JP2003248110A - Antidazzle reflection preventive film, polarizing plate and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antidazzle reflection preventive film superior in image display grade which faithfully reproduces black display, that is, makes to obtain the so-called steadiness of black, while having sufficient reflection preventive performance. <P>SOLUTION: The antidazzle reflection preventive film having at least one layer of antidazzle hard coat layers on a transparent support includes at least one kind of translucent particles having an average particle diameter of 60% or more and less than 95% to a layer thickness of at least one layer of the antidazzle hard coat layers, and at least one kind of translucent particles having an average particle diameter of 105% or more and less than 140% to the layer thickness. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antireflection film having an antiglare property, a polarizing plate using the same, and a display device.

[0002]

2. Description of the Related Art Antiglare antireflection films are generally used in cathode ray tube displays (CRTs), plasma displays (PDs).
P), electroluminescence display (EL
D) or an image display device such as a liquid crystal display device (LCD), in order to prevent a decrease in contrast and reflection of an image due to reflection of external light, the reflectance is reduced by light scattering by surface protrusions and thin film interference. Has the function of reducing
It is placed on the top of the display. In designing the surface shape of the antiglare layer, the thickness of the antiglare hard coat layer as disclosed in JP-A-8-309910 is set to 50 to 90% of the average particle size of the synthetic resin particles, whereby the antiglare property is obtained. Techniques for achieving both transparency have been proposed.

In recent years, techniques for improving the image display quality such as wide viewing angle, high-speed response, and high definition of liquid crystal displays have been advancing in recent years.
It has become clear that it is extremely important for the user's needs because there is "blackness in black display at N hours", that is, "how black can be displayed in black".

On the other hand, the antiglare technique utilizing the surface scattering by the surface protrusions in order to prevent the deterioration of the contrast due to the reflection of the external light and the reflection of the image is, on the other hand, due to such surface scattering, the white blur or the black is generated. The problem of not tightening is hugged, which is a problem that must be solved when using the antiglare antireflection film.

Therefore, regarding the design of the antiglare layer, it is necessary to design the surface shape that achieves both the antireflection property and the tightness of black, and the technique described in JP-A-8-309910 solves the above problem. It wasn't something.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an anti-glare property having an excellent image display quality that faithfully reproduces black display while obtaining sufficient anti-reflection performance, so-called black tightness is obtained. It is to supply an antireflection film. Further, it is to provide a polarizing plate and a display device using such an antiglare antireflection film.

[0007]

According to the present invention, an antiglare antireflection film, a polarizing plate and a display device having the following constitution are provided, and the above object is achieved.

(1) In an antiglare antireflection film having at least one antiglare hard coat layer on a transparent support, at least one antiglare hard coat layer,
At least 60 with respect to the layer thickness of the antiglare hard coat layer
% And less than 95%, and at least one first light-transmissive particle, and 105% or more and 140% with respect to the same layer thickness.
An antiglare antireflection film comprising at least one kind of second translucent particles having an average particle size of less than 1%. (2) The first translucent particles have an average particle size of 70% or more and less than 95% with respect to the layer thickness of the antiglare hard coat layer, and the second translucent particles have a layer thickness of the same layer. On the other hand, the antiglare antireflection film as described in (1), which has an average particle size of 105% or more and less than 130%. (3) The first translucent particles have an average particle size of 80% or more and less than 95% of the layer thickness of the antiglare hard coat layer, and the second translucent particles have a layer thickness of the same layer. On the other hand, it has an average particle size of 105% or more and less than 120% (1), (2)
The antiglare antireflection film described in. (4) The layer thickness of at least one antiglare hard coat is
It is characterized by being 3 μm or more and less than 6 μm (1) to
The antiglare antireflection film as described in (3). (5) The layer thickness of at least one antiglare hard coat is
4 μm or more and less than 5 μm (1) to
The antiglare antireflection film as described in (4). (6) The refractive index of at least one antiglare hard coat layer and the refractive index of at least one kind of light-transmitting particles contained in the antiglare layer are in the range of 0.05 to 0.15. The antiglare antireflection film as described in (1) to (5), which is different. (7) In the surface projection shape of the antiglare antireflection film, the total is 95% from the smaller angle of the inclination angle distribution.
Characterized in that the frequency angle is less than 20 °,
The antiglare antireflection film as described in (1) to (6). (8) In the surface projection shape of the antiglare antireflection film, the total is 95% from the side with the smaller angle of inclination angle distribution.
Characterized in that the angle of frequency is less than 15 °,
The antiglare antireflection film as described in (1) to (7). (9) In the surface projection shape of the antiglare antireflection film, the average distance (Sm) between the projections is 30 μm or more and 70 μm or more.
The antiglare antireflection film as described in (1) to (8), which is less than m. (10) In the surface projection shape of the antiglare antireflection film, the average distance (Sm) between the projections is 40 μm or more and 60 or more.
It is less than μm, the antiglare antireflection film as described in (1) to (9). (11) The antiglare antireflection film as described in (1) to (11), wherein the transparent support is triacetyl cellulose. (12) The antiglare antireflection film as described in (1) to (11), which has a low refractive index layer on the antiglare hard coat layer. (13) The antiglare antireflection film as described in (1) to (12), wherein the low refractive index layer has a refractive index of 1.38 to 1.49. (14) A polarizing plate using the antiglare antireflection film as described in (1) to (13) as one of two protective films of a polarizer in a polarizing plate. (15) Among the two protective films of the polarizer in the polarizing plate, a film other than the antiglare antireflection film is an optical compensation film having an optical compensation layer containing an optically anisotropic layer, The optically anisotropic layer is a layer having a negative birefringence composed of a compound having a discotic structural unit, the disc surface of the discotic structural unit is inclined with respect to the surface protective film surface, and the discotic The polarizing plate according to (13), wherein the angle formed by the disc surface of the structural unit and the surface of the surface protective film changes in the depth direction of the optically anisotropic layer. (16) The protective film on the side opposite to the antiglare antireflection film of the polarizing plate described in (14) or (15) has λ /
A circularly polarizing plate having an antireflection function, comprising four plates. (17) In the method in which the polarizer of the polarizing plate is stretched by applying tension while holding both ends of a continuously supplied polymer film by holding means, at least 1.1 to 20.0 in the film width direction. When the film is stretched twice, the difference in the advancing speed in the longitudinal direction of the holding device at both ends of the film is within 3%, and the angle between the film advancing direction at the exit of the step of holding the both ends of the film and the substantial stretching direction of the film is 20 7
(14) to (1), which is a polarizer manufactured by a stretching method in which the film traveling direction is bent so as to be inclined by 0 ° while holding both ends of the film.
The polarizing plate according to 6). (18) The antiglare antireflection film according to (1) to (13) or the polarizing plate with an antiglare antireflection film according to (14) to (17) is used on the outermost surface of a display. A display device characterized by. (19) The display device according to (18) has at least one polarizing plate of TN, STN, VA, IPS,
A display device, which is a liquid crystal display device of OCB mode transmission type, reflection type, or semi-transmission type. (20) The display device according to (18) is a transmissive or semi-transmissive liquid crystal display device having at least one polarizing plate, and polarization selection is performed between the polarizing plate on the side opposite to the viewing side and the backlight. A liquid crystal display device, wherein a polarization separation film having a layer is arranged.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The basic structure of an antiglare antireflection film suitable as an embodiment of the present invention will be described with reference to the drawings.

The embodiment schematically shown in FIG. 1 is an example of the antiglare antireflection film of the present invention. In this case, the antiglare antireflection film 1 includes a transparent support 2 and an antiglare hard coat layer. 3 and the low refractive index layer 4 in this order. In the antiglare hard coat layer 3, the antiglare imparting particles 5 which are translucent particles or the internal scattering imparting particles 6 which are translucent particles are further dispersed.

