JP5010813B2 - Antiglare antireflection film, production method thereof, polarizing plate using antiglare antireflection film, and liquid crystal display device using the polarizing plate - Google Patents

Description

  The present invention relates to an antiglare antireflection film, a production method thereof, a polarizing plate and a liquid crystal display device, and more specifically, an antiglare antireflection film having an antiglare layer and a low refractive index layer, a production method thereof, and the antireflection film. The present invention relates to a polarizing plate using a dazzling antireflection film as a surface protective film, and a liquid crystal display device using the polarizing plate.

  Anti-glare film is 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. In addition, in recent years, with the increase in the definition of display devices, as a means of improving minute luminance unevenness (called glare) with an anti-glare film, anti-glare property having higher internal scattering than surface scattering in addition to surface scattering. The technique regarding a film is disclosed (patent documents 1-5).

  In recent years, as disclosed in Patent Documents 6 to 8 and the like, when a light scattering film is used on the outermost surface of a display device, the reflection has an effect of suppressing surface reflection of external light in a bright room. It is known that a film having a prevention function is preferable. Patent Document 6 describes that even when a low refractive index layer is provided on the antiglare layer by wet coating and dry film formation, the surface haze does not change from that of the antiglare layer.

  However, when the antireflection layer is formed by a wet coating method that is more cost-effective than dry film formation such as vapor deposition or sputtering, a part of the surface irregularities of the antiglare film is filled when the antireflection layer is formed. Therefore, it was found that if the surface was optimized up to the antiglare layer, it would deviate from the original surface design after the antireflection layer was formed. Specifically, when a part of the components of the antireflection layer formed by the wet coating method flows into the concave and convex portions formed by the antiglare layer, the interval between the convex and convex portions is widened, and the concave and convex portions are visually observed. Since the non-uniformity is strongly observed, when mounted on a display device and observed, the user feels uncomfortable feeling that is not up to the antiglare layer. In addition, it was found that the surface haze is also greatly reduced.

JP 2000-304648 A Japanese Patent No. 3507719 Japanese Patent Laid-Open No. 11-3276608 Japanese Patent No. 3515401 Japanese Patent No. 3515426 Japanese Patent No. 3507719 JP 2001-100004 A JP 2003-270409 A

In short, the present situation is that an antiglare antireflection film whose surface irregularities are optimized after the formation of an antireflection layer by a wet coating method has not yet been proposed.
Accordingly, an object of the present invention is to provide an antiglare antireflection film having an optimized surface irregularity after formation of an antireflection layer by a wet coating method.
Another object of the present invention is to provide a production method capable of producing the above antiglare and antireflection film with high productivity.
Furthermore, another object of the present invention is to provide a polarizing plate and a liquid crystal display device using the antiglare antireflection film.

As a result of intensive studies to solve the above-described problems, the present inventors have found that the above-described problems can be solved and the object can be achieved, and the present invention has been completed.
That is, the present invention is as follows.
1.
An antiglare antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, which satisfies the following conditions I), VI) and VII): .
I) The haze value (hi) resulting from internal scattering of the antiglare antireflection film is (hi) ≦ 50%.
VI) Haze value (hs, AGAR) due to surface scattering of the antiglare layer and haze value (hs, AGAR) due to surface scattering of the antiglare antireflection film after forming the low refractive index layer The ratio (hs, AGAR) / (hs, AG) is 0.2 <(hs, AGAR) / (hs, AG) <0.6.
VII) The haze value (hs, AGAR) resulting from surface scattering of the antiglare antireflection film is 2.0% ≦ (hs, AGAR) ≦ 7.0%.
2.
2. The antiglare antireflection film as described in 1 above, wherein the haze value (hi) resulting from internal scattering of the antiglare antireflection film satisfies the following condition III).
III) The haze value (hi) resulting from internal scattering of the antiglare antireflection film is (hi) ≦ 30%.
3.
3. The antiglare antireflection film as described in 2 above, wherein a haze value (hi) resulting from internal scattering of the antiglare antireflection film is 18% or more.
4).
4. The antiglare antireflection film as described in any one of 1 to 3 above, wherein the antiglare antireflection film has a center line average roughness Ra of 0.05 to 0.25 μm.
5.
4. The antiglare antireflection film as described in any one of 1 to 3 above, wherein the image clarity according to JIS K7105 is 5% to 50% when measured at an optical comb width of 0.5 mm.
6).
The antiglare layer is formed by dispersing at least one kind of translucent fine particles having an average particle diameter of 0.5 to 10 μm in a translucent resin, and has a refractive index of the translucent fine particles and the translucent resin. The absolute value of the difference is 0.001 to 0.300, and the translucent fine particles are layers in which 3 to 30% by mass is contained in the total solid content of the antiglare layer. 4. The antiglare antireflection film as described in any one of 3 above.
7).
The translucent resin is a cross-linked poly (meth) acrylate-based polymer having a (meth) acrylate monomer having at least trifunctional or higher functionality as a main component and the translucent fine particles having an acrylic content of 50 to 100 mass percent. 6. The antiglare antireflection film as described in 6 above.
8).
A cross-linked poly (styrene-acrylic) copolymer in which the translucent resin has a (meth) acrylate monomer having at least trifunctional or higher functionality and the translucent fine particles have a styrene content of 1 to 100 mass percent, or 6. The antiglare antireflection film as described in 6 above, which is a crosslinked polystyrene.
9.
The antiglare layer is formed from a coating composition containing the translucent resin, the translucent fine particles and a plurality of types of solvents, and the plurality of types of solvents do not dissolve the transparent support. And an antiglare antireflection film as described in 6 above, which comprises a small amount of a solvent having a hydroxyl group.
10.
10. The antiglare antireflection film as described in 9 above, wherein the vapor pressure of the small amount solvent is lower than that of the main solvent at an arbitrary temperature within a range of 20 to 30 ° C.
11.
10. The antiglare antireflection film as described in 9 above, wherein the mass ratio of the main solvent and the small amount solvent is in the range of 99: 1 to 50:50 as the former: the latter.
12
A composition having a thermosetting property and / or a photocurable property, wherein the low refractive index layer mainly comprises 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; 12. The antiglare antireflection film as described in any one of 1 to 11 above, which is formed by coating.
13.
The low refractive index layer is (A) the fluoropolymer, (B) inorganic fine particles having an average particle diameter of 30% to 100% of the thickness of the low refractive index layer, and (C) the following general formula (1) ), A hydrolyzate thereof, a hydrolyzate thereof, and a partial condensate thereof, and a cured film formed by applying and curing a curable composition containing one or more components. 13. The antiglare antireflection film as described in 12 above.
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.)
14
The low refractive index layer is applied and cured with a curable composition containing one or more components selected from hydrolyzate of organosilane represented by the following general formula (2) and partial condensate thereof. The antiglare antireflection film as described in any one of 1 to 11 above, which is a cured film formed by
General formula (2)
(R ¹⁰ ) _l Si (X) _4-l
(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. L represents an integer of 0 to 3.)
15.
The low refractive index layer is composed of (A) inorganic fine particles having an average particle diameter of 30% to 100% of the thickness of the low refractive index layer, and (B) an organosilane represented by the general formula (2). 15. The antiglare as described in 14 above, which is a cured film formed by applying and curing a curable composition containing one or more components selected from a hydrolyzate and a partial condensate thereof. Antireflection film.
16.
Both the antiglare layer and the low refractive index layer contain a curable coating containing any one or more of the organosilane represented by the general formula (1), a hydrolyzate thereof, and a partial condensate thereof. 14. The antiglare antireflection film as described in 13 above, which is a cured film formed by applying and curing the composition.
17.
16. The antiglare antireflection film as described in 13 or 15 above, wherein the inorganic fine particles are inorganic fine particles containing a silicon oxide having a hollow structure and a refractive index of 1.17 to 1.40 as a main component. .
18.
The antistatic layer according to any one of the above items 1 to 17, further comprising a transparent antistatic layer having at least one conductive material, wherein the antiglare antireflection film has a surface resistance value logSR of 12 or less. Dazzling antireflection film.
19.
19. A method for producing an antiglare antireflection film as described in any one of 1 to 18 above, wherein the coating composition for an antiglare layer and / or low refraction contains translucent fine particles, a translucent resin and a solvent. The coating composition for the rate layer is applied from the slot of the tip lip by bringing the land of the tip lip of the slot die in close proximity to the surface of the web of the transparent support that is continuously supported by a backup roll. A method for producing an antiglare antireflection film, comprising a step of coating an antiglare layer and / or a low refractive index layer on a transparent support.
20.
In the polarizing plate formed by laminating a polarizing film and two protective films for protecting both the front side and the back side of the polarizing film, the antiglare antireflection film according to any one of 1 to 18 above is provided on one side. A polarizing plate characterized by being used for a protective film.
21.
Of the two protective films for forming the polarizing plate, the film not including the antiglare antireflection film is composed of a plurality of layers, and is on the surface opposite to the surface to be bonded to the polarizing film. An optical compensation film comprising an optically anisotropic layer, wherein the optically anisotropic layer is a layer made of a compound having a discotic structural unit, and the disc surface of the discotic structural unit is against the protective film surface The angle formed by the disc surface of the discotic structural unit and the surface of the protective film is changed in the depth direction of the optically anisotropic layer. Polarizer.
22.
A liquid crystal display device comprising at least one polarizing plate as described in 20 or 21 above.
23.
23. The liquid crystal display device as described in 22 above, wherein the diagonal of the display screen is 20 inches or more.
In addition, although this invention is related to the matter as described in said 1-23, the other matter (For example, the matter as described in following (1)-(25) etc.) was described for reference.

