3
(6) The centerline average roughness Ra of the antireflection film is 0.01 to 0.08 μm, and the image clarity according to JIS K7105 is 75.0% when measured with an optical comb width of 0.5 mm. The amount of light I ⁴⁵ ° reflected in the direction inclined by + 45 ° with respect to the amount of light I ₀ incident at −60 ° with respect to the vertical direction from the low refractive index layer side is 99.0%. ) The antireflection film according to item (5), wherein
Formula (1 ′) −LOG ₁₀ (I ⁴⁵ ° / I ₀ ) ≧ 4.5
(7) The internal scattering layer contains a translucent resin and one or more translucent particles, has a thickness of 3 μm to 12 μm, and a translucent particle size of 3 to 4 μm. The translucent particles contain 5 to 30% by weight of the total solid content, the refractive index of the translucent resin is in the range of 1.52 ± 0.02, and 30% or more of the translucent particles are translucent. Item 3. The optical film according to Item (1) or (4) or the item (2) to (6), wherein the refractive index difference with the resin is 0.008 or more and 0.05 or less. Antireflection film.
(8) The antireflection film as described in item (7), wherein the density of the translucent fine particles is from 0.8 to 3.2 g / m ² .
(9) The translucent particles having a refractive index difference from the translucent resin of 0.008 or more and 0.05 or less are composed of a crosslinked poly (styrene-acrylic) copolymer or a crosslinked acrylic resin, and the copolymer Or the ratio of the acryl-type structural group of an acrylic resin is 20-100 mass%, The antireflection film as described in item (7) or (8) characterized by the above-mentioned.
(10) The internal scattering layer is formed by applying, drying, and curing a coating composition containing a translucent resin, translucent fine particles, and a plurality of types of solvents on a transparent support. Item 10. The optical film according to item (1), (4) or (7) or the antireflection film according to any one of items (2) to (9).
(11) The low refractive index layer comprises (A) a fluorine-containing compound having thermosetting and / or ionizing radiation curability, (B) inorganic fine particles, and (C) an organo represented by the following general formula (1). Formed by applying and curing a curable composition containing at least two of at least one selected from silane, hydrolyzate of organosilane, and partial condensate of hydrolyzate of organosilane The antireflection film according to any one of Items (2) to (10), which is a cured film.
General formula (1)
(R ¹⁰ ) _m -Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)
(12) The antireflection film as described in item (11), wherein the fluorine-containing compound having thermosetting property and / or ionizing radiation curable property contains fluorine atoms in a range of 35 to 80% by mass.
(13) The antireflection according to item (11) or (12), wherein the inorganic fine particles are inorganic fine particles having an average particle size of 10% to 100% of the thickness of the low refractive index layer. the film.
(14) The inorganic fine particles according to any one of (11) to (13), wherein the inorganic fine particles are inorganic fine particles having a hollow structure in the particles and having a refractive index of 1.17 to 1.40. Antireflection film.
(15) A curable coating composition in which both the internal scattering layer and the low refractive index layer contain a hydrolyzate of organosilane represented by the general formula (1) and / or a partial condensate thereof. The antireflection film according to any one of Items (2) to (14), which is a cured film formed by applying and curing an object.
(16) A transparent conductive layer is provided between the internal scattering layer and the transparent support, or between the internal scattering layer and the low refractive index layer. ), (4), (7) or the optical film according to (10) or the antireflection film according to any one of items (2) to (15).
(17) A term having a transparent conductive layer between the internal scattering layer and the transparent support, and / or containing conductive particles in the internal scattering layer. The optical film according to 1), (4), (7), (10) or (16) or the antireflection film according to any one of items (2) to (16).
(18) In the polarizing plate comprising a polarizing film and two protective films protecting both the front side and the back side of the polarizing film, at least one of the protective films is any one of Items (2) to (17) A polarizing plate, which is the antireflection film described in 1.
(19) A polarizing plate, wherein one of the two protective films is the antireflection film according to any one of Items (2) to (17), and the other is an optical compensation film.
(20) An image display device comprising at least one antireflection film according to any one of items (2) to (17) or a polarizing plate according to item (18) or (19).
(21) Any one of Items (2) to (17) is provided on a surface of a liquid crystal display device having a polarizer on both surfaces of the liquid crystal cell and having at least one retardation compensation element between the liquid crystal cell and the polarizer. A liquid crystal display device comprising the antireflective film according to claim 1.
(22) A method for producing an antireflection film according to any one of items (2) to (17), wherein the antireflection film comprises a light-transmitting particle, a light-transmitting resin, and a layer having an internal scattering property containing a solvent. The coating composition and / or the coating composition for the low refractive index layer and / or the coating composition for the transparent conductive layer is supported on the surface of the web of the transparent substrate supported by a backup roll and continuously running. Coating a layer having internal scattering properties and / or a low refractive index layer on the transparent support by applying a coating composition from the slot of the tip lip in close proximity to the land of the tip lip. A method for producing an antireflective film, comprising:

  According to the present invention, it is possible to provide an antireflection film that satisfies both high antireflection properties and reduction of white blur at the same time, and has good front contrast and oblique contrast when used in an image display device. Furthermore, the antireflection film can be provided with high productivity.

  Hereinafter, the present invention will be described in more detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

A basic configuration of one preferred embodiment of the antireflection film of the present invention will be described with reference to the drawings.
Here, FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the antireflection film of the present invention.
An antireflection film 1 of the present embodiment shown in FIG. 1 includes a transparent support 2, an internal scattering layer 3 formed on the transparent support 2, and a low refractive index layer 4 formed on the internal scattering layer 3. Consists of. By forming the low refractive index layer 4 on the internal scattering layer 3 with a thickness of about ¼ of the wavelength of light, surface reflection can be reduced by the principle of thin film interference. In the present invention, white blur can be improved without having a low refractive index layer, but in order to obtain a sufficient effect, it is preferable to have a low refractive index layer.

  The internal scattering layer 3 is a layer having internal scattering properties, and includes a translucent resin and translucent particles 5 dispersed in the translucent resin. The layer 3 having internal scattering properties preferably has a hard coat property. In the present embodiment, an example in which one layer having internal scattering properties is formed is exemplified, but a plurality of layers, for example, two to four layers may be formed.

  In order to prevent charging, it is desirable to have a transparent conductive layer between the layer 3 having internal scattering property and the transparent support 2 or between the layer 3 having internal scattering property and the low refractive index layer 4. It is particularly desirable to have a transparent conductive layer between the internal scattering layer 3 and the transparent support 2. In addition, it is particularly effective for preventing static charge to have a transparent conductive layer between the layer 3 having internal scattering property and the transparent support 2 and having conductive particles in the layer having internal scattering property. . In addition to the transparent conductive layer, a functional layer such as a moisture-proof layer may be provided between the layer 3 having internal scattering properties and the transparent support 2.

The refractive index of each layer constituting the antireflection film of the present invention preferably satisfies the following relationship.
Refractive index of internal scattering layer> refractive index of transparent support> refractive index of low refractive index layer Further, the present invention provides an antireflection film that is particularly excellent in terms of reducing white blur in a bright room and improving contrast. For this purpose, it is necessary to suppress the effect of preventing reflection using surface scattering, and therefore it is necessary to sufficiently reduce the reflection by reducing the integrated reflectance. For this purpose, the difference na−nb between the refractive index (na) of the internal scattering layer and the refractive index (nb) of the low refractive index layer needs to be 0.04 or more. 0.05 or more and 0.35 or less are preferable, 0.07 or more and 0.35 or less are more preferable, 0.10 or more and 0.35 or less are particularly preferable, and 0.17 or more and 0.30 or less are preferable. Further preferred. If the difference in refractive index between the two is too small, the reflectance cannot be lowered sufficiently, and reflection of the reflected image on the surface cannot be sufficiently prevented. On the other hand, when the difference in refractive index is too large, there are problems such as a decrease in film strength and an increase in color. In order to obtain a specific refractive index difference, there are two methods of increasing the refractive index of the internal scattering layer and decreasing the refractive index of the low-refractive index layer, and either method can be used. Thus, the refractive index of the internal scattering layer is more preferably in the range of 1.50 to 1.54. Therefore, in order to increase the refractive index difference, the refractive index of the low refractive index layer should be lowered. Is preferred. Even with the same refractive index difference, a lower refractive index of the low refractive index layer is preferable from the viewpoint of color reduction.

  The refractive index (na) of the internal scattering layer is preferably 1.50 or more, more preferably 1.50 or more and 1.70 or less, and further preferably 1.50 or more and 1.65 or less. By increasing the refractive index of the internal scattering layer to a specific value or more, the refractive index difference with the low refractive index layer can be increased, and the reflectance can be reduced, but if the refractive index is too high, This is not preferable because the difference in refractive index between the translucent particles and the translucent resin becomes too large and the internal haze value becomes too large. Moreover, since the material which can be used is limited and becomes high-cost, it is not preferable. Therefore, 1.50 to 1.54 is particularly desirable. In the present invention, the refractive index of the internal scattering layer is a value obtained from the refractive index of the coating film containing a solid content excluding the translucent particles.

In the antireflection film of the present invention, the light quantity I ⁴⁵ ° reflected in the direction inclined 45 ° with respect to the light quantity I ₀ incident with an inclination of −60 ° with respect to the vertical direction from the low refractive index layer side is expressed by the above formula (1). ) Is desirable. FIG. 2 is a schematic view of an optical system for measuring such scattering characteristics. As shown in FIG. 2, the direction perpendicular to the surface of the antireflection film is defined as 0 °, and the counterclockwise direction is defined as minus and the clockwise direction is defined as plus. I ₀ in the formula (1) represents the amount of light incident in the direction of −60 ° toward the low refractive index layer of the antireflection film. The amount of incident light can be adjusted with a light source.
On the other hand, the light receiver is arranged in the + 45 ° direction, and the amount of reflected light measured by the light receiver is I ⁴⁵ ° (note that I ⁵⁰ ° in equation (2) and I ⁴⁰ ° in equation (3) are also (This is the value of the amount of light measured in the same manner with the light receivers arranged in the + 50 ° direction and the + 40 ° direction, respectively.) As the above measuring apparatus, for example, a “goniophotometer” manufactured by Murakami Color Materials Laboratory Co., Ltd. can be used.
In FIG. 2, I ₀ and I ⁴⁵ ° are measured with the antireflection film attached to the polarizing plate in order to approximate the black display condition of the display device. The surface opposite to the surface having the prevention layer may be treated with black ink and measured as having no back surface reflection.

The larger the value of (−LOG ₁₀ (I ⁴⁵ ° / I ₀ )) in the formula (1), the smaller the scattered light in the 45 ° direction, and the white blurring when viewed from the 45 ° direction. It becomes good. As shown in Formula (1), the value of (-LOG ₁₀ (I ⁴⁵ ° / I ₀ )) is preferably 4.3 or more, and more preferably 4.5 or more. If it is less than 4.3, white blur in a bright room is not sufficient for the target level of the present invention.

