JPH11183711A - Antireflection material and polarizing film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection material and a polarizing film which show excellent antireflection property, with which a sharp image without glittering can be obtd. without decreasing the image contrast, which has optically stable and excellent wear resistance and chemical resistance and excellent adhesion property with a roughened layer. SOLUTION: This antireflection material 10 consists of a transparent base body 11 and a roughened layer 12 and a surface layer successively formed on one or both surfaces of the base body. The surface layer consists of a high refractive index layer near the roughened layer side and a low refractive index layer on the surface side having a smaller refractive index than that of the high refractive index layer. The roughened layer 12 contains a UV-curing resin containing an epoxy compd. and a photo-cation polymn. initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display (LC).
D), plasma display (PDP), CRT, EL
The present invention relates to an antireflection material having excellent antifouling properties, antireflection properties, chemical resistance, and abrasion resistance in an image area, and a polarizing film using the same.

[0002]

2. Description of the Related Art Image display devices represented by LCDs, PDPs, CRTs, and ELs (hereinafter referred to as "displays") are widely used in various fields including televisions and computers, and have remarkable developments. Has achieved. At the beginning of the development of this display, colorization was a keyword of development, but recently Hi-Vision has become one of the keywords, and efforts have been made to improve image definition, image quality, and power consumption. Has been devoted.
These displays, which play an important role in the man-machine interface, are expected to become more widespread with the arrival of the multimedia age, and in particular, the use of mobile phones, PHS, and other various types of mobile terminals is expected to significantly expand. Is done.

As a display for a portable terminal, a lightweight,
LCDs with features such as compactness and versatility are considered to dominate the market, but these mobile terminals are equipped with a touch panel and can be operated directly with a plastic pen or finger. Is coming. Therefore, demands for abrasion resistance, chemical resistance, and prevention of dirt on the display surface are increasing. In addition, when these devices are used in relatively bright places such as outdoors, there is an increasing demand for prevention of reflection of external light such as sunlight or fluorescent light on a display, that is, prevention of reflection. In particular, the demand for antireflection is permeating various displays from small to large.

[0004] As a method for preventing reflection, a method of directly roughening the surface of a substrate by a sand blast method or an embossing method, a method of providing a coating layer containing a filler on the surface of the substrate, and a method of preventing the reflection of the substrate surface In general, the image is blurred by scattering or diffusing light by a method of forming a porous film having a sea-island structure. However, since the reflectance of the surface has not changed, there has been a problem that when the degree of surface roughening is large, the surface becomes white and the image contrast of the display is reduced.

[0005] In order to solve this problem, there is known a method in which a material having a high refractive index and a material having a low refractive index are alternately provided to suppress the reflectance on the outermost surface of the display. Forming a low refractive index material such as MgF or SiO _2, etc. TiO _2, ZrO ₂ may be mentioned as a high refractive index material, typically and gas phase method, such as those materials deposition or sputtering, a sol-gel method or the like Is done. However, the vapor phase method requires expensive processing equipment,
The sol-gel method is not suitable for processing a large area, and has a problem in economical efficiency because coating and firing are repeated. Furthermore, as a deposition method, although it is also suggested to film formation by the wet coating method, the film thickness control in characteristics necessary for 10 to 10 ² nm order is insufficient current, color unevenness (interference unevenness)
And so on.

The method of providing a filler-type roughened layer on the surface of a base material can relatively easily control the size of the irregularities on the surface of the roughened layer by controlling the particle size and the content of the filler, and the production can be performed easily. Currently, it is used favorably because of its advantages such as easiness. As the resin used for the coating agent, those having excellent permeability, heat resistance, abrasion resistance, chemical resistance, etc. are desirable, but the base material is often a highly transparent plastic film having poor heat resistance. For this reason, UV curable resins are preferably used. As examples thereof, JP-A-1-105738 and JP-A-5-162261 using UV curable resin and silica pigment as constituents have been reported.

However, the system composed of a UV-curable resin and a silica pigment exhibits a low-viscosity liquid state until the film is cured by UV irradiation after the coating is applied to the substrate, so that the surface is roughened. There was a problem that the fillers in the layer adhered to each other and aggregated (orange peel). In this case, it was particularly remarkable when the content of the filler was increased or when the coating material was diluted with a solvent or the like.

There is no problem if the distance between the irregularities of the roughened layer is smaller than the pixel pitch of the display, but if it is larger, glare occurs due to interference. In recent years, as the resolution of the display is moving toward higher definition, the height and spacing of the irregularities of the roughened layer have also been required to be finer. The agglomeration described above has been a major hindrance to the densification of the irregularities.

[0009] Surface members for applications such as touch panels, which are operated by directly touching the display surface with a pen or finger, are required to have high abrasion resistance, chemical resistance, and contamination prevention. For these requirements, the adhesion at the interface between the layers is important in addition to the hardness of the substrate, the roughened layer, the surface layer, and the respective hardness. As a base material for these surface members, triacetyl cellulose (hereinafter, TAC) or polyethylene terephthalate (hereinafter, PET), which is inexpensive and has excellent optical characteristics, is usually used. Cannot be used for applications such as touch panels because the adhesiveness of these was not always sufficient.

[0010]

SUMMARY OF THE INVENTION Accordingly, the present invention provides an excellent anti-reflection property and a high image contrast by preventing reflection of external light such as sunlight and fluorescent light on a display. Without lowering, it is possible to obtain a clear image without glare and the like, and it is not only optically stable and shows excellent chemical resistance, but also has a high adhesion strength between the base material and the roughened layer. It is an object of the present invention to provide an antireflective material which is excellent in abrasion property and durable even when used for a touch panel or the like. Another object of the present invention is to provide a polarizing film using the above-mentioned antireflection material, and particularly to significantly improve the performance of a full-color liquid crystal display and the like.