(1) An antiglare antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, which satisfies the following conditions I) and II): .
I) The haze value (hi) resulting from internal scattering of the antiglare antireflection film is (hi) ≦ 50%.
II) Haze value (hs, AGAR) resulting from surface scattering of the antiglare layer and haze value (hs, AGAR) resulting from surface scattering of the antiglare antireflection film after forming the low refractive index layer The ratio (hs, AGAR) / (hs, AG) is 0.05 <(hs, AGAR) / (hs, AG) <1.
(2) The antiglare antireflection film as described in (1) above, wherein the haze value (hi) resulting from internal scattering of the antiglare antireflection film satisfies the following condition III).
III) The haze value (hi) resulting from internal scattering of the antiglare antireflection film is (hi) ≦ 30%.
(3) The antiglare antireflection film as described in (1) above, wherein the following conditions IV) and V) are satisfied.
IV) Haze value (hs, AG) resulting from surface scattering of the antiglare layer and haze value (hs, AGAR) resulting from surface scattering of the antiglare antireflection film after the low refractive index layer is formed Ratio (hs, AGAR) / (hs, AG) is 0.05 <(hs, AGAR) / (hs, AG) ≦ 0.2.
V) The haze value (hs, AGAR) resulting from surface scattering of the antiglare antireflection film is 1.0% ≦ (hs, AGAR) ≦ 5.0%.
(4) The antiglare antireflection film as described in (1) above, which satisfies the following conditions VI) and VII):
VI) Haze value (hs, AGAR) due to surface scattering of the antiglare layer and haze value (hs, AGAR) due to surface scattering of the antiglare antireflection film after forming the low refractive index layer The ratio (hs, AGAR) / (hs, AG) is 0.2 <(hs, AGAR) / (hs, AG) <0.6.
VII) The haze value (hs, AGAR) resulting from surface scattering of the antiglare antireflection film is 2.0% ≦ (hs, AGAR) ≦ 7.0%.
(5) The antiglare property according to any one of (1) to (4) above, wherein the antiglare antireflection film has a center line average roughness Ra of 0.05 to 0.25 μm. Antireflection film.
(6) The image sharpness according to JIS K7105 is 5% to 50% when measured with an optical comb width of 0.5 mm, according to any one of (1) to (4), Antiglare antireflection film.
(7) The antiglare layer comprises at least one kind of translucent fine particles having an average particle diameter of 0.5 to 10 μm dispersed in a translucent resin, and the translucent fine particles and the translucent resin The absolute value of the difference in refractive index is 0.001 to 0.300, and the translucent fine particle is a layer containing 3 to 30% by mass in the total solid content of the antiglare layer. The antiglare antireflection film according to any one of (1) to (4).
(8) The cross-linked poly (meth) acrylate-based heavy polymer in which the translucent resin contains at least a trifunctional or higher (meth) acrylate monomer as a main component and the translucent fine particles have an acrylic content of 50 to 100 mass percent. The antiglare antireflection film as described in (7) above, which is a coalescence.
(9) A crosslinked poly (styrene-acrylic) copolymer in which the translucent resin contains a (meth) acrylate monomer having at least trifunctional or higher functionality and the translucent fine particles have a styrene content of 1 to 100 mass percent. The antiglare antireflection film as described in (7) above, which is a polymer or crosslinked polystyrene.
(10) The antiglare layer is formed from a coating composition containing the translucent resin, the translucent fine particles, and a plurality of types of solvents, and the plurality of types of solvents dissolves the transparent support. The antiglare antireflection film as described in (7) above, which comprises a main solvent which is not used and a small amount of solvent having a hydroxyl group.
(11) The antiglare antireflection film as described in (10) above, wherein the vapor pressure of the small amount solvent is lower than that of the main solvent at an arbitrary temperature within a range of 20 to 30 ° C.
(12) The antiglare antireflection film as described in (10) above, wherein the mass ratio of the main solvent and the small amount solvent is in the range of 99: 1 to 50:50 as the former: the latter. .
(13) The low refractive index layer has thermosetting and / or photocuring properties mainly comprising a fluorine-containing polymer containing fluorine atoms in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. The antiglare antireflection film according to any one of (1) to (12), which is formed by applying a composition.
(14) The low refractive index layer is (A) the fluoropolymer, (B) inorganic fine particles having an average particle diameter of 30% to 100% of the thickness of the low refractive index layer, and (C) the following general It is a cured film formed by applying and curing a curable composition containing at least one component of organosilane represented by formula (1), a hydrolyzate thereof, and a partial condensate thereof. The antiglare antireflection film as described in (13) above.
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.)
(15) The low refractive index layer is coated with a curable composition containing one or more components selected from a hydrolyzate of organosilane represented by the following general formula (2) and a partial condensate thereof. The antiglare antireflection film as described in any one of (1) to (12) above, which is a cured film formed by curing.
General formula (2)
(R ¹⁰ ) _l Si (X) _4-l
(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. L represents an integer of 0 to 3.)
(16) The low refractive index layer is represented by (A) inorganic fine particles having an average particle diameter of 30% or more and 100% or less of the thickness of the low refractive index layer, and (B) the general formula (2). (15) A cured film formed by applying and curing a curable composition containing one or more components selected from hydrolyzate of organosilane and partial condensate thereof. The antiglare antireflection film described in 1.
(17) Both the antiglare layer and the low refractive index layer contain one or more components of the organosilane represented by the general formula (1), a hydrolyzate thereof, and a partial condensate thereof. The antiglare antireflection film as described in (13) above, which is a cured film formed by applying and curing a curable coating composition.
(18) The antiglare layer contains one or more components of the organosilane represented by the general formula (1) and / or the general formula (2), a hydrolyzate thereof, and a partial condensate thereof. The antiglare antireflection film as described in (15) above, which is a cured film formed by applying and curing a curable coating composition.
(19) The above (14) or (16), wherein the inorganic fine particles are inorganic fine particles containing a silicon oxide having a hollow structure and a refractive index of 1.17 to 1.40 as a main component.
) Antiglare antireflection film described in the above.
(20) The transparent antistatic layer having at least one conductive material, wherein the antiglare antireflection film has a surface resistance value logSR of 12 or less, (1) to (19) The anti-glare antireflection film according to any one of the above.

(21) The method for producing an antiglare and antireflection film according to any one of (1) to (20), wherein the coating is for an antiglare layer containing translucent fine particles, a translucent resin and a solvent. A slot of the tip lip of the slot die is brought close to the surface of the web of the transparent support, which is continuously supported by a backup roll, and the coating composition for the low refractive index layer is applied to the surface of the transparent die web. The manufacturing method of the anti-glare antireflection film characterized by including the process of apply | coating an anti-glare layer and / or a low refractive index layer on the said transparent support body by apply | coating.
(22) In the polarizing plate formed by laminating a polarizing film and two protective films for protecting both the front side and the back side of the polarizing film, the antiglare according to any one of (1) to (20) above A polarizing plate characterized by using an antireflection film as a protective film on one side.
(23) Of the two protective films for forming the polarizing plate, the film not including the antiglare antireflection film is composed of a plurality of layers and is opposite to the surface to be bonded to the polarizing film. An optical compensation film comprising an optically anisotropic layer on the surface, the optically anisotropic layer being a layer comprising a compound having a discotic structural unit, and the disc surface of the discotic structural unit being the protective film And the angle formed by the disc surface of the discotic structural unit and the protective film surface is changed in the depth direction of the optically anisotropic layer. The polarizing plate as described in 22).
(24) A liquid crystal display device comprising at least one polarizing plate according to (22) or (23).
(25) The liquid crystal display device according to (24), wherein the diagonal of the display screen is 20 inches or more.

ADVANTAGE OF THE INVENTION According to this invention, the anti-glare antireflection film with which the surface unevenness | corrugation was optimized after formation of the antireflection layer (low refractive layer) by the wet application method is provided.
Moreover, according to this invention, the manufacturing method which can manufacture said anti-glare antireflection film with high productivity is provided.
Furthermore, according to this invention, the polarizing plate and liquid crystal display device using said anti-glare antireflection film are provided.

  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 a preferred embodiment of the antiglare 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 antiglare antireflection film having antiglare properties of the present invention.
An antiglare antireflection film 1 of the present embodiment shown in FIG. 1 includes a transparent support 2, an antiglare layer 3 formed on the transparent support 2, and a low refraction formed on the antiglare layer 3. The rate layer 4. By forming the low refractive index layer on the antiglare layer with a film thickness of about ¼ of the wavelength of visible light, surface reflection can be reduced by the principle of thin film interference.
The antiglare layer 3 is preferably composed of a translucent resin and translucent fine particles 5 dispersed in the translucent resin.
The refractive index of each layer constituting the antiglare antireflection film in the present invention preferably satisfies the following relationship.
The refractive index of the antiglare layer> the refractive index of the transparent support> the refractive index of the low refractive index layer In the present invention, the antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties, In the present embodiment, a single layer is exemplified, but a plurality of layers, for example, two to four layers may be used. Moreover, although you may provide directly on a transparent support body like this embodiment, you may provide via other layers, such as an antistatic layer and a moisture-proof layer.

The anti-glare antireflection film of the present invention has a center line average roughness Ra of 0.01 to 0.25 μm, preferably 0.05 to 0.25 μm, and a 10-point average roughness Rz of Ra as the surface uneven shape. Is designed so that the surface with an average mountain valley distance Sm of 1 to 150 μm, an average mountain valley distance Sm of 20 μm or less, and an inclination angle of 0 to 5 degrees is 10% or more. However, it is preferable because sufficient antiglare property and a visually uniform matte feeling can be achieved. When high anti-glare property is required, sufficient anti-glare property can be obtained by setting Ra to 0.08 or more. If it is 0.25 or less, glare, surface whitening when external light is reflected, etc. Good without any problems. On the other hand, a low anti-glare property is sufficient for applications with a long observation distance such as TV applications, and in that case, Ra is preferably in the range of 0.05 to 0.08.
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.