  Further, haze caused by surface scattering of the antireflection film (hereinafter referred to as surface haze) is preferably less than 3%, more preferably 2% or less, and 1.5% or less. Is particularly preferable, and 1.0 or less is more preferable. If it exceeds 3%, white blur is not sufficient for the target level of the present invention.

  The antireflection film preferably has a haze caused by internal scattering (hereinafter referred to as internal haze) of 15% to 40%, and more preferably 20% to 32%. The lower the internal haze, the lower the front contrast, but the lower the contrast improvement effect in the oblique direction. If the internal scattering exceeds 40%, contrast deterioration or image blur may occur.

Further, the integrated reflectance of the antireflection film needs to be 4.6% or less. In the present invention, since scattering due to surface irregularities is suppressed in order to reduce white blur, a sufficient effect can be obtained by reducing the reflectance in order to prevent reflection. Therefore, the integrated reflectance is preferably 3.5% or less, more preferably 2.5% or less, and further preferably 2.0% or less. Particularly preferably, it is 1.5% or less. The specular reflectance is preferably 3.3% or less, more preferably 3.0% or less, still more preferably 2.0% or less, and particularly preferably 1.7% or less. Most preferably, it is 1.4% or less. A transmittance of 90% or more is preferable because reflection of external light can be suppressed, reflection of an image on the surface is reduced, and visibility is improved.
The image sharpness according to JIS K7105 is preferably 30% to 99.9% when measured with an optical comb width of 0.5 mm because sufficient white blurring prevention can be obtained. More preferably, it is 45% to 99.9%, More preferably, it is 65 to 99.9%.
Further, the minimum reflectance of the reflected light in the CIE 1976 L ^* a ^* b ^* color space under the C light source is in the range of a ^* value −2 to 2, b ^* value −3 to 3, 380 nm to 780 nm. A ratio between the value and the maximum value of 0.5 to 0.99 is preferable because the color of the reflected light becomes neutral. Moreover, when the b ^* value of the transmitted light under the C light source is set to 0 to 3, the yellow color of white display when applied to a display device is reduced, which is preferable.

  Furthermore, the antireflection film of the present invention is designed so that the center line average roughness Ra is 0.01 to 0.25 μm, and the 10-point average roughness Rz is 10 times or less of Ra as the surface uneven shape. Is preferable in order to reduce white blur due to surface irregularities. Ra is more preferably 0.01 to 0.15 μm. When emphasizing the effect of preventing reflection, it is preferably 0.05 μm or more, and more preferably 0.05 to 0.08 μm. In a general production method, it is difficult to reduce Ra to 0.01 μm or less, and when it exceeds 0.15 μm, problems such as glare and white blur may occur.

Next, the internal scattering layer of the antireflection film will be described below.
[Internal scattering layer]
The internal scattering layer is formed for the purpose of imparting to the film an internal scattering property and preferably a hard coat property for improving the scratch resistance of the film. Accordingly, it preferably contains a translucent resin capable of imparting hard coat properties, translucent fine particles for imparting internal scattering properties, and a solvent.

(Translucent fine particles)
The average particle size of the translucent fine particles is preferably 0.5 to 10 μm, more preferably 2.0 to 6.0 μm. More preferably, it is 3.0-4.0 micrometers. If the average particle size is less than 0.5 μm, the light scattering angle distribution spreads to a wide angle, which may cause blurring of characters on the display. On the other hand, when the thickness exceeds 10 μm, it is necessary to increase the thickness of the internal scattering layer, which causes problems such as an increase in curling and an increase in material cost.
Specific examples of the light-transmitting fine particles include, for example, poly ((meth) acrylate) particles, cross-linked poly ((meth) acrylate) particles, polystyrene particles, cross-linked polystyrene particles, cross-linked poly (acryl-styrene) particles, melamine resin particles, Preferred examples include resin particles such as benzoguanamine resin particles. Of these, cross-linked polystyrene particles, cross-linked poly ((meth) acrylate) particles, and cross-linked poly (acryl-styrene) particles are preferably used. By adjusting the refractive index of the light-sensitive resin, the internal haze and surface haze can be adjusted to the desired ranges, and the combination of the light-transmitting resin and the light-transmitting fine particles, the solvent of the coating composition, the addition amount, etc. are adjusted. By doing so, the center line average roughness can be in a desired range.

Specifically, a translucent resin (having a refractive index after curing of 1.50 to 1.54) mainly composed of a tri- or higher functional (meth) acrylate monomer that is preferably used for an internal scattering layer described later is used. In this case, it is preferable to combine light-transmitting fine particles made of a crosslinked poly (meth) acrylate polymer having an acrylic content of 20 to 100% by mass, and in particular, both the light-transmitting resin and the crosslinked poly (acryl-styrene) are combined. A combination with translucent fine particles made of a polymer (refractive index: 1.48 to 1.58) is preferred.
Here, the “translucent resin having a trifunctional or higher functional (meth) acrylate monomer as a main component” means that a repeating unit composed of a trifunctional or higher functional (meth) acrylate monomer is 50 to 100 in the translucent resin. It means that it is contained by weight. The content of the repeating unit composed of a tri- or higher functional (meth) acrylate monomer is preferably 60 to 100% by weight.

  Further, two or more kinds of translucent fine particles having different particle diameters may be used in combination.

The translucent fine particles are preferably blended in the formed internal scattering layer so as to be contained in an amount of 5 to 30% by mass in the total solid content of the internal scattering layer. More preferably, it is 8-25 mass%. More preferably, it is 8-15 mass%. If it is less than 3% by mass, the internal scattering property is insufficient, and if it exceeds 30% by mass, problems such as image blur, surface turbidity and glare may occur.
The density of the light-transmitting particulate material is preferably 0.8~3.2g / m ^2, more preferably 0.9~2.8g / m ^2.

The refractive indexes of the translucent resin and the translucent fine particles are preferably in the above range. The difference in refractive index between the translucent resin and the translucent fine particles (the refractive index of the translucent fine particles−the refractive index of the translucent resin) is preferably 0.008 to 0.15 as an absolute value. More preferably, it is 0.01-0.10. Particularly preferably, translucent particles in the range of 0.008 to 0.05 are used in an amount of 30% or more of the total translucent particles. By setting the range as described above, it is possible to obtain good performance such as image blur, surface turbidity, and contrast.
The refractive index of the light-transmitting fine particles is determined by measuring the turbidity by dispersing an equal amount of the light-transmitting fine particles in the solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the degree becomes minimum with an Abbe refractometer.
Further, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. When the translucent resin is curable, it indicates the refractive index after curing.

  The thickness of the internal scattering layer is preferably 3 to 12 μm, more preferably 3 to 9 μm, still more preferably 4.5 to 8 μm, and particularly preferably 5 to 7 μm. If it is too thin, the hard property will be insufficient, and if it is too thick, problems such as curling and brittleness will deteriorate and workability will deteriorate, costs will increase, and unevenness will easily occur. Is preferred.

  It has been found that there is an optimum range in more detail regarding the density of the translucent particles of the internal scattering layer and the refractive index range of the translucent particles used and the content of each particle when two types of particles are used. Table 11 summarizes the relationship. Two types of particles are preferably used because the desired internal haze value and surface haze value can be obtained by adjusting the ratio without changing the amount of particles. Three or more kinds of particles can be used, but there is a problem that the system becomes complicated. In the preferred ranges in the table, preferred internal haze values and surface haze values can be obtained, and it is possible to obtain good performance such as image blur, surface turbidity, and contrast, and better performance in a more preferred range. It is possible to obtain The refractive index difference of the particle | grains in a table | surface shows the refractive index difference of the translucent particle and translucent resin used for an internal scattering layer.

(Translucent resin)
The translucent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3- Chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide-modified products and caprolactone-modified products of the above esters, vinylbenzene and its derivatives [eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2- Acryloyl ethyl ester, 1,4-divinylcyclohexanone], vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

In order to make the binder polymer have a high refractive index, the monomer structure has a high refractive index containing at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. A monomer, a monomer having a fluorene skeleton in the molecule, or the like can also be selected.
Specific examples of the high refractive index monomer include (meth) acrylates having a fluorene skeleton, bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenylthioether, etc. Is mentioned. Two or more of these monomers may be used in combination.

Polymerization of these monomers can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Therefore, the internal scattering layer is composed of a monomer for forming a translucent resin such as the above-mentioned ethylenically unsaturated monomer, a photo radical initiator or a thermal radical initiator, translucent fine particles, and an inorganic material as described later if necessary. It can be formed by preparing a coating liquid containing a filler and curing the coating liquid on a transparent support by ionizing radiation or a polymerization reaction with heat.

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

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

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

  The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.

(Inorganic filler)
For the internal scattering layer, the refractive index of the layer is adjusted to finely adjust the haze value resulting from internal scattering, and the refractive index difference from the low refractive index layer is adjusted to provide a preferable range of reflectance and color. Therefore, in addition to the above-mentioned translucent fine particles, an inorganic filler may be contained. The inorganic filler is preferably made of an oxide of at least one metal selected from silicon, titanium, zirconium, aluminum, indium, zinc, tin, and antimony. Moreover, it is preferable that an average particle diameter is 0.2 micrometer or less, More preferably, it is 0.1 micrometer or less, More preferably, it is 0.06 micrometer or less. Such an inorganic filler generally has a specific gravity higher than that of an organic material and can increase the density of the coating composition, and therefore has the effect of slowing the sedimentation rate of the light-transmitting fine particles. Such an inorganic filler does not scatter because its particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

The surface of the inorganic filler used for the internal scattering layer is also preferably subjected to a silane coupling treatment or a titanium coupling treatment. In this case, a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used.
The amount of the inorganic filler added is preferably 10 to 90% of the total mass of the internal scattering layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.

(Organosilane compound)
An organosilane compound can be used for the internal scattering layer. The addition amount of the organosilane compound is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, and still more preferably 0.05 to 10% by mass, based on the total solid content of the containing layer (addition layer). 0.1 to 5% by mass is particularly preferable.
As the organosilane compound used for the internal scattering layer, the same organosilane compound as described later for the low refractive index layer can be used.

(Surfactant for internal scattering layer)
For the internal scattering layer, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defects, etc., either a fluorine-based surfactant or a silicone-based surfactant or both of them are used for forming the internal scattering layer. It is preferably contained in the coating composition. By increasing the surface uniformity, it becomes possible to apply at high speed, and productivity can be improved. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film appears with a smaller addition amount.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): Resin consisting of a corresponding repeating unit, an acrylic resin containing a repeating unit corresponding to the monomer (i) below, a methacrylic resin, or a vinyl monomer copolymerizable therewith (for example, the monomer (i) below is preferred) Are useful.

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom. m represents an integer of 1 to 6, and n represents an integer of 2 to 4.