[0011]

Means for Solving the Problems (1) Contents of antireflection material The present inventor has mainly used a roughened layer in order to increase the adhesion strength between a transparent substrate made of PET or TAC and the roughened layer. As a result of repeated studies on the resin as a component, it has been found that it is extremely effective to include an ultraviolet (UV) curable resin containing an epoxy compound and a cationic photopolymerization initiator in the resin. Therefore, the antireflection material of the present invention has been made based on the above findings. In an antireflection material in which a roughened layer and a surface layer are sequentially provided on one or both surfaces of a transparent substrate, the surface layer has a rough surface. A high-refractive-index layer on the roughened layer side, and a low-refractive-index layer on the surface side having a smaller refractive index than the high-refractive-index layer. The roughened layer contains an epoxy compound and a cationic photopolymerization initiator. It is characterized by containing an ultraviolet curable resin. Hereinafter, more preferred embodiments of the present invention will be described in detail.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Transparent substrate As the transparent substrate used for the antireflection material of the present invention, a known transparent film, glass, or the like can be used. Specific examples thereof include polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyarylate, polyimide, polyether, polycarbonate (PC), polysulfone, polyether sulfone,
Various resin films, such as cellophane, aromatic polyamide, polyethylene, polypropylene, and polyvinyl alcohol, and glass substrates, such as quartz glass and soda glass, can be used in sheet form. When used for PDP and LCD, PET, TAC and PC are desirable. The higher the transparency of the transparent substrate, the better, but the light transmittance (J
ISC-6714) is preferably 80% or more, more preferably 90% or more. The thickness of the transparent substrate is preferably thinner from the viewpoint of weight reduction, but in consideration of its productivity,
It is preferable to use one having a range of 10 to 200 μm. Moreover, corona treatment, plasma treatment,
It is preferable to perform a surface treatment such as a fluorine treatment or a sputter treatment, or to apply a surfactant, a silane coupling agent, or the like. By performing such a treatment, the surface energy of the transparent substrate increases, and the adhesion strength to the roughened layer can be reliably increased. In this case, the surface energy of the transparent substrate is preferably in the range of 30 to 60 dyne / cm.

Further, an antistatic layer may be provided on the surface of the transparent substrate in order to prevent dirt such as dust electrostatically adhering to the display surface. The antistatic layer is made of aluminum,
A method of providing a metal oxide film such as a metal such as tin or ITO or the like by vapor deposition or sputtering, etc .; a metal fine particle or whisker such as aluminum or tin; a fine particle or whisker obtained by doping a metal oxide such as tin oxide with antimony; , 7,8,8-tetracyanoquinodimethane and charge transfer complex formed between electron donor (donor) such as metal ion and organic cation as filler, polyester resin, acrylic resin, epoxy resin Etc. and provided by solvent coating or the like, or a method in which polypyrrole, polyaniline or the like doped with camphorsulfonic acid or the like is provided by solvent coating or the like. The transmittance of the antistatic layer is 80% for optical applications
The above is preferred.

B. Next, the roughened layer in the present invention will be described. The surface-roughened layer in the present invention contains an ultraviolet-curable resin, and the ultraviolet-curable resin has an epoxy compound as a main component, and a cationic photopolymerization initiator as a polymerization initiator as essential components. In order to control the properties of the paint and the coating film such as the viscosity, crosslink density, heat resistance and chemical resistance of the ultraviolet curable resin, it is preferable to mix an acrylic compound.
The advantages of using the UV-curable resin of the present invention for the roughened layer are as follows when compared with conventional radical-reaction-type UV-curable resins.

Good adhesion to the transparent substrate. In particular, since it has excellent adhesion to a transparent substrate composed of saponified TAC, which is said to have little adhesion, it is necessary to obtain a laminate in which a polarizing substrate, a transparent substrate, and a roughened layer are firmly adhered. Can be. Less oxygen inhibition. Very little cure shrinkage. Excellent pigment dispersibility.

Examples of the epoxy compound include glycidyl ethers such as tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and bisphenol A diglycidyl ether;
Examples include monomers and oligomers such as epoxy esters such as 3-phenoxypropyl acrylate and bisphenol A-diepoxy-acrylic acid adduct, and alicyclic epoxies represented by the following chemical formula.

[0017]

Embedded image

Examples of the cationic photopolymerization initiator include compounds having the following chemical formula. These compounds may be used alone or as a mixture of two or more.

[0019]

Embedded image

The amount of the cationic photopolymerization initiator is desirably in the range of 0.1 to 5.0% by weight based on the main component. If the amount is less than 0.1 or more than 5.0, ultraviolet curing is insufficient.

The acrylic compound to be mixed with the ultraviolet-curable resin includes lauryl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate,
Monofunctional acrylates such as 2-hydroxypropyl acrylate and 2-hydroxy-3-phenoxy acrylate, neopentyl glycol diacrylate, 1,6-
Acrylic acids such as polyfunctional acrylates such as hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol acrylate, dipentaerythritol hexaacrylate, trimethylolpropane acrylate benzoate, and trimethylolpropane benzoate. Monofunctional methacrylates such as derivatives, 2-ethylhexyl methacrylate, n-stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate;
Monomers and oligomers such as methacrylic acid derivatives such as polyfunctional methacrylates such as 6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, and glycerin dimethacrylate; glycerin dimethacrylate hexamethylene diisocyanate; pentaerythritol triacrylate hexamethylene diisocyanate; Can be given.

The volume shrinkage rate (calculated by the following method) associated with the curing of the roughened layer using the ultraviolet-curable resin is 20
% Is desirable. If the volume shrinkage is more than 20%, the curl becomes remarkable when the transparent substrate is a film,
When the substrate is made of a rigid material such as glass, the adhesion of the roughened layer is reduced.

[0023]

## EQU1 ## Volume shrinkage: D = (S−S ′) / S × 100 S: specific gravity before curing S ′: specific gravity after curing (specific gravity is measured by the B method pycnometer method of JIS K-7112)

The higher the transparency of the UV-curable resin, the better, and the light transmittance (JIS C-6714) is preferably 80% or more, more preferably 90% or more, like the transparent substrate.

As a method for roughening, a type in which a filler is contained in the above resin is preferable. Fillers include inorganic white pigments such as silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, and titanium dioxide, acrylic resins, polystyrene resins, polyethylene resins, epoxy resins, silicone resins, and organic transparent materials such as beads. Alternatively, white pigments and the like can be given.
In particular, organic fillers that are spherical and do not exhibit lubricating properties are preferable.By using spherical fillers, the portions that protrude from the surface of the roughened layer become gentle, so that dirt such as oil becomes less likely to adhere and dirt that adheres. Easier to wipe.

The particle diameter D of such a filler (JIS
B9921) is 60% by weight or more in the range of 0.5 μm ≦ D ≦ 6.0 μm, and 6.0 μm <D ≦ 10.0 μm.
Is less than 20% by weight, 10 μm <D ≦ 15.
It is desirable that those in the range of 0 μm are 5% by weight or less, and those of more than 15.0 μm are 1% by weight or less. Furthermore, particles larger than 15.0 μm are preferably not contained (0%) if possible, and in particular, 0.5 μm ≦ D ≦
80% by weight or more in the range of 6.0 μm, 6.0 μm
<D ≦ 10.0 μm is less than 10% by weight,
It is preferable not to include those in the range of 0 μm <D ≦ 15.0 μm at all. 0.5% by weight of the filler in the range of 0.5 μm ≦ D ≦ 6.0 μm, and 6.0 μm <D ≦ 10.0 μm
weight% of fillers in the range of m, further 10 μm <
When the weight% of the filler in the range of D ≦ 15.0 μm is less than 60%, less than 20%, and less than 5%, respectively, the antireflection effect of the display deteriorates and 6.0 μm <D
When the filler in the range of ≦ 10.0 μm is 20% by weight or more, or the filler in the range of 10 μm <D ≦ 15.0 μm is 5% by weight, glare is generated on the display image. The amount of the filler is preferably in the range of 0.5 to 30% in terms of the total solid content of the roughened layer. In particular, a range of 1 to 15% is preferable. When the amount is 0.5% or less, the antireflection effect becomes insufficient. When the amount is 30% or more, not only transparency and image contrast are deteriorated, but also
The durability such as wear resistance and environmental resistance is deteriorated. The refractive index of the filler (B method according to JIS K-7142)
The closer to the refractive index of the curable resin, the better. If the refractive index of the filler is different from the refractive index of the curable resin, light is diffused at the interface between the filler and the resin, and transparency is impaired. As an example of the filler having these characteristics, an organic filler, particularly, a crosslinked acrylic bead is suitable.