The antiglare antireflection film of the present invention has at least one antiglare hard coat layer on a transparent support and, if necessary, further has a low refractive index layer thereon.
The film strength can be increased by lowering the reflectance and, if necessary, providing a smooth hard coat layer under the antiglare hard coat layer.

The antiglare hard coat layer of the present invention will be described below. The antiglare hard coat layer is a binder for imparting hard coat properties, translucent particles for imparting antiglare properties and internal scattering properties, and high refractive index, prevention of crosslinking shrinkage, or high strength. Inorganic fine particle filler,
Are formed from etc.

The antiglare hard coat layer of the present invention must contain at least two kinds of transparent fine particles having different particle diameters. Whether the material type is different or the same, the material is not limited as long as the requirements of the present invention are satisfied. As a result of intensive studies aimed at achieving both antireflection performance and black tightness, as a result, the average particle size of the first translucent particles among at least two kinds of translucent particles is 60% or more and less than 95% of the thickness of the coat layer,
Preferably 70% or more and less than 95%, more preferably 80%
% Or more and less than 95%. The average particle size of the second translucent particles is 105% or more and less than 140%, preferably 10%.
5% or more and less than 130%, more preferably 105% or more 1
It is less than 20%. Even if the first light-transmissive particles are less than 60% and the second light-transmissive particles are 140% or more, the performance of the present invention (anti-reflection performance and black tightness are compatible). It cannot be realized. Further, at least two kinds of particles are 95% or more based on the thickness of the hard coat layer of the antiglare layer
Even if the difference is less than 105%, it cannot be realized.

The thickness of the antiglare hard coat layer of the present invention is preferably 3 μm or more and less than 6 μm, more preferably 4 μm or more and less than 5 μm. If the antiglare layer is formed with a thickness of less than 3 μm, the scratch resistance (pencil hardness) may be deteriorated, and if it exceeds 6 μm, the brittleness and the coating property (the viscosity of the coating solution may increase and the coating may be difficult) may deteriorate. This is because it occurs. In addition, considering the appropriate range of the particle size of the translucent particles (described later), which is necessary to combine high-definition suitability (even in a high-definition liquid crystal display, the lens effect by the surface protrusions of the antiglare layer does not cause glare). The thickness of the antiglare layer is preferably within the above range. The thickness of the antiglare hard coat layer is examined by a cross-section TEM (transmission electron microscope). The definition of the thickness of the antiglare hard coat layer is as follows: from the most antiglare hardcoat layer side part of the lower layer component of the antiglare hard coat layer (or the support component when there is no lower layer). The thinnest portion of the layer where there are no light-transmitting fine particles is taken as a reference and the vertical distance therebetween is taken.

The antiglare hard coat layer contains translucent particles,
For example, particles of an inorganic compound or organic polymer (resin) particles are contained. The refractive index of the translucent fine particles should be selected in relation to the refractive index of the antiglare hard coat layer other than the translucent particles, but is in the range of 1.40 to 1.80. It is preferable. Specific examples of the translucent particles include, for example, silica particles (for example, Seahosta series manufactured by Nippon Shokubai Co., Ltd. Refractive index = 1.43), alumina particles (for example, Sumiko Random series manufactured by Sumitomo Chemical Co., Ltd. Refractive index = 1.64), particles of inorganic compounds such as TiO ₂ particles, or crosslinked acrylic particles (for example, MX series manufactured by Soken Chemical Co., Ltd. Refractive index = 1.49), crosslinked styrene particles (for example, SX series manufactured by Soken Chemical Co., Ltd.) Resin particles such as refractive index = 1.61), crosslinked melamine particles, and crosslinked benzoguanamine particles (for example, Eposter series manufactured by Nippon Shokubai Co., Ltd. Refractive index = 1.68) are preferred. Of these, crosslinked styrene particles are preferable. The shape of the translucent particles may be either spherical or amorphous, but spherical particles having a uniform surface protrusion shape are preferred. As described above, the translucent particles are not limited as long as the material types are two or more kinds or the same as long as the particle diameters are different. The light-transmitting particles, the content of the formed antiglare hard coat layer is preferably 100-1000 mg / m ^2, antiglare hard coat layer as more preferably a 300 to 800 / m ² Contained in. Further, among the translucent particles, the particles imparting the antiglare property are preferably particles having a particle diameter larger than the thickness of the antiglare layer, since these particles are efficient. On the other hand, different from the refractive index of the antiglare layer, the particles that contribute to internal scattering may be particles that impart the antiglare property, or / and further do not contribute to the antiglare property, It may be embedded particles. In this case, in order not to raise the anti-glare property too much,
It is preferable that the particles have a particle diameter smaller than the thickness of the antiglare layer. The range of particle size is as described above.

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

As the monomer having two or more ethylenically unsaturated groups, an ester of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, Pentaerythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and (Eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide), and Methacrylamide may be mentioned. Two or more of the above monomers may be used in combination.

Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenylthioether and the like. Two or more kinds of these monomers may be used in combination.

Polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a heat radical initiator. Therefore, a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator,
An antiglare antireflection film can be formed by preparing a coating liquid containing matte particles and an inorganic filler, coating the coating liquid on a transparent support, and then curing the coating liquid by a polymerization reaction by ionizing radiation or heat. Examples of the photo-radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, -amyloxime ester, tetramethylthiuram monosulfide and thioxanthones. In particular, a photocleavable photoradical polymerization initiator is preferable. Regarding the photo-cleavable photo-radical polymerization initiator, the latest UV curing technology (P.159, Issuer; Kazuhiro Takahashi, Publisher; Technical Information Institute, 1991)
Yearly issue)

Commercially available photocleavable photoradical polymerization initiators include Irgacure (6 manufactured by Ciba-Geigy Co., Ltd.).
51, 184, 907) and the like. The photopolymerization initiator is 0.1 to 1 with respect to 100 parts by mass of the polyfunctional monomer.
It is preferably used in the range of 5 parts by mass, more preferably in the range of 1 to 10 parts by mass. A photosensitizer may be used in addition to the photopolymerization initiator. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-
Mention may be made of butylphosphine, Michler's ketone and thioxanthone.

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

Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into a polymer, The crosslinked structure may be introduced into the binder polymer by the reaction. Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group and an active methylene group. Vinyl sulfonic 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. You may use the functional group which shows crosslinkability as a result of a decomposition reaction like a block isocyanate group. That is, in the present invention, the crosslinkable functional group may be one that does not immediately show a reaction but shows reactivity as a result of decomposition. The binder polymer having these crosslinkable functional groups can form a crosslinked structure by heating after coating.

In order to adjust the refractive index of the antiglare layer, the hardcoat antiglare layer is made of silicon, titanium, zirconium, aluminum, indium, zinc, tin or antimony in addition to the above-mentioned light-transmitting particles. It is composed of an oxide of at least one metal selected from among them, and has an average particle size of 0.2 μm.
Or less, preferably 0.1 μm or less, more preferably 0.
It is preferable that an inorganic filler having a size of 06 μm or less is contained. The shape of the inorganic filler is not particularly limited, and for example, spherical, plate-shaped, fibrous, rod-shaped, amorphous, hollow, etc. are preferably used, but spherical is more preferable because of better dispersibility. This inorganic filler can contribute to prevention of curling and improvement of surface hardness depending on the filling amount. When the antiglare layer contains an inorganic filler, the refractive index of the antiglare layer is determined by the respective refractive indexes of the transparent resin and the inorganic filler constituting the antiglare layer, and their mixing ratio. The refractive index difference between the refractive index of the antiglare layer and the internal scattering particles of the translucent particles is 0.05 to
0.15 is preferable. If it is less than 0.05, the internal scattering property is low, a large volume of internal scattering particles must be contained, and there is a concern that the film strength of the antiglare antireflection film may decrease, which is not preferable. On the other hand, if it exceeds 0.15, the scattering angle of scattered light becomes large, which is unfavorable for the character blurring. Most preferably, the refractive index difference is 0.07 to 0.13. The magnitude of the refractive index of the antiglare layer hard coat layer and the translucent particles is not particularly limited, but in order to further reduce the character blur, within the range of the refractive index difference described above, the translucent particles It is preferable to lower the refractive index of the hard coating layer for the anti-glare layer than the refractive index, and for the anti-glare anti-reflection film to have a lower reflectance, the anti-glare layer harder than the refractive index of the translucent particles. It is preferable to increase the refractive index of the coat layer and it is appropriately selected depending on the design concept.