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

The amount of the fluoroaliphatic group-containing monomer represented by the general formula (A) used in the fluorine-based polymer is preferably 10 mol% or more based on each monomer of the fluorine-based polymer, more preferably 15 to It is 70 mol%, More preferably, it is the range of 20-60 mol%.
Further, the amount of the monomer represented by the general formula (b) used in the fluorine-based polymer is preferably 1 mol% or more based on each monomer of the fluorine-based polymer, more preferably 5 to 70 mol%. More preferably, it is the range of 10-60 mol%.

  Examples of the specific structure of the fluoropolymer composed of the fluoroaliphatic group-containing monomer represented by the general formula (i) are shown below, but this is not restrictive. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

By using a fluorine-based polymer composed of the monomer represented by the general formula (a), the surface energy of the internal scattering layer is reduced due to segregation of functional groups containing F atoms on the surface of the internal scattering layer, and the Further, when the low refractive index layer is overcoated, there may be a problem that the antireflection performance deteriorates. This is presumably because minute unevenness that cannot be visually detected in the low refractive index layer deteriorates because the wettability of the curable composition used for forming the low refractive index layer deteriorates.
To solve such problems, by adjusting the structure and amount of the fluorine-based polymer, the surface energy of the internal scattering layer preferably in ^{20mN · m -1 ~50mN · m -1} , more preferably it was found that it is effective to control the ^{30mN · m -1 ~40mN · m -1} . In order to realize the surface energy as described above, F / C, which is a ratio of a peak derived from a fluorine atom and a peak derived from a carbon atom, measured by X-ray photoelectron spectroscopy is 0.1 to 1.5. is required.

  Alternatively, by selecting a fluorine-based polymer that is extracted by the solvent that forms the upper layer when the upper layer is applied, it is not unevenly distributed on the lower layer surface (= interface), so that the adhesion between the upper layer and the lower layer is provided. The surface energy of the internal scattering layer before coating the low refractive index layer can be reduced by preventing a decrease in surface free energy that can provide an antireflection film having high surface resistance even in high-speed coating and having high scratch resistance. The purpose can also be achieved by controlling the range. Examples of such materials include acrylic resins, methacrylic resins, and vinyl monomers copolymerizable therewith, including repeating units corresponding to fluoroaliphatic group-containing monomers represented by the following general formula c: And the following (iv) monomers are preferred).

In the general formula C, R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and still more preferably an oxygen atom. m is an integer from 1 to 6 (more preferably from 1 to 3, more preferably 1), and n is an integer from 1 to 18 (more preferably from 4 to 12, and even more preferably from 6 to 8). Represents. R ²² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. X ² is preferably an oxygen atom.
In addition, two or more kinds of fluoroaliphatic group-containing monomers represented by the general formula C may be contained in the fluorine-based polymer as constituent components.

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

The amount of the fluoroaliphatic group-containing monomer represented by the general formula C used in the fluoropolymer is preferably 10 mol% or more based on each monomer of the fluoropolymer, and more preferably 50 to It is 100 mol%, More preferably, it is the range of 60-100 mol%.
The amount of the monomer represented by the general formula d used in the fluorine-based polymer is preferably 0 mol% or more, more preferably 0 to 50 mol% based on each monomer of the fluorine-based polymer. More preferably, it is the range of 0-40 mol%.

  Hereinafter, examples of specific structures of fluoropolymers containing a repeating unit corresponding to the fluoroaliphatic group-containing monomer represented by formula (c) are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  Further, if the decrease in surface energy is prevented when the low refractive index layer is overcoated on the internal scattering layer, the deterioration of the antireflection performance can be prevented. For this reason, when coating the internal scattering layer, the surface tension of the coating solution is lowered by using a fluoropolymer to improve surface uniformity, maintaining high productivity by high-speed coating, corona treatment, UV treatment, By using surface treatment techniques such as heat treatment, saponification treatment, and solvent treatment, the surface energy of the internal scattering layer before application of the low refractive index layer can be controlled within the above range by preventing the reduction of the surface free energy. be able to. A particularly preferable surface treatment method is corona treatment.

  Moreover, you may add a thixotropic agent in the coating composition for forming an internal scattering layer. Examples of the thixotropic agent include silica and mica of 0.1 μm or less. In general, the content of these additives is preferably about 1 to 10 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin.

The preferred weight average molecular weight of the fluoropolymer is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of a fluorine-type polymer is the range of 0.001-5 mass% with respect to a coating liquid, Preferably it is the range of 0.005-3 mass%, More preferably, it is 0.01-1. It is the range of mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient, and if it exceeds 5% by mass, the coating film may not be sufficiently dried or the performance as a coating film (for example, reflectance) , May have an adverse effect on the scratch resistance).

(solvent)
Since the layer having internal scattering properties is often wet-coated directly on the transparent support, the solvent used in the coating composition is an important factor. The solvent sufficiently dissolves various solutes such as the light-transmitting resin, does not dissolve the light-transmitting particles, does not easily generate coating unevenness and drying unevenness in the coating to drying process, and does not dissolve the support. It is preferable to satisfy requirements such as (necessary for preventing failure such as deterioration of flatness and whitening) and conversely swelling the support to the minimum extent (necessary for adhesion).
As the solvent, it is preferable to contain as a main solvent at least a solvent that does not swell the transparent support and does not dissolve the transparent support. As specific examples of the main solvent, when triacetyl cellulose is used for the support, various ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.), various cellosolves (ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.), In addition, various alcohols (propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol, etc.), toluene and the like are preferably used.

In addition, the transparent support is selected from the above, by adding a small amount of a highly swellable solvent to the main solvent having a low swellability of the transparent support without deteriorating other performance and surface condition. Adhesiveness can be improved. Specifically, methyl isobutyl ketone and toluene are used as the main solvent, and methyl ethyl ketone, acetone, cyclohexanone, propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol and the like are used as a small amount of solvent. It is particularly preferable to use methyl isobutyl ketone and toluene as the main solvent and methyl ethyl ketone and cyclohexanone as the small amount of solvent. Further, for controlling the hydrophilicity of the solvent, propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol and the like can be added and used, and propylene glycol and ethylene glycol are particularly preferably used. be able to.
The mixing ratio of the main solvent and the small amount of solvent is preferably 99: 1 to 50:50, more preferably 95: 5 to 60:40, by weight. If it exceeds 50:50, the variation in the surface quality in the drying step after coating increases, which is not preferable.

  Moreover, surface irregularities can be adjusted by adding a small amount of a solvent having a hydroxyl group to the main solvent selected from the above, which is preferable. Since the small amount of the solvent having a hydroxyl group can increase the surface unevenness by remaining until after the main solvent in the drying step of the coating composition, the vapor pressure at a certain temperature within the range of 20 to 30 ° C. Preferably it is low relative to the main solvent. For example, a preferable example is a combination of propylene glycol (vapor pressure at 20.0 ° C .: 0.08 mmHg) as a small amount solvent having a hydroxyl group with respect to methyl isobutyl ketone (vapor pressure at 21.7 ° C .: 16.5 mmHg) as the main solvent. As mentioned. The mixing ratio of the main solvent and the small amount solvent having a hydroxyl group is preferably 100: 0 to 50:50, and more preferably 100: 0 to 80:20, by weight. If it exceeds 50:50, the stability of the coating solution and the variation in surface quality in the drying step after coating increase, which is not preferable. In particular, in order to suppress surface scattering due to surface irregularities as in the present invention, it is more preferably 100: 0 to 97: 3.

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

The low refractive index layer is a cured film formed, for example, by applying, drying and curing a curable composition containing a fluorine-containing polymer as a main component. Here, “a curable composition containing a fluorine-containing polymer as a main component” means that the fluorine-containing polymer is contained in an amount sufficient to function as a binder polymer when a low refractive index layer is formed. And the preferable range of content of a fluoropolymer is as below-mentioned.
The low refractive index layer preferably contains at least one of inorganic fine particles and an organosilane compound in addition to the fluorine-containing polymer. The material for forming the low refractive index layer will be described below.

(Fluoropolymer for low refractive index layer)
The fluorine-containing polymer has a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less when it is made into a cured coating, and heat or ionizing radiation. A polymer that is crosslinked by the above is preferable from the viewpoint of improving productivity in the case of applying and curing a roll film while conveying the web.
Also, when the antireflection film is attached to the image display device, the lower the peel strength from the commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, so the peel strength should be 500 gf (4.9 N) or less Preferably, 300 gf (2.96 N) or less is more preferable, and 100 gf (0.98 N) or less is most preferable. Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch. Therefore, the surface hardness is preferably 0.3 GPa or more, and more preferably 0.5 GPa or more.

  The fluorine-containing polymer used for the low refractive index layer is preferably a fluorine-containing polymer containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. Examples of such a fluorine-containing polymer include hydrolyzates and dehydration condensates of perfluoroalkyl group-containing silane compounds [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane]. And a fluorine-containing copolymer having a fluorine-containing monomer unit and a cross-linking reactive unit as constituent units. In the case of a fluorinated copolymer, the main chain preferably consists of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom.

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

  Examples of the crosslinking reactive unit include a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether; carboxyl group, hydroxy group, amino group, sulfo group A structural unit obtained by polymerization of a monomer having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. And a structural unit in which a crosslinkable reactive group such as a (meth) acryloyl group is introduced by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group).

  In addition to the fluorine-containing monomer unit and the cross-linking reactive unit, from the viewpoint of solubility in a solvent, film transparency, and the like, a monomer not containing a fluorine atom is appropriately copolymerized to introduce another polymerization unit. You can also. There are no particular limitations on the monomer units that can be used in combination, such as olefins [ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.], acrylic esters [methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2 -Ethylhexyl], methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers [methyl Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters [vinyl acetate, vinyl propionate, vinyl cinnamate, etc.], acrylamides [N-tertbutylacrylamide, N-silane] B hexyl acrylamide], methacrylamides, and acrylonitrile derivatives.

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

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

  A preferred form of the fluorine-containing polymer for the low refractive index layer is a copolymer represented by the general formula 1.

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

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

  In the general formula 1, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

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

x, y, and z represent the mol% of each constituent component, and preferably 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65, and more preferably 35 ≦ x ≦ 55 and 30 ≦ y ≦. 60, 0 ≦ z ≦ 20, particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10. However, x + y + z = 100.
A particularly preferred form of the copolymer used in the present invention is General Formula 2.

In general formula 2, X represents the same meaning as in general formula 1, and the preferred range is also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable.
x, y, z1 and z2 represent mol% of each repeating unit, and x and y preferably satisfy 30 ≦ x ≦ 60 and 5 ≦ y ≦ 70, respectively, more preferably 35 ≦ x ≦ 55. 30 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55 and 40 ≦ y ≦ 55. z1 and z2 preferably satisfy 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65, more preferably 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10, and 0 ≦ z1 ≦ 10, 0 It is particularly preferable that ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.

For the copolymer represented by the general formula 1 or 2, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized. As the reprecipitation solvent used at this time, isopropanol, hexane, methanol and the like are preferable.
Preferable specific examples of the copolymer represented by the general formula 1 or 2 include those described in [0035] to [0047] of JP-A-2004-45462, and the method described in the publication Can be synthesized.

