JP3352921B2 - Antireflection material and polarizing film using the same - Google Patents

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 including outdoor use, there is an increasing demand for preventing reflection of external light such as sunlight or fluorescent light on a display, that is, antireflection. . At present, these demands are spreading not only to portable terminal devices but also to various displays ranging from small to large.

[0004]

With respect to antireflection,
2. Description of the Related Art Conventionally, an image is scattered or diffused like a frosted glass, and an image is blurred. In order to scatter or diffuse light, it is basic to roughen the light incident surface, and this roughening treatment is performed by directly roughening the substrate surface by sandblasting, embossing, etc. And a method of providing a coating layer containing a filler on the surface of the substrate, and a method of forming a porous film having a sea-island structure on the surface of the substrate.

A method of providing a coating layer containing a filler on the surface of a base material can relatively easily control the size of the irregularities on the roughened surface by the particle size of the filler, and is easy to manufacture. Currently favored for its advantages. 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. Examples thereof include JP-A-1-1055738 and JP-A-5-162, in which a UV-curable resin and a silica pigment are constituent elements.
261 have been reported.

[0006] However, the silica pigment proposed above is
When a roughened layer is used because of high oil absorbency, oils such as fingerprints are easily absorbed, so that it has a disadvantage that it is easily stained. In addition, this dirt is difficult to remove with a cloth impregnated with a solvent such as alcohol, and the silica has a sharply protruding structure on the surface of the roughened layer. Fibers of the cloth
There is a problem that the image becomes white and the image contrast of the display decreases.

As another method for preventing reflection, a material having a high refractive index and a material having a low refractive index are alternately laminated to form a multilayer (multi-coat), whereby the reflection on the surface is suppressed, and a good antireflection effect is obtained. It is known to gain. Usually SiO ₂
, And a high refractive index material such as TiO ₂ and ZrO ₂ are alternately formed by vapor deposition or a sol-gel method. Proposals have been made to provide these layers on the roughened layer containing silica,
Even such a technique has the same problem that the dirt is difficult to wipe off. The cause is that the silica protrudes sharply from the surface of the roughened layer, so that the unevenness of the surface layer of the multi-coat layer becomes sharp according to the shape, and the same problem as described above occurs, and the silica This is because a part of the particles can easily penetrate through the surface layer and absorb oil such as fingerprints.

In addition, the above-mentioned multi-coating is not suitable for processing large areas when a vapor phase method such as vapor deposition is used, and requires a high processing apparatus. In the case of a sol-gel method, coating and firing are repeated. For this reason, the production cost is high and there is a problem in economics, and since the surface has a purple or green color, stains are more conspicuous than those without a multicoat. On the other hand, in order to prevent the occurrence of such stains, it has been proposed to provide a fluorine-based material on the surface-roughened layer by coating or the like. However, in order to solve the problem, the influence of the surface-roughened layer is large. Not reached.

[0009] Further, as the resolution of the display has been improved, the height and spacing of the irregularities of the roughened layer have also been required to be fine. The high definition of an image is mainly based on an increase in the density of image dots. It is good if the interval between the concavities and convexities is smaller than the pitch of the image dots, but if it is large, glare occurs due to interference. In order to obtain a clear image with good anti-reflection properties and no glare, first, the height and spacing of the irregularities must be controlled so as to be small and have no variation.

[0010] However, the dispersibility of the roughened layer composed of the UV-curable resin and the silica pigment is not always sufficient, and the roughened layer before UV curing exhibits a low-viscosity liquid state. Because the paint is applied to the substrate,
Before irradiation, the fillers in the roughened layer adhere to each other and aggregate (orange peel). In particular, when increasing the content of the filler for the purpose of densifying the unevenness of the surface of the roughened layer, or when diluting the paint of the roughened layer with a solvent or the like in order to control the thickness of the roughened layer. Especially remarkable.

The present invention has been made in view of the above-mentioned circumstances in the prior art, and exhibits excellent anti-reflection properties by preventing reflection of external light such as sunlight and fluorescent lights on a display. And, without deteriorating the image contrast, it is possible to obtain a clear image without glare and the like, and it is of course excellent in optical stability and excellent abrasion resistance, chemical resistance, It is an object of the present invention to provide an anti-reflective material exhibiting contamination. Another object of the present invention is to provide a polarizing film using the above-described antireflection material, and in particular, to significantly improve the performance of a full-color liquid crystal display or the like.

(1) Contents of Antireflective Material The present inventors have repeatedly studied the characteristics of the surface layer of the antireflective material in order to improve the contamination resistance of the surface of an LCD or the like. And found that there is a correlation between them. Then, as a result of quantitative analysis of the correlation, the critical surface tension of the surface of an LCD or the like is 2
When it is 0 dyne / cm or less, it has been found that, for example, dirt due to oil on the fingertip does not easily adhere, and even if it adheres, it can be easily wiped off. Therefore, the present invention has been made based on the above-described findings, and an antireflection material having a roughened layer and a surface layer sequentially provided on one or both surfaces of a transparent substrate, directly or via another layer, has a surface. The critical surface tension of the layer is 20d
yne / cm or less , and the roughened layer
Cured by either radiation or heat or a combination
It is characterized by comprising a resin and a spherical filler . Hereinafter, more preferred embodiments of the present invention will be described in detail.