As the crosslinked acrylic beads, an acrylic monomer such as acrylic acid and its ester, methacrylic acid and its ester, acrylamide, acrylonitrile and the like, a polymerization initiator such as persulfuric acid, and a crosslinking agent such as ethylene glycol dimethacrylate are used. Crosslinked acrylic beads comprising a polymer and a copolymer obtained by polymerization by a suspension polymerization method or the like can be suitably used. In particular, a configuration using methyl methacrylate as the acrylic monomer is preferable. Since the crosslinked acrylic beads thus obtained are spherical and do not exhibit oil absorption, when used in a roughened layer, excellent stain resistance can be exhibited.

In the present invention, as a method for providing a roughened layer, a filler such as cross-linked acrylic beads and, if necessary, water or an organic solvent are mixed in the above-mentioned ultraviolet-curable resin. The paint shaker, sand mill,
Pearl mill, ball mill, attritor, roll mill,
High-speed impeller disperser, jet mill, high-speed impact mill,
It is dispersed by ultrasonic dispersing machine etc. to make paint or ink, which is air doctor coating, blade coating, knife coating, reverse coating,
Transfer roll coating, gravure roll coating, kiss coating, cast coating,
Coating such as spray coating, slot orifice coating, calendar coating, electrodeposition coating, dip coating, die coating, relief printing such as flexo printing, intaglio printing such as direct gravure printing, offset gravure printing, lithographic printing such as offset printing, screen A single layer or multiple layers are provided on one or both sides of the transparent substrate by a printing method such as stencil printing such as printing, and when a solvent is contained, a coating layer or a printing layer is irradiated by ultraviolet irradiation through a heat drying process. And the like. In addition, as the ultraviolet rays to be radiated, ultraviolet rays emitted from light rays such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. In order to improve the dispersibility of the paint, the filler may be surface-modified with an organic or inorganic material such as a fat or oil, a silane coupling agent, or a metal oxide.

In order to improve the coating suitability or printing suitability of paints and inks, if necessary, a leveling agent such as silicone oil, polyethylene wax, carnauba wax, higher alcohols, bisamides, oils and fats such as higher fatty acids, isocyanates, etc. Additives such as hardening agents, ultrafine particles of 0.1 μm or less, such as calcium carbonate, silica sol, and synthetic mica, can be used as appropriate. Further, an antistatic agent may be added to prevent dirt such as dust electrostatically adhering to the display surface. As the antistatic agent, the materials described for the above antistatic layer can be applied as they are.

The thickness of the roughened layer is in the range of 0.5 to 10 μm, preferably 1 to 5 μm. When the roughened layer is thinner than 0.5 μm, the abrasion resistance of the roughened layer is deteriorated, and poor curing is caused by oxygen inhibition such as when an ultraviolet curable resin is used. When the thickness is more than 10 μm, curling is caused by curing shrinkage of the resin, microcracks are generated in the roughened layer, and adhesion to the transparent substrate is reduced. Although the transparency of the anti-reflective material is affected by the refractive index of the roughened layer, the refractive index is
The closer to the refractive index of the transparent substrate, the better, and the range is 1.4.
5 to 1.70 is preferred. If it exceeds this range, the antireflection effect will be impaired.

C. Surface layer (a) High refractive index layer The high refractive index layer is provided directly on the surface of the roughened layer or via another layer such as an adhesive layer. Use a binder resin with a high refractive index to increase the refractive index,
It is carried out by adding ultrafine particles having a high refractive index to the binder resin, or by using them in combination. The refractive index of the high refractive index layer is always higher than that of the roughened layer, and is preferably in the range of 1.55 to 2.70. If the refractive index is lower than that of the roughened layer, or if the refractive index is out of the range, the antireflection effect is impaired. The resin used for the high refractive index layer is arbitrary as long as it is transparent, and a thermosetting resin, a thermoplastic resin, a radiation (including ultraviolet) curable resin, or the like can be used. As thermosetting resins, phenolic resins, melamine resins, polyurethane resins, urea resins, diallyl phthalate resins, guanamine resins, unsaturated polyester resins, amino alkyd resins,
Melamine-urea co-condensation resin, guanamine resin, silicon resin, polysiloxane resin and the like can be used, and if necessary, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, Adjusters and the like can be added.

Examples of the radiation-curable resin include (meth) acrylates of polyfunctional compounds such as polyester resins, polyether resins, acrylic resins, epoxy resins, alkyd resins, polybutadiene resins, spirol acetal resins, urethane resins, and polyhydric alcohols. And monofunctional monomers and polyfunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, styrene, methylstyrene, and N-vinylpyrrolidone as reactive diluents. .

When the above resin is used as an ultraviolet-curable resin, acetylenone, benzophenone, α-amyloxime ester, Michler benzoyl benzoate, tetramethylthiuram monosulfide, thioxanthone, or the like may be used as a photopolymerization initiator. N- as sensitizer
Butylamine, triethylamine and the like can be used as a mixture.

In order to increase the refractive index of the resin, a resin containing an aromatic ring or a halogenated element such as Br, I, or Cl is selected. Examples of the resin containing an aromatic ring include styrene resins such as polystyrene, PET, and polycarbonate of bisphenol A. Examples of the resin containing a halogenated element include polyvinyl chloride and polytetrabromobisphenol A glycidyl ether. Resins containing S, N, P, etc. also have a high refractive index,
For example, polyvinyl pyridine, polybisphenol S glycidyl ether and the like can be mentioned.