(Inorganic fine particles for low refractive index layer)
The amount of the inorganic fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance may deteriorate. It is preferable to be inside.
Since the inorganic fine particles are contained in the low refractive index layer, a low refractive index is desirable. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle diameter of the inorganic fine particles is preferably 30% or more and 100% or less, more preferably 35% or more and 80% or less, and still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced. Therefore, it is preferable to be within the above range. The inorganic fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Here, the average particle diameter of the inorganic fine particles can be measured by a Coulter counter.

In order to further reduce the increase in the refractive index of the low refractive index layer, the inorganic fine particles preferably have a hollow structure, and the refractive index of the inorganic fine particles is 1.17 to 1.40, more preferably 1. It is 17-1.35, More preferably, it is 1.17-1.30. Here, the refractive index represents the refractive index of the entire particle, and does not represent the refractive index of only the inorganic material of the outer shell in the case of inorganic fine particles having a hollow structure. At this time, when the radius of the cavity in the particle is a and the radius of the particle shell is b, the porosity x represented by the following formula (II) is preferably 10 to 60%, more preferably 20 to 60. %, Most preferably 30-60%.
(Formula II)
^{x = (4πa 3/3)} / (4πb 3/3) × 100

If the refractive index of hollow inorganic fine particles is made lower and the porosity is increased, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Therefore, from the viewpoint of scratch resistance, the refractive index is 1 Particles with a low refractive index of less than .17 do not hold.
The refractive index of the inorganic fine particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

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

Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. Of these, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during the preparation of the layer coating solution. It is preferable to make it contain.
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 for low refractive index layer and its derivatives)
The curable composition contains at least one selected from the group consisting of an organosilane compound, a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate of the organosilane. In particular, it is preferable in terms of achieving both the antireflection ability and the scratch resistance.
Hereinafter, a reaction solution containing a hydrolyzate of organosilane or a partial condensate thereof is also referred to as a “sol component”.
This organosilane compound, or its sol component, functions as a binder for the low refractive index layer by applying the curable composition and then condensing in a drying and heating step to form a cured product. Moreover, when it has the said fluoropolymer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

The organosilane compound is preferably represented by the following general formula [A].
Formula [A]
(R ¹⁰ ) _m -Si (X) _4-m
In the general formula [A], R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X may be different even in the same, respectively.
The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.

When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.
Among the organosilane compounds represented by the general formula [A], an organosilane compound having a vinyl polymerizable substituent represented by the following general formula [B] is preferable.

In the general formula [B], R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

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

n represents 0 or 1. n is preferably 0. When there are a plurality of Xs, the plurality of Xs may be the same or different.
R ¹⁰ has the same meaning as in formula [A], preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as in the general formula [A], preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred.

  Two or more compounds of the general formula [A] and general formula [B] may be used in combination. Although the specific example of a compound represented by general formula [A] and general formula [B] is shown, it is not limited to the following.

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

  When used as a sol component, the hydrolyzate of the organosilane compound or the partial condensate of the hydrolyzate is generally produced by treating the organosilane compound in the presence of a catalyst. . Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. In the present invention, it is preferable to use a metal chelate compound, an acid catalyst of inorganic acids and organic acids. Inorganic acids are preferably hydrochloric acid and sulfuric acid, and organic acids are preferably those having an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and further, acid dissociation constants in hydrochloric acid, sulfuric acid and water. Is preferably an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferably an organic acid having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

As the metal chelate compound, (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

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

  Moreover, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the composition for a low refractive index layer. This will be further described below.

The β-diketone compound and / or β-ketoester compound is preferably a β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ^5, which is a composition for a low refractive index layer. It acts as a stability improver. Here, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating to the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate or partial condensate of the organosilane compound by these metal chelate compounds is promoted. It is thought that the action which suppresses the effect | action to make and the effect | action which improves the storage stability of the composition obtained is made. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

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

The compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass based on the total solid content of the low refractive index layer.
The organosilane compound may be added directly to the curable composition (coating liquid for internal scattering layer, low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance. It is preferable to prepare a hydrolyzate of the compound or a partial condensate thereof, and adjust the curable composition using the obtained reaction solution (sol solution). In the present invention, first, the hydrolysis of the organosilane compound is performed. Or a composition containing a partial condensate thereof and a metal chelate compound, and a liquid in which a β-diketone compound and / or a β-ketoester compound is added to at least one of an internal scattering layer or a low refractive index layer It is preferable to coat the coating liquid so that it is contained.

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

(Sol-gel material)
Various sol-gel materials can also be used as the material for the low refractive index layer. As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

(Other substances contained in the composition for the low refractive index layer)
In addition to the aforementioned fluorine-containing polymer, inorganic fine particles, and organosilane compound, various additives, radical polymerization initiators, and cationic polymerization initiators can be added to the low refractive index layer composition as necessary. . At this time, the concentration of solids such as additives is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably. It is about 1% to 20% by mass.

  Curing agents such as polyfunctional (meth) acrylate compounds, polyfunctional epoxy compounds, polyisocyanate compounds, aminoplasts, polybasic acids or anhydrides thereof from the viewpoint of interfacial adhesion with the lower layer directly in contact with the low refractive index layer Can also be added in small amounts. When adding these, it is preferable to set it as the range of 30 mass% or less with respect to the total solid of a low refractive index layer film | membrane, It is more preferable to set it as the range of 20 mass% or less, The range of 10 mass% or less It is particularly preferable that

  In addition, for the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, a known silicone compound or fluorine compound antifouling agent, slipping agent, and the like may be appropriately added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferred silicone compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), manufactured by Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (named above) but not limited thereto.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), but alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl groups) , A perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C). ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , —CH ₂ C H ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, defender MCF-300 (trade name), etc., but are not limited thereto.

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

  In addition, an inorganic filler other than the above-described inorganic fine particles can be added to the composition for a low refractive index layer in an addition amount within a range that does not impair the desired effect of the present invention. As the inorganic filler, those described above can be used.

(Solvent for low refractive index layer)
As a solvent used in the coating composition for forming the low refractive index layer, it is possible to dissolve or disperse each component, to easily form a uniform surface in the coating process and the drying process, and to ensure liquid storage stability. Various solvents selected from the viewpoint of having an appropriate saturated vapor pressure can be used. From the viewpoint of the drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of a solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C)
), Ethers such as ethyl formate (54.2 ° C.), methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.) ), 2-butanone (same as methyl ethyl ketone, 79.6 ° C.), methanol (64.5 ° C.), ethanol (78.3 ° C.), 2-propanol (82.4 ° C.), 1-propanol ( Alcohols such as 97.2 ° C., cyano compounds such as acetonitrile (81.6 ° C.) and propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C or higher include, for example, octane (125.7 ° C), toluene (110.6 ° C), xylene (138 ° C), tetrachloroethylene (121.2 ° C), chlorobenzene (131.7 ° C), Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.), Examples thereof include 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

[Transparent conductive layer]
The antireflection film of the present invention is preferably provided with a transparent conductive layer for the purpose of antistatic from the viewpoint of preventing static electricity on the film surface. The transparent conductive layer is effective when there is a demand for lowering the surface resistance value from the display side or when dust on the surface or the like becomes a problem. As a method of forming the transparent conductive layer, for example, a method of applying a conductive coating solution containing conductive particles and a reactive curable resin, or a metal or metal oxide forming a transparent film is deposited or sputtered. And a known method such as a method of forming a conductive thin film. In the case of coating, the method is not particularly limited, and an optimal method is selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, etc., depending on the properties of the coating liquid and the coating amount. Just do it.
The transparent conductive layer can be formed on the transparent support or the internal scattering layer directly or via a primer layer that strengthens adhesion with them.

  The thickness of the transparent conductive layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and further preferably from 0.05 to 5 μm. When used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin. The surface resistance of the transparent conductive layer is preferably 105 to 1012 Ω / sq, more preferably 105 to 109 Ω / sq, and most preferably 105 to 108 Ω / sq. The surface resistance of the transparent conductive layer can be measured by a four probe method.

It is preferable that the transparent conductive layer is substantially transparent. Specifically, the haze of the transparent conductive layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. preferable. The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The transparent conductive layer preferably has excellent strength, and the specific antistatic layer has a pencil hardness of 1 kg (as defined in JIS-K-5400), preferably H or higher. More preferably, it is more preferably 3H or more, and most preferably 4H or more.

(Electrically conductive particles)
The average particle diameter of the primary particles of the conductive particles used for the transparent conductive layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive particles in the formed transparent conductive layer is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.
The specific surface area of the energizing particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The conductive particles are preferably inorganic fine particles made of a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred.
The conductive particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and a halogen atom are mentioned. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

The conductive particles may be surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

The ratio of the conductive inorganic fine particles in the transparent conductive layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.
Two or more kinds of conductive particles may be used in combination in the transparent conductive layer.

  The conductive particles can be used in the transparent conductive layer in a dispersion state. As the dispersion medium for the conductive particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1 Methoxy-2-propanol). Among these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable. The conductive particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with pins), a high speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill, and a sand grinder mill and a high speed impeller mill are particularly preferable. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

(Binder for transparent conductive layer)
The transparent conductive layer can use a crosslinked polymer as a binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked. The anionic group has a function of maintaining the dispersed state of the conductive particles. The crosslinked structure has a function of strengthening the transparent conductive layer by imparting a film forming ability to the polymer.

  Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group.
The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group.
In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—).
The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group).

The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group).
In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group.
The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group).
The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked structure.

The anionic group is bonded directly to the main chain of the polymer or bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group.
Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.
The anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated.
The linking group that binds the anionic group and the polymer main chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof.

  The crosslinked structure chemically bonds (preferably covalently bonds) two or more main chains. The cross-linked structure is preferably covalently bonded to three or more main chains. The cross-linked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

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

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. In addition, even if the amino group, the quaternary ammonium group and the benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure, the same effect can be obtained.

In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group.
The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6.

  The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the crosslinked polymer having an anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. % Is more preferable, and 0.1 to 28% by mass is most preferable.

  For example, the following reactive organosilicon compound described in JP-A-2003-39586 can be used in combination with the binder. The reactive organosilicon compound is used in the range of 10 to 100% by weight with respect to the total of the ionizing radiation curable resin and the reactive organosilicon compound. In particular, when the ionizing radiation curable organosilicon compound (3) below is used, it is possible to form a conductive layer using only this as a resin component.

(1) Silicon alkoxide is a compound represented by RmSi (OR ') n, wherein R and R' represent an alkyl group having 1 to 10 carbon atoms, and m and n are integers such that m + n = 4, respectively. . For example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, Tetrapenta-iso-propoxysilane, tetrapenta-n-proxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyl tributoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl ethoxy silane, dimethyl methoxy silane, dimethyl propoxy silane, dimethyl butyl Kishishiran, methyldimethoxysilane, methyldiethoxysilane, hexyl trimethoxysilane.