Inorganic film used for the antiglare hard coat layer
As a concrete example of the filler, TiO 2₂, ZrO₂, Al
₂O₃, In₂O₃, ZnO, SnO₂, Sb₂O₃, IT
O, SiO ₂Etc. SiO₂, TiO₂, And
And ZrO₂Among the inorganic fillers,
Is preferred. The surface of the inorganic filler is silane coupling
It is also preferable that it is treated with titanium or titanium coupling.
A functional group that can react with the binder species on the filler surface.
A surface treatment agent having is preferably used. These inorganic
The amount of the filler added is based on the total mass of the antiglare hard coat layer.
It is preferably 10 to 90%, more preferably 2
0 to 70%, particularly preferably 30 to 50%
It It should be noted that such an inorganic filler has a particle size that depends on the wavelength of light.
Since it is sufficiently small, scattering does not occur and it can be used as a resin binder.
The composite in which the filler is dispersed is, as described above, optically
Behaves as a uniform substance.

The refractive index of the antiglare hard coat layer comprising a resin binder of the present invention or the antiglare hard coat layer comprising a resin binder containing an inorganic filler has a refractive index of 1.4.
It is preferably 8 to 1.70, and more preferably 1.48 to 1.65. In order to make the refractive index in the above range, as described above, the kind and amount ratio of the resin binder and the inorganic filler may be appropriately selected. How to select can be easily known in advance experimentally.

The surface projection shape of the anti-stringing antireflection film of the present invention has a material type, a particle size, an addition amount, and further a resin, or a resin and an inorganic material of the translucent fine particles which impart antiglare property and internal scattering property. The thickness of the antiglare layer composed of a composite of fillers, the solvent composition of the coating solution, the amount of wet coating, the drying conditions, the curing conditions for the ionizing radiation curable resin, and the like can be mentioned as control factors, among which the influence of large. As a result of our investigation, even if the anti-glare anti-reflection film gives the same anti-glare property, the shape of each surface projection is different for expressing the total anti-glare property,
It was found that when the display power was turned off or when the liquid crystal was displayed in black, the appearance of black in appearance (conversely, whiteness) was different due to the difference in the surface scattering property. If the protrusion inclination angle of the surface protrusions is large, the surface scattering property in a wide-angle range becomes strong, so that the tightness of black is impaired, it becomes whitish, and the sense of quality is lost. It was clarified in a detailed study that the black tightening has a good correlation with the angle of 95% frequency from the smaller angle side of the projection inclination angle distribution, and is preferably less than 20 °, more preferably less than 15 °, It is preferably less than 13 °. The average surface projection inclination angle, which correlates well with the antiglare property, is more preferably 1 to 5 °, more preferably 1.5 to 4.5 °, and further preferably 2 to 4 °.

Similarly, in the surface projection shape of the antiglare antireflection film of the present invention, the average distance (Sm) between the projections is also important, and in order not to impair the tightness of black, it is 30 μm.
Or more and less than 70 μm, more preferably 40 μm or more and 60
It is less than μm. If it is less than 30 μm, the existence probability of the protrusions that contribute to surface scattering becomes too large, and it becomes whitish, which is contrary to our aim of tightening black. On the other hand, when the thickness exceeds 70 μm, the existence probability of the protrusions shown in the smooth portion becomes small, and the user feels so-called “roughness”, which is also not preferable in terms of display quality.

The antiglare hard coat layer of the present invention comprises a fluorine-based or silicone-based surfactant, in order to secure surface uniformity such as coating unevenness, drying unevenness and point defects.
Alternatively, both can be contained in the coating composition for forming the antiglare layer. In particular, a fluorine-based surfactant is preferably used because it has an effect of improving surface failures such as coating unevenness, drying unevenness, point defects and the like of the antiglare antireflection film of the present invention with a smaller addition amount. Preferable examples of the fluorine-based surfactant include perfluoroalkylsulfonic acid amide group-containing nonion such as Florade FC-431 manufactured by 3M, Megafac F-171, F-172, and F- manufactured by Dainippon Ink and Chemicals. 173, F-17
Examples include perfluoroalkyl group-containing oligomers such as 6PF. Examples of the silicone-based surfactants include polydimethylsiloxane whose side chains and main chain terminals are modified with various substituents such as oligomers such as ethylene glycol and propylene glycol.

However, by using the above-mentioned surfactant, the functional group containing an F atom and / or the functional group having a Si atom is segregated on the surface of the antiglare layer, so that the antiglare layer can be formed. There is a possibility that the surface energy decreases and the antireflection performance deteriorates when the low refractive index layer is overcoated on the antiglare layer. It is presumed that this is because the wettability of the coating composition used for forming the low-refractive index layer deteriorates, and thus the minute unevenness of the film thickness of the low-refractive index layer that cannot be visually detected deteriorates. In order to solve such a problem, the surface energy of the antiglare layer is preferably 25 mN · m by adjusting the structure and addition amount of a fluorine-based and / or silicone-based surfactant.
To ^{-1 ~70mN} · m ^-1, more preferably 35 mN · m ^-1
˜70 mN · m ⁻¹ is effective, and as will be described later, the coating solvent for the low refractive index layer is 50 to 100
It was found in the study that it is effective to have a boiling point of 100% by weight or less. Also,
In order to realize the above surface energy, X
F / C which is the ratio of the peak derived from the F atom and the peak derived from the C atom measured by line photoelectron spectroscopy is 0.40 or less, and / or Si which is the ratio between the peak derived from the Si atom and the peak derived from the C atom. It is also known that / C needs to be 0.30 or less.

In the antiglare antireflection film of the present invention, a so-called smooth hard coat layer having no antiglare property is preferably used for the purpose of improving the film strength, and it is preferably used between the transparent support and the antiglare hard coat layer. Is painted on.

The materials used for the smooth hard coat layer are the same as those mentioned for the antiglare hard coat layer, except that the transparent particles for imparting the antiglare property are not used. Alternatively, it is formed from a mixture of a resin binder and an inorganic filler.

In the smooth hard coat layer of the present invention, silica and alumina are preferable as the inorganic filler in terms of strength and versatility, and silica is particularly preferable. The surface of the inorganic filler is preferably subjected to silane coupling treatment, and a surface treating agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.

The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 70%, and particularly preferably 30 to 50%. The thickness of the smooth hard coat layer is preferably 1 to 10 μm, more preferably 2 to 7 μm,
More preferably, it is 3 to 5 μm.

The low refractive index layer of the present invention will be described below. The refractive index of the low refractive index layer of the antiglare antireflection film of the present invention is 1.38 to 1.49, preferably 1.38 to.
It is in the range of 1.44. Further, it is preferable that the low refractive index layer satisfies the following mathematical formula (I) from the viewpoint of lowering the reflectance.

Mλ / 4 × 0.7 <n ₁ d ₁ <mλ / 4 × 1.3 Formula (I)

In the equation, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is 500 to 55.
It is a value in the range of 0 nm. Note that satisfying the above mathematical formula (I) means m satisfying the mathematical formula (I) in the above wavelength range.
Means that it is a positive odd number, usually 1.