As the high refraction ultrafine particles, for example, Zn
O (refractive index n = 1.9), TiO ₂ (n = 2.3 to ₂ .
7) By containing fine particles of CeO ₂ (n = 1.95), an effect of shielding ultraviolet rays can be obtained. Also,
By containing fine particles of SnO ₂ (n = 1.95) or ITO (n = 1.95) doped with antimony, an antistatic effect is imparted and dust adhesion can be prevented. Other fine particles include Al ₂ O ₃ (n
_{= 1.63), La 2 O 3} (n = 1.95), ZrO
₂ (n = 2.05) and Y ₂ O ₃ (n = 1.87). These ultrafine particles are used singly or as a mixture, and those in the form of a colloid dispersed in an organic solvent or water are good in terms of dispersibility. Preferably, the thickness is 5 to 20 nm.

In order to provide the high refractive index layer directly on the roughened layer,
The above-mentioned materials are diluted in a solvent, for example, provided on the surface-roughened layer by a method such as spin coater, roll coater, printing, etc., and dried, and then heat or radiation (in the case of ultraviolet light, use the above-described photopolymerization initiator. Do) or the like. In this case, the thickness of the high refractive index layer after drying is 0.05 to 0.5 mm.
The coating thickness is adjusted to be 15 μm. If the thickness of the high refractive index layer is out of this range, the antireflection effect may be impaired.

(B) Low Refractive Index Layer In the present invention, a low refractive index layer having a smaller refractive index is provided on the high refractive index layer in order to obtain a better antireflection function. Hereinafter, the low refractive index layer will be described. Although the composition of the low refractive index layer is not particularly limited, it is preferable that the low refractive index layer be configured so that its critical surface tension is 20 dyne / cm or less. Critical surface tension is 20
When it is larger than dyne / cm, it becomes difficult to remove the dirt attached to the low refractive index layer. Further, in order to improve the antireflection effect, the low refractive index layer preferably has a refractive index of 1.45 or less. Examples of materials having these characteristics include LiF (refractive index n = 1.4), MgF ₂ (n
= 1.4), 3NaF.AlF ₃ (n = 1.4), Al
F ₃ (n = 1.4) Na ₃ AlF ₆ (n = 1.33) Si
Inorganic materials such as O ₂ (n = 1.45) are finely divided, and inorganic low-reflection materials, fluorine-based and silicone-based organic compounds, thermoplastic resins, and thermosetting, which are contained in an acrylic resin or an epoxy resin, etc. Organic low-reflection materials such as a mold resin and a radiation-curable resin. Among them, a fluorine-based fluorinated material is particularly preferable in terms of preventing contamination.

Examples of the fluorine-containing material include a vinylidene fluoride copolymer, a fluoroolefin / hydrocarbon olefin copolymer, a fluorine-containing epoxy resin, and a fluorine-containing epoxy acrylate which are dissolved in an organic solvent and are easy to handle. , Fluorinated silicone, fluorinated alkoxysilane, TFRON AF1600 (manufactured by DuPont, n = 1.30), CYTOP (manufactured by Asahi Glass Co., Ltd., n = 1.34), 17FM (Mitsubishi Rayon Co., Ltd.) Refractive index n = 1.35), Opstar JN-7212
(Manufactured by Nippon Synthetic Rubber Co., Ltd., n = 1.40), LR20
1 (manufactured by Nissan Chemical Industries, Ltd., n = 1.38). These can be used alone or in combination of two or more.

Also, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 2- (perfluoro- 9-methyldecyl) ethyl methacrylate, 3- (perfluoro-8-methyldecyl) 2
A fluorine-containing methacrylate such as -hydroxypropyl methacrylate, a fluorine-containing acrylate such as 3-pafluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, or 2- (perfluoro-9-methyldecyl) ethyl acrylate; 3
-Perfluorodecyl 1,2-epoxypropane, 3-
Examples thereof include epoxides such as (perfluoro-9-methyldecyl) -1,2-epoxypropane, radiation-curable fluorine-containing monomers such as epoxy acrylate, oligomers, and prepolymers. These can be used alone or in combination of two or more.

Further, a low-reflection material in which a sol in which ultrafine silica particles of 5 to 30 nm are dispersed in water or an organic solvent and a fluorine-based film-forming agent are mixed may be used. The sol obtained by dispersing the ultrafine silica particles of 5 to 30 nm in water or an organic solvent can be prepared by dealkalizing alkali metal ions in an alkali silicate by ion exchange or neutralizing the alkali silicate with a mineral acid. A known silica sol obtained by condensing an active silicic acid known by a method, etc., a known silica sol obtained by condensing an alkoxysilane with hydrolysis in an organic solvent in the presence of a basic catalyst, An organic solvent-based silica sol (organo silica sol) obtained by substituting water in the aqueous silica sol with an organic solvent by a distillation method or the like is used. These silica sols can be used in both aqueous and organic solvent systems. It is not necessary to completely replace water with an organic solvent when producing an organic solvent-based silica sol. The silica sol is S
a solid content of 0.5 to 50 wt% concentration as iO _2. Various structures such as spherical, needle-like, and plate-like structures can be used for the ultrafine silica particles in the silica sol.

As the film-forming agent, alkoxysilane, hydrolyzate of metal alkoxide or metal salt, fluorine-modified polysiloxane and the like can be used. By using such a film-forming agent, the critical surface tension of the low refractive index layer is reduced, and the adhesion of oil can be suppressed. In the present invention, the low-refractive-index layer is prepared by diluting the above-mentioned material in, for example, a solvent, spin-coater, roll-coater, and printing on the high-refractive-index layer by a method such as printing. Can be obtained by using the above-mentioned photopolymerization initiator). Radiation-curable fluorine-containing monomers, oligomers, and prepolymers are excellent in stain resistance, but have poor wetting properties, and depending on the composition, may cause problems such as repelling a low refractive index layer on a high refractive index layer, or a low refractive index. The acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group described as the above-mentioned radiation-curable resin used for the surface-roughening layer may cause a problem that the refractive index layer is peeled off from the high refractive index layer. It is desirable to appropriately mix and use monomers, oligomers and prepolymers having an isomerizable unsaturated bond. When the transparent substrate is TA
In the case of a resin film such as C or PET, the material of the low refractive index layer is preferably a radiation-curable resin because it is easily damaged by heat.

The low refractive index layer uses these low reflection materials,
Wet coating method by roll coating or printing, vacuum evaporation, sputtering, plasma CVD,
It is provided on the high refractive index layer by a gas phase method such as ion plating. When provided by a wet coating method, as necessary, a leveling agent such as silicone oil, polyethylene wax, carnauba wax, higher alcohol, bisamide, higher fatty acid, as well as a roughened layer, in order to improve coating suitability or printability. Oils and fats such as isocyanate, hardeners such as isocyanate, and additives such as ultrafine particles of 0.05 μm or less such as calcium carbonate, silica sol, and synthetic mica can be appropriately used.