[0013]

DETAILED DESCRIPTION OF THE INVENTION A. Transparent substrate As the transparent substrate used in 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, polysulfone, polyethersulfone, cellophane, aromatic polyamide, polyethylene, polypropylene, and polyvinyl alcohol. A resin film and a glass substrate such as quartz glass and soda glass can be suitably used. When used for PDP and LCD, P
ET and TAC are preferred.

The higher the transparency of these transparent substrates, the better, but the light transmittance (JIS C-6714) is preferably 80% or more, more preferably 90% or more. When the transparent substrate is used for a small and lightweight liquid crystal display, the transparent substrate is more preferably a film. The thickness of the transparent substrate is more thin from the viewpoint of weight reduction is desirable, in view of its productivity, 1 [mu] m 5 .mu.m
It is preferable to use those in the range of

Further, the transparent substrate is subjected to a surface treatment such as an alkali treatment, a corona treatment, a plasma treatment, a fluorine treatment, a sputtering treatment, a surfactant, a silane coupling agent or the like, or a surface modification treatment such as a Si deposition. By doing so, the adhesion between the roughened layer and the transparent substrate can be improved. 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 formed by depositing a metal such as aluminum or tin, or a metal oxide film such as ITO by vapor deposition, sputtering, etc., and applying antimony or the like to fine metal particles such as aluminum or tin or whisker or metal oxide such as tin oxide. Doped fine particles and whiskers, and those obtained by converting a charge transfer complex formed between 7,7,8,8-tetracyanoquinodimethane and electron donors (donors) such as metal ions and organic cations into polyester are used as polyester. Resin, acrylic resin,
It can be provided by a method of dispersing in an epoxy resin or the like and providing by solvent coating or the like, a method of providing polypyrrole, polyaniline or the like doped with camphorsulfonic acid or the like by solvent coating or the like. The transmittance of the antistatic layer is preferably 80% or more for optical applications.

B. Next, the roughened layer in the present invention will be described. As the resin constituting the roughened layer of the present invention, a resin that is cured by any one or combination of radiation and heat can be used. As the radiation-curable resin, a composition obtained by appropriately mixing monomers, oligomers, and prepolymers having a polymerizable unsaturated bond such as an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group is used. Examples of the monomer include styrene, methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, and the like. Examples of the oligomer and prepolymer include acrylates such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, alkite acrylate, melamine acrylate, and silicone acrylate, unsaturated polyester, and epoxy compounds. These may be used alone or in combination. Monomers are preferred if the flexibility of the cured film is required. In order to further reduce the crosslinking density, it is preferable to use monofunctional or bifunctional acrylate monomers. When severe durability such as resistance, abrasion resistance and solvent resistance is required, it is preferable to increase the amount of the monomer and use a trifunctional or higher functional acrylate monomer.

In order to cure the radiation-curable resin as described above, radiation such as, for example, ultraviolet rays, electron beams, or X-rays may be applied. If necessary, a polymerization initiator can be appropriately added. When curing with ultraviolet light,
It is necessary to add a photopolymerization initiator. As a photopolymerization initiator, diethoxyacetophenone, 2-hydroxy-2
Acetophenones such as -methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, benzoinmethyl Benzoin ethers such as ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl 4'-methyl-diphenyl sulfide, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy)
Benzophenones such as ethyl] benzenemethanaminium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2,4 diethylthioxanthone,
Thioxanthones such as -chloro-4-dichlorothioxanthone; and 2,4,6 trimethylbenzoyldiphenylbenzoyl oxide. These can be used alone or in combination of two or more. Further, as an accelerator (sensitizer), an amine compound such as N, N-dimethylparatoluidine and 4,4′-diethylaminobenzenephenone can be mixed and used. The content of the photopolymerization initiator is preferably in the range of 0.1 to 10% by weight based on the radiation-curable resin. More or less than this range will degrade the effect.

In the present invention, it is particularly preferable to use an epoxy compound which can be cured by ultraviolet rays as the radiation-curable resin and to contain at least a cationic polymerization initiator as a photopolymerization initiator for the following reasons. Less oxygen inhibition. Very little cure shrinkage. Excellent adhesion to transparent substrates. In particular, among the transparent substrates, the TAC film used for the polarizing film, which has little adhesion, shows good adhesion, and particularly, excellent adhesion with the saponified TAC is achieved.
The effect that the decrease in the antiglare property due to the saponification treatment is also improved by such adhesion is achieved.

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 adducts, and alicyclic epoxies represented by the following chemical formula.

[0020]

Embedded image

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

[0022]

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 % by weight or more than 5.0 % by weight, ultraviolet curing is insufficient.