Materials for forming the low refractive index layer of the present invention will be described below. In the low refractive index layer, as a low refractive index binder, a kinetic friction coefficient of 0.03 to 0.15, a fluorine-containing polymer crosslinked by heat or ionizing radiation having a contact angle of 90 to 120 ° with water, and a film for improving film strength An inorganic filler is preferably used.

As the crosslinkable fluoropolymer used in the low refractive index layer, a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-
In addition to tetradecyl) triethoxysilane) and the like, fluorine-containing polymers having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as constitutional units can be mentioned. Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (eg, fluoroethylene, vinylidene fluoride,
Tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.), partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, biscoat 6FM (Osaka Organic chemistry) and M-2
020 (manufactured by Daikin) and the like, fully or partially fluorinated vinyl ethers and the like.

Examples of the monomer for imparting a crosslinkable group include a (meth) acrylate monomer having a crosslinkable functional group in the molecule such as glycidyl methacrylate, as well as a carboxyl group, a hydroxyl group, an amino group and a sulfonic acid group. Examples thereof include (meth) acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). The latter is after copolymerization,
It is known in JP-A-10-25388 and JP-A-10-147739 that a crosslinked structure can be introduced.

Further, not only a polymer having the above-mentioned fluorine-containing monomer as a constituent unit, but also a copolymer with a monomer not containing a fluorine atom may be used. The monomer unit that can be used in combination is not particularly limited, and examples thereof include olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic acid esters (methyl acrylate,
Methyl acrylate, ethyl acrylate, acrylic acid 2-
Ethylhexyl), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutyl acrylamide, N-cyclohexyl acrylamide, etc.), methacrylamides, acrylonitrile derivatives, and the like. .

As the inorganic filler used in the low refractive index layer, those having a low refractive index are preferably used. Preferred inorganic fillers are silica and magnesium fluoride, and silica is particularly preferred. The average particle size of the inorganic filler is 0.0
It is preferably from 01 to 0.2 μm, and 0.001 to
More preferably, it is 0.05 μm. It is preferable that the particle size of the filler is as uniform (monodisperse) as possible. The amount of the inorganic filler added is 5 to 7 of the total mass of the low refractive index layer.
It is preferably 0% by mass, more preferably 10 to 50% by mass, and particularly preferably 15 to 30% by mass.

It is also preferable that the inorganic filler is surface-treated before use. The surface treatment method includes physical surface treatment such as plasma discharge treatment and corona discharge treatment and chemical surface treatment using a coupling agent, and the use of a coupling agent is preferable. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) including the compound of the general formula (1) described later is preferably used. When the inorganic filler is silica, the silane coupling treatment is particularly effective. The compound of the general formula (1) may be used as a surface treatment agent for the inorganic filler of the low refractive index layer for preliminarily performing a surface treatment before preparation of the layer coating solution, and may be further used as an additive during the preparation of the layer coating solution. It may be added as the above to be contained in the layer.

The solvent composition of the coating liquid used for forming the antiglare hard coat layer and the low refractive index layer according to the present invention may be either single or mixed, and when mixed, the boiling point is 100 ° C. or less. The solvent is preferably 50 to 100%, more preferably 80 to 100%, and still more preferably 90 to 100%. When the solvent having a boiling point of 100 ° C. or less is 50% or less, the drying rate becomes very slow, the coated surface state deteriorates, and the coating film thickness becomes uneven, so that the optical characteristics such as reflectance also deteriorate. In the present invention, this problem is solved by using a coating solution containing a large amount of a solvent having a boiling point of 100 ° C. or less.

Examples of the solvent having a boiling point of 100 ° C. or lower include hexane (boiling point 68.7 ° C.) and heptane (98.4).
℃), cyclohexane (80.7 ℃), benzene (8
Hydrocarbons such as 0.1 ° C.), dichloromethane (39.
8 ° C), chloroform (61.2 ° C), carbon tetrachloride (7
6.8 ° C), 1,2-dichloroethane (83.5 ° C),
Halogenated hydrocarbons such as trichlorethylene (87.2 ° C), diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C), etc. Ethers, ethyl formate (54.2 ° C), methyl acetate (57.8 ° C), ethyl acetate (77.1 ° C), esters such as isopropyl acetate (89 ° C), acetone (5
6.1 ° C., 2-butanone (= methyl ethyl ketone, 7
Ketones such as 9.6 ° C, methanol (64.5
), Ethanol (78.3 ° C), 2-propanol (82.4 ° C), alcohols such as 1-propanol (97.2 ° C), acetonitrile (81.6 ° C), propionitrile (97.4 ° C). C.) and other cyano compounds, carbon disulfide (46.2.degree. C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.
Examples of the solvent having a boiling point of 100 ° C. or higher include octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.).
C), chlorobenzene (131.7 C), dioxane (101.3 C), dibutyl ether (142.4).
C), isobutyl acetate (118 C), cyclohexanone (155.7 C), 2-methyl-4-pentanone (= M
IBK, 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. Preferably,
Cyclohexanone and 2-methyl-4-pentanone.

The coating solution for the antiglare hard coat layer and the low refractive index layer of the present invention is prepared by diluting the components of the antiglare hard coat layer and the low refractive index layer of the present invention with the solvent having the above composition. It The concentration of the coating solution is preferably adjusted appropriately in consideration of the viscosity of the coating solution, the specific gravity of the material, etc.
The amount is preferably 1 to 20% by mass, more preferably 1 to 10% by mass.

At least one layer of the antiglare hard coat layer and the low refractive index layer of the antiglare antireflection film of the present invention contains a compound of the following general formula (1) when it has scratch resistance. Preferred to. Formula ^{(1) (R 1) m} -Si (OR 2) n formula (1) wherein, R ¹ represents a substituted or unsubstituted alkyl group or an aryl group. R ² represents a substituted or unsubstituted alkyl group or acyl group. m is 0
Represents an integer of 3. n represents an integer of 1 to 4. The sum of m and n is 4. The compound represented by formula (1) will be described. In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or aryl group. As the alkyl group, methyl, ethyl, propyl, isopropyl,
Hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like can be mentioned. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 1 carbon atoms.
6, particularly preferably 1 to 6. Examples of the aryl group include phenyl and naphthyl, and the phenyl group is preferable.

The substituent is not particularly limited, but may be halogen (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group,
Carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl, etc.), aryl group (phenyl, naphthyl, etc.), aromatic heterocyclic group (furyl, pyrazolyl, pyridyl, etc.), alkoxy group (Methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy (phenoxy, etc.), alkylthio group (methylthio, ethylthio, etc.), arylthio group (phenylthio, etc.), alkenyl group (vinyl, 1-propenyl, etc.), alkoxysilyl Groups (trimethoxysilyl, triethoxysilyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl,
Ethoxycarbonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl etc.), acylamino group (acetylamino, benzoyl) Amino, acrylamino, methacrylamino, etc.) and the like are preferable.

Of these, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group and an acylamino group are more preferable, and an epoxy group and a polymerizable acyloxy group (acryloyloxy group) are particularly preferable. , Methacryloyloxy), and a polymerizable acylamino group (acrylamino, methacrylamino). Further, these substituents may be further substituted. R ² represents a substituted or unsubstituted alkyl group or acyl group. The explanation of the alkyl group, the acyl group and the substituent is the same as that of R ¹ . R ² is preferably an unsubstituted alkyl group or an unsubstituted acyl group, and particularly preferably an unsubstituted alkyl group. m is 0
Represents an integer of 3; n represents an integer of 1 to 4. The sum of m and n is 4. When there are a plurality of R ¹ or R ² ,
A plurality of R ¹ or R ² may be the same or different. m is preferably 0, 1, or 2,
Particularly preferably, it is 1. Specific examples of the compound represented by formula (1) are shown below, but the invention is not limited thereto.