The thickness for the low refractive index layer to exhibit a good antireflection function can be calculated by a known calculation formula. According to a known document (Science Library, Physics 9 "Optics", pp. 70-72), when the incident light is perpendicularly incident on the low refractive index layer, the low refractive index layer does not reflect light, and It is said that the condition for% transmission should satisfy the following relational expression. In the formula, N ₀ is the refractive index of the low refractive index layer, Ns is the refractive index of the high refractive index layer, h is the thickness of the low refractive index layer, and λ ₀ is the wavelength of light.

[0044]

[Number 2] N ₀ = Ns ^1/2 Equation _{(1) N 0 h = λ} 0/4 formula (2)

According to the above equation (1), the reflection of light is 100
It can be seen that in order to prevent the percentage, the material should be selected such that the refractive index of the low refractive index layer becomes the square root of the refractive index of the lower layer (high refractive index layer). However, in practice, it is difficult to find a material that completely satisfies the formula, and a material as close as possible is selected. In the formula (2), the optimum thickness of the low refractive index layer as an antireflection film is calculated from the refractive index of the low refractive index layer selected in the formula (1) and the wavelength of light. For example, the refractive indices of the high refractive index layer and the low refractive index layer are 1.50 and 1.3, respectively.
8. When the wavelength of light is set to 550 nm (standard of visibility) and these values are substituted into the above equation (2), the thickness of the low refractive index layer is about 0.1 μm, preferably 0.10 μm. ±
A range of 0.01 μm is calculated to be optimal. Thus, the low-refractive-index layer needs to be extremely thin and very evenly provided (in-plane variations in thickness cause color unevenness due to interference with the high-refractive-index layer). Therefore, as a method for providing the low refractive index layer, a gas phase method is preferable.

Further, an antistatic agent is added to the low refractive index layer to prevent contamination such as dust which electrostatically adheres to the display surface, or an antistatic layer is provided on the low refractive index layer. Is also good. As the antistatic agent, the materials described for the above antistatic layer can be applied as they are.

The anti-reflective material of the present invention thus produced has a HAZE value of 3 to 3 according to JIS K7105.
It is preferably in the range of 0, particularly preferably in the range of 5 to 15. In this case, if this value is less than 3, the effect of light diffusion is small, and a so large antireflection effect cannot be obtained. On the other hand, when the HAZE value exceeds 30, the image contrast is poor and the visibility is poor, and the function as a display is undesirably reduced. In addition, HAZE
The value means the haze value. The diffuse transmittance (Hd%) and the total light transmittance (Ht%) are measured using an integrating sphere light transmittance measuring device, and calculated by the following formula. I do.

[0048]

Haze value = Hd / Ht × 100

The surface roughness is Ra;
30 μm, Sm; 10 to 50 μm, preferably 15 to 2
A range of 5 μm is good. When Ra is smaller than 0.03 μm, the anti-glare property deteriorates due to a decrease in light diffusivity. 0.
If it is larger than 30 μm, HAZE increases and image contrast deteriorates. When Sm is smaller than 10 μm, the anti-glare property is deteriorated. If it is larger than 50 μm, the glare of the image becomes severe. (2) Contents of Polarizing Film A polarizing film can be formed by providing the antireflection material having the above structure on one surface of a film-shaped polarizing substrate. It is also possible to laminate a protective material on the other surface of the polarizing substrate. Hereinafter, the details of the polarizing film of the present invention will be described.

A. Polarizing Substrate The polarizing substrate is composed of a material capable of forming a transparent film, and specifically, polyvinyl alcohol, polyvinylene, or the like can be used. Then, a polarizing substrate can be obtained by stretching such a material to form a film. For example, it is preferable to use a polyvinyl alcohol (PVA) film obtained by uniaxially stretching polyvinyl alcohol adsorbing iodine or a dye as the dichroic element. A polarizing substrate having a thickness of 10 to 80 μm is used. Specifically, the polarizing substrate can be obtained by stretching the PVA film about 3 to 4 times in the uniaxial direction and impregnating the stretched PVA film into higher-order iodine ions.

B. Transparent Substrate and Protective Material The PVA film obtained above has shortcomings due to lack of strength and the like, and is liable to be torn and has a large shrinkage ratio with respect to a change in humidity. The transparent substrate and the protective material are respectively laminated. These are adhered to both surfaces of the polarizing substrate with a polyester adhesive, a polyacrylic adhesive, a polyurethane adhesive, a polyvinyl acetate adhesive, or the like.

For the transparent substrate, the aforementioned materials are used.
As the protective material, a transparent polymer compound film, for example, a cellulosic film such as TAC, a polyester film, a polycarbonate film and the like are used. Among them, TAC is particularly preferable. The thickness of these films is preferably from 10 to 2000 μm. Further, it is preferable to improve the water resistance of the films by using a gelling agent such as boric acid, or by performing a heat treatment or formalization on these films. Further, in order to improve the adhesion to the polarizing substrate, it is preferable to perform a surface treatment such as a saponification treatment or a corona treatment so that the surface energy of the bonding surface with the polarizing substrate becomes 50 dyne / cm or more.

Hereinafter, the antireflection material and the polarizing film of the present invention will be described in more detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing the structure of an antireflection material of the present invention. An antireflection material 10 has a roughened layer 12 on one surface of a transparent substrate 11.
It is a structure which has. A surface layer composed of a high-refractive index layer and a low-refractive index layer is formed on the surface of the roughened layer 12, but is not shown because the surface layer is extremely thin (the same applies hereinafter). . FIG. 2 is a schematic cross-sectional view showing the configuration of the polarizing film 20 of the present invention. An antireflection material 23 having a transparent substrate 21 and a roughened layer 22 is provided on one side of a polarizing substrate 24. Indicates that the protection member 25 is provided on the other surface.

FIG. 3 shows the structure of a liquid crystal display 30 in which the anti-glare property is improved by the anti-reflection material of the present invention. The liquid crystal display 30 is formed by laminating a liquid crystal panel 31 on the upper surface and a back light source 32 such as a light guide plate (EL) or a lamp on the lower surface. As the liquid crystal panel 31, for example, a twisted nematic (TN) liquid crystal cell or the like can be used.

In the TN liquid crystal cell, an alignment film is formed by applying a polyimide solution on the transparent electrode surfaces 33 'and 34' of two glass substrates 33 and 34 having transparent electrodes having a desired pattern. , This is orientated by a rubbing operation,
Thereafter, a nematic liquid crystal 35 is injected between the glass substrates 33 and 34, and the periphery of the glass substrates 33 and 34 is sealed with an epoxy resin or the like. The nematic liquid crystal 35 is twist-aligned by 90 ° by the action of the alignment film. Two glass substrates 33 of such a TN liquid crystal cell,
On the opposite side of the back light source 34, a polarizing film 36 whose both surfaces of the polarizing substrate 24 are protected by an antireflective material 23 having a roughened layer 22 and a protective material 25 shown in FIG. The liquid crystal panel 31 is formed on the rear light source side by attaching a polarizing film 37 having no roughening layer so that the polarization angles are twisted by 90 ° with respect to each other.