Further, the antiglare antireflection film of the present invention is characterized in that its optical characteristics have a haze caused by internal scattering (hereinafter referred to as internal haze) of 50% or less, and for TV applications of 20 inches or more. For applications where glare is unlikely to be a problem, it is preferably 30% or less. In addition, haze (hereinafter referred to as (hs, AGAR)) due to surface scattering at the interface between the antiglare antireflection film and air after forming the low refractive index layer is 0.3% to 10%. %, More preferably 2% to 7% for applications requiring high antiglare properties, and more preferably 1% to 5% for applications where low antiglare properties are appropriate. . If the surface haze is less than 0.3%, the antiglare property is insufficient, and if it exceeds 10%, problems such as whitening of the surface when external light is reflected are undesirable.
The antiglare antireflection film of the present invention has a sufficient antiglare property and image that the image clarity according to JIS K7105 is 5% to 50% when measured at an optical comb width of 0.5 mm. This is preferable since both improvement of blur and dark room contrast reduction can be achieved. Moreover, it is preferable that the specular reflectance is 2.5% or less and the transmittance is 90% or more because reflection of external light can be suppressed and visibility is improved.

Next, the antiglare layer will be described below.
(Anti-glare layer)
<Scattering characteristics>
The scattering characteristics of the antiglare layer of the present invention are designed so that the surface design is optimized after an antireflection layer (low refractive index layer) is deposited thereon by a wet coating method. In the present invention, the surface haze (hs, AGAR) of the antiglare antireflection film is used as an index of the surface design, and the surface haze (hs, AG) of the antiglare layer is set so that the above-described preferable range can be realized. The ratio (hs, AGAR) / (hs, AG) / (hs, AGAR) / (hs, AG) was found to be achieved by satisfying a predetermined relationship. That is, (hs, AGAR) / (hs, AG) in the present invention is
0.05 <(hs, AGAR) / (hs, AG) <1,
1) When low anti-glare property is required, (hs, AGAR) / (hs, AG)
0.05 <(hs, AGAR) / (hs, AG) ≦ 0.2, and
1.0 ≦ (hs, AGAR) ≦ 5.0%
2) When high anti-glare property is appropriate,
0.2 <(hs, AGAR) / (hs, AG) <0.6, and
2.0% ≦ (hs, AGAR) ≦ 7.0%
It is preferable to satisfy. Although (hs, AGAR) / (hs, AG) is also affected by the factors of the formation process of the antireflection layer (low refractive index layer) formed on the antiglare layer by the wet coating method, US Pat. No. 6,502,943. The above-mentioned range is preferable under the condition that the antireflection layer can be formed on the concavo-convex surface without unevenness of coating by the wet coating method as disclosed in Japanese Patent Application No. 2002-148404.

The antiglare layer is formed for the purpose of contributing to the film antiglare properties due to surface scattering and preferably hard coat properties 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 antiglare 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. By setting the average particle size to 0.5 μm or more, the light scattering angle distribution is good and there is no fear of causing character blur on the display. Moreover, if it is 10 micrometers or less, since the film thickness of an anti-glare layer does not become thick, curl does not become large and material cost can also be suppressed.
Specific examples of the translucent fine particles include, for example, poly ((meth) acrylate) particles, crosslinked poly ((meth) acrylate) particles, polystyrene particles, crosslinked polystyrene particles, crosslinked poly (acryl-styrene) particles, and 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, surface haze, and centerline average roughness of the present invention can be achieved. Specifically, a translucent resin (having a refractive index after curing of 1.50 to 1.1) mainly composed of a tri- or higher functional (meth) acrylate monomer preferably used in the antiglare layer of the present invention as described later. 53) and a combination of translucent fine particles made of a crosslinked poly (meth) acrylate polymer having an acrylic content of 50 to 100 mass percent, and particularly preferably the translucent resin and styrene content of 1 to 100 mass percent. A combination with translucent fine particles (having a refractive index of 1.48 to 1.54) made of a crosslinked poly (styrene-acrylic) copolymer is preferred.

  Further, two or more kinds of translucent fine particles having different particle diameters may be used in combination. It is possible to impart an antiglare property with the light-transmitting fine particles having a larger particle diameter, and to reduce the roughness of the surface with the light-transmitting fine particles having a smaller particle diameter.

In the present invention, the refractive index of the translucent resin and the translucent fine particles is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the kind and amount ratio of the light-transmitting resin and the light-transmitting fine particles may be appropriately selected. How to select can be easily known experimentally in advance.
In the present invention, 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 0.001 to an absolute value. It is 0.030, More preferably, it is 0.001-0.020, More preferably, it is 0.001-0.015. If it is within the above range, problems such as film character blur, a decrease in dark room contrast, and white turbidity of the surface do not occur.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring the refractive index with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. The refractive index of the light-transmitting fine particles is obtained by measuring the turbidity by dispersing an equal amount of the light-transmitting fine particles in a solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

The translucent fine particles are blended in the formed antiglare layer so as to be contained in an amount of 3 to 30% by mass in the total solid content of the antiglare layer. More preferably, it is 5-20 mass%. When it is 3% by mass or more, sufficient antiglare property is obtained, and when it is 30% by mass or less, problems such as image blurring, surface turbidity and glare do not occur.
Moreover, the density of the translucent fine particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

  The film thickness of the antiglare layer is preferably 1 to 10 μm, and more preferably 1.2 to 8 μm. If it is too thin, the hard property is insufficient, and if it is too thick, curling and brittleness may be deteriorated and workability may be lowered.

<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.
In order to increase the refractive index of the binder polymer, the monomer structure has a high refractive index including 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. It is also possible to select a monomer having a ratio, a monomer having a fluorene skeleton in the molecule, and the like.

  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. Among the above, as described above, a tri- or higher functional (meth) acrylate monomer is preferable.

  Specific examples of the high refractive index monomer include (meth) acrylates having a fluorene skeleton, bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, etc.・ It is mentioned. Two or more of these monomers may be used in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, the antiglare 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, a translucent fine particle, 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 a polymerization reaction by ionizing radiation or 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 described in the latest UV curing technology (p.159, issuer; Kazuhiro Takashiro, 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.

The binder 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.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, translucent fine particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then polymerized by ionizing radiation or heat. It can be cured by reaction to form an antiglare layer.

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, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

In addition to the above light-transmitting fine particles, silicon, titanium, zirconium, aluminum, indium, zinc, tin are used for the antiglare layer in order to adjust the refractive index of the layer and reduce the haze value caused by internal scattering. And an inorganic filler comprising an oxide of at least one metal selected from antimony and having an average particle diameter of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less. Good. Since these inorganic fillers generally have a specific gravity higher than that of organic substances and can increase the density of the coating composition, they also have the effect of slowing the sedimentation rate of the light-transmitting fine particles.
The surface of the inorganic filler used in the antiglare layer is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
When using these inorganic fillers, the addition amount is preferably 10 to 90% of the total mass of the antiglare layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
Such 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.
An organosilane compound can be used for the antiglare layer. The addition amount of the organosilane compound is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass, still more preferably 0.05 to 10% by mass, based on the total solid content of the antiglare layer. 1-5 mass% is especially preferable.

<Surfactant for antiglare layer>
The antiglare layer of the present invention is formed with an antiglare layer formed of either a fluorine-based or silicone-based surfactant, or both, in order to ensure surface uniformity such as coating unevenness, drying unevenness, and point defects. It is preferable to contain it in the coating composition. 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 antiglare antireflection film of the present invention appears in a smaller addition amount.
The purpose is to increase productivity by giving high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): Acrylic resin, methacrylic resin characterized by containing corresponding repeating units, or containing repeating units corresponding to monomers (i) and (ii) below, and copolymerizable therewith Copolymers with vinyl monomers are useful.

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

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

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

In the general formula (II), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specifically, it represents a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents an alkyl group including a linear, branched or cyclic alkyl group or poly (alkyleneoxy) 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 used in the fluoropolymer used in the antiglare layer of the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably 15 to 70. It is mol%, More preferably, it is the range of 20-60 mol%.

The preferred mass average molecular weight of the fluoropolymer used in the antiglare layer of the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the antiglare layer of the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass with respect to the coating solution. More preferably, it is the range of 0.01-1 mass%. When the addition amount of the fluorine-based polymer is 0.001% by mass or more, the effect is sufficient, and by setting it to 5% by mass or less, the coating film is sufficiently dried and good performance as a coating film (for example, reflection) Rate, scratch resistance).

  Hereinafter, although the example of the specific structure of the fluorine-type polymer containing the repeating unit corresponding to the fluoro aliphatic group containing monomer represented by general formula (I) is shown, it is not this limitation. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

However, the use of such a fluoropolymer reduces the surface energy of the antiglare layer due to segregation of functional groups containing F atoms on the surface of the antiglare layer, resulting in low refraction on the antiglare layer. When the rate layer is overcoated, there arises 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 antiglare layer preferably in ^{20mN · m -1 ~50mN · m -1} , more preferably 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.

  In addition, when the upper layer is applied, by selecting a fluorine-based polymer that is extracted by the solvent that forms the upper layer, it is not unevenly distributed on the lower layer surface (= interface), so that adhesion between the upper layer and the lower layer is achieved. The surface energy of the antiglare layer before coating the low refractive index layer can be reduced by maintaining the surface uniformity even at high speed coating and preventing the decrease in surface free energy that can provide an antireflection film with high scratch resistance. The purpose can also be achieved by controlling the range. Examples of such a material include an acrylic resin, a methacrylic resin, and a vinyl copolymerizable therewith, containing a repeating unit corresponding to a fluoroaliphatic group-containing monomer represented by the following general formula (III): It is a copolymer with a monomer.

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

In the general formula (III), R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and 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.
In addition, two or more kinds of fluoroaliphatic group-containing monomers represented by the general formula (III) may be contained in the fluoropolymer as a constituent component.

(Iv) A monomer represented by the following general formula (IV) that can be copolymerized with the above (iii) can also be used.
Formula (IV)

In the general formula (IV), R ²³ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. Y ² represents an oxygen atom, a sulfur atom or —N (R ²⁵ ) —, more preferably an oxygen atom or —N (R ²⁵ ) —, and 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 further 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. .