In the present invention, it is preferable to use an epoxy compound curable by ultraviolet rays as the radiation-curable resin and to use a cationic photopolymerization initiator as a polymerization initiator as described above. In order to control the properties of the paint and the coating film such as density, heat resistance and chemical resistance, it is preferable to mix an acrylic compound which can be cured by ultraviolet rays. Examples of such an acrylic compound include lauryl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl acrylate. Hydroxy-3-
Monofunctional acrylates such as phenoxy acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol acrylate, dipentaerythritol hexaacrylate, trimethylolpropane acrylate benzoate Acid esters, acrylic acid derivatives such as polyfunctional acrylates such as trimethylolpropane benzoate, 2-ethylhexyl methacrylate, n-
Monofunctional methacrylates such as stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxybutyl acrylate; polyfunctional such as 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, and glycerin dimethacrylate Examples include monomers and oligomers such as methacrylic acid derivatives such as methacrylate, and urethane acrylates such as glycerin dimethacrylate hexamethylene diisocyanate and pentaerythritol triacrylate hexamethylene diisocyanate.

The volume shrinkage rate (calculated by the following method) accompanying the curing of the roughened layer using the radiation-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.

[0026]

## 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)

In the present invention, a stabilizer (thermal polymerization inhibitor) such as hydroquinone, p-benzoquinone, or t-butylhydroquinone may be added to the radiation-curable resin. The amount of addition is preferably in the range of 0.1 to 5.0% by weight based on the radiation-curable resin.

Examples of the thermosetting resin that can be used for the surface roughening layer include phenol resins, furan resins, xylene / formaldehyde resins, ketone / formaldehyde resins, urea resins, melamine resins, aniline resins, alkyd resins, and unsaturated resins. Examples thereof include a polyester resin and an epoxy resin. These may be used alone or in combination. When the transparent substrate is a plastic film, the thermosetting temperature cannot be set high.
In particular, when using PET or TAC, it is desirable that the thermosetting resin used can be cured at 100 ° C. or lower.

The higher the transparency of the curable resin used for the surface roughening layer, the better, and the light transmittance (JIS C-6714).
Is 80% or more, preferably 90%, as in the transparent substrate.
% Or more is preferable. The transparency of the antireflection material is affected by the refractive index of the curable resin, but the refractive index is 1.4.
It is preferably in the range of 5 to 1.70, particularly 1.5 to 1.65, and if it exceeds this range, the antireflection effect will be impaired.

By adding a filler to the roughened layer and roughening the surface of the roughened layer, the antireflection effect can be improved. 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 is deteriorated 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)
It is preferably equivalent to a curable resin. When the refractive index of the filler is different from that of the curable resin, light diffuses at the interface between the filler and the resin, and the transparency is impaired. As an example of the filler having the same refractive index as the curable resin, 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 crosslinker 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. Also, the crosslinked acrylic beads include oils and fats to improve the dispersibility of the paint,
Surface modification with an organic or inorganic material such as a silane coupling agent or a metal oxide may be performed.

In the present invention, as a method of providing a roughened layer on one or both sides of a transparent substrate directly or via another layer, the above-mentioned UV-curable resin is prepared by adding crosslinked acrylic beads or the like to the resin. Mix spherical filler and water or organic solvent as needed, paint it with 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, letterpress printing such as flexo printing, intaglio printing such as direct gravure printing, offset gravure printing, plate printing such as offset printing, screen It is provided in a single layer or multiple layers on one or both sides of the transparent substrate by a printing technique such as stencil printing such as printing, and when a solvent is contained, it is subjected to a heat drying step and then to radiation (in the case of ultraviolet rays, photopolymerization is started. A method is required in which the coating layer or the printed layer is cured by irradiation or the like. When the radiation is an electron beam, 50 to 1000 KeV emitted from various electron beam accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformation type, Insulating core transformer type, Linear type, Dynamitron type and High frequency type. In the case of ultraviolet rays, 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 coating suitability or printability 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. If it is thicker than 10 μm,
Curling occurs due to curing shrinkage of the resin, microcracks occur in the roughened layer, and adhesion to the transparent substrate is reduced.

C. Surface Layer Next, the surface layer of the present invention has a critical surface tension of 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 surface layer. Further, in order to improve the antireflection effect, it is preferable that the refractive index of the surface layer is lower than the refractive index of the roughened layer and is 1.45 or less. As a material having these characteristics, for example, LiF (refractive index n
= 1.4), MgF ₂ (n = 1.4), 3NaF · Al
F ₃ (n = 1.4), AlF ₃ (n = 1.4) Na ₃ Al
Inorganic materials such as F ₆ (n = 1.33) are made into fine particles, and inorganic low-reflection materials, fluorine-based or silicone-based organic compounds, thermoplastic resins, and thermosetting are contained in acrylic resins, epoxy resins, and the like. Organic low-reflection materials such as a mold resin and a radiation-curable resin. Among them, a fluorine-containing fluorine material is particularly preferable in terms of preventing contamination.

As the above-mentioned fluorine-containing material, a vinylidene fluoride copolymer, a fluoroolefin / hydrocarbon olefin copolymer, a fluorine-containing epoxy resin, a fluorine-containing epoxy acrylate which is dissolved in an organic solvent and is 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.