When a drive signal is applied to the transparent electrodes of the TN liquid crystal panel 31, an electric field is generated between the electrodes to which the signals are applied. At that time, due to the electronic anisotropy of the liquid crystal molecules,
Since the major axis of the liquid crystal molecules is parallel to the direction of the electric field, the optical rotatory power of the liquid crystal molecules is lost, and as a result, the light does not pass through the liquid crystal panel. The display of the image is recognized as visual information by contrast based on the difference in light transmission at this time. In the above liquid crystal display 30,
An image can be displayed by transmitting the light through the liquid crystal panel 31 and giving a contrast to a portion of the liquid crystal panel 31 where light is transmitted and a portion where light is not transmitted.

FIG. 4 is a sectional view showing the structure of another liquid crystal display using the antireflection material 10 of the present invention. In FIG. 4, the liquid crystal panel 41 has two glass substrates 43, 4
4, a nematic liquid crystal 45 interposed therebetween, an upper polarizing film 46 having no roughening layer, a lower polarizing film 47 having no roughening layer, and a lower polarizing film 47 located outside the glass substrates 43 and 44. It is composed of an antireflection material 10 laminated on a polarizing film 46. The liquid crystal display 40 is formed by laminating a liquid crystal panel 41 and a back light source 32 located on the lower surface thereof.

[0058]

The present invention will be described in more detail by way of examples. In the following description, “parts” means “parts by weight”. <Example 1> First, the following dispersion obtained by dispersing a mixture of cross-linked acrylic beads and toluene in a sand mill for 30 minutes, and the following base coating were stirred for 15 minutes with a disper, and the mixed coating was coated to a film thickness. One side of a saponified TAC, which is a transparent substrate having a transmittance of 80 μm and a transmittance of 92%, is applied by a reverse coating method, dried at 100 ° C. for 2 minutes, and then a condensing high pressure mercury lamp having a UV lamp output of 120 w / cm is used. The irradiation distance (distance from the center of the lamp to the coated surface) was 10 cm, and the processing speed (U on the coated substrate side) was used.
UV irradiation was performed at a speed of 5 m / min (speed with respect to a V lamp) to cure the coating film. Thus, a thickness of 2.5 μm,
A roughened layer having a HAZE value of 16.5 and a refractive index of 1.53 was formed.

Thereafter, a high-refractive-index layer paint having the following composition was applied to the surface-roughened layer by reverse gravure coating, dried at 100 ° C. for 2 minutes, and then output with a UV lamp of 1
Using one 20 w / cm condensing high pressure mercury lamp, UV irradiation was performed at an irradiation distance (distance from the lamp center to the coating surface) of 10 cm and a processing speed (speed of the coating substrate side relative to the UV lamp) of 5 m / min. Then, the coating film was cured. Thickness 0.1
A high refractive index layer having a thickness of μm and a refractive index of 1.70 was formed.

Next, a low-refractive-index layer paint having the following composition was applied onto the high-refractive-index layer by reverse gravure coating, and dried and cured at 120 ° C. for 6 hours to have a thickness of 0.1 μm and a refractive index of 1 μm. .38 to form an antireflective material of the present invention.

[Blending of dispersion] 9 parts of crosslinked acrylic beads (trade name: MX150, particle size 1.5 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 210 parts of toluene

[Blending of base paint] 45 parts of acrylic compound dipentaerythritol triacrylate 45 parts of epoxy compound (trade name: celloxite 2021, manufactured by Daicel Chemical Industries, Ltd.) 2 parts of cationic photopolymerization initiator represented by the following chemical formula

[0063]

Embedded image

・ Isopropyl alcohol 5 parts [Blending of high refractive index layer paint] ・ UV monomer 50 parts (trade name: MPG manufactured by Sumitomo Seika Co., Ltd.) ・ Photocationic polymerization initiator 1 part (trade name: MPI03, Midori Kagaku Co., Ltd.)・ 30 parts of ITO ・ 3 parts of dispersant (trade name: PC30 manufactured by Nisshin Oil Co., Ltd.) ・ 320 parts of MIBK ・ 320 parts of toluene [Blending of low refractive index layer paint] ・ 10 parts of silica sol (SiO _{2 with a} particle diameter of 15 nm) Ethanol dispersion containing 30% by weight of silica particles) Film-forming agent 15 parts (Hydrolysate of tetraethoxysilane: calculated as SiO ₂ , solid content concentration 6%) Solvent: Ethanol 53 parts

Example 2 The procedure of Example 1 was repeated, except that the composition of the surface-roughened layer was changed as follows.
An antireflection material having a roughened layer having an AZE value of 22.0 and a refractive index of 1.55 was obtained.

[Blending of dispersion] 4 parts of crosslinked acrylic beads (trade name: MX300, particle size 3.0 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 205 parts of toluene

[Blending of base paint] 45 parts of acrylic compound (tripentaerythritol polyacrylate) 45 parts of epoxy compound (trade name: Cyracure UVR-6110, manufactured by Union Carbide Co., Ltd.) 2 parts (trade name: Cyracure UVI-6990, manufactured by Union Carbide Co., Ltd.) ・ 5 parts of isopropyl alcohol

Example 3 The procedure of Example 1 was repeated, except that the composition of the surface-roughened layer was changed as follows.
An antireflection material having a roughened layer having an AZE value of 13.0 and a refractive index of 1.54 was obtained.

[Blending of Dispersion] Crosslinked acrylic beads (trade name: MX150, particle size 1.5 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 3 parts (trade name: MX300, particle size 3.0 μm ± 0. 5, Soken Chemical Co., Ltd.) 3 parts ・ Toluene 210 parts

[Blending of base paint] ・ Acrylic compound: tetradipentaerythritol polyacrylate: 15 parts Neopentyl glycol diacrylate: 30 parts ・ Epoxy compound: 45 parts (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co.) Cationic polymerization initiator 2 parts (trade name: Cyracure UVI-6990, manufactured by Union Carbide) 5 parts of isopropyl alcohol

Example 4 The procedure of Example 1 was repeated, except that the composition of the surface-roughened layer was changed as follows.
An antireflection material having a roughened layer having an AZE value of 9.0 and a refractive index of 1.54 was obtained.