[0049]

[Chemical 1]

[0050]

[Chemical 2]

[0051]

[Chemical 3]

[0052]

[Chemical 4]

[0053]

[Chemical 5]

[0054]

[Chemical 6]

Among these specific examples, (1), (1
2), (18), (19) and the like are particularly preferable. The appropriate addition amount of the compound of the general formula (1) is preferably 1 to 300% by mass of the total solid content of the layer containing the compound, and 3 to 20%.
0 mass% is more preferable, and 5 to 100 mass% is the most preferable. The compound represented by the general formula (1) is preferably contained in the coating liquid for the layer to be contained and applied.

A plastic film is preferably used as the transparent support of the antiglare antireflection film of the present invention. As the polymer forming the plastic film, cellulose ester (eg, triacetyl cellulose, diacetyl cellulose, typically Fuji Photo Film Co., Ltd. TAC-TD80U, TD80UF, etc.), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene) Naphthalate),
Examples thereof include polystyrene, polyolefin, norbornene-based resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate,
Is preferred, and triacetyl cellulose is particularly preferred.
Triacetyl cellulose is composed of a single layer or a plurality of layers. A single layer of triacetyl cellulose is disclosed in JP-A-7-11.
No. 055 and the like, which are prepared by drum casting, band casting, or the like, and the latter triacetyl cellulose composed of a plurality of layers are disclosed in JP-A-61-94725 and JP-B-62-43846. It is prepared by the so-called co-casting method. That is, raw material flakes are used as a solvent for halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.) A solution (referred to as a dope) in which various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slip agent, and a peeling accelerator are added as necessary to a horizontal endless solution. When casting with a dope supply means (called a die) on a support consisting of a metal belt or a rotating drum, a single layer is cast in a single layer if it is a single layer, and if it is a plurality of layers, a high concentration is obtained. A low concentration dope is co-cast on both sides of the cellulose ester dope, dried on the support to some extent, and the film to which rigidity has been imparted is peeled from the support, and then, A process comprising passed through a drying section by species of the conveying means to remove the solvent.

Dichloromethane is a typical solvent for dissolving triacetyl cellulose as described above. However, from the viewpoint of the global environment and working environment, it is preferable that the solvent does not substantially contain 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). When a dope of triacetyl cellulose is prepared using a solvent that does not substantially contain dichloromethane or the like, a special dissolution method as described below is essential.

The first melting method is called a cooling melting method and will be described below. First, the temperature around room temperature (-10 to 40 ° C)
Add gradually triacetyl cellulose into the solvent with stirring. Next, the mixture is -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to-).
20 ° C, most preferably -50 to -30 ° C). For cooling, for example, a dry ice / methanol bath (-
75 ° C) or cooled diethylene glycol solution (-30
~ -20 ° C). When cooled in this way,
The mixture of triacetyl cellulose and solvent solidifies. Furthermore, this is 0-200 degreeC (preferably 0-150 degreeC,
More preferably 0 to 120 ° C., most preferably 0 to 5
When heated to 0 ° C.), a solution in which triacetyl cellulose flows in the solvent is formed. The temperature may be raised by leaving it at room temperature or by heating it in a warm bath.

The second method is called a high temperature melting method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (-10 to 40 ° C) while stirring. The triacetyl cellulose solution of the present invention is
It is preferable to add triacetyl cellulose to a mixed solvent containing various solvents and swell it in advance. In this method, the dissolution concentration of triacetyl cellulose is preferably 30% by mass or less, but from the viewpoint of drying efficiency during film formation,
It is preferable that the concentration is as high as possible. Next, the organic solvent mixed liquid is 70 to 2 under a pressure of 0.2 MPa to 30 MPa.
It is heated to 40 ° C (preferably 80 to 220 ° C, more preferably 100 to 200 ° C, most preferably 100 to 1).
90 ° C). Next, since these heated solutions cannot be applied as they are, it is necessary to cool them below the lowest boiling point of the solvent used. In that case, it is common to cool to −10 to 50 ° C. and return to normal pressure. For cooling, a high-pressure high-temperature container or line containing a triacetylcellulose solution may be left alone at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water. The cellulose acetate film substantially free of halogenated hydrocarbons such as dichloromethane and the method for producing the same are disclosed in JIII Journal of Technical Disclosure (Kokai No. 2001-1745, 2).
Published March 15, 001, Published Technical Report 2001-17
45).

When the antiglare antireflection film of the present invention is used in a liquid crystal display device, it is arranged on the outermost surface of the display by providing an adhesive layer on one surface. When the transparent support is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is cost effective to use the antiglare antireflection film of the present invention as a protective film as it is. Then it is preferable.

The polarizing plate with the antiglare and antireflection film of the present invention can be obtained by forming an outermost layer mainly comprising a fluoropolymer on a transparent support and then performing saponification treatment. The saponification treatment is carried out by a known method, for example, by immersing the film in an alkaline solution for an appropriate time. After the immersion in the alkaline solution, it is preferable that the film is sufficiently washed with water or immersed in a dilute acid to neutralize the alkaline component so that the alkaline component does not remain in the film.
By the saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is made hydrophilic. The hydrophilized surface is particularly effective in improving the adhesion to the polarizing film containing polyvinyl alcohol as a main component. Also, since the dust in the air does not easily adhere to the hydrophilic surface, it is difficult for dust to enter between the deflecting film and the antiglare antireflection film when it is adhered to the deflecting film, thus preventing point defects due to the dust. It is effective to do. The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support on the side opposite to the side having the outermost layer is 40 ° or less. It is more preferably 30 ° or less, and particularly preferably 20 ° or less.

The polarizing plate with the antiglare antireflection film of the present invention comprises the antiglare antireflection film as at least one of the two protective films of the polarizing layer. By using the antiglare antireflection film of the present invention on the outermost surface, it is possible to obtain a polarizing plate that is prevented from reflecting external light, has high definition suitability, and has excellent antifouling property, scratch resistance and the like. You can Further, in the polarizing plate of the present invention, the antiglare antireflection film also serves as a protective film, whereby the manufacturing cost can be reduced.

When the antiglare antireflection film of the present invention is used as one side of the surface protective film of a polarizer, the surface of the transparent support opposite to the surface on which the antireflection layer is formed is saponified with alkali. It is necessary to do so as described above. Specific means for the alkali saponification treatment can be selected from the following two. (1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing the film in an alkaline solution at least once. (2) Before or after forming the antireflection layer on the transparent support, an alkaline solution is applied to the surface of the antiglare antireflection film opposite to the surface on which the antiglare antireflection film is formed, Only the back surface of the film is saponified by heating, washing with water and / or neutralization. (1) is excellent in that it can be processed in the same step as a general-purpose triacetyl cellulose film, but since the antiglare antireflection film surface is saponified, the surface is alkali-hydrolyzed and the film deteriorates. There is a concern that there is a concern that if the dried solid matter of the saponification treatment liquid component remains, it will become dirty. In that case, although it is a special process, (2) is excellent.

The antiglare antireflection film of the present invention can be formed by the following method, but is not limited to this method. First, a coating liquid containing components for forming each layer is prepared. Next, the coating solution for forming the antiglare hard coat layer is subjected to reverse gravure method (classified into gravure coat method, micro gravure coat method, etc.), dip coat method, air knife coat method, curtain coat method, A roller coating method, a wire bar coating method and an extrusion coating method (see US Pat. No. 2,681,294) are applied on a transparent support, followed by heating and drying. The microgravure coating method is particularly preferable. Then, it is irradiated with light or heated to polymerize and cure the monomer for forming the antiglare hard coat layer. Thereby, an antiglare hard coat layer is formed. Here, if necessary, a smooth hard coat layer may be applied and cured by the same method before applying the antiglare hard coat layer.
Next, in the same manner, a coating solution for forming the low refractive index layer is applied on the antiglare hard coat layer, and light irradiation or heating is performed to form the low refractive index layer. In this way, the antiglare antireflection film of the present invention is obtained.