Further, 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. 5
A sol in which ultrafine silica particles of about 30 nm are dispersed in water or an organic solvent can be obtained by, for example, dealkalizing alkali metal ions in alkali silicate by ion exchange or neutralizing alkali silicate with a mineral acid. A known silica sol obtained by condensing active silicic acid known in the above, a known silica sol obtained by condensing an alkoxysilane with hydrolysis in the presence of a basic catalyst in an organic solvent, and further the above aqueous silica sol An organic solvent-based silica sol (organo-silica sol) obtained by substituting the water therein 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 SiO
_{As 2,} it contains a solid content of 0.5 to 50% by weight.
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, and fluorine-modified polysiloxane can be used. In particular, the critical surface tension of the surface layer is reliably set to 20 dyn.
In order to make e / cm or less, it is preferable to use the film- forming agent as described above, and in particular, a fluorine compound is preferable. The surface layer of the present invention is prepared by diluting the above-mentioned material with, for example, a solvent, providing the surface-roughened layer with a method such as a spin coater, a roll coater, or printing, and then drying. (Using a photopolymerization initiator) and the like. Radiation-curable fluorine-containing monomers, oligomers, and prepolymers have excellent stain resistance, but have poor wettability, and depending on the composition, may cause problems such as repelling the surface layer on the roughened layer, or the surface layer may be rough. Since the problem of peeling from the surface roughening layer may occur, polymerizable non-polymerizable resins such as acryloyl, methacryloyl, acryloyloxy, and methacryloyloxy groups described above as the radiation-curable resin used for the roughened layer. It is desirable to appropriately mix and use monomers, oligomers and prepolymers having a saturated bond. When a transparent substrate is made of a plastic film such as PET or TAC which is easily damaged by heat, it is preferable to select a radiation-curable resin as a material for these surface layers.

In order to improve the coating suitability or printing suitability of the paint or ink of the surface layer, if necessary, as in the case of the roughened layer, a leveling agent such as silicone oil, polyethylene wax, carnauba wax, higher alcohol, bisamide, Fats such as higher fatty acids, curing agents such as isocyanate, calcium carbonate and silica sol, synthetic mica 0.05
Additives such as ultrafine particles having a size of not more than μm can be appropriately used. Further, an antistatic agent may be added to the surface layer to prevent contamination such as dust that electrostatically adheres to the display surface, or an antistatic layer may be provided on the surface layer. As the antistatic agent, the materials described for the above antistatic layer can be applied as they are.

The thickness of the surface layer can be calculated by a known calculation formula. According to a known document (Science Library, Physics 9 "Optics", pp. 70-72), when incident light is perpendicularly incident on the surface layer, the surface layer does not reflect light and transmits 100%. It is said that the condition of satisfies the following relational expression. In the formula, N ₀ is the refractive index of the surface layer, N _s is the refractive index of the roughened layer, h is the thickness of the surface layer,
λ ₀ indicates the wavelength of light.

[0043]

[Number 2] N ₀ = N _s ^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 a material having a refractive index of the surface layer to be the square root of the refractive index of the lower layer (roughened layer) should be selected in order to prevent the percentage. However, in practice, it is difficult to find a material that completely satisfies this equation, and a material as close as possible is selected. In the above equation (2), the optimum thickness of the surface layer as an antireflection film is calculated from the refractive index of the surface layer selected in the equation (1) and the wavelength of light. For example, the refractive index of the roughened layer and the refractive index of the surface layer are 1.50 and 1.38, respectively, and the light wavelength is 5
When these values are substituted into the above equation (2), the thickness of the surface layer is optimally around 0.1 μm, preferably within the range of 0.1 ± 0.01 μm. Is calculated as

The anti-reflection 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.

[0046]

Haze value = Hd / Ht × 100

[0047] (2) the contents of the polarizing film A. Polarizing Film-1 A polarizing film can be formed by providing the antireflection material having the above structure on one surface of a film-like polarizing substrate. Here, 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.

B. Polarizing Film-2 Another polarizing film of the present invention is a first protective material comprising a transparent substrate having a surface roughening layer having an anti-reflection function and a surface layer sequentially provided on one surface of the above-mentioned film-like polarizing substrate (the above-mentioned polarizing material). (1)
Is provided, and a second protective material is provided on the other surface. Specifically, a PVA film is stretched about 3 to 4 times in a uniaxial direction, and a polyester-based adhesive and a polyacrylic resin are applied to both sides of a polarizing substrate obtained by impregnating a stretched PVA film in higher-order iodine ions. It is preferable that the first and second protective materials are laminated with a system-based adhesive, a polyurethane-based adhesive, a polyvinyl acetate-based adhesive, or the like. PV obtained above
The A film has a defect that it is apt to be torn due to lack of strength and the like and has a large shrinkage ratio with respect to a change in humidity. Therefore, protective materials are laminated on both sides of the polarizing substrate. As the transparent substrate and the second protective material used for the first protective material, a transparent polymer compound film,
For example, a cellulosic film such as triacetyl cellulose, a polyester film, a polycarbonate film and the like are used. Among them, triacetyl cellulose is particularly preferred. The thickness of the film is 10 to 2000 μ
m is preferred. 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 adhesiveness with the polarizing substrate, the surface energy of the bonding surface with the polarizing substrate is 50 dyn.
It is preferable to perform a surface treatment such as a saponification treatment or a corona treatment so as to have e / 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. Although a surface layer is formed on the surface of the roughened layer 12, the surface layer is not shown because it is extremely thin (the same applies to the following description). FIG. 2 is a schematic cross-sectional view showing the configuration of the polarizing film 20 of the present invention. The first protective material 23 having a roughened layer 22 on a transparent substrate 21 on one side of a polarizing substrate 24, that is, an anti-reflection material Indicates that the second protective material 25 is formed 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 substrates, and the periphery of the glass substrate is sealed with an epoxy resin or the like. The nematic liquid crystal is twist-aligned by 90 ° by the action of the alignment film. On the opposite sides of the two glass substrates of the TN liquid crystal cell from the rear light source, a first protective material and a second protective material (not shown) each having a surface layer (not shown) and a roughened layer 22 are provided. Polarizing film 36 (2
2 and 36, and a polarizing film 37 without a roughening layer on the back light source side, so that the polarizing angles are twisted by 90 ° with respect to each other. 31 are formed.