(2) Silane coupling agent For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxy Silane, aminosilane, methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3 (Trimethoxysilyl) propyl] ammonium chloride, methyl trichlorosilane, dimethyl dichlorosilane, and the like.

(3) Ionizing radiation curable silicon compound A plurality of groups that undergo reactive crosslinking by ionizing radiation, for example, organosilicon compounds having a molecular weight of 5,000 or less having a polymerizable double bond group. Such reactive organosilicon compounds may be one end vinyl functional polysilane, both end vinyl functional polysilane, one end vinyl functional polysiloxane, both end vinyl functional polysiloxane, or a vinyl functionality obtained by reacting these compounds. Examples include polysilane, vinyl functional polysiloxane, and the like.

  Examples of other compounds include (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane.

  In order to further develop the antistatic function, as disclosed in Japanese Patent Application Laid-Open No. 2003-39586, the conductive particles are dispersed in the internal scattering layer of the present invention to have a function as an anisotropic conductive film. It is also preferable.

[Transparent support]
A plastic film is preferably used as the transparent support of the antireflection film. As the polymer forming the plastic film, cellulose acylate (eg, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, typically TAC-TD80U, TD80UL, etc. manufactured by Fuji Photo Film), Polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON Corporation), Etc. Among these, triacetyl cellulose, polyethylene terephthalate, norbornene resin, and amorphous polyolefin are preferable, and triacetyl cellulose is particularly preferable.

  Cellulose acylate consists of a single layer or a plurality of layers. A single-layer cellulose acylate is prepared by drum casting or band casting disclosed in Japanese Patent Application Laid-Open No. 7-11055, and the latter cellulose acylate is a feature of the published patent publication. It is produced by the so-called co-casting method disclosed in Japanese Utility Model Publication Nos. 61-94725 and 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose ester dope, and the film is dried to some extent on the support to release the rigid film, and then peeled off from the support. A process comprising passed through a drying section by species of the conveying means to remove the solvent.

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

  Various cellulose acylate films as described above (films made of triacetyl cellulose and the like) and production methods thereof are described in JIII Journal of Technical Disclosure No. 2001-1745 (issued on March 15, 2001). Yes.

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

[About other layers]
[Other layers]
Examples of other layers that may be provided between the transparent support and the internal scattering layer of the present invention include a moisture-proof layer, an adhesion improving layer, and a rainbow unevenness (interference unevenness) preventing layer. These layers can be formed by a known method.

[Method for producing antireflection film]
The antireflection film of the present invention can be formed by the following method, but is not limited to this method.
(Coating solution adjustment)
First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating or before and after that.

  In the coating solution for forming the internal scattering layer, almost all foreign matters having a size corresponding to the dry film thickness (about 50 nm to 120 nm) of the low refractive index layer directly formed thereon are indicated (indicating 90% or more). It is preferable to perform filtration that can be removed. Since the light-transmitting fine particles for imparting water are equal to or greater than the film thickness of the low refractive index layer, the filtration is preferably performed on the intermediate liquid to which all materials other than the light-transmitting fine particles are added. In addition, when a filter capable of removing foreign substances having a small particle diameter as described above is not available, almost all foreign substances corresponding to the wet film thickness (about 1 to 10 μm) of the layer directly formed thereon are removed. It is preferable to perform filtration. By such means, the point defects of the layer formed directly thereon can be reduced.

(Application)
Next, a coating solution for forming an internal scattering layer and, if necessary, a low refractive index layer is applied onto the transparent support by a coating method such as an extrusion method (die coating method) or a micro gravure method, dry. Thereafter, the monomer and curable resin for forming the internal scattering layer or the low refractive index layer are cured by light irradiation and / or heating. Thereby, an internal scattering layer and a low refractive index layer are formed.

In order to supply the antireflection film with high productivity, an extrusion method (die coating method) is preferably used. In particular, a die coater that can be preferably used in a region with a small amount of wet coating (20 cc / m ² or less) such as an internal scattering layer or an antireflection layer will be described below.
<Die coater configuration>
FIG. 3 is a cross-sectional view of a coater using the slot die according to the embodiment of the present invention. The coater 10 is applied to the web W supported by the backup roll 11 and continuously applied from the slot die 13 as a bead 14a to form a coating film 14b on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular as shown in FIG. 3, for example, or semicircular. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  A tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is formed in a tapered shape, and a flat portion 18 called a land is formed at the tip. In the land 18, the upstream side in the traveling direction of the web W with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

4A shows the cross-sectional shape of the slot die 13 in comparison with the conventional one, FIG. 4A shows the slot die 13 shown in FIG. 3, and FIG. 4B shows the conventional slot die 30. ing. In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13, the downstream lip land length I _LO is shortened, so that application with a wet film thickness of 20 μm or less can be performed with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is not less than 30 μm and not more than 100 μm, preferably not less than 30 μm and not more than 80 μm, more preferably not less than 30 μm and not more than 60 μm. If the land length I _LO of the downstream lip is shorter than 30 μm, the edge or land of the tip lip is likely to be chipped, streaks are likely to occur in the coating film, and consequently application is impossible. In addition, it becomes difficult to set the position of the wetting line on the downstream side, and there is a problem that the coating liquid tends to spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, when the land length I _LO of the downstream lip is longer than 100 μm, the bead itself cannot be formed, so that it is impossible to apply the thin layer.

Further, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be lowered, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream side lip land 18b and the web W of the upstream side lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap _GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

FIG. 5 is a perspective view showing the slot die and its periphery in the coating process according to the present embodiment. On the opposite side of the web W in the direction of travel, a decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a (FIG. 3) so that sufficient decompression adjustment can be performed. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and there are gaps G _B and G between the back plate 40a and the web W and between the side plate 40b and the web W, respectively. _S exists. 6 and 7 are cross-sectional views showing the decompression chamber 40 and the web W that are close to each other. The side plate and the back plate may be integrated with the chamber main body as shown in FIG. 5, or may have a structure fastened to the chamber with screws 40c or the like so that the gap can be appropriately changed as shown in FIG. In any structure, portions that are actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W of the decompression chamber 40, when the vacuum chamber 40 is installed beneath the web W and the slot die 13 as shown in FIG. 5, the uppermost end of the back plate 40a to the web W (Fig. 6, Fig. 7).

Is preferably placed in the gap G _B between the back plate 40a and the web W is larger than the gap G _L between the end lip 17 and the web W of the slot die 13, beads vicinity due to the eccentricity of the backup roll 11 thereby The change in the degree of decompression can be suppressed. For example, when the gap G _L between the end lip 17 and the web W of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web W is preferably 100μm or 500μm or less.

<Material and accuracy>
The longer the length of the tip lip on the web traveling direction side in the web running direction, the more disadvantageous it is for bead formation. Become stable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.
Further, regarding the material of the tip lip of the slot die, if a material such as stainless steel is used, the length of the slot die tip lip in the web running direction is set to 30 to 100 μm as described above. Even within this range, the accuracy of the tip lip cannot be satisfied. Therefore, in order to maintain high processing accuracy, it is important to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Cemented carbides include carbide carbide particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.
In order to realize high-precision coating, the length of the land on the web traveling direction side of the tip lip and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of these two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness of the tip lip and the backup roll is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.

<Application speed>
By achieving the accuracy of the backup roll and the tip lip as described above, the coating method preferably used in the present invention has high film thickness stability during high-speed coating. Furthermore, since the coating method according to this embodiment is a pre-measuring method, it is easy to ensure a stable film thickness even during high-speed coating. With respect to a coating solution having a low coating amount such as the antireflection film of the present invention, the above coating method can be applied at high speed with good film thickness stability. Although application is possible by other application methods, the dip coating method inevitably causes vibration of the application liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method, stepped unevenness is likely to occur due to eccentricity and deflection of the roll related to coating. Moreover, since these coating methods are post-measuring methods, it is difficult to ensure a stable film thickness. In the production method of the present invention, coating at 25 m / min or more is preferable from the viewpoint of productivity.

<Wet application amount>
When forming the internal scattering layer, it is preferable to apply the coating liquid in the range of 6 to 30 μm as the wet coating thickness directly or via another layer on the base film, and further from the viewpoint of preventing drying unevenness. A range of 3 to 20 μm is more preferable. Further, when forming the low refractive index layer, it is preferable to apply the coating composition in the range of 1 to 10 μm as the wet coating thickness directly on the internal scattering layer or via another layer. More preferably, it is applied in the range of 6 μm.

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

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

  It is also possible to control the surface irregularities to some extent by the drying conditions. In this invention, it discovered that the formation of surface unevenness | corrugation can be suppressed by applying a dry wind early after application | coating, and made it possible to control to a preferable surface unevenness | corrugation range.

(Curing)
After the solvent drying zone, the coating is cured by passing through a zone where the coating is cured by ionizing radiation and / or heat on the web. For example, if the coating film is UV curable, it is to cure each layer by irradiating an irradiation amount of ultraviolet rays of 10mJ / cm ² ~1000mJ / cm ² by an ultraviolet lamp preferred. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation. Further, when it is necessary to purge nitrogen gas or the like to lower the oxygen concentration in order to promote surface hardening, the oxygen concentration is preferably 0.01% to 5%, and the distribution in the width direction is 2% or less in terms of oxygen concentration. Is preferred.

  Further, when the curing rate (100-residual functional group content) of the internal scattering layer becomes a certain value less than 100%, a low refractive index layer is provided thereon and the low refractive index layer is formed by ionizing radiation and / or heat. If the curing rate of the lower internal scattering layer is higher than that before providing the low refractive index layer when the is cured, the adhesion between the internal scattering layer and the low refractive index layer is improved, which is preferable.

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

  When producing a polarizing plate using an antireflection film as one of the surface protective films of two polarizing films, the antireflection film is used as a transparent support on the side opposite to the side having the antireflection structure. It is preferable to improve the adhesion on the adhesive surface by hydrophilizing the surface of the film, that is, the surface to be bonded to the polarizing film. The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol. As the hydrophilic treatment of the antireflection film, the following saponification treatment is preferably performed.

(Saponification treatment)
(1) Method of immersing in an alkaline solution This is a technique in which an antireflection film is immersed in an alkaline solution under appropriate conditions, and all surfaces having reactivity with alkali on the entire surface of the film are saponified, and special equipment Is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set depending on the material and configuration of the antireflection film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

  In the saponification treatment, the lower the contact angle with water on the surface of the transparent support opposite to the side having the internal scattering layer or the low refractive index layer, the better from the viewpoint of adhesiveness to the polarizing film. In such a dipping method, alkali damage is caused from the surface having the internal scattering layer and the low refractive index layer to the inside at the same time, so that it is important to set the necessary minimum reaction conditions. When the contact angle to water of the transparent support on the opposite surface is used as an index of damage to each layer due to alkali, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or more, there is a problem in the adhesion to the polarizing film, which is not preferable. On the other hand, if it is less than 10 degrees, the damage received by the antireflection film is too large, and the physical strength is impaired, which is not preferable.