The microgravure coating method used for coating each layer of the antiglare and antireflection film of the present invention is a diameter of about 10 to 100 mm, preferably about 20 to 50 mm.
With the gravure roll engraved with a gravure pattern on the entire circumference under the support, and while rotating the gravure roll in the reverse direction with respect to the transport direction of the support, excess coating liquid is applied from the surface of the gravure roll by a doctor blade. The coating method is characterized in that a predetermined amount of the coating liquid is scraped off and the coating liquid is transferred onto the lower surface of the support at a position where the upper surface of the support is in a free state to apply the coating liquid. A transparent support in the form of a roll is continuously unwound, and at least one layer out of at least one of the anti-glare hard coat layer and the low refractive index layer containing a fluoropolymer is formed on one side of the unwound support. It can be applied by the gravure coating method.

As the coating conditions by the microgravure coating method, the number of lines of the gravure pattern engraved on the gravure roll is preferably 50 to 800 lines / inch, and 100
~ 300 lines / inch is more preferable, the depth of the gravure pattern is preferably 1 to 600 µm, more preferably 5 to 200 µm, and the rotation speed of the gravure roll is 3 to 800 r.
It is preferably pm, more preferably 5 to 200 rpm, and the transport speed of the support is 0.5 to 100.
It is preferably m / min, more preferably 1 to 50 m / min.

The antiglare antireflection film of the present invention thus formed has a haze value of 10 to 70%, preferably 30 to 50%, and an average reflectance of 450 nm to 650 nm of 2 or less. It is 0.2% or less, preferably 1.9% or less.

When the antiglare antireflection film of the present invention has a haze value and an average reflectance in the above ranges, good antiglare antireflection property can be obtained without deterioration of the transmitted image.

The antiglare antireflection film of the present invention is used for a liquid crystal display device (LCD) and a plasma display panel (P
DP), electroluminescence display (EL
D) and a cathode ray tube display (CRT). Since the antiglare antireflection film of the present invention has a transparent support, it is used by adhering the transparent support side to the image display surface of a display device.

The antiglare antireflection film of the present invention comprises a polarizer, a transparent support and an optical compensation film composed of an optically anisotropic layer in which the orientation of the discotic liquid crystal is fixed, and a polarizing film composed of a light scattering layer. It is preferably used in combination with a plate. Further, the film other than the antireflection film of the two protective films of the polarizer in the polarizing plate is an optical compensation film having an optical compensation layer containing an optically anisotropic layer, and the optically anisotropic layer is A layer having a negative birefringence composed of a compound having a discotic structural unit, wherein the disc surface of the discotic structural unit is inclined with respect to the surface protective film surface, and the disc surface of the discotic structural unit is A polarizing plate in which the angle formed with the surface of the surface protective film changes in the depth direction of the optically anisotropic layer is more preferable. The polarizing plate composed of the light scattering layer is described in, for example, JP-A No. 11-305010. More specifically, the antiglare antireflection film of the present invention, when used as one side of a surface protective film of a polarizer, includes twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), In-plane switching (IP
S), an optically compensated bend cell (OCB), and other modes of transmission type, reflection type, or semi-transmission type liquid crystal display device. Especially for liquid crystal display devices of TN mode and IPS mode,
As described in JP 2001-100043 A, an optical compensation film having a viewing angle widening effect is provided on the surface opposite to the antireflection film of the present invention out of two protective films on the front and back of the polarizer. When used, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

As the polarizing film, any polarizing film can be applied. For example, when a polyvinyl alcohol-based film is continuously supplied and stretched by applying tension while holding both ends thereof by the holding means, the holding means from the substantial holding start point to the substantial holding release point at one end of the film The locus L1 and the locus L2 of the holding means from the substantial holding start point at the other end to the substantial holding release point have the relationship of the following formula (2) with respect to the distance W between the left and right substantial holding release points, and
The straight line connecting the left and right substantial holding start points is substantially orthogonal to the center line of the film introduced into the holding step, and the straight line connecting the left and right substantial holding release points is approximately the center line of the film sent to the next step. It may be stretched so as to be orthogonal to each other (see FIG. 2. US Patent Publication No. 2002-884).
See 0A1. ) Formula (2) | L2-L1 |> 0.4W

When used in a transmissive or semi-transmissive liquid crystal display device, a commercially available brightness enhancement film (polarization separation film having a polarization selection layer, for example Sumitomo 3M Co., Ltd.)
D-BEF etc.) manufactured in this way can be used to obtain a display device with higher visibility. Also, λ
When used in combination with a / 4 plate, it can be used as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display for reducing light reflected from the surface and inside. Furthermore, the antireflection layer of the present invention can be formed on a transparent support such as PET or PEN and applied to an image display device such as a plasma display panel (PDP) or a cathode ray tube display device (CRT).

In order to explain the present invention in detail, examples will be given below, but the present invention is not limited thereto.

[0074]

【Example】

Example Sample 1 (Preparation of Coating Solution for Antiglare Hard Coat Layer) UV curable hard coat solution (Desolite KZ7317, JSR) containing commercially available silica (fine particle silica, average particle size of about 15 nm).
Co., Ltd., solid content concentration about 72%, SiO ₂ content in solid content about 38%, polymerizable monomer DPHA, containing a polymerization initiator)
61.3 parts by weight was diluted with 8.4 parts by weight of methyl isobutyl ketone. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet light was 1.51. In addition to this solution,
Cross-linked polystyrene particles with an average particle size of 3.5 μm (trade name:
SX-350H, 25% methyl isobutyl ketone dispersion of Soken Chemical Industry Co., Ltd.
11.0 parts by mass of a dispersion liquid dispersed at 0 rpm for 30 minutes was added, and then 25% of crosslinked polystyrene particles having an average particle diameter of 5 μm (trade name: SX-500H, manufactured by Soken Chemical Industry Co., Ltd., refractive index 1.61). 14.4 parts by mass of a dispersion liquid in which the methyl isobutyl ketone dispersion liquid was dispersed by a Polytron disperser at 10,000 rpm for 30 minutes was added. Furthermore, 4.9 parts by mass of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution for the antiglare hard coat layer.

(Preparation of Coating Solution A for Low Refractive Index Layer) Thermally crosslinkable fluoropolymer (JN-722) having a refractive index of 1.42.
8, solid content concentration 6%, manufactured by JSR Corporation) 55.2 parts by mass of colloidal silica dispersion (MEK-ST, average particle size 10 to 20 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.)
4.8 parts by mass, 28.0 parts by mass of methyl ethyl ketone, 2.8 parts by mass of cyclohexanone, and 9.2 parts by mass of 3-acryloxypropyltrimethoxysilane (manufactured by KBM-5103 Shin-Etsu Chemical Co., Ltd.) were added and stirred. After, the hole diameter is 1μ
m through a polypropylene filter to prepare a low refractive index layer coating liquid A.

The antiglare hard coat layer coating liquid and the low refractive index layer coating liquid A were coated as follows. (1) Application of antiglare hard coat layer Triacetyl cellulose film (T
AC-TD80UL, manufactured by Fuji Photo Film Co., Ltd. is unwound in a roll form, and the above-mentioned coating solution for an antiglare hard coat layer is formed into a microgravure pattern having a number of lines of 110 lines / inch and a depth of 35 μm and a diameter of 50 mm. Using a gravure roll and a doctor blade, apply at a gravure roll rotation speed of 40 rpm and a conveying speed of 10 m / min,
After drying at 120 ° C. for 2 minutes, using an air-cooled metal halide lamp of 240 W / cm (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge with an oxygen concentration of 0.1% or less, an illuminance of 40
The coating layer was cured by irradiating it with ultraviolet rays of 0 mW / cm ² and an irradiation amount of 300 mJ / cm ² to form an antiglare hard coat layer having a dry film thickness of 4.3 μm, and the film was wound. The hard coat layer of the antiglare layer had a refractive index of 1.51.