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, and a lower polarizing film 4 having no roughening layer located outside the glass substrate.
7 and an anti-reflection material 10 (10 and 46 corresponding to the above-mentioned polarizing film-1) laminated on the polarizing film on the upper side. The liquid crystal display 40 is
It is formed by laminating a liquid crystal panel 41 and a back light source 32 located on the lower surface thereof.

[0054]

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 crosslinked acrylic beads and toluene in a sand mill for 30 minutes, and the following base paint were stirred for 15 minutes with a disper, and the mixed paint was mixed with a film having a thickness of Triacetyl cellulose (trade name: 80 μm, transparent substrate having a transmittance of 92%)
Fuji Tack UVD80, manufactured by Fuji Photo Film Co., Ltd., coated on one side with a refractive index of 1.49) by a reverse coating method, dried at 100 ° C. for 2 minutes, and output 120 w / cm.
UV light irradiation at a irradiation distance (distance from the center of the lamp to the coating surface) of 10 cm and a processing speed (speed with respect to the mercury lamp on the coating substrate side) of 5 m / min. Was cured. Thus, a thickness of 1.7
A roughened layer having a thickness of 1.5 μm and a refractive index of 1.53 was formed. After that,
Fluorine- containing silica sol (LR20 manufactured by Nissan Chemical Industries, Ltd.)
1 (total solid content: 4%, solvent: ethanol / butyl cellosolve = 50/50, manufactured by Nissan Chemical Industry Co., Ltd.) was applied on the roughened layer by spin coating.
After drying at 00 ° C. for 1 minute, heat cure at 120 ° C. for 6 hours, thickness 0.1 μm, refractive index 1.38, critical surface tension 1
A surface layer of 1 dyne / cm was formed, and a HAZE value of 10.
5. An antireflection material of the present invention having a reflectance of 1.4% was obtained.

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

[Blending of base paint]-Acrylic compound 45 parts of dipentaerythritol triacrylate-Epoxy compound 45 parts (trade name: Celloxite 2021, Daicel Chemical Industries)-2 parts of photocationic polymerization initiator of the following chemical formula

[0057]

Embedded image

・ Isopropyl alcohol 5 parts

<Example 2> An antireflection material of the present invention was obtained in the same manner as in Example 1 except that the composition of the roughened layer was changed as follows. The thickness and the refractive index of the roughened layer are 3.8 respectively.
μm, 1.52, critical surface tension of surface layer is 11.0 dy
ne / cm, the HAZE value of the antireflection material, and the reflectance were 22.0 and 1.3%, respectively.

[Blending of dispersion liquid] 4 parts of crosslinked acrylic beads (trade name: MX300, particle size 3.0 ± 0.5 μm, refractive index 1.50, manufactured by Soken Chemical Co., Ltd.) 4 parts of crosslinked acrylic beads (product Name: MX500, particle size 5.0 ± 0.5 μm, refractive index 1.50, manufactured by Soken Chemical Co., Ltd.) ・ Toluene 200 parts

[Blending of base paint]-Acrylic compound 45 parts Tripentaerythritol polyacrylate-Epoxy compound 45 parts (trade name: Cyracure UVR-6110, manufactured by Union Carbide Co., Ltd.)-Photocationic polymerization initiator 2 (Product name: Cyracure UVI-6990, manufactured by Union Carbide Co., Ltd.) ・ Isopropyl alcohol 5 parts

<Example 3> An antireflection material of the present invention was obtained in the same manner as in Example 1 except that the dispersion of the roughened layer and the base paint were changed as follows. The thickness and refractive index of the roughened layer are 2.8 μm and 1.55 respectively, the critical surface tension of the surface layer is 11.0 dyne / cm, and the anti-reflective material HAZE
The value and the reflectance were 22.0 and 1.3%, respectively.