  Hereinafter, although the example of the specific structure of the fluorine-type polymer containing the repeating unit corresponding to the fluoro aliphatic group containing monomer represented by general formula (III) is shown, it is not this limitation. 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 surface energy is prevented from being lowered when the low refractive index layer is overcoated on the antiglare layer, the deterioration of the antireflection performance can be prevented. When applying an anti-glare layer, the surface tension of the coating solution is lowered by using a fluoropolymer to improve surface uniformity and maintain high productivity by high-speed application. After application of the anti-glare layer, corona treatment, UV treatment, heat treatment, saponification Corona treatment is particularly preferred using surface treatment techniques such as treatment and solvent treatment, but the surface energy of the antiglare layer before application of the low refractive index layer is controlled within the above range by preventing the surface free energy from decreasing. You can also achieve your goals.

Moreover, you may add a thixotropic agent in the coating composition for forming the glare-proof layer of this invention. 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.

Since the antiglare layer of the present invention is often wet-coated directly on a transparent support, the solvent used in the coating composition is an important factor. As requirements, it is necessary to sufficiently dissolve various solutes such as the above-mentioned translucent resin, not to dissolve the above-mentioned translucent fine particles, to prevent coating unevenness and drying unevenness from being applied to drying, and to dissolve the support. Not necessary (necessary for failure prevention such as deterioration of flatness and whitening), and conversely, swelling the support to the minimum extent (necessary for adhesion).
As a specific example, when triacetylcellulose is used for the support, various ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.) and various cellosolves (ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.) are used as the main solvent. Preferably used. Moreover, antiglare property 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 particularly preferable. Since the small amount solvent having a hydroxyl group can strengthen the antiglare property by remaining until after the main solvent in the drying step of the coating composition, the main solvent can be used at any temperature within the range of 20 to 30 ° C. The vapor pressure of the small amount solvent is preferably lower than that of the 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 99: 1 to 50:50, more preferably 95: 5 to 70:30 in terms of mass ratio as the former: the latter. Within the said range, stability of a coating liquid becomes favorable.

Next, the low refractive index layer will be described below.
(Low refractive index layer)
The low refractive index layer used in the present invention has a thermosetting property and / or a photocuring property mainly comprising a fluorine-containing polymer containing fluorine atoms in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. It is preferably formed by applying a composition having the same.
The refractive index of the low refractive index layer in the antiglare antireflection film of the present invention is 1.30 to 1.55, preferably 1.35 to 1.45. Within the above range, good antireflection performance can be obtained.
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, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

The curable composition used when forming the low refractive index layer preferably contains (A) a fluorine-containing polymer, (B) inorganic fine particles, and (C) an organosilane compound. Another preferred example includes an organosilane compound (C), an organosilane compound (C) and an inorganic fine particle (B).
The material for forming the low refractive index layer is described below.
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.
<Fluoropolymer for low refractive index layer>
(A) When the fluoropolymer has a cured coating, the dynamic friction coefficient of the coating is 0.03 to 0.00.
20. When the contact angle to water is 90 to 120 °, the sliding angle of pure water is 70 ° or less, and the polymer is crosslinked by heat or ionizing radiation, when the roll film is applied and cured while transporting the web, etc. In view of improving productivity.
Also, when the antiglare antireflection film of the present invention is mounted on an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, so the peel strength is 500 gf ( 4.9 N) or less, preferably 300 gf (2.9 N) or less, and most preferably 100 gf (0.98 N) or less. 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 in 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. In addition to hydrolyzate and dehydration condensate of alkyl group-containing silane compound [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], a fluorine-containing monomer unit and a crosslinking reactive unit are constituted. Examples thereof include a fluorine-containing copolymer as a unit. 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.

The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing 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 used in the present invention 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 a linking site on the polymer main chain side, and ** represents a linking site on the (meth) acryloyl group side. m represents 0 or 1;

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

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

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

x, y, and z represent mol% of each constituent component, and 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65 are preferable, and 35 ≦ x ≦ 55, and 30 ≦ y ≦ 65 are more preferable. 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 unit of 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 each 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.
The copolymer represented by the general formula 1 or 2 can be obtained by, for example, introducing a (meth) acryloyl group into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any of the above-described methods. 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>
(B) 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 be deteriorated. It is preferable to be inside.
Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride and silicon oxide (silica). In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle size 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 size of the silica fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the 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 is 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 preferably 1.17 to 1.40, more preferably. 1.17 to 1.35, more preferably 1.17 to 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 outer shell is b, the porosity x represented by the following formula (II) is (formula II)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably, it is 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.
If the refractive index of the 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. 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 was 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 referred to as“ small size inorganic fine particles ”). 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.
As described above, the inorganic fine particles have an average particle diameter of 30 to 100% of the thickness of the low refractive index layer as described above, have a hollow structure, and have a refractive index of 1.17 to 1. What is 40 is used especially preferably.

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 preparation of the layer coating solution. It is preferable to make it contain in a layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

Next, (C) the organosilane compound will be described.
<Organosilane compound for low refractive index layer>
The curable composition contains (C) an organosilane compound, a hydrolyzate thereof, and / or a partial condensate thereof (hereinafter, the obtained reaction solution is also referred to as “sol component”). From the viewpoint of scratch resistance, it is particularly preferable from the viewpoint of achieving both antireflection ability and scratch resistance.
This 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 process to form a cured product. In the present invention, (C) the organosilane compound forms a binder having a three-dimensional structure as a mixture with the fluorine-containing polymer or by irradiation with heat and / or actinic rays alone.
The organosilane compound is preferably represented by the following general formula (1).
General formula (1)
(R ¹⁰ ) _m -Si (X) _4-m
Moreover, when using a sol component as a single binder, the organosilane compound represented by following General formula (2) is used preferably.
General formula (2)
(R ¹⁰ ) _l Si (X) _4-l
In the general formulas (1) and (2), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I 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. l represents an integer of 0 to 2, and is preferably a mixture of one having 0 and the other.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively.
The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (such as phenoxycarbonyl), carbamoyl groups (such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl), 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 (1), an organosilane compound having a vinyl polymerizable substituent represented by the following general formula (3) is preferable.
General formula (3)

In the general formula (3), 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 preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond 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. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as in formula (1), 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 formula (1), 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 kinds of the compounds represented by general formula (1), general formula (2), and general formula (3) may be used in combination. Although the specific example of a compound represented by General formula (1) and General formula (3) below is shown, it is not limited.

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

Moreover, as a preferable example of General formula (2), following (a)-(d) whose l is 0-3 is mentioned.
(A) Si (X) ₄
(B) RSi (X) ₃
(C) R ₂ Si (X) ₂
(D) R ₃ Si (X)

  The component (a) will be specifically described. Specific examples of the compound include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. Etc. Tetramethoxysilane or tetraethoxysilane is particularly preferable.

Next, the component (b) will be described. In the component (b), R represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. For example, alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, γ-chloropropyl group, vinyl group, CF ₃ CH ₂ CH ₂ CH _2- , C ₂ F ₅ CH ₂ CH ₂ CH _2- , C ₃ F ₇ CH ₂ CH ₂ CH _2- , C ₂ F ₅ CH ₂ CH _2- , CF ₃ OCH ₂ CH ₂ CH _2- , C ₂ F ₅ OCH ₂ CH ₂ CH _2- , C ₃ F ₇ OCH ₂ CH ₂ CH _2- , (CF ₃ ) ₂ CHOCH ₂ CH ₂ CH _2- , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH _2- , 3- (perfluorocyclohexyloxy) propyl, H ( CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH _2- , H (CF ₂ ) ₄ CH ₂ CH ₂ CH _2- , 3-glycidoxypropyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group, Examples include 3-mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group. X in the organosilane is —OH, a halogen atom, or preferably an alkoxy group having 1 to 5 carbon atoms or an acyloxy group having 1 to 4 carbon atoms. For example, chlorine atom, methoxy group, ethoxy group, n -Propyloxy group, i-propyloxy group, n-butyloxy group, sec-butyloxy group, tert-butyloxy group, acetyloxy group and the like can be mentioned.

Specific examples of these components (b) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltriethoxysilane. Methoxysilane, i-propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, CF ₃ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₂ H ₅ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₂ F ₅ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₃ F ₇ OCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CF ₃ ) ₂ CHOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , 3- (perfluorocyclohexyloxy) propylsilane and the like can be mentioned.

  Among these, organosilane having a fluorine atom is preferable. Moreover, when using organosilane which does not have a fluorine atom as R, it is preferable to use methyltrimethoxysilane or methyltriethoxysilane. Said organosilane may be used individually by 1 type, and can also use 2 or more types together.

Next, the component (c) will be described. The component (c) is an organosilane represented by the general formula R ₂ Si (X) ₂ (wherein R is the same as R defined in the organosilane used in the component (b)). However, the plurality of Rs may not be the same substituent. In the composition of the present invention, a hydrolyzate and / or partial condensate obtained by hydrolysis and condensation serves as a binder in the composition and softens the coating film to improve alkali resistance. It is.

Specific examples of these organosilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxy. silane, di -i- propyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy _{silane, (CF 3 CH 2 CH 2} ) 2 Si (OCH 3) 2, (CF 3 CH 2 CH 2 CH 2) 2 Si (OCH _{3) 2, (C 3 F} 7 OCH 2 CH 2 CH 2) 2 Si (OCH 3) 2, _{[H (CF 2) 6 CH 2} OCH 2 CH 2 CH 2 ] _{2 Si (OCH 3) 2,} (C ₂ F ₅ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) _{2 and the} like, and an organosilane having a fluorine atom is preferable. Moreover, when using organosilane which does not have a fluorine atom as R, dimethyldimethoxysilane and dimethyldiethoxysilane are preferable. Moreover, the organosilane represented by (c) component may be used individually by 1 type, or 2 or more types can also be used together.