(2) Coating of Low Refractive Index Layer The film coated with the hard-coating antiglare layer was unwound again, and the coating liquid A for the low refractive index layer was drawn with 200 lines / inch and a depth of 35 μm. Diameter 5 with gravure pattern
Using 0 mm micro gravure roll and doctor blade, gravure roll rotation speed 40 rpm, transport speed 1
Apply at 0 m / min, dry for 2 minutes at 80 ° C, and then 240 W / c under nitrogen purge with oxygen concentration of 0.1% or less.
m air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² , and subsequently 140 ° C.
Was thermally crosslinked for 8 minutes to form a low-refractive index layer having a thickness of 0.096 μm, which was then wound up. The refractive index of the low refractive index layer is 1.43
Met. (Completion of the antiglare antireflection film of Example sample 1)

[0079]

[Table 1]

(Saponification Treatment of Antiglare Antireflection Film) The following treatment was carried out for Example Sample 1. A 1.5 N aqueous solution of sodium hydroxide was prepared and kept at 50 ° C.
Further, a 0.01N dilute sulfuric acid aqueous solution was prepared. The produced antiglare antireflection film was immersed in the above-mentioned sodium hydroxide aqueous solution for 2 minutes and then immersed in water to thoroughly wash out the sodium hydroxide aqueous solution. Next, after dipping in the above dilute sulfuric acid aqueous solution for 1 minute, it was dipped in water to thoroughly wash out the dilute sulfuric acid aqueous solution. Furthermore, this antiglare antireflection film 1
It was thoroughly dried at a temperature of 00 ° C. In this way, a saponification-treated antiglare antireflection film was produced. Thereby, T of the back surface of the antiglare antireflection film of Example sample 1
AC was hydrophilized by saponification treatment.

(Preparation of polarizing plate of antiglare antireflection film,
(Mounting) Next, an antiglare antireflection polarizing plate was prepared using the saponified Example Sample 1. Furthermore, a commercially available high-definition type notebook PC (manufactured by DELL, 15-inch UX)
GA notebook PC), the anti-glare anti-reflection film on the outer surface is peeled off cleanly together with the adhesive layer, and the adhesive layer is applied again to the saponified back surface TAC so that the anti-glare anti-reflection layer faces the outer surface, and then is laminated. , Implemented.

(Evaluation of Antiglare Antireflection Film) The obtained film was evaluated for the following items.

(1) Evaluation of Antiglare Property The prepared antiglare antireflection film was mounted on a 15-inch UXGA notebook PC manufactured by DELL Co., Ltd., and a bare fluorescent lamp (8000 cd / m ² ) without a louver was projected. The degree of blurring of the reflection image of the fluorescent lamp was visually evaluated according to the following criteria. I do not know the outline of the fluorescent lamp (there is sufficient antiglare property): ○ The fluorescent lamp is blurred, but the outline can be identified: △ Almost no fluorescent lamp is blurred (insufficient antiglare property): ×

(2) Surface Protrusion Inclination Angle The surface protrusion inclination angle of the produced anti-glare antireflection film was measured using a “micro map” machine manufactured by RYOKA SYSTEM. The sampling area for measurement is 800 μm × 800 μm. The “surface projection inclination angle distribution” described in Table 1 indicates the angle at which the frequency is 95% when integrated from the side with the smallest inclination angle distribution (see FIG. 2).

(3) Average inter-projection distance The average inter-projection distance (Sm) of the prepared antiglare antireflection film was measured by Kosaka Laboratory Ltd. Surfco.
It was measured using an rder Model 3E-3F machine.

(4) Tightness of black The produced antiglare antireflection film was mounted on a 15-inch UXGA notebook PC manufactured by DELL Co., Ltd., and was displayed in black, and the tightness of black was judged by visual sensory evaluation. . The black appears to tighten. (The larger the number of ○, the better): ○ to ○○○○○ The black tightening is slightly inferior. : △ There is no black tightening. : ×

(5) Roughness The antiglare antireflection film thus prepared was mounted on a 15-inch UXGA notebook PC manufactured by DELL, and the power supply was turned off.
It was set to F, and the surface roughness was judged by visual sensory evaluation. Good texture. (The larger the number of ○, the better): ○ to ○○○ There is a feeling of roughness. : ×

[Example Samples, Comparative Example Samples]
The thickness of the antiglare layer, the antiglare imparting particles (first type particles), and the internal scattering imparting particles (second type particles) of the antiglare antireflection film produced according to Example sample 1 Particle size,
The evaluation results of the ratio (%) of each particle to the thickness of the antiglare layer, the antiglare property and the tightness of black are shown. Example Sample 1
A sample prepared in exactly the same manner as in Example Sample 1 except that the thickness of the antiglare layer, the particle size of the antiglare property-imparting particles, the amount used, the particle size of the internal scattering property imparting particles, and the amount used were adjusted according to Are referred to as Example Samples 2 to 30 and Comparative Example Samples 1 to 18.

Next, Example samples 2 to 30 and Comparative example sample 1
~ 18 of the saponified film is laminated with a polarizing plate to prepare a polarizing plate with antiglare and antireflection, and using this polarizing plate, a liquid crystal display device having an antiglare and antireflection layer disposed on the outermost layer is prepared. As a result, the liquid crystal displays of Examples 1 to 30 have excellent contrast because they have no reflection of external light, have a good black tightness during black display, and have excellent visibility and appearance. It became a device. On the other hand, Comparative Example Samples 1
18 is 140% of particles for imparting antiglare property (first kind of particles)
Or less than 60% of the internal scattering property imparting particles (second type particles), or the antiglare property imparting particles and the internal scattering property imparting particles fall within the range of 95% or more and less than 105% of the layer thickness. It can be seen that, if it enters, or if there is only one type of light-transmitting particles used in the stringing layer hard coat layer, the desired surface shape cannot be obtained, and the tightness of black is sharply impaired. Further, with respect to the tightness of black, the particle size of the particles for imparting antiglare property, which is thicker than the thickness of the antiglare layer, is 105% or more and less than 140%, preferably 105% or more and less than 130%, more preferably 105.
% Or more and less than 120% and smaller than the thickness of the antiglare layer,
The particle diameter of the internal scattering property imparting particles is 60% or more and less than 95%, preferably 70% or more and less than 95%, more preferably 80%.
It is understood that it is necessary to be above 95%,
An excellent display device can be realized.

Further, with respect to the sample of Example 1, the amount of the antiglare-imparting particles used and the internal amount of the antiglare-imparting particles were changed without changing the thickness of the antiglare layer, the particle size of the antiglare-imparting particles, and the particle size of the internal scattering-imparting particles. The sample was prepared in exactly the same manner as the sample of Example 1 except that the sample was prepared so as to have the surface inclination angle and the average inter-projection distance described in Table 2 while adjusting only the amount of the scattering-imparting particles used. Example samples 31 to 47.

[0091]

[Table 2]

It can be further seen from the results in Table 2 that the surface inclination angle distribution 95% value against black tightness is less than 20 °, preferably less than 15 °, and more preferably less than 13 °. An excellent display device capable of achieving a good black tightness and having a better black tightness and no rough feeling when the average inter-projection distance Sm value is 30 μm or more and less than 70 μm, more preferably 40 μm or more and less than 60 μm. It can be seen that

[Example Sample 1A] A polarizing film was prepared by the following method. The PVA film was immersed in an aqueous solution of 2.0 g / l of iodine and 4.0 g / l of potassium iodide at 25 ° C. for 240 seconds, and further immersed in an aqueous solution of 10 g / l of boric acid for 60 seconds at 25 ° C. Introduced into the tenter stretching machine in the form of
It was stretched 5.3 times, and the tenter was bent in the stretching direction as shown in FIG. 3, and thereafter the width was kept constant. After being dried in an atmosphere of 80 ° C., it was separated from the tenter. The difference in transport speed between the left and right tenter clips was less than 0.05%, and the angle between the center line of the film introduced and the center line of the film sent to the next step was 46 °. Where | L1-L2 |
Is 0.7 m, W is 0.7 m, and | L1-L2 | = W
Had a relationship. Substantial stretching direction A at the tenter outlet
x-Cx was inclined by 45 ° with respect to the center line 22 of the film sent to the next step. Wrinkles at the tenter exit,
No film deformation was observed.