(2) Method of applying alkaline solution As a means for avoiding damage to each film in the above-mentioned immersion method, the alkaline solution is applied only to the surface opposite to the surface having the internal scattering layer or antireflection film under appropriate conditions. An alkaline solution coating method of heating, washing with water and drying is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, and peeling due to alkali solution, so it is not desirable to use the immersion method. Is possible.

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

(3) Method of saponification by protecting the internal scattering layer and antireflection layer with a laminate film When the internal scattering layer and / or the low refractive index layer is insufficient in resistance to an alkaline solution, as in (2) above Then, after forming the final layer, the laminate film is bonded to the surface on which the final layer is formed, and then immersed in an alkaline solution to hydrophilize only the side of the triacetyl cellulose opposite to the surface on which the final layer has been formed. The laminate film can be peeled off. Even in this method, only the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed is subjected to the hydrophilization treatment necessary for the polarizing plate protective film without damaging the internal scattering layer and the low refractive index layer. Can do. Compared with the method (2), the laminate film is generated as waste, but there is an advantage that a device for applying a special alkaline solution is unnecessary.

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

(5) Method of forming an internal scattering layer or an antireflection layer on a previously saponified triacetyl cellulose film Saponified by, for example, pre-immersing the triacetyl cellulose film in an alkaline solution, directly or on the other surface An internal scattering layer and a low refractive index layer may be formed through the layers. In the case of saponification by dipping in an alkali solution, the interlaminar adhesion between the internal scattering layer or another layer and the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the internal scattering layer or other layer is formed is treated by corona discharge, glow discharge or the like to remove the hydrophilic surface, and then the internal scattering layer or other layer. Can be dealt with by forming Further, when the internal scattering layer or other layer has a hydrophilic group, the interlayer adhesion may be good.

Below, the polarizing plate using the antireflection film of this invention and the liquid crystal display device using this polarizing plate are demonstrated.
[Polarizer]
The preferable polarizing plate of this invention has the antireflection film of this invention as at least one of the protective film (protective film for polarizing plates) of a polarizing film. As described above, the polarizing plate protective film has a water contact angle of 10 on the surface of the transparent support opposite to the side having the internal scattering layer and the low refractive index layer, that is, the surface to be bonded to the polarizing film. It is preferable to be in the range of degrees to 50 degrees.
By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having a light scattering function or an antireflection function excellent in physical strength and light resistance can be produced. Can be realized.
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, In addition, it is possible to improve the visibility and contrast in a bright room of a liquid crystal display device, and to produce a polarizing plate that can greatly widen the vertical and horizontal viewing angles.

(Optical compensation film)
By using the optical compensation film for the polarizing plate, the viewing angle characteristics of the liquid crystal display screen can be improved, and the optical compensation film can be preferably used on the opposite side of the antireflection film of the present invention across the polarizer. The compensation form may be affixed on the protective film on one side of the polarizing plate with an adhesive, or may be used as a protective film on one side. From the viewpoint of the thickness of the polarizing plate, it is particularly desirable to use the antireflection film of the present invention as the protective film on one side and the optical compensation film as the protective film on the opposite side across the polarizer. An optical compensation film may contain a specific optical anisotropy by adding a substance having optical anisotropy to the film itself, stretching the film, or both. Alternatively, an optically anisotropic layer (retardation layer) may be provided on the film.
As the optical compensation film, a known film can be used, but in terms of widening the viewing angle, a film having a layer having optical anisotropy made of a compound having a discotic structural unit is desirable. Wide view films (WV-A, WV-SA) made by Fuji Photo Film are available, but not limited to these.
Further, in order to improve the contrast and color of the liquid crystal display, the optical anisotropy (Re, Rth) is small and substantially optically isotropic, and further the optical anisotropy (Re , Rth) having a small wavelength dispersion is preferably used, and in the case of a reflective display, it is also preferable to use a film having a function of a λ / 4 plate composed of one or a plurality of films.
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.

(Polarizing film)
As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, at the time of stretching by applying tension while holding both ends of a continuously supplied polymer film by a holding means, the film is stretched at least 1.1 to 20.0 times in the film width direction, and the film is held at both ends. The direction of travel of the film is such that the angle between the direction of travel of the film at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be manufactured by a stretching method in which both ends of the film are bent. In particular, a film whose absorption axis is inclined by 45 ° with respect to the longitudinal direction is preferably used from the viewpoint of productivity of the polarizing plate.
The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

[Image display device]
The antireflection film of the present invention includes a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode tube display (CRT), a field emission display (FED), and a surface electric field display (SED). The present invention can be applied to such an image display device. Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

  It is particularly preferable to prepare a polarizing plate using the antireflection film of the present invention as one side of the surface protective film of the polarizing film and use it on the surface of the liquid crystal display device. In this case, transmissive and reflective types of modes such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB), etc. Alternatively, it can be preferably used for a transflective liquid crystal display device. In particular, it can be preferably used for VA, IPS, OCB, etc. as a use for large liquid crystal televisions, etc., and it can also be preferably used for TN, STN, etc. if it is used for small and medium display devices. For applications such as liquid crystal televisions, the diagonal of the display screen is 13 inches or more, particularly preferably 20 inches or more. Since the antireflection film of the present invention has a surface haze value, roughness and the like in a preferable range, there is substantially no problem of glare and it can be used without limitation with regard to definition, but it is XGA or less (aspect ratio) In a display device of 3: 4, it can be particularly preferably used for 1024 × 768 or less).

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625 (in Japanese Patent Publication No. 176625), and (2) a liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

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

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

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

(Synthesis of perfluoroolefin copolymer (1))

A 40 ml stainless steel autoclave with a stirrer was charged with 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide, and the system was degassed and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 0.53 MPa (5.4 kgf / cm ² ). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa (3.2 kgf / cm ² ), the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1). The resulting polymer had a refractive index of 1.421.

(Preparation of sol solution)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. Thereafter, 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 dispersion A)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20 mass%, silica particle refractive index 1.31, change size according to Preparation Example 4 of JP-A-2002-79616. Preparation) 30 g of acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 g of diisopropoxyaluminum ethyl acetate were added to and mixed with 500 g, and 9 g of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 g 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. There was no generation of foreign matter in the dispersion, and the viscosity when the solid content concentration was adjusted with cyclohexanone to 20% by mass was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion Ag was analyzed by gas chromatography, it was 1.5%.

[Example 1]
(Preparation of coating solution A for internal scattering layer)
71.0 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PET-30, Nippon Kayaku Co., Ltd.) and 3.0 g of a polymerization initiator (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) , 0.1 g of fluorine-based surface modifier (FP-149), 11.9 g of silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a mixed solvent of methyl isobutyl ketone and methyl ethyl ketone, The solute was completely dissolved by stirring for 60 minutes with an air disper. The refractive index of the coating film obtained by applying this solution and then curing with ultraviolet rays was 1.520. 6.3 g of crosslinked poly (styrene) particles having an average particle size of 3.5 μm (refractive index of 1.600) and crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50, refraction) (Rate 1.536) 7.7 g was dispersed with a Polytron disperser at 10,000 rpm for 20 minutes, added as a 30% methyl isobutyl ketone dispersion, methyl isobutyl ketone and methyl ethyl ketone were added, and the ratio of methyl isobutyl ketone to methyl ethyl ketone was 70 pairs. 30. After adjusting the solid content concentration to 45% by mass, the mixture was stirred with an air disper for 10 minutes.
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution A for internal scattering layer.

(Adjustment of coating solution A for low refractive index layer)
With respect to 783.3 parts by mass (47.0 parts by mass as a solid content) of OPSTA JTA113 (thermally crosslinkable fluorine-containing silicone polymer composition liquid (solid content: 6%): manufactured by JSR Corporation), dispersion A was 195 Mass parts (silica + 39.0 parts by mass as surface treatment agent solid content), colloidal silica dispersion (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, Nissan Chemical Co., Ltd. 30.0 parts by mass (9.0 parts by mass as solid content) and 17.2 parts by mass of sol liquid a (5.0 parts by mass as solids) were added. The coating liquid A for low refractive index was prepared by diluting with cyclohexane and methyl ethyl ketone so that the solid content concentration of the entire coating liquid was 6% by mass and the ratio of cyclohexane and methyl ethyl ketone was 10:90. The refractive index of the layer formed by this coating solution was 1.39.

(1) Coating of internal scattering layer A 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unrolled in a roll form, and the die coat shown by the following apparatus configuration and coating conditions The coating solution A for the internal scattering layer was applied by the method, dried at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds, and then air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under a nitrogen purge. Then, the coating layer was cured by irradiating ultraviolet rays having an irradiation energy intensity of 90 mJ / cm ² to form an internal scattering layer having a thickness of 7.2 μm and wound up. By controlling the time to start applying the drying air in 2 to 10 seconds after coating, the appearance of surface irregularities was controlled. The particle density in the formed film was 1.21 g / m 2.

Basic conditions: The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and the length of the slot 16 The one with a length of 50 mm was used. The gap between the upstream lip land 18a and the web W is 50 μm longer than the gap between the downstream lip land 18b and the web W (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web W _GL was set to 50 μm. Further, the gap G _B between the gap G _S, and the back plate 40a and the web W between the side plate 40b and the web W in the vacuum chamber 40 were both 200 [mu] m.

(2) Coating of low refractive index layer The triacetyl cellulose film coated with the internal scattering layer coating liquid A and coated with the internal scattering layer is unwound again, and the low refractive index layer coating liquid A is used as described above. After being dried at 120 ° C. for 150 seconds, further dried at 140 ° C. for 8 minutes, and then purged with nitrogen in an atmosphere with an oxygen concentration of 0.1%, an air-cooled metal halide lamp (eye graphics) Ltd.) was used an irradiation energy intensity 300 mJ / cm ^2, to form a low refractive index layer having a thickness of 100 nm, it was wound.
(3) Saponification treatment of antireflection film After the formation of the low refractive index layer, the sample was subjected to the following treatment.
A 1.5 mol / l aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
In this way, a saponified antireflection film was produced. This is Example 1-1.

  Examples 1-2 to 1 were produced in the same manner as in Example 1-1 except that the addition amount of the two types of particles of the coating liquid A for the internal scattering layer was changed so as to obtain the particle ratio and particle density shown in Table 2. -5 was produced.

  Instead of the crosslinked poly (acryl-styrene) particles having an average particle diameter of 3.5 μm (copolymerization composition ratio = 50/50, refractive index 1.536) of the coating liquid A for the internal scattering layer, a bridge having an average particle diameter of 3.5 μm Poly (acryl-styrene) particles (copolymerization composition ratio = 30/70, refractive index 1.561) were used, and the addition amount of the two types of particles was changed so that the particle ratio and particle density shown in Table 2 were obtained. Example 1-6 was produced in the same manner as in Example 1-1 except for the above.