[Blending of Dispersion] Crosslinked acrylic beads (trade name: MX150, particle size 1.5 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 3 parts (trade name: MX300, particle size 3.0 μm ± 0. 5, Soken Chemical Co., Ltd.) 3 parts ・ Toluene 210 parts

[Blending of base paint]-Acrylic compound 15 parts of dipentaerythritol polyacrylate 30 parts of tripentaerythritol polyacrylate-45 parts of epoxy compound (trade name: Lapicure DVE-3, manufactured by ISP)-Photocationic polymerization Initiator 2 parts (trade name: BBI-102, manufactured by Midori Kagaku) ・ Isopropyl alcohol 5 parts

Example 5 The same procedure as in Example 1 was carried out except that the composition of the roughened layer was changed as follows, and the thickness was 2.5 μm.
An antireflection material having a roughened layer having an AZE value of 6.7 and a refractive index of 1.53 was obtained.

[Blending of Dispersion] 3 parts of crosslinked acrylic beads (trade name: MX300, particle size 1.5 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 210 parts of toluene

[Blending of base paint]-Acrylic compound 1,6 hexanediol dimethacrylate 20 parts Pentaerythritol triacrylate hexamethylene diisocyanate 30 parts-Epoxy compound 45 parts (trade name: Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.)-Photocation 2 parts of polymerization initiator (trade name: MPI03, manufactured by Midori Kagaku Co., Ltd.) 5 parts of isopropyl alcohol <Example 6> A thickness of 0 was obtained in the same manner as in Example 1 except that the components of the high refractive index layer were changed as follows. .1 μm, refractive index 1.9
6 was obtained. [Blend of high refractive index layer paint] ・ 50 parts of UV monomer (trade name: MPG, manufactured by Sumitomo Seika Co., Ltd.) ・ 1 part of cationic photopolymerization initiator (trade name: MPI03, manufactured by Midori Kagaku Co., Ltd.) ・ 30 parts of TiO ₂・3 parts of dispersant (trade name: PC30 manufactured by Nisshin Oil Co., Ltd.) 320 parts of MIBK 320 parts of toluene <Example 7> In the same manner as in Example 6 except that the low refractive index layer was provided as follows, The antireflection material of the present invention was obtained. Formation of low-refractive-index layer: SiO ₂ was provided on the high-refractive-index layer by a sputtering method so as to have a layer thickness of 0.1 μm. The refractive index of the low refractive index layer of this example was 1.45.

Comparative Example 1 A film having a thickness of 3.6 μm and a thickness of 3.6 μm was prepared in the same manner as in Example 1 except that the components of the roughened layer were changed as follows.
An antireflection material having a roughened layer having an AZE value of 11.0 and a refractive index of 1.51 was obtained.

[Blending of dispersion] 3 parts of crosslinked acrylic beads (trade name: MX300, particle size 1.5 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 200 parts of toluene

[Blending of base paint] ・ Acrylate compound Dipentaerythritol polyacrylate 50 parts Pentaerythritol tetraacrylate 20 parts Hydroxyethyl acrylate 22 parts ・ Radical photopolymerization initiator 5 parts (trade name: Irgacure 184, manufactured by Ciba Geigy)・ 50 parts of isopropyl alcohol

(Comparative Example 2) Thickness 80 μm, transmittance 92%
Was used as an antireflection material for comparison.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the composition of the roughened layer was changed as follows, and the thickness was 4.2 μm.
An antireflection material having a roughened layer having an AZE value of 17.5 and a refractive index of 1.54 was obtained. [Blending of dispersion] Crosslinked acrylic beads 6 parts (trade name: MR-7G, manufactured by Soken Chemical Co., Ltd. Particle size: 0.5 to 6.0 μm 60% by weight Particle size: more than 6.0 μm・ 25 parts by weight of toluene

[Blending of base paint]-Acrylic compound 42 parts Dipentaerythryl triacrylate-Trimethylolpropane triacrylate 42 parts-Photocationic polymerization initiator of the following chemical formula 10 parts

[0083]

Embedded image

・ Isopropyl alcohol 5 parts

Comparative Example 4 The procedure of Example 5 was repeated, except that the composition of the surface-roughened layer was changed as follows, and the thickness was 3.0 μm.
An antireflection agent having an AZE value of 13.0 and a roughened layer having a refractive index of 1.50 was obtained. [Blending of dispersion]-2 parts of cross-linked acrylic beads (trade name: MX300, particle size 3.0 µm ± 0.5, manufactured by Soken Chemical Co., Ltd.)-100 parts of toluene

[Blending of base paint] 40 parts of polyester-based thermoplastic resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) 70 parts of toluene 100 parts of MEK (Comparative Example 5) Up to the roughened layer of Example 1 The provided material was used as an antireflection material for comparison. (Comparative Example 6) Except that the kind and the compounding amount of the filler of the roughened layer were changed as described below, and that the high refractive index layer was not provided, the thickness was 3.0 µm, Haze
An antireflection material having a roughened layer having a value of 35.0 and a refractive index of 1.53 was obtained.・ 20 parts of filler (trade name: MX300, particle size 3.0 ± 0.5 μm, manufactured by Soken Chemical Co., Ltd.)

Using the anti-reflection material 10 obtained in Examples 1 to 7 and Comparative Examples 1 to 6, a polarizing film 20 having the structure shown in FIG. 2 was produced. Next, the polarizing film 20
(Indicated by reference numeral 36 in FIG. 3) was attached to the glass substrate 33 as shown in FIG. Further, regarding the antireflection material 10 obtained in Comparative Example 2,
A laminate was prepared by laminating a polarizing film that had not been subjected to a surface roughening treatment with an adhesive so that the saponified TAC surface side was the bonding surface, and this laminate was formed as shown in FIG. And a liquid crystal display 40 was obtained.

The image size of each liquid crystal display 30 is, for example, 10.4 inches and the resolution is, for example, 80.
With 0 dots x 600 dots, the following methods were used to evaluate image contrast, image glare, and anti-glare properties. The abrasion resistance (adhesion between the transparent substrate and the roughened layer) and the chemical resistance were also evaluated based on the following methods.

The image contrast is JIS C7072.
1988, the contrast ratio of the liquid crystal display panel (C
R) It was evaluated according to the measuring method. FIG. 5 shows the positional relationship between the light source 60, the liquid crystal panel 61, and the photometer 62 in the evaluation of the image contrast. In this case, the distance between the light source 60 and the liquid crystal panel 61 was set to, for example, 1 cm, the distance between the liquid crystal panel 61 and the photometer 62 was set to, for example, 50 cm, and the aperture angle of the photometer 62 was set to, for example, 5 °. The light source 60 is a 5 W EL, and the photometer 62 is LS-1 manufactured by Minolta Camera.
00 was used. When CR is 4 or more, ◎, 3 or more, 4
In the case of less than ○, 2 or more and less than 3 were evaluated as Δ, and less than 2 was evaluated as ×.