[Blending of Dispersion] Spherical silica (trade name: Hypressica FQ particle size: 1.0 ± 0.1 μm, refractive index: 1.45, manufactured by Ube-Nitto Kasei Co., Ltd.) 3 parts (trade name: Hypressika) UF Particle size 2.5 ± 0.1 μm, refractive index 1.43, Ube Nitto Kasei Co., Ltd. 4 parts ・ Cross-linked acrylic beads 2 parts (trade name: MX300, particle size 3.0 ± 0.5 μm, (Refractive index 1.50, manufactured by Soken Chemical Co., Ltd.) ・ Toluene 210 parts

[Blending of base paint] Acrylic compound tetrapentaerythritol polyacrylate 15 parts Neopentyl glycol diacrylate 30 parts Epoxy compound 45 parts (trade name: Epicoat 828 manufactured by Yuka Shell Epoxy Co.) Photo cationic polymerization Initiator 2 parts (trade name: Cyracure UVI-6990, manufactured by Union Carbide Co., Ltd.)-Isopropyl alcohol 5 parts

<Example 4> On a roughened layer provided in the same manner as in Example 1, a fluorine-containing thermosetting resin Opstar JN-
7212 (total solid concentration 5%, solvent MIBK, manufactured by Nippon Synthetic Rubber Co., Ltd.) by spin coating,
After drying at 100 ° C. for 1 minute, heat curing at 100 ° C. for 2 hours, thickness 0.1 μm, refractive index 1.40, critical surface tension 1
A surface layer of 8 dyne / cm was formed and a HAZE value of 11.
0, an antireflection material of the present invention having a reflectivity of 1.6% was obtained.

Example 5 A roughened layer was formed in the same manner as in Example 1 except that the dispersion and the base paint were changed as described below, and a fluorine-containing ultraviolet-curable resin OPSTAR T was formed thereon.
M007 (total solid content 5%, solvent MIBK, manufactured by Nippon Synthetic Rubber Co., Ltd.) was applied and dried at 100 ° C. for 1 minute.
Using one condensing high-pressure mercury lamp with a UV lamp output of 120 w / cm, UV irradiation 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. Irradiation was performed to cure the coating film to form a surface layer having a thickness of 0.1 μm, a refractive index of 1.41, and a critical surface tension of 15 dyne / cm, thereby obtaining an antireflection material of the present invention. The thickness and the refractive index of the roughened layer were 5.6 μm and 1.51, respectively, and the HAZE value and the reflectance of the antireflection material were 28.0 and 1.0%, respectively.

[Blending of dispersion] Crosslinked acrylic beads (trade name: MX150, particle size 1.5 ± 0.5 μm, refractive index 1.50, manufactured by Soken Chemical Co., Ltd.) 10 parts (trade name: MX300, particle size 3.0 ± 0.5 μm, refractive index 1.50, manufactured by Soken Chemical Co., Ltd.) 4 parts (trade name: MX500, particle size 5.0 ± 0.5 μm, refractive index 1.50, manufactured by Soken Chemical Company) 2 parts・ Spherical silica (trade name: High Pressica UF, particle size 6.5 ± 0.1 μm, refractive index 1.43, Ube Nitto Kasei Co., Ltd.) 1 part ・ Toluene 200 parts

[Blending of base paint]-Acrylic compound 1,6 hexanediol dimethacrylate 45 parts Pentaerythritol triacrylate hexamethylene diisocyanate 45 parts-Photopolymerization initiator 5 parts (trade name: Irgacure 184, manufactured by Ciba Geigy)-Isopropyl Alcohol 10 parts

<Example 6> A paint obtained by mixing the following dispersion liquid and a base paint in the same manner as in Example 1 was applied to a film having a thickness of 75 μm.
One side of a transparent substrate polyethylene terephthalate film having a transmittance of 89% was applied by a reverse coating method, and thereafter the same procedure as in Example 1 was performed to obtain an antireflection material of the present invention. The thickness and refractive index of the roughened layer are 2.5 μm and 1.51, respectively, and the critical surface tension of the surface layer is 1
1.0 dyne / cm, the HAZE value and the reflectance of the antireflection material were 9.0 and 1.4%, respectively.

[Blending of Dispersion] 3 parts of crosslinked acrylic beads (trade name: MX300, particle size 3.0 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 Kyoei Chemical Co., Ltd.) 2 parts of cationic polymerization initiator (trade name: MPI03, manufactured by Midori Kagaku) ・ 5 parts of isopropyl alcohol

Comparative Example 1 The procedure of Example 1 was repeated except that the dispersion and the base paint were changed as follows.
Forming a roughened layer with a refractive index of 1.52, without providing a surface layer,
A comparative antireflection material having a HAZE value of 13.2 and a reflectance of 2.6% was obtained.

[Blending of dispersion] 5 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] ・ Acrylic compound 1,6 hexanediol dimethacrylate 45 parts Pentaerythritol triacrylate hexamethylene diisocyanate 45 parts ・ Photopolymerization initiator 5 parts (trade name: Irgacure 184, Ciba-Geigy) ・ Isopropyl Alcohol 10 parts

(Comparative Example 2) A thickness of 3.0 μm, a HAZE value of 35.0, and a reflectance of 2 were obtained in the same manner as in Example 1 except that the kind and the amount of the crosslinked acrylic beads of the roughened layer were changed as follows. A 0.0% comparative anti-reflective material was obtained. The critical surface tension of the surface layer was 22 dyne / cm.・ 20 parts of crosslinked acrylic beads (trade name: MX300, particle size 3.0 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.)