(Preparation of coating solution B for internal scattering layer)
70.9 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PET-30, manufactured by Nippon Kayaku Co., Ltd.) and 3.4 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) , 0.1 g of fluorine-based surface modifier (FP-149), 13.0 g of silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) are added to methyl isobutyl ketone and methyl ethyl ketone, The solute was completely dissolved by stirring for 60 minutes. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.523. 12.6 g of a crosslinked poly (acryl-styrene) particle having an average particle size of 3.5 μm (copolymerization composition ratio = 30/70, refractive index 1.561) was dispersed with a Polytron disperser at 10,000 rpm for 20 minutes and 30% methyl isobutyl. It added as a ketone dispersion liquid, methyl isobutyl ketone and methyl ethyl ketone were added, solid content concentration was adjusted to 43.5 mass%, and it stirred for 10 minutes with the air disper. The ratio of methyl isobutyl ketone and methyl ethyl ketone was adjusted to 80:20.
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution B for internal scattering layer.

Example 1-7 was produced by the same production method as Example 1-1 except that the layer coating solution B was used. The layer thickness of Example 1-7 was 5.8 μm, and the particle density in the formed film was 0.90 g / m ² .

  A part of crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 30/70, refractive index 1.561) having a mean particle size of 3.5 μm in the coating liquid B for internal scattering layer is crosslinked poly (acryl-styrene). Example 1-7, except that instead of the particles (copolymerization composition ratio = 50/50, refractive index 1.536), the addition amount of the two kinds of particles was changed so that the particle ratio and particle density shown in Table 2 were obtained. Examples 1-8 to 11 were produced by the same production method.

  Part of the crosslinked poly (acryl-styrene) particles (copolymerization composition ratio = 30/70, refractive index 1.561) having an average particle size of 3.5 μm in the coating liquid B for internal scattering layer was crosslinked with poly (styrene) particles ( Example 1-12, except that the addition ratio of the two kinds of particles was changed so that the particle ratio and particle density shown in Table 2 were obtained instead of the refractive index 1.600). 13 was produced.

Example 1-14 was produced in the same manner as in Example 1-1 except that the low refractive index layer was not applied.

  Comparative Examples 1-1 to 1-1 using the same production method as Example 1-1, except that the addition amount of the two types of particles of coating liquid A for internal scattering layer was changed so as to achieve the particle ratio and particle density shown in Table 2 -4 was produced.

  The same production method as in Example 1-1, except that the addition amount of the two types of particles in the coating solution for internal scattering layer used in Example 1-8 was changed so that the particle ratio and particle density shown in Table 2 were obtained. Comparative Examples 1-5 to 1-8 were produced.

  Example 1-1 except that the addition amount of the two types of particles of the coating liquid A for internal scattering layer was changed so as to obtain the particle ratio and particle density shown in Table 2, the coating amount was adjusted, and the film thickness was changed. Comparative Example 1-9 was produced by the same production method.

  Compared with the same production method as in Example 1-7, except that the amount of particles of the coating liquid B for internal scattering layer was changed so that the particle density shown in Table 2 was changed, the coating amount was adjusted, and the film thickness was changed. Examples 1-10 were made.

(Evaluation of film)
About the obtained film, the following items were evaluated. The results are shown in Table 3.
(1) Reflection photogoniometer A glass plate with a thickness of 1 mm (micro slide glass product number S9111, manufactured by MATSANAMI) on both sides of the back and front surfaces of a polarizing plate with a smooth surface bonded in a crossed nicols state. The antireflection film of the invention was bonded to the side opposite to the side on which the antireflection layer was applied with an adhesive sheet to produce a sample piece for measurement. Subsequently, using a “goniophotometer” machine manufactured by Murakami Color Materials Laboratory Co., Ltd., the incident angle is set to 0 °, and the light receiver is measured in increments of 0.1 ° from 90 ° to 180 ° to −90 °. Then, the total light quantity I _a which is the sum of them was measured.
Subsequently, the incident angle is set to −60 °, and the sample piece is in the range of 40 ° to 50 ° with respect to the incident light quantity I ₀ inclined by −60 ° with respect to the vertical direction from the low refractive index layer side. The amount of reflected light was measured in increments of 0.1 °, the numerical value was read for the amount of light I ⁴⁵ ° reflected in the direction inclined ⁴⁵ °, and the value of −LOG ₁₀ (I ⁴⁵ ° / I ₀ ) at each angle was calculated.
(2) Integral reflectivity The back side of the film was treated with a black ink after the back surface was made with sandpaper, and the surface side was removed using a spectrophotometer (manufactured by JASCO Corporation) with no back reflection. The integrated spectral reflectance was measured in the wavelength region of 380 to 780 nm. The arithmetic average value of the integrated reflectance of 450 to 650 nm was used for the result.
(3) Specular reflectance The back side of the film was treated with black ink after making the back side with sandpaper, and the surface side was removed using a spectrophotometer (manufactured by JASCO Corporation) in a state where the back side reflection was eliminated. In the wavelength region of 380 to 780 nm, specular spectral reflectance at an incident angle of 5 ° was measured. The arithmetic average value of the specular reflectance of 450-650 nm was used for the result.

(4) Haze The following measurements measured the total haze (H), internal haze (Hi), and surface haze (Hs) of the obtained film.
[1] The total haze value (H) of the film obtained according to JIS-K7136 was measured.
[2] A few drops of silicone oil were added to the front and back surfaces of the obtained film on the low refractive index layer side, and two glass plates (micro slide glass product number S 9111, manufactured by MATSANAMI) having a thickness of 1 mm were used from the front and back. The two glass plates and the obtained film are optically closely attached, and the haze is measured with the surface haze removed, and only silicone oil is sandwiched between two separately measured glass plates. The value obtained by subtracting the haze measured in step 1 was calculated as the internal haze (Hi) of the film.
[3] A value obtained by subtracting the internal haze (Hi) calculated in [2] from the total haze (H) measured in [1] was calculated as the surface haze (Hs) of the film.
(5) Image clarity The transmitted image clarity was measured with an optical comb width of 0.5 mm in accordance with JIS K7105.

(6) Centerline average roughness The centerline average roughness Ra of the film obtained according to JIS-B0601 was measured.

(7) Reflection A face was reflected on the sample piece for photogoniometer measurement in (1), and the intensity of the reflected image was evaluated according to the following criteria.
Reflection is weak and reflection is hardly noticed: ○
Reflection is strong and I am worried about reflections: △
Reflection is very strong and reflection is very worrisome: ×

<Test results>
In all of the samples of Examples 1-1 to 1-13, the transmitted image sharpness was in the range of 60 to 99%, and the value of −LOG ₁₀ (I ⁴⁵ ° / I ₀ ) was 4.3. It was between ˜5.0.
Moreover, since the sample piece used for the photogoniometer is cut by the polarizing plate whose back surface reflected light is orthogonal, the appearance is close to the black display of the panel, but the sample pieces of Examples 1-1 to 1-13 are Visually, white blur was reduced and it looked black. On the other hand, the sample pieces of Comparative Examples 1-9 and 10 glowed white from the vicinity of the specular reflection to the off-axis region, and had an appearance close to white blur. Example 1-14 is inferior to Examples 1-1 to 13 in terms of white blurring and reflection, but at practically no problem level, and is not the result of fully exhibiting the effects of the present invention. It was.

(Adjustment of coating liquid B for low refractive index layer)
Perfluoroolefin copolymer (1) 15.2 g, hollow silica sol (refractive index 1.31, average particle size 60 nm, solid content 20%) 2.1 g, reactive silicone X-22-164B (trade name; Shin-Etsu) Chemical Industry Co., Ltd.) 0.3 g, sol solution a 7.3 g, photopolymerization initiator (Irgacure 907 (trade name), Ciba Specialty Chemicals Co., Ltd.) 0.76 g, methyl ethyl ketone 301 g, cyclohexanone 9.0 g After addition and stirring, the mixture was filtered through a polypropylene filter having a pore size of 5 μm to prepare a coating solution B for a low refractive index layer. The refractive index of the layer formed by this coating solution was 1.40.

(Preparation of coating solution C for low refractive index layer)
It is formed from this coating solution by reducing the amount of OPSTA JTA113 (thermally crosslinkable fluorine-containing silicone polymer composition liquid (solid content: 6%): manufactured by JSR Corporation) and increasing the amount of dispersion A-1. The coating solution C was prepared in the same manner as the coating solution A except that the refractive index of the coating layer was changed to 1.36.

(Preparation of coating solution D for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.44 containing polysiloxane and hydroxyl group (JTA113, solid content concentration 6%, manufactured by JSR Corporation) 13 g, colloidal silica dispersion MEK-ST-L (trade name, average) Particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 1.3 g, sol solution a 0.6 g, methyl ethyl ketone 5 g, cyclohexanone 0.6 g were added, and after stirring, filtered through a polypropylene filter having a pore size of 1 μm. Then, a low refractive index layer coating solution D was prepared. The refractive index of the layer formed with this coating solution was 1.45.

  Moreover, when the antireflective film was similarly produced except having replaced the coating liquid A for low refractive index layers of Example 1-1 with the coating liquid C for low refractive index layers, the integration of Examples 1-1 to 13 was performed. The average reflectance was improved to 1.1 to 1.3%.

Further, the coating solution A for the low refractive index layer of Example 1-1 was replaced with the coating solution B for the low refractive index layer, and the drying after coating was changed to 100 ° C. for 30 seconds and the ultraviolet ray was irradiated with an irradiation energy intensity of 900 mJ / cm ² . When an antireflection film was produced in the same manner except for the above, the integrated reflectance was 1.6 to 1.9%, which was slightly larger than Examples 1-1 to 1-13, but for the low refractive index layer. Since the coating liquid C was used in combination with thermosetting, the scratch resistance could be improved.

  Moreover, except having replaced the coating liquid A for low refractive index layers of Example 1-1 with the coating liquid D for low refractive index layers, the antireflection film was produced like Example 1-1 to 1-13. However, the integrated reflectance was 2.6 to 2.9%, which was larger than those of Examples 1-1 to 1-13. Although the reflection was less than when no antireflection film was used, the reflection was not sufficient as compared with the case where other low refractive index layer coating solutions were used.

[Example 2]
(Preparation of polarizing plate)
80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.), which was immersed in an aqueous 1.5 mol / L, 55 ° C. NaOH solution for 2 minutes, then neutralized and washed with water, and Examples 1 was prepared by adsorbing iodine to polyvinyl alcohol and stretching the antireflection film prepared in Step 1 (saponified: Example 1-1 to Example 1-14, Comparative Example 1-1 to Comparative Example 1-10). A polarizing plate was prepared by adhering and protecting both sides of the polarizer. These were designated as Example 2-1 to Example 2-14 and Comparative Examples 2-1 to 2-10, respectively.
Moreover, a polarizing plate was produced using the saponified triacetyl cellulose film as a protective film on both sides, and it was set as Comparative Example 2-11.

[Example 3]
(Evaluation of polarizing plate)
What replaced the polarizing plate of Example 2-1-Example 2-14 produced in Example 2, and Comparative Example 2-1-Comparative Example 2-11 instead of the polarizing plate by the side of visual recognition of liquid crystal television. Produced. As the liquid crystal television, “LC-37GD4” (MVA method) manufactured by Sharp Corporation was used.
About the obtained display apparatus, the following items were evaluated. The results are shown in Table 4.

(1) White blurring For the LCD TV panel (VA mode) having the definition and image size described in the table, the surface-side polarizing plate is replaced with the polarizing plate of the example, the entire surface is displayed in black, and the dark room is Then, a bare fluorescent lamp (8000 cd / m ² ) without a louver was projected from an angle of 60 degrees above, and the whitening state (white blur) of the entire surface when viewed from the front was evaluated according to the following criteria.
White blur is not anxious and preferable: ◎
Slightly clear white blur, but relatively preferable: ○
Somewhat worrisome white blurring: △
White blurring is conspicuous and undesirable: ×
(2) Dark Room Contrast Using the LCD panel prepared in (1) above, front contrast and oblique contrast were measured in a dark room. The contrast in the oblique direction was an average of polar angles of 60 ° in four directions of 45 °.
(3) Dark room black display (visual)
Using the LCD panel produced in (1) above, black display was performed in a dark room, and the following criteria were evaluated visually from the front.
Less amount of light is preferable: ○
Unfavorable amount of light leakage: ×
(4) Diagonal white gradation collapse (visually)
Using the LCD panel produced in the above (1), a whitish image was displayed in a dark room, and white gradation collapse was visually evaluated from the polar angle of 80 ° in the oblique direction of 45 ° according to the following criteria.
I don't mind the loss of gradation: ○
I'm worried about the loss of gradation: ×
(5) Reflection Reflected fluorescent lamp (8000 cd / m ² ) without a louver is projected on the obtained LCD TV from an angle of 45 degrees, and the degree of reflection of the fluorescent lamp when observed from the direction of −45 degrees is as follows. Evaluation based on the criteria.
The outline of the fluorescent lamp is not reflected so much that it is almost unknown: ◎
Fluorescent light is reflected slightly, but I do not mind: ○
Fluorescent light is reflected and I'm interested: △
Fluorescent light is completely reflected: ×

  In Comparative Examples 3-1, 3-4, and 3-8, the front contrast was greatly reduced, and the appearance of the images was not good. In Comparative Examples 3-2, 3-3, and 3-5 to 3-7, the contrast in the oblique direction was not sufficiently improved, and the appearance of the image was not good. Moreover, white looked a little yellowish. Comparative Examples 3-10 and 3-11 had a problem in terms of reflection. In all of Examples 3-1 to 13, the reduction in the contrast in the front direction was small, the effect of improving the contrast in the oblique direction was high, and the display performance of the display when viewed from all directions was excellent. Example 3-14 shows a good contrast improving effect equivalent to that of Example 3-1, but a sufficient effect was not obtained as compared with other examples in terms of white blurring and reflection.

From the results shown in Table 4, the following is clear.
The antireflection film of the present invention is excellent in visibility because white blurring in black display is reduced. Further, when applied to a liquid crystal television, it is possible to achieve both prevention of deterioration of front contrast and improvement of contrast in an oblique direction.

[Example 4]
As a protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell and a protective film on the liquid crystal cell side of the polarizing plate on the backlight side, a viewing angle widening film (wide view film SA12B, Fuji Photo Film Co., Ltd.) )), A liquid crystal display device having a very wide viewing angle in the vertical and horizontal directions, extremely excellent visibility, and high display quality was obtained.

[Example 5]
The internal scattering layer and the low refractive index layer of Example 1-1 were applied by a bar coating method. Although the number 10 bar was used for the internal scattering layer and the number 2.9 bar was used for the low refractive index layer, streaky surface unevenness occurred at a coating speed of 15 m / min or less in the internal scattering layer. In the refractive index layer, streaky surface unevenness occurred at a coating speed of 20 m / min or more.

It is sectional drawing which shows typically one preferable embodiment of the antireflection film of this invention. It is the schematic of the apparatus which measures the reflected light quantity to the 40-50 degree direction when it injects from the -60 degree direction of the antireflection film of this invention. It is sectional drawing of the coater 10 using the slot die 13 which implemented this invention. (A) shows the cross-sectional shape of the slot die 13 of the present invention, and (B) shows the cross-sectional shape of the conventional slot die 30. It is a perspective view which shows the slot die 13 of the application | coating process which implemented this invention, and its periphery. It is sectional drawing which shows the pressure reduction chamber 40 and the web W which are adjoining (the backplate 40a is integral with the chamber 40 main body). It is sectional drawing which shows the pressure reduction chamber 40 and the web W which are adjoining (back plate 40a is fastened to chamber 40 with screw 40c).

Explanation of symbols

1 Film (Anti-reflective film)
2 Transparent Support 3 Internal Scattering Layer 4 Low Refractive Index Layer 5 Translucent Fine Particle 10 Coater 11 Backup Roll 13 Slot Die 14 Coating Solution 14a Bead 14b Coating 15 Pocket 16, 33 Slot 16a Slot Opening 14b Coating 17 Tip Lip 18 Land (flat part)
18a upstream lip land 18b downstream lip land 30 slot die 31a upstream lip land 31b downstream lip land 40 decompression chamber 40a back plate 40b side plate 40c screw W web
Lo overbite length _{G B, G S, G L} gap

Claims (21)

  It has a layer having at least internal scattering on the transparent support, and the image sharpness according to JIS K7105 is 30.0% to 99.9% when measured with an optical comb width of 0.5 mm. An optical film characterized in that the haze value resulting from is less than 3% and the haze value resulting from internal scattering is from 15 to 40%.   An antireflection film in which at least an internal scattering layer and a low refractive index layer are laminated in this order on a transparent support, and the refractive index of the low refractive index layer is 0.04 or more than that of the internal scattering layer Low, the integrated reflectance of the antireflection film is 3.5% or less, and the image clarity according to JIS K7105 is 30.0% to 99.9% when measured with an optical comb width of 0.5 mm. An antireflection film having a haze value due to scattering of less than 3% and a haze value due to internal scattering of 15 to 40%.   The antireflection film according to claim 2, wherein the specular reflectance is 0.5% or more and 3.3% or less.   The center line average roughness Ra of the optical film or the antireflection film is 0.01 to 0.25 μm, and the ten-point average roughness Rz is 5 times or more of Ra. The optical film according to claim 2 or the antireflection film according to claim 2 or 3. The centerline average roughness Ra of the antireflection film is 0.01 to 0.12 μm, and the image clarity according to JIS K7105 is 45.0% to 90.0 when measured with an optical comb width of 0.5 mm. The amount of light I ⁴⁵ ° reflected in the direction inclined + 45 ° with respect to the amount of light I ₀ incident with an inclination of −60 ° with respect to the vertical direction from the low refractive index layer side satisfies the following formula (1). The antireflection film according to claim 2, wherein:
Formula (1) -LOG ₁₀ (I ⁴⁵ ° / I ₀ ) ≧ 4.3
  The layer having the internal scattering property contains a translucent resin and one or more translucent particles, has a thickness of 3 μm to 12 μm, and has a particle size of 3 to 4 μm. The light-transmitting particles are contained in an amount of 5 to 30% by weight of the total solid content, the refractive index of the light-transmitting resin is in the range of 1.52 ± 0.02, and 30% or more of the light-transmitting particles and the light-transmitting resin. The optical film according to claim 1 or 4, or the antireflection film according to any one of claims 2 to 5, wherein a difference in refractive index is 0.008 or more and 0.05 or less. The density of translucent fine particles is 0.8-3.2 g / m < ² >, The antireflection film of Claim 6 characterized by the above-mentioned.   The translucent particles having a refractive index difference from the translucent resin of 0.008 or more and 0.05 or less are composed of a crosslinked poly (styrene-acrylic) copolymer or a crosslinked acrylic resin, and the copolymer or the acrylic resin The ratio of the acrylic constituent group is 20 to 100% by mass, and the antireflection film according to claim 6 or 7.   The internal scattering layer is formed by applying, drying, and curing a coating composition containing a translucent resin, translucent fine particles, and a plurality of types of solvents on a transparent support. The optical film according to any one of claims 1, 4, and 6, or the antireflection film according to any one of claims 2 to 8. The low refractive index layer is (A) a fluorine-containing compound having thermosetting and / or ionizing radiation curability, (B) inorganic fine particles, and (C) an organosilane compound represented by the following general formula (1): It is formed by applying and curing a curable composition containing at least two of at least one selected from the hydrolyzate of the organosilane and the partial condensate of the hydrolyzate of the organosilane. It is a cured film, The antireflection film in any one of Claims 2-9 characterized by the above-mentioned.
General formula (1)
(R ¹⁰ ) _m -Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)   The antireflection film according to claim 10, wherein the fluorine-containing compound having thermosetting property and / or ionizing radiation-curing property contains fluorine atoms in a range of 35 to 80% by mass.   The antireflection film according to claim 10 or 11, wherein the inorganic fine particles are inorganic fine particles having an average particle size of 10% to 100% of the thickness of the low refractive index layer.   The antireflection film according to claim 10, wherein the inorganic fine particles are inorganic fine particles having a hollow structure in the particles and a refractive index of 1.17 to 1.40.   Both the internal scattering layer and the low refractive index layer are coated with a curable coating composition containing a hydrolyzate of organosilane represented by the general formula (1) and / or a partial condensate thereof. The antireflection film according to claim 2, which is a cured film formed by curing.   5. A transparent conductive layer is provided between the internal scattering layer and the transparent support, or between the internal scattering layer and the low refractive index layer. The optical film in any one of 6 or 9, or the antireflection film in any one of Claims 2-14.   5. A transparent conductive layer is provided between the internal scattering layer and the transparent support, and / or conductive particles are contained in the internal scattering layer. The optical film according to any one of, 6, 9 or 15, or the antireflection film according to any one of claims 2 to 15.   The polarizing plate which consists of a polarizing film and two protective films which protect both the front side and back side of this polarizing film, At least one of this protective film is an antireflection film in any one of Claims 2-16 A polarizing plate characterized by the above.   A polarizing plate, wherein one of the two protective films is the antireflection film according to any one of claims 2 to 16, and the other is an optical compensation film.   An image display device comprising at least one antireflection film according to claim 2 or at least one polarizing plate according to claim 17 or 18.   It has a polarizer on both surfaces of a liquid crystal cell, and has the antireflection film according to claim 2 on the surface of a liquid crystal display device having at least one phase difference compensation element between the liquid crystal cell and the polarizer. A liquid crystal display device.   It is a manufacturing method of the antireflection film in any one of Claims 2-16, Comprising: Coating composition for the layer which has internal scattering property containing translucent particle | grains, translucent resin, and a solvent, and / or The coating composition for the low refractive index layer and / or the coating composition for the transparent conductive layer is brought close to the land of the tip lip of the slot die on the surface of the transparent support web which is continuously supported by a backup roll. And applying a coating composition from the slot of the tip lip to coat an internal scattering layer and / or a low refractive index layer on the transparent support. The manufacturing method of a prevention film.

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