Next, the component (d) will be described. The component (d) is an organosilane represented by the general formula R ₃ Si (X) (wherein R is the same as R defined for the organosilane used in the component (b)). However, the plurality of Rs may not be the same substituent. In the composition of this invention, while functioning to make a film | membrane hydrophobic, it improves the alkali resistance of a coating film.
Specific examples of these triorganosilanes are trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-i-propylmethoxysilane. , Tri-i-propylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane and the like.

  In the present invention, the proportion of each component of (a) to (d) is 0 to 150 mass%, preferably 5 to 100 mass%, more preferably 10 to 60 mass% of component (b) based on component (a). % By mass. (B) component is 0-100 mass% on the basis of (a) component, Preferably it is 1-60 mass%, More preferably, it is 1-40 mass%. (C) A component is 0-10 mass% on the basis of (a) component, Preferably it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%. (D) component is 0-10 mass% on the basis of (a) component, Preferably it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%. Among the components (a) to (d), when the proportion of the component (a) is less than 30% by mass, the adhesion and curability of the coating film obtained are lowered.

  The hydrolyzate and / or partial condensate of the organosilane compound 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-butoxyethyl acetoacetate 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 (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  In the present invention, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the curable composition. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention, and is used as a stability improver for the curable composition used in the present invention. It works. 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 with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. Within the above range, good storage stability can be obtained.

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 antiglare layer, low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance to prepare the organosilane compound. It is preferable to prepare a hydrolyzate and / or partial condensate of a silane compound and prepare the curable composition using the obtained reaction solution (sol solution). In the present invention, first, the organosilane compound A composition containing a hydrolyzate and / or a partial condensate and a metal chelate compound is prepared, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto is added to at least an antiglare layer or a low refractive index layer. It is preferable to coat it in a single layer coating solution.
In the present invention, both the antiglare layer and the low refractive index layer contain a hydrolyzate of organosilane and / or a partial condensate thereof represented by the general formula (1). A cured film formed by applying and curing is preferred.

  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. Further, when the binder is formed by the sol component alone, the fluorine-containing polymer is not included.

  An inorganic filler other than the above-described inorganic fine particles can be added to the curable composition in an addition amount within a range that does not impair the desired effect of the present invention. As the inorganic filler, an inorganic filler in the antiglare layer is preferable, and it is particularly preferable to add a material that can impart conductivity, such as indium, tin, and antimony, within a range that does not greatly affect the refractive index.

[Other substances contained in curable composition for low refractive index layer]
The curable composition is prepared by adding various additives, a radical polymerization initiator, and a cationic polymerization initiator to the (A) fluorine-containing polymer, (B) inorganic fine particles, and (C) the organosilane compound as necessary. Further, they are prepared by dissolving them in a suitable solvent. At this time, the concentration of the solid content 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 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, 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, R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink, 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 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. 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.

[Solvent for low refractive index layer]
As a solvent used in the curable composition for forming the low refractive index layer of the present invention, it is possible to dissolve or disperse each component, it is easy to form a uniform surface in the coating process and the drying process, and liquid storage Various solvents selected from the viewpoints of ensuring the property and 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), ethers such as tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as Luketone, 79.6 ° C, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.
Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C), dibutyl ether (142.4 ° C), isobutyl acetate (118 ° C), cyclohexanone (155.7 ° C), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C) 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

<Transparent support>
As the transparent support of the antiglare antireflection film of the present invention, it is preferable to use a plastic 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 Nippon Zeon), 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 prepared by the so-called co-casting method disclosed in Japanese Utility Model Publication Nos. 61-94725 and 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose 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, due to the recent trend of thinning display devices, there is a great need for thinning of the polarizing plate. When such a thin cellulose acylate film is used as a transparent support for the antiglare antireflection film of the present invention, the solvent, film thickness, crosslinking shrinkage ratio, etc. of the layer directly applied to the cellulose acylate film are optimal. It is preferable to avoid the problems such as handling and application suitability by making it easier.
<About other layers>
As another layer that may be provided between the transparent support and the antiglare layer of the present invention, a transparent antistatic layer (when there is a request such as lowering the surface resistance value from the display side, there is dust on the surface etc. A hard coat layer (when the antiglare layer alone is insufficient in hardness), a moisture proof layer, an adhesion improving layer, a rainbow unevenness (interference unevenness) preventing layer, and the like.
These layers can be formed by a known method.

  Among them, a transparent antistatic layer is formed, and the surface resistance value LogSR of the antiglare antireflection film of the present invention is 12 or less, preferably 11 or less. Examples of the conductive material specified for the transparent antistatic layer include ultrafine particles of metal oxides such as tin oxide, indium oxide, zinc oxide and titanium nitride, and tin oxide and indium oxide are particularly preferable. A transparent antistatic layer can be obtained by dispersing a curable monomer, a coupling agent, and the like in such a conductive material in a suitable organic solvent, and applying and curing the substrate on a substrate such as a triacetyl cellulose film. The surface resistance value LogSR is measured by a method according to JIS-K-7194.

  The antiglare antireflection film of the present invention can be formed by the following method, but is not limited to this method.

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

Filtration capable of removing almost all foreign substances (pointing to 90% or more) corresponding to the dry film thickness (about 50 nm to 120 nm) of the low refractive index layer directly formed on the coating solution for forming the antiglare layer It is preferable to Since the light-transmitting fine particles for imparting light diffusivity are equal to or greater than the film thickness of the low refractive index layer, the filtration is performed on the intermediate liquid to which all materials other than the light-transmitting fine particles are added. Is preferred. 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 antiglare layer and, if necessary, a low refractive index layer is applied onto a 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 antiglare layer or the low refractive index layer are cured by light irradiation and / or heating. Thereby, an anti-glare layer and a low refractive index layer are formed.

In order to supply the antiglare antireflection film of the present invention 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 the antiglare layer or the antireflection layer of the present invention, will be described below.

<Die coater configuration>
FIG. 2 is a sectional view of a coater using a slot die embodying 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 cross section of the pocket 15 is configured by a curve and a straight line. For example, the pocket 15 may be substantially circular as shown in FIG. 2 or may be 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 like 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.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat part 18 called a land. 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.

FIG. 3 shows a cross-sectional shape of the slot die 13 in comparison with a conventional one, (A) shows the slot die 13 of the present invention, and (B) shows a conventional slot die 30. 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 of the present invention, the downstream side lip land length I _LO is shortened, whereby the wet film thickness of 20 μm or less can be applied 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 30 μm.
m to 100 μm, preferably 30 μm to 80 μm, and more preferably 30 μm to 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. 4 is a perspective view showing a slot die and its periphery in a coating process in which the present invention is implemented. 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 so that sufficient decompression can be adjusted. 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. 5 and 6 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 placed under the web W and the slot die 13 as shown in FIG. 4, from the uppermost end of the back plate 40a to the web W Indicates the gap.

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 traveling direction side of the web in the web running direction, the more disadvantageous it is for bead formation.If this length varies between arbitrary locations in the slot die width direction, It becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.
Further, when the material of the tip lip of the slot die is made of a material such as stainless steel, 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 of the present invention is a pre-measuring method, it is easy to ensure a stable film thickness even during high-speed coating. The coating method of the present invention can be applied at high speed and with good film thickness stability to a coating solution having a low coating amount such as the antiglare antireflection film of the present invention. 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. From the viewpoint of productivity, it is preferable to apply at a rate of 25 m / min or more by using the production method of the present invention.

<Wet application amount>
When forming the antiglare layer, it is preferable to apply the coating liquid in a range of 6 to 30 μm as a wet coating thickness directly or via another layer on the base film, from the viewpoint of preventing drying unevenness. Furthermore, the range of 3-20 micrometers is more preferable. Moreover, when forming a low refractive index layer, it is preferable to apply | coat a coating composition in the range of 1-10 micrometers as wet coating film thickness directly or via another layer on an anti-glare layer, More preferably, it is applied in the range of 5 μm.

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

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

[Curing]
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 antiglare layer becomes a certain value of less than 100%, the low refractive index layer of the present invention is provided on the antiglare layer to reduce the amount by ionizing radiation and / or heat. When the refractive index layer is cured, if the curing rate of the lower antiglare layer is higher than before the low refractive index layer is provided, the adhesion between the antiglare layer and the low refractive index layer is improved, which is preferable.

The antiglare antireflection film of the present invention produced as described above can be used for a liquid crystal display device by using this to produce a polarizing plate. In this case, it arrange | positions on the outermost surface of a display by providing an adhesive layer on one side. The antiglare 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 creating a polarizing plate using the antiglare antireflection film of the present invention as one of the surface protective films of two polarizing films, the antiglare antireflection film has an antireflection structure. It is preferable to improve the adhesion on the adhesive surface by hydrophilizing the surface of the transparent support opposite to the side, that is, the surface to be bonded to the polarizing film.

[Saponification]
(1) Method of immersing in an alkali solution This is a technique in which a light scattering film or an antireflection film is immersed in an alkali solution under appropriate conditions to saponify all surfaces that are reactive with alkali on the entire surface of the film. Since no special equipment is required, it 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 according to the material and configuration of the light scattering film and the antireflection film, and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface of the transparent support opposite to the surface having the antiglare layer and the low refractive index layer is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle with water on the surface of the transparent support opposite to the side having the antiglare layer or the low refractive index layer, the better from the viewpoint of adhesiveness to the polarizing film. At the same time, since it is damaged by alkali from the surface having the antiglare layer and the low refractive index layer to the inside, it is important to set the reaction conditions to the minimum necessary. 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 is too great, and physical strength is impaired.