Regarding the image glare, the liquid crystal display 40
Was connected to a personal computer so that the opening screen of a Windows, version 3.1 paint brush could be displayed, and the presence or absence of image glare in this monochrome display was evaluated by visual judgment of any 10 persons.
○ If less than 3 people felt glare, 3 or more,
A case where less than 7 people felt glare was rated as Δ, and a case where 7 or more people felt glare was rated as x.

As for the antiglare property, the image clarity in an optical comb width of 2 mm was measured in a transmission mode using an image clarity measuring device ICM-1DP (JISK7105) manufactured by Suga Test Instruments Co., Ltd. In this measurement test, the smaller the numerical value of the measurement data, the higher the anti-glare property. Here, less than 50% was evaluated as ○, more than 50%, less than 70% as Δ, and more than 70% as X. In order to prevent reflection from the back surface of the surface layer of the anti-reflective material, the back surface was rubbed with steel wool # 0000 manufactured by Nippon Steel Wool Co., then painted with black magic, and the specular reflection at 5 ° was measured. The measurement is based on JI
SZ8701, wavelength range 400-700nm
The average value of the Y values by the C light source was defined as the surface reflectance. In order to obtain a good antireflection effect, the content needs to be 1.0% or less, and if it is 0.5% or less, the characteristics are quite good.

The adhesion was evaluated by observing whether or not the transparent substrate and the roughened layer were in close contact with each other. In this evaluation, Comparative Example 2 having no roughened layer was excluded. In addition, abrasion resistance was tested for the examples and comparative examples. In the wear resistance test, steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. was attached to a paperboard abrasion tester (manufactured by Kumagaya Riki Kogyo Co., Ltd.), and the low refractive index layer surface of the antireflective material (the low refractive index layer was formed). The comparative example that is not shown is the outermost layer)
Was reciprocated 50 times with a load of 200 g. Then, the change δH (based on the following calculation) of the HAZE value of that portion was measured with a Haze meter manufactured by Toyo Seiki Co., Ltd. In this measurement test, the larger the measured value, the worse the wear resistance. In addition, HAZ
The measurement of the E value was performed using the antireflection material alone. Also, HAZ
The E value change δH is calculated from the HAZE value after the test to the HA value before the test.
It was calculated by dividing the ZE value. HAZE value change δH = HAZE value after test-H before test
AZE value

The chemical resistance was evaluated as x when the surface layer was rubbed 50 times with a cotton swab (manufactured by Johnson Co.) containing isopropyl alcohol and acetone, and then the layers were significantly changed such as peeling. The case where there was no change was evaluated as ○, and the middle was evaluated as △. The refractive index of the roughened layer was measured by Abbe refractive index (manufactured by Atago). The refractive indices of the high refractive index layer and the low refractive index layer were measured by spin coating of glass having a known refractive index on each layer using an ellipsometer (manufactured by Mizojiri Kogyo KK).

[0094]

[Table 1]

As is clear from Table 1, Example 1 in which the roughened layer contains an epoxy compound and a cationic photopolymerization initiator.
In Nos. To 7, the adhesion between the transparent substrate and the roughened layer was excellent, and the optical properties and durability were good. On the other hand, Comparative Examples 1 to
In No. 4, since the surface-roughened layer does not contain the ultraviolet-curable resin as in the example, the adhesiveness between the transparent substrate and the surface-roughened layer is poor, so that the substrate is peeled off, and no abrasion resistance is obtained. Not only that, the dispersion of the filler was poor, causing a glare problem (Comparative Examples 1 and 3) and a chemical resistance problem (Comparative Examples 3 and 4). Further, Comparative Example 2 was inferior in anti-glare properties because there was no roughened layer. Furthermore, Comparative Example 5 has a high reflectance because it has no high refractive index layer and low refractive index layer, and Comparative Example 6 has a high filler content and does not have a high refractive index layer. Because of HA
The ZE value was large, and the image contrast was low.

[0096]

As described above, according to the present invention, excellent antireflection properties are exhibited by preventing the reflection of external light such as sunlight and fluorescent lights on the display, and the image contrast is reduced. Without any glare, it is possible to obtain a clear image without glare, optically stable, excellent abrasion resistance, chemical resistance, and with an anti-reflective material with excellent adhesion of the roughened layer A polarizing film can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view illustrating a configuration of an antireflection material of the present invention.

FIG. 2 is a schematic cross-sectional view showing a configuration of a polarizing film using the antireflection material of the present invention.

FIG. 3 is a schematic cross-sectional view illustrating a configuration of a liquid crystal display including a polarizing film using an antireflection material.

FIG. 4 is a schematic sectional view showing the configuration of another liquid crystal display including a polarizing film using an antireflection material.

FIG. 5 is a schematic view showing a layout of an image contrast measuring device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 ... Anti-reflective material, 11 ... Transparent base, 12 ... Roughened layer, 20 ... Polarized film with a roughened layer, 21 ... Transparent base,
22: roughened layer, 23: surface layer, 24: polarizing substrate, 25
... Protective material, 30 ... Liquid crystal display, 31 ... Liquid crystal panel, 32
... Back light source, 33, 34 ... Glass substrate, 33 ', 34'
... Transparent electrode surface, 35 ... Nematic liquid crystal, 36 ... Polarizing film, 40 ... Liquid crystal display, 41 ... Liquid crystal panel, 42 ... Back light source, 43,44 ... Glass substrate, 45 ... Nematic liquid crystal, 46,47 ... Polarizing film, Reference numeral 60 denotes a light source, 61 denotes a liquid crystal panel, and 62 denotes a photometer.

Claims (4)

[Claims] 1. An anti-reflective material comprising a transparent substrate provided with at least a roughening layer and a surface layer on one or both surfaces in that order, wherein the surface layer comprises a high refractive index layer on the side of the roughening layer, A reflection layer having a lower refractive index layer on the surface side having a smaller refractive index than the refractive index layer, wherein the roughened layer contains an ultraviolet curable resin containing an epoxy compound and a cationic photopolymerization initiator. Prevention material. 2. The high refractive index layer is provided on the roughened layer by a coating method, and the low refractive index layer is provided on the high refractive index layer by a gas phase method. 2. The antireflective material according to 1. 3. The roughened layer contains a spherical filler,
The particle diameter D of the spherical filler is 0.5 μm ≦ D ≦ 6.
60% by weight or more of particles in the range of 0 μm, 6.0 μm <D
9. less than 20% by weight of particles in the range of ≦ 10.0 μm;
The particles according to claim 1 or 2, wherein particles having a range of 0 µm <D ≤ 15.0 µm have a particle size distribution of 5% by weight or less, and particles having a particle size of more than 15 µm have a particle size distribution of 1.0% by weight or less. Anti-reflective material. 4. A protective material of the anti-reflection material according to claim 1, on the other surface of the transparent substrate on which the roughening layer and the surface layer are not provided, via a polarizing substrate. A polarizing film characterized by laminating.