Comparative Example 3 The procedure of Example 3 was repeated, except that the following pigments were used for the acrylic beads in the roughened layer, the thickness was 3.0 μm, the HAZE value was 29.0, and the reflectance was 1.1%. Comparative antireflection material was obtained. The critical surface tension of the surface layer was 23 dyne / cm. -Silica pigment (trade name: Sylysia # 456, manufactured by Fuji Silysia Chemical Ltd., particle size: 0.5 to 6.0 [mu] m, 50% Particle size: over 6.0 [mu] m, 40%)

(Comparative Example 4) Thickness 80 μm, transmittance 92%
Was used as an anti-reflection material for comparison. The critical double-sided tension of the surface is 36 dyne
/ Cm.

Comparative Example 5 A comparative antireflection material having a critical surface tension of 42 dyne / cm was obtained in the same manner as in Example 1 except that the surface layer paint having the following composition was used. HA of anti-reflective material
The ZE value was 11.3 and the reflectance was 1.3%. [Blending of surface layer paint] ・ Silica sol (Ethanol dispersion containing 30% by weight of ultrafine silica particles as SiO ₂ with a particle diameter of 15 nm) 10 parts ・ Film forming agent (Calculated as hydrolyzate SiO ₂ of tetraethoxysilane) 15% solid solvent 53 parts

Comparative Example 6 A comparative antireflection material having a critical surface tension of the surface layer of 25 dyne / cm was obtained in the same manner as in Example 1 except that the dispersion and the base paint were changed as follows. The thickness of the roughened layer is 3.0 μm, and the refractive index is 1.
The anti-reflection material had a HAZE value of 2.3 and a reflectance of 1.9%. [Blending of dispersion]-2 parts of crosslinked acrylic beads (trade name: MX300, particle size: 3.0 [mu] m ± 0.5, manufactured by Soken Chemical Co., Ltd.)-100 parts of toluene [Blending of base paint]-Polyester-based thermoplastic resin 40 (Product name: Byron 200, manufactured by Toyobo) 70 parts of toluene 100 parts of MEK

Using the anti-reflection materials 10 obtained in Examples 1 to 6 and Comparative Examples 1 to 6, anti-glare properties, image glare, reflectance, abrasion resistance, chemical resistance, critical surface tension, contamination resistance The properties were measured and evaluated by the following methods.

Using the antireflection material 10, a polarizing film 20 having the structure shown in FIG. 2 was produced. Next, as shown in FIG.
3 to obtain a liquid crystal display 30. Example 6
With respect to the antireflection material 10 obtained in the above, 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 PET surface side was the lamination surface. As shown in FIG.
6 to obtain a liquid crystal display 40. The image size of each liquid crystal display 30 was, for example, 10.4 inches and the resolution was, for example, 800 × 600 dots, and the image contrast was evaluated by the following method.

The anti-glare property was measured by an image clarity measuring device I manufactured by Suga Test Instruments Co., Ltd.
The measurement was performed using a CM-1DP (JIS K7105) in a transmission mode with an optical comb width of 2 mm. The smaller the measured value, 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.
Image glare was measured in the transmission mode with an optical comb width of 0.125 mm using the same measuring device as used for the evaluation of the antiglare property. The larger the measured value, the less the image glare. Here, 1
0% or more was evaluated as ○, 5% or more and less than 10% as Δ, and less than 5% as X. The reflectance was measured using a spectrophotometer UV3100 (manufactured by Shimadzu Corp.), measuring 5 ° regular reflection in a wavelength range of 400 to 700 nm, and expressed as a Y value corrected for visibility according to JIS Z8701. The measurement was performed by completely painting the non-measurement surface with black magic.

The abrasion resistance was determined by attaching steel wool # 0000 manufactured by Nippon Steel Wool Co. to a paperboard abrasion tester (manufactured by Kumagaya Riki Kogyo Co., Ltd.) and applying a load of 2 to the surface layer of the anti-reflective material.
Reciprocate 50 times at 00g. Then, HA of that part
The change δH of the ZE value (based on the following calculation) was measured by a HAZE meter manufactured by Toyo Seiki. The larger the measured value, the worse the wear resistance. The measurement of the HAZE value was performed using the antireflection material alone. HAZE value change δH = HAZE value after test-H before test
AZE value

The chemical resistance was evaluated as x when there was a remarkable change such as peeling of the roughened layer after rubbing the surface layer surface with a cotton swab (manufactured by Johnson) containing isopropyl alcohol for 50 reciprocations. The case was evaluated as ○, and the middle was evaluated as Δ. The critical surface tension is determined by measuring the contact angle of the surface layer of the anti-reflective material with water and methylene iodide by the Wilhelmy method, and substituting into the following equation described in Basic Science of Coating (published by Yuji Harasaki, published by Maki Shoten) pp. 170-171. Zism
from am plot, it was determined from the value of γ _{LV °} extrapolated to COSθ-1. COS θ = 1 + b (γ _c −γ _{LV ゜} ) where γ _{LV ゜} ≧ γ _c θ: contact angle of solid / liquid, γ _{LV ゜} : surface tension of liquid, γ _c : critical surface tension, b: constant