(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 antiglare layer or the low refractive index layer under appropriate conditions. An alkaline solution coating method of coating, 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 after being unwound from a roll-shaped support, a series of steps are added in addition to the above-described antiglare antireflection film production process. You may carry out by operation. 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 for protecting and saponifying an antiglare layer and a low refractive index layer with a laminate film When the antiglare layer and / or the low refractive index layer is insufficient in resistance to an alkaline solution as in the above (2) In addition, after forming the final layer, after laminating the laminate film on the surface on which the final layer has been formed and then immersing it in an alkali solution, only the surface of the triacetyl cellulose opposite to the surface on which the final layer has been formed is hydrophilized, Thereafter, 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 damage to the antiglare layer and the low refractive index layer. Can do. Compared with the method (2), there is an advantage that a laminate film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

(4) Method of immersing in alkaline solution after forming up to antiglare layer Up to antiglare layer is resistant to alkaline solution, but when low refractive index layer is insufficiently resistant to alkaline solution, after forming up to antiglare 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 antiglare layer. Although the manufacturing process becomes complicated, there is an advantage that the interlayer adhesion between the antiglare 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 for forming an antiglare layer or a low refractive index layer on a previously saponified triacetyl cellulose film Saponified by, for example, pre-immersing a triacetyl cellulose film in an alkali solution, either directly or on the other side An antiglare layer and a low refractive index layer may be formed through these layers. In the case of saponification by dipping in an alkaline solution, interlayer adhesion between the antiglare layer or other layers and the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the antiglare layer or other layer is formed is treated with corona discharge, glow discharge, etc. to remove the hydrophilic surface, and then the antiglare layer or other layer. Can be dealt with by forming Further, when the antiglare layer or other layer has a hydrophilic group, the interlayer adhesion may be good.

Below, the polarizing plate using the light-scattering film or 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 anti-glare 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 antiglare layer or 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 antiglare antireflection film of the present invention as a protective film for a polarizing plate, a light scattering function having excellent physical strength and light resistance, or a polarizing plate having an antireflection function can be produced, and the cost can be greatly reduced. The apparatus can be thinned.
Also, a polarizing plate using the antiglare antireflection film of the present invention as one of the protective films for a polarizing plate and an optical compensation film having optical anisotropy described later as the other protective film of the polarizing film is prepared. This further improves the visibility and contrast in the bright room of the liquid crystal display device, and makes it possible to produce a polarizing plate that can greatly widen the vertical and horizontal viewing angles.

[Optical compensation layer]
By providing the polarizing plate with an optical compensation layer (optically anisotropic layer), the viewing angle characteristics of the liquid crystal display screen can be improved.
A known layer can be used as the optical compensation layer. However, in terms of widening the viewing angle, the optical compensation layer has a layer having optical anisotropy made of a compound having a discotic structural unit, and the discotic compound has a circular shape. The disc surface is inclined with respect to the protective film surface, and the angle formed by the disc surface of the discotic compound and the protective film surface changes with the distance from the protective film surface (the depth of the optically anisotropic layer). An optical compensation layer characterized in that it varies in the vertical direction) is preferred.
The angle preferably increases as the distance from the protective film surface side of the optically anisotropic layer made of the discotic compound increases.
When the optical compensation layer is used as a protective film for the polarizing film, the protective film is composed of a plurality of layers, and includes an optically anisotropic layer on the surface opposite to the surface to be bonded to the polarizing film. The surfaces on the mating side are preferably saponified, and it is preferable to carry out the saponification.

[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, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction 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 produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

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

<Liquid crystal display device>
The polarizing plate using the antiglare antireflection film of the present invention is an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). Can be applied to. Since the anti-glare antireflection film of the present invention has a transparent support, the transparent support is bonded to the image display surface of the image display device.

  The antiglare antireflection film of the present invention is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS) when used as one side of a surface protective film of a polarizing film. ), Transmissive, reflective, or transflective liquid crystal display devices such as an optically compensate bend cell (OCB). In particular, it can be preferably used for VA, IPS, OCB, etc., for applications such as large liquid crystal televisions, and can also be preferably used for TN, STN, etc., if it is used for display devices with small and medium definition. For applications such as large liquid crystal televisions, it is particularly preferable for a display screen having a diagonal of 20 inches or more and a definition of XGA or less (1024 × 768 or less in a display device having an aspect ratio of 3: 4). Can be used. Since the antiglare antireflection film of the present invention has substantially no internal haze, it has a glare for a 20-inch screen with a definition exceeding XGA (1024 × 768 in a display device having an aspect ratio of 3: 4). Since it exceeds the permissible level, it is not preferred when emphasizing glare. Further, since the degree of glare occurs due to the relationship between the size of the pixel and the surface unevenness of the antiglare film on the surface, the definition becomes UXGA (aspect ratio 3 :) when the size of the display device is 30 inches. If it is 40 inches, the definition can be preferably used up to QXGA (2048 × 1536 in a display device with an aspect ratio of 3: 4) 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) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening 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.
In addition, regarding Examples 1-3, 2-3, and 3-3, “Example” should be read as “Reference Example”.

[Example 1]
(Synthesis of perfluoroolefin copolymer (1))

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

(Preparation of sol solution a)
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 coating solution A for antiglare layer)
25.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 46.3 g of methyl isobutyl ketone. Furthermore, 1.3 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. Next, 0.04 g of fluorine-based surface modifier (FP-149), 5.2 g of silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), cellulose acetate butyrate (CAB) having a molecular weight of 40,000 -531-1, Eastman Chemical Co., Ltd.) 0.50 g was added and stirred with an air disper for 120 minutes to completely dissolve the solute. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.520.
Finally, 30 of crosslinked poly (acryl-styrene) particles having an average particle diameter of 3.5 μm (copolymerization composition ratio = 50/50, refractive index 1.536) dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser. After adding 25.2 g of% methyl isobutyl ketone dispersion, the mixture was stirred with an air disperser for 10 minutes.
The mixed solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution A for an antiglare layer.

(Preparation of coating solution B for antiglare layer)
46.3 g of methyl isobutyl ketone (vapor pressure at 21.7 ° C .: 16.5 mmHg) used as the main solvent was changed to 40.0 g, and propylene glycol (vapor pressure at 20.0 ° C .: 0 as a small amount solvent having a hydroxyl group). 0.08 mmHg) was added in the same manner as antiglare layer coating solution A, except that 6.3 g was added.

(Preparation of coating solution C for antiglare layer)
12.7 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) was diluted with 16.7 g of methyl isobutyl ketone, and colloidal silica dispersion MiBK-ST (trade name, average) 42.3 g of a particle size of 15 nm, a solid content concentration of 30%, manufactured by Nissan Chemical Co., Ltd.) was added. Furthermore, 1.3 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. Next, 0.04 g of fluorine-based surface modifier (FP-149), 5.2 g of silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), cellulose acetate butyrate (CAB) having a molecular weight of 40,000 -531-1, Eastman Chemical Co., Ltd.) 0.50 g was added and stirred with an air disper for 120 minutes to completely dissolve the solute. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.500.
Finally, crosslinked poly (methyl methacrylate) particles having an average particle size of 3.0 μm dispersed in this solution for 20 minutes at 10,000 rpm with a Polytron disperser (crosslinking agent = containing 10% ethylene glycol dimethacrylate, refractive index 1.492) 21.0 g of 30% methyl isobutyl ketone dispersion was added and stirred with an air disperser for 10 minutes.
The mixed solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare an antiglare layer coating solution C.

(Preparation of coating solution D for antiglare layer)
5% by mass of the crosslinked poly (acryl-styrene) particles having an average particle size of 3.5 μm (copolymerization composition ratio = 50/50, refractive index 1.530) was used as the conductive material Bright GNR4,6-EH (gold-nickel coat) A coating solution D for an antiglare layer was prepared in the same manner as the coating solution A for an antiglare layer, except that the resin beads were replaced with resin beads (manufactured by Nippon Chemical Industry Co., Ltd.).

(Preparation of coating solution for transparent antistatic layer)
100 g of Pertron C-4456-S7 (45% solid content ATO-dispersed hard coat agent, trade name) manufactured by Nippon Pernox Co., Ltd., 30 g of cyclohexanone, 10 g of methyl ethyl ketone, silane coupling agent (3-acryloxypropyltrimethoxysilane ( KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.)) 1.5) was added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 10 μm to prepare a coating solution for a transparent antistatic layer.
The coating solution for transparent antistatic layer is coated on a triacetyl cellulose (TAC) substrate so as to have a film thickness of 2 μm / m ² , dried at 70 ° C. for 1 minute, and then subjected to UV (ultraviolet) light of 54 mJ under a nitrogen purge. Irradiated and half cured. The surface resistance value logSR of the obtained transparent antistatic layer was 11Ω / □.

(Adjustment of coating solution A 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 Co., Ltd. 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 Then, 0.6 g of the sol solution a, 5 g of methyl ethyl ketone and 0.6 g of cyclohexanone were added, stirred, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a low refractive index layer coating solution A. The refractive index of the layer formed with this coating solution was 1.45.

(Adjustment of coating liquid B for low refractive index layer)
(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. Prepared) 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 9 g of ion-exchanged water. 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 to 20% by mass with cyclohexanone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion A was analyzed by gas chromatography, it was 1.5%.

(Preparation of coating solution B)
The dispersion A was 195 with respect to 783.3 parts by mass (47.0 parts by mass as the solid content) of OPSTAR JTA113 (thermally crosslinkable fluorine-containing silicone polymer composition liquid (solid content: 6%): manufactured by JSR Corporation). Parts by mass (silica + 39.0 parts by mass as surface treatment agent solids), colloidal silica dispersion (silica, MEK-ST particle size difference, average particle size 45 nm, solids 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 B 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 with this coating solution was 1.39.

(Preparation of coating solution C 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 were added. After stirring, the mixture was filtered through a polypropylene filter having a pore size of 5 μm to prepare a coating solution C for a low refractive index layer. The refractive index of the layer formed with this coating solution was 1.40.

(Adjustment of coating liquid D for low refractive index layer)
A flask was charged with 100 g of 3-glycidoxypropyltrimethoxysilane, 1000 g of trifluoropropyltrimethoxysilane, 400 g of heptadecafluorodecyltrimethoxysilane, 500 g of tetraethoxysilane, and 200 g of isobutanol. Next, 419 g of 0.25 N aqueous acetic acid was added dropwise little by little. After completion of dropping, the mixture was stirred at room temperature for 3 hours. Next, 6 g of aluminum acetylacetonate was added, and stirring was further performed for 3 hours. Thereafter, 600 g of isopropyl alcohol was added and 100 g of the liquid obtained by filtration through a polypropylene filter having a pore size of 1 μm was further used for hollow silica (particle size 60 nm, shell thickness 10 nm, solid content concentration 20%, main solvent 97 g of isopropyl alcohol (trade name: manufactured by CS60-IPA Catalyst Kasei Kogyo Co., Ltd.) is added, stirred, and then subjected to multi-stage filtration with a polypropylene filter having a pore size of 30 μm, 10 μm, and 1 μm to apply for a low refractive index layer. Liquid D was prepared.

[Example 1]
(1) Coating of antiglare layer As a transparent support, a 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the following apparatus configuration and coating are applied. The coating solution A for the antiglare layer is applied by the die coating method indicated by the conditions, dried at 30 ° C. for 15 seconds and at 100 ° C. for 20 seconds, and further air-cooled metal halide lamp (eye graphics (160 The coating layer was cured by irradiating ultraviolet rays with an irradiation amount of 90 mJ / cm ² to form an antiglare layer having an antiglare property having a thickness of 6 μm and wound up.

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. In accordance with the liquid physical properties of each coating solution, in the case of anti-glare layer: coating solutions A, C and D for anti-glare layer: coating speed = 20 m / min, wet coating amount = 17.5 ml / m ² , anti-glare In the case of layer coating solution B: coating speed = 40 m / min, wet coating amount = 17.5 ml / m ² , low refractive index layer: coating speed = 40 m / min, wet coating amount = 5.0 ml / m ² Application was performed. The application width was 1300 mm and the effective width was 1280 mm.

(2) Coating of low refractive index layer The triacetyl cellulose film coated with the antiglare layer coating liquid A and coated with the antiglare 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 and further dried at 140 ° C. for 8 minutes, a 240 W / cm air-cooled metal halide lamp (eye graphics) under an atmosphere with an oxygen concentration of 0.1% by nitrogen purge. Ltd.) was used to an irradiation dose of 300 mJ / cm ^2, to form a low refractive index layer having a thickness of 100 nm, it was wound.
(3) Saponification treatment of antiglare 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 produced antiglare 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 manner, a saponified antiglare antireflection film was produced. This is Example 1-1.

  The antiglare layer was applied in the same manner as in Example 1-1 except that the antiglare layer coating liquid A was changed to the antiglare layer coating liquids B, C, and D, and the coating liquid B was applied at a coating speed of 40 m / min. Then, a low refractive index layer was applied and saponified in the same manner as in Example 1-1. What applied the coating liquid B for glare-proof layers was set to Example 1-2, what applied the coating liquid C for glare-proof layers was set to Example 1-3, and what applied the coating liquid D for glare-proof layers was applied. This is Example 1-4.

[Comparative Example 1]
In addition, on the antiglare layer formed in the same manner as in Example 1-1, a SiO ₂ vapor-deposited layer as a low refractive index layer was subjected to a vacuum degree of 4 × 10 ⁻⁵ Toor, a voltage of 8 KV, and a current of 20 to 40 mA. The film thickness was 100 nm. Further, a composition obtained by diluting KP-801M (manufactured by Shin-Etsu Chemical Co., Ltd.) to 0.007% with PF5080 (manufactured by Sumitomo 3M) as an antifouling layer was applied and dried at 80 ° C. for 1 minute to obtain a film thickness of about 5 nm. An antifouling layer was formed. The antiglare antireflection film thus obtained was saponified on one side only by applying an alkali solution on the side of the support on which the low refractive index layer was not formed by the method described in this specification. This is referred to as Comparative Example 1-1.
Further, an antiglare antireflection film of Comparative Example 1-2 was produced in the same manner as Example 1-1 except that the antiglare layer of Example 1-1 was formed at a coating speed of 50 m / min.

(Evaluation of antiglare film / antiglare antireflection film)
The obtained film was evaluated for the following items after the antiglare layer was formed (referred to as an antiglare film) and after the low refractive index layer was formed (referred to as an antiglare antireflection film). The results are shown in Table 1.

(1) Haze Total haze (h), internal haze (hi), surface haze (hs, AG) or (hs, AGAR) of the obtained film was measured by the following measurement.
1. The total haze value (h) of the film obtained according to JIS-K7136 is measured.
2. A few drops of silicone oil were added to the surface and the back surface of the low refractive index layer side of the obtained film, and sandwiched from the front and back using two 1 mm thick glass plates (micro slide glass product number S 9111, manufactured by MATSANAMI), Two glass plates and the obtained film were optically adhered to each other, and the haze was measured in a state where surface haze was removed, and measurement was performed by sandwiching only silicone oil between two separately measured glass plates. The value obtained by subtracting haze was calculated as the internal haze (hi) of the film.
3. The value obtained by subtracting the internal haze (hi) calculated in 2 above from the total haze (h) measured in 1 above was calculated as the surface haze (hs, AGAR) of the film.
In addition, (hs, AG) is a value obtained by calculating (hi) in the same manner as 2 above for an antiglare film not provided with a low refractive index layer, and subtracting (hi) from the total haze (h). is there.
From the above, the surface haze hs ratio (hs, AGAR) / (hs, AG) between the antiglare antireflection film and the antiglare film was calculated.
(2) Anti-glare property The obtained film is projected from a 45 degree angle with a louvered bare fluorescent lamp (8000 cd / m ² ), and the degree of blur of the reflected image when observed from the -45 degree direction is as follows. Evaluated by criteria.
I do not know the outline of the fluorescent lamp at all, but it is too anti-glare and clouded.
I don't know the outline of the fluorescent light (moderate anti-glare): ◎
Slightly understand the outline of the fluorescent lamp (moderate antiglare): ○
The fluorescent lamp is blurred, but the outline can be identified: △
Fluorescent lamp is hardly blurred: ×

(4) Average reflectance After forming the low refractive index layer and applying the saponification treatment, the back surface of the antiglare antireflection film is sandpaper and then treated with black ink to eliminate back surface reflection. Then, the integrated spectral reflectance at an incident angle of 5 ° was measured on the surface side using a spectrophotometer (manufactured by JASCO Corporation) in a 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.
(5) Centerline average roughness (Ra)
According to JIS-B0601, the low refractive index layer was formed, and the centerline average roughness Ra of the film after saponification treatment was measured.
(6) Transmission image clarity The transmission image clarity was measured with an optical comb width of 0.5 mm according to JIS K7105. The results are shown in Table 2.

From Table 1, since the anti-glare antireflection film of this example forms the low refractive index layer by wet coating, in the comparative example in which the anti-glare layer is optimized up to the stage of the anti-glare film, the formation of the low refractive index layer is performed. The anti-glare antireflection film of the present invention has a predetermined ratio between the surface haze value of the anti-glare film and the surface haze after the formation of the low refractive index layer, whereas the anti-glare property deviates from the optimum region later. Since it was designed to be within the range, it can be seen that the antiglare property after the formation of the low refractive index layer as the final form is an optimum region.
From Table 2, it can be seen from the characteristic values that the antiglare property of the antiglare and antireflection film of the present invention is in the optimum region.

Further, when an antiglare antireflection film was produced in the same manner except that the coating liquid A for low refractive index layer in Example 1-1 was replaced with the coating liquid B for low refractive index layer, the average reflectance was 1. Improved to 2%.
Further, the antiglare property was similarly changed except that the coating liquid A for the low refractive index layer in Example 1-1 was replaced with the coating liquid C for the low refractive index layer, and the ultraviolet light after coating was changed to an irradiation amount of 900 mJ / cm ² . When an antireflection film was produced, the average reflectance was improved to 1.5%. Further, since the coating liquid C for the low refractive index layer is used in combination with thermosetting, the scratch resistance can be improved.
Further, the coating solution A for the low refractive index layer of Example 1-1 was replaced with the coating solution D for the low refractive index layer, and similarly coated on the antiglare layer, dried at 80 ° C. for 5 minutes, and further 120 ° C. And a low refractive index layer having a thickness of 100 nm is formed and wound, and only the surface of the support on which the low refractive index layer is not formed is made of an alkaline solution in the same manner as in Comparative Example 1-1. One-side saponification treatment was performed by coating. The antiglare antireflection film thus formed has an average reflectance improved to 1.0%.

[Example 2]
(Preparation of polarizing plate)
An 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd., hereinafter referred to as TAC film) was immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes and then neutralized and washed with water. And an antiglare antireflection film (saponified: Example 1-1 to Example 1-4, Comparative Example 1-1, 1-2) prepared in Example 1, and iodine to polyvinyl alcohol. A polarizing plate was prepared by adhering and protecting both sides of a polarizing film prepared by adsorption and stretching. The transparent support surface of the antiglare antireflection film prepared in Example 1 was adhered to the polarizing film. These were designated as Example 2-1 to Example 2-4 and Comparative Examples 2-1 and 2-2, respectively.
In addition, 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 2-3.

[Example 3]
(Evaluation of polarizing plate)
The polarizing plates of Example 2-1 to Example 2-4, Comparative Example 2-1, Comparative Example 2-2, and Comparative Example 2-3 produced in Example 2 were combined in the combinations shown in Table 3, and each liquid crystal A part of the polarizing plate on the viewer side of the television was peeled off and replaced with the polarizing plate (Example 3-1 to Example 3-4, Comparative Example 3-1, Comparative Example 3-2, respectively). Comparative example 3-3). About the obtained display apparatus, the following items were evaluated. The results are shown in Table 3.

(1) 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 presence of a fluorescent light cannot be recognized, and the entire surface appears white: ●
I do not know the outline of the fluorescent lamp at all, but I can recognize the existence of the fluorescent lamp:
The outline of the fluorescent lamp is slightly understood, but it is hardly reflected: ○
Fluorescent light is blurred but slightly reflected: △
Fluorescent light is completely reflected: ×

(2) Whitening Fluorescence when louvered exposed fluorescent lamp (8000 cd / m ² ) is projected from an angle of 45 degrees on the obtained liquid crystal television and viewed from the −45 degree direction with the viewing angle raised and lowered in the same plane. The degree of scattering (= whitening) in the off-axis direction near the specular reflection of the lamp was visually evaluated according to the following criteria.
No scattering in the off-axis direction: ◎
Scattering in the off-axis direction is hardly noticed: ○
Scattering in the off-axis direction is slightly worrisome: △
Scattering in the off-axis direction is anxious: ×

From the results shown in Table 3, the polarizing plate using the antiglare antireflection film of the present invention for the protective film on the surface side achieves both antireflection and improvement of whitening when applied to a liquid crystal display device. You can see that you can.
Further, an antiglare antireflection film was prepared in the same manner as in Example 1 except that the above-described transparent antistatic layer was formed between the antiglare layer and the transparent support in Example 1, and the same as in Example 2. When applied to a liquid crystal television in the same manner as in Example 3 with the polarizing plate, dust on the surface was improved.

[Example 4]
The antiglare antireflection film of Examples 1-1 to 1-4 was used for the protective film on the viewing side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell, and the protective film on the liquid crystal cell side of the polarizing plate on the backlight side. As a wide viewing angle film (Wide View Film SA 12B, manufactured by Fuji Photo Film Co., Ltd.), a liquid crystal display device having a very wide viewing angle in the vertical and horizontal directions, excellent visibility, and high display quality. Obtained.

It is sectional drawing which shows typically one preferable embodiment of the anti-glare antireflection film which has anti-glare property. It is sectional drawing of the coater using the slot die which implemented this invention. (A) shows the cross-sectional shape of the slot die of this invention, (B) is a figure which shows the cross-sectional shape of the conventional slot die. It is a perspective view which shows the slot die of the application | coating process which implemented this invention, and its periphery. It is sectional drawing which shows the pressure reduction chamber and web W which adjoin (back plate 40a is integral with the chamber 40 main body). It is sectional drawing which shows the pressure reduction chamber and web W which are adjoining (back plate 40a is fastened to chamber 40 with screw 40c).

Explanation of symbols

1 Antiglare film (Antireflection film)
2 Transparent Support 3 Antiglare Layer 4 Low Refractive Index Layer 5 Translucent Fine Particle 10 Coater 11 Backup Roll W Web 13 Slot Die 14 Coating Solution 14a Bead 14b Coating 15 Pocket 16 Slot 16a Slot Opening 17 Tip Lip 18 Land 18a Upstream lip land 18b Downstream lip land I _UP Land length I of upstream lip land 18a _LO Land length of downstream lip land 18b LO Over bit length (web of downstream lip land 18b and upstream lip land 18a Difference in distance from W)
G _L End lip 17 and web W gap (downstream lip land 18b and web W gap)
30 the gap G _S side plate 40b and the web W between the conventional slot-die 31a upstream lip land 31b downstream lip land 32 pocket 33 slot 40 vacuum chamber 40a back plate 40b side plate 40c screws G _B back plate 40a and the web W Gap between

Claims (23)

An antiglare antireflection film having at least an antiglare layer and a low refractive index layer on a transparent support, which satisfies the following conditions I), VI) and VII): .
I) The haze value (hi) resulting from internal scattering of the antiglare antireflection film is (hi) ≦ 50%.
VI) Haze value (hs, AGAR) due to surface scattering of the antiglare layer and haze value (hs, AGAR) due to surface scattering of the antiglare antireflection film after forming the low refractive index layer The ratio (hs, AGAR) / (hs, AG) is 0.2 <(hs, AGAR) / (hs, AG) <0.6.
VII) The haze value (hs, AGAR) resulting from surface scattering of the antiglare antireflection film is 2.0% ≦ (hs, AGAR) ≦ 7.0%. The antiglare antireflection film according to claim 1, wherein the haze value (hi) resulting from internal scattering of the antiglare antireflection film satisfies the following condition III).
III) The haze value (hi) resulting from internal scattering of the antiglare antireflection film is (hi) ≦ 30%. The antiglare antireflection film according to claim 2, wherein the antiglare antireflection film has a haze value (hi) due to internal scattering of 18% or more. The center line average roughness Ra of the antiglare and antireflection film, anti-glare and anti-reflection film according to any one of claims 1 to 3, characterized in that a 0.05～0.25Myuemu. The antiglare antireflection film according to any one of claims 1 to 3 , wherein the image clarity according to JIS K7105 is 5% to 50% when measured at an optical comb width of 0.5 mm. . The antiglare layer is formed by dispersing at least one kind of translucent fine particles having an average particle diameter of 0.5 to 10 μm in a translucent resin, and has a refractive index of the translucent fine particles and the translucent resin. The absolute value of the difference is 0.001 to 0.300, and the translucent fine particles are a layer formed by containing 3 to 30% by mass in the total solid content of the antiglare layer. The antiglare antireflection film according to any one of to 3 . The translucent resin is a cross-linked poly (meth) acrylate-based polymer having a (meth) acrylate monomer having at least trifunctional or higher functionality as a main component and the translucent fine particles having an acrylic content of 50 to 100 mass percent. The anti-glare antireflection film according to claim 6 . A cross-linked poly (styrene-acrylic) copolymer in which the translucent resin has a (meth) acrylate monomer having at least trifunctional or higher functionality and the translucent fine particles have a styrene content of 1 to 100 mass percent, or The antiglare antireflection film according to claim 6 , which is a crosslinked polystyrene. The antiglare layer is formed from a coating composition containing the translucent resin, the translucent fine particles and a plurality of types of solvents, and the plurality of types of solvents do not dissolve the transparent support. And an antiglare antireflection film according to claim 6 , which comprises a small amount of a solvent having a hydroxyl group. The antiglare antireflection film according to claim 9 , wherein the vapor pressure of the small amount solvent is lower than that of the main solvent at an arbitrary temperature within a range of 20 to 30 ° C. The antiglare antireflection film according to claim 9 , wherein a mass ratio of the main solvent and the small amount solvent is in a range of 99: 1 to 50:50 as the former: the latter. A composition having a thermosetting property and / or a photocurable property, wherein the low refractive index layer mainly comprises 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; anti-glare and anti-reflection film according to any one of claims 1 to 11, characterized by being formed coated. The low refractive index layer is (A) the fluoropolymer, (B) inorganic fine particles having an average particle diameter of 30% to 100% of the thickness of the low refractive index layer, and (C) the following general formula (1) ), A hydrolyzate thereof, a hydrolyzate thereof, and a partial condensate thereof, and a cured film formed by applying and curing a curable composition containing one or more components. The antiglare antireflection film according to claim 12 .
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 low refractive index layer is applied and cured with a curable composition containing one or more components selected from hydrolyzate of organosilane represented by the following general formula (2) and partial condensate thereof. anti-glare and anti-reflection film according to any one of claims 1 to 11, characterized in that a cured film formed Te.
General formula (2)
(R ¹⁰ ) _l Si (X) _4-l
(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. L represents an integer of 0 to 3.) The low refractive index layer is composed of (A) inorganic fine particles having an average particle diameter of 30% to 100% of the thickness of the low refractive index layer, and (B) an organosilane represented by the general formula (2). The protective film according to claim 14 , which is a cured film formed by applying and curing a curable composition containing at least one component selected from a hydrolyzate and a partial condensate thereof. Dazzling antireflection film. Both the antiglare layer and the low refractive index layer contain a curable coating containing any one or more of the organosilane represented by the general formula (1), a hydrolyzate thereof, and a partial condensate thereof. The antiglare antireflection film according to claim 13 , which is a cured film formed by applying and curing the composition . The anti-glare antireflection according to claim 13 or 15 , wherein the inorganic fine particles are inorganic fine particles containing a silicon oxide having a hollow structure and a refractive index of 1.17 to 1.40 as a main component. the film. A transparent antistatic layer having a conductive material at least one layer, wherein a surface resistance value logSR of the anti-glare and anti-reflection film is 12 or less, according to any one of claims 1 to 17 Antiglare antireflection film. A method for producing an antiglare antireflection film according to any one of claims 1 to 18 , wherein the coating composition for an antiglare layer contains translucent fine particles, a translucent resin, and a solvent, and / or low. The coating composition for the refractive index layer is applied from the slot of the tip lip by bringing the land of the tip lip of the slot die close to the surface of the web of the transparent support that is continuously supported by a backup roll, and A method for producing an antiglare antireflection film, comprising a step of coating an antiglare layer and / or a low refractive index layer on the transparent support. The polarizing plate formed by laminating a polarizing film and two protective films for protecting both the front side and the back side of the polarizing film, respectively, the antiglare antireflection film according to any one of claims 1 to 18 on one side A polarizing plate characterized by being used for a protective film. Of the two protective films for forming the polarizing plate, the film not including the antiglare antireflection film is composed of a plurality of layers, and is on the surface opposite to the surface to be bonded to the polarizing film. An optical compensation film comprising an optically anisotropic layer, wherein the optically anisotropic layer is a layer made of a compound having a discotic structural unit, and the disc surface of the discotic structural unit is against the protective film surface are inclined Te, and the angle between the disc plane and the protective film surface of the discotic structural unit, according to claim 20, characterized in that it is changed in the depth direction of the optically anisotropic layer Polarizing plate. A liquid crystal display device comprising at least one polarizing plate according to claim 20 or 21 . The liquid crystal display device according to claim 22 , wherein the diagonal of the display screen is 20 inches or more.

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