Furthermore, PVA (PVA-produced by Kuraray Co., Ltd.)
117H) This was laminated with Fuji Photo Film Co., Ltd. Fujitac (cellulose triacetate, retardation value 3.0 nm) saponified with a 3% aqueous solution and dried at 80 ° C. to obtain a polarizing plate with an effective width of 650 mm. It was The absorption axis direction of the obtained polarizing plate was inclined by 45 ° with respect to the longitudinal direction. The transmittance of this polarizing plate at 550 nm was 43.7%, and the polarization degree was 99.97%. Further, when it was cut into a size of 310 × 233 mm as shown in FIG. 4, a polarizing plate having an absorption axis inclined by 45 ° with respect to the side was obtained with an area efficiency of 91.5%.

Next, the saponified film of Example Sample 1 was attached to the above polarizing plate to prepare a polarizing plate with antiglare and antireflection. When a liquid crystal display device in which an antiglare antireflection layer is disposed on the outermost layer is manufactured using this polarizing plate, excellent contrast is obtained because external light is not reflected, and the pixel size is small and high. Even for high-definition LCDs of image quality type, it is a display device with excellent visibility and appearance, with no glare, no blurring of letters, and good black tightness.

[Example Sample 1B] "Fujitac (cellulose triacetate, retardation value 3.0 nm) manufactured by Fuji Photo Film Co., Ltd." in the production of a polarizing plate in which the 45 ° absorption axis was tilted in Example Sample 1A above. Instead of the above, the saponified film of Example Sample 1 was laminated to prepare an antiglare and antireflection polarizing plate. When a liquid crystal display device in which an antiglare antireflection layer was disposed on the outermost layer was produced using this polarizing plate, excellent contrast was obtained because external light was not reflected, as in Example Sample 1. Even in a high-definition high-definition liquid crystal display with a small pixel size, the display device has excellent visibility and appearance, with no glare, no character blurring, and good black tightness.

[Example Sample 1C]
After dipping in a 1.5N NaOH aqueous solution at 55 ° C. for 2 minutes, neutralizing and washing with water to saponify the back surface of the film, the triacetyl cellulose film having a thickness of 80 μm (TAC-TD80U, A film prepared by saponifying Fuji Photo Film Co., Ltd. under the same conditions was adsorbed with iodine in polyvinyl alcohol and stretched to adhere and protect both sides of a polarizer to prepare a polarizing plate. A liquid crystal display device of a notebook computer equipped with a transmissive TN liquid crystal display device (a polarization separation film having a polarization selection layer, Sumitomo 3M Co., Ltd.) D-BEF (made between the backlight and the liquid crystal cell) was replaced with a polarizing plate on the viewing side, and excellent contrast was obtained because external light was not reflected, and the pixel size was small. Even with high-definition high-definition liquid crystal displays, there is no glare, there is no blurring of letters, the tightness of black is good, and there is very little background reflection that has become a liquid crystal display device with excellent visibility and appearance. A display device having a very high display quality was obtained.

[Sample Sample 1D] The protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell to which the sample sample 1 of the above Example is attached, and the liquid crystal cell side of the polarizing plate on the backlight side. In the film, the disc surface of the discotic structural unit is inclined with respect to the transparent support surface, and the angle formed by the disc surface of the discotic structural unit and the transparent support surface changes in the depth direction of the optical anisotropic layer. Angle widening film having an optical compensation layer (Wide View Film SA-12B, manufactured by Fuji Photo Film Co., Ltd.)
The high-definition liquid crystal display with excellent contrast in a bright room and a small pixel size has no glare, no blurring of letters, and good black tightness, and excellent visibility. A display device having an external appearance, a wide viewing angle in the vertical and horizontal directions, and a very high display quality was obtained.

[Example Sample 1E] Example Sample 1 was attached to a glass plate on the surface of an organic EL display device with an adhesive, and reflection on the glass surface was suppressed, resulting in extremely high visibility. A display device having a good appearance was obtained.

Example 1F Example 1 was used to prepare a polarizing plate with a single-sided antireflection film, and a λ / 4 plate was attached to the opposite side of the polarizing plate having the antireflection film, When it was attached to a glass plate on the surface of the organic EL display device, the surface reflection and the reflection from the inside of the surface glass were cut, and a display device having a very high visibility and a good appearance was obtained.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a layer structure of an antiglare antireflection film.

FIG. 2 is a schematic diagram illustrating the meaning of 95% value of scattering angle distribution.

FIG. 3 is a schematic view of a tenter stretching machine used in Examples.

FIG. 4 is a schematic diagram showing cutting of a polarizing plate used in Examples.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Antiglare antireflection film 2 Transparent support 3 Antiglare hard coat layer 4 Refractive index layer 5 Antiglare particles 6 Internal scattering property particles (a) Film introduction direction (b) Film conveying direction to the next step (A) Step of introducing the film (b) Step of stretching the film (c) Step of sending the stretched film to the next step A1 Position at which the film is caught by the holding means and starting position of the film stretching (substantially holding start point: right) ) B1 film biting position into holding means (left) C1 film stretching starting point position (substantially holding start point: left) Cx film separation position and film stretching end point reference position (substantially holding release point: left) Ay film stretching End point reference position (substantially hold release point:
Right) | L1-L2 | Stroke difference between left and right film holding means W Substantial width θ at the end of the stretching process of the film θ Angle between the stretching direction and the film advancing direction 11 Center line of the introducing side film 12 Center of the film sent to the next process Line 13 Trajectory of film holding means (left) 14 Trajectory of film holding means (right) 15 Introducing film 16 Film 17 and 17 'sent to the next process Left and right film holding start (biting) points 18 and 18' Left and right Departure point from film holding means 21 Center line of introduction side film 22 Center line of film sent to next step 23 Trail of film holding means (left) 24 Trail of film holding means (right) 25 Introduction side film 26 Next step Films to be fed 27, 27 'Left and right film holding start (biting) points 28, 28' Left and right film holding means detachment points 8 Polarizer absorption axis 82 longitudinally

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02F 1/1335 510 G09F 9/00 313 5G435 G09F 9/00 313 G02B 1/10 A F term (reference) 2H042 BA02 BA13 BA15 BA20 2H049 BA02 BB16 BB65 BC22 2H091 FA08X FA37X FD06 FD14 GA16 2K009 AA12 AA15 BB28 CC09 DD02 4F100 AA20 AJ05 AK12 AK17 AT00A BA02 BA07 DE01B GB41 JK12B JN01A JN30B YY00B 5G435 AA02 FF03 FF05 FF06 HH04 LL08

Claims (3)

[Claims] 1. An antiglare antireflection film having at least one antiglare hard coat layer on a transparent support, wherein at least one antiglare hard coat layer comprises at least one antiglare hard coat layer. At least one first translucent particle having an average particle size of 60% or more and less than 95% with respect to the layer thickness of the coat layer, and having an average particle size of 105% or more and less than 140% with respect to the layer thickness. An antiglare antireflection film comprising at least one kind of second translucent particles. 2. A polarizing plate, wherein the antiglare antireflection film according to claim 1 is used as one of two protective films for a polarizer in a polarizing plate. 3. A display device, wherein the antiglare antireflection film according to claim 1 or the polarizing plate with the antiglare antireflection film according to claim 2 is used on the outermost surface of a display. .