As for the stain resistance, one drop of rapeseed oil was dropped on the surface of the surface layer with a dropper, and the dropped rapeseed oil was rubbed 20 times with a Bencott made by Asahi Kasei Corporation containing ligroin. After that, take a SEM photograph of the wiped surface,
The presence or absence of scratches on the surface and adhesion of Bencott fibers were checked. The case where scratches and fibers of Bencott fibers were remarkably observed on the roughened layer was evaluated as x, the case where there was no change was evaluated as ○, and the middle was evaluated as Δ. Screen contrast is JIS C7072 1988
The evaluation was made in accordance with the method for measuring the contrast ratio (CR) of the liquid crystal display panel in the above. FIG. 4 shows a positional relationship between the light source 101, the liquid crystal panel, and the photometer 104 in the evaluation of the image contrast. In this case, the distance between the light source 101 and the liquid crystal panel 2 was set to, for example, 1 cm, the distance between the liquid crystal panel 2 and the photometer was set to, for example, 50 cm, and the aperture angle of the photometer was set to, for example, 5 °. The light source used was 5 W EL, and the photometer used was LS-100 manufactured by Minolta Camera. CR is 4
The above cases are indicated by ◎, the cases of 3 or more and less than 4 are indicated by ○, the same,
A case of 2 or more and less than 3 was evaluated as Δ, and a case of less than 2 was evaluated as ×. Table 1 shows the evaluation results.

[0086]

[Table 1]

As is clear from the results shown in Table 1, all the antireflection materials of the present invention obtained good characteristics, whereas all of the antireflection materials of Comparative Examples had a critical surface tension of 2%.
Since it is larger than 0 dyne / cm, there is a problem with stain resistance.
Have. In addition, Comparative Example 2 is inferior in transparency and image contrast due to the large content of filler, and Comparative Example 3 is inferior in image contrast due to large filler particle size and has a glare problem. Comparative Example 4 had problems of antiglare property and abrasion resistance because the roughened layer and the surface layer were not provided. Further, Comparative Example 6 had heat-resistant resin instead of curable resin in the roughened layer. Since the plasticized resin is used, it has poor wear resistance and chemical resistance.

[0088]

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. Anti-reflective materials and polarizing films that can provide clear images without glare without optical glare, exhibit optically stable, excellent wear and chemical resistance, and have excellent stain resistance. 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: first protective material, 24: polarizing substrate, 25: second 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… Polarized film, 60…
Light source, 61: liquid crystal panel, 62: photometer.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI G02B 5/30 G02F 1/1335 G02F 1/1335 G09F 9/00 318A G09F 9/00 318 H01J 5/16 H01J 5/16 G02B 1 / 10 A (72) Inventor Kazuhiro Yamazaki 3-1 Yosoba-cho, Shizuoka-shi, Shizuoka Pref. In the Information Media Division of Hamikawa Paper Mill Co., Ltd. (72) Inventor Masanori Sakumoto No. 3 at Yomune-cho, Shizuoka-shi, Shizuoka No. 1 In the Information Media Division of Hamakawa Paper Mill, Ltd. (56) References JP-A-6-273740 (JP, A) JP-A-9-236702 (JP, A) (58) Fields investigated (Int. Cl. ^7, DB name) G02B 5/02 G02B 1/11 G02B 5/30

Claims (6)

(57) [Claims] 1. An anti-reflective material having a roughened layer and a surface layer sequentially provided on one or both surfaces of a transparent substrate, directly or via another layer, has a critical surface tension of 20%.
dyne / cm or less, wherein the roughened layer comprises a resin and a spherical filler that are cured by at least one of radiation and heat or a combination thereof, and is an antireflective material. 2. The anti-reflection material according to claim 1, wherein the spherical filler is a crosslinked acrylic bead. 3. The method according to claim 1, wherein the resin is at least an acrylic compound.
2. The anti-reflection material according to claim 1 , wherein the anti-reflection material is an ultraviolet curable resin containing a substance, an epoxy compound and a cationic photopolymerization initiator. 4. The method according to claim 1, wherein the resin is at least an epoxy compound.
UV containing a cationic photopolymerization initiator represented by the following chemical formula
The resin according to claim 1, wherein the resin is a line-curable resin.
Anti-reflective material. Embedded image 5. The particle diameter D of the spherical filler is 0.5 μm.
60% by weight or more of particles in the range of m ≦ D ≦ 6.0 μm;
Less than 20% by weight of particles in the range of 6.0 μm <D ≦ 10.0 μm, 5% by weight or less of particles in the range of 10.0 μm <D ≦ 15.0 μm, and more than 1% of particles larger than 15.0 μm. The anti-reflection material according to claim 1, wherein the anti-reflection material has a particle size distribution of 0% by weight or less. 6. A transparent substrate-side surface of a first protective material having a roughened layer and a surface layer sequentially provided on one surface of a transparent substrate directly or through another layer. In a polarizing film on which a second protective material is laminated, a critical surface tension of the surface layer is 20 dyne / cm or less, and a resin and a spherical filler in which the roughened layer is cured by at least one of radiation and heat or a combination thereof. A polarizing film, comprising: