JPH11209717A - Coating material for coating on film, anti-reflection film using the same, polarized film, and coating on film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coated film that has a largely increased adhesion to a transparent substrate, retains high reliability even under the conditions of high temperature and humidity and shows excellent optical characteristics, abrasion resistance and chemical resistance. SOLUTION: An anti-reflecting material is prepared by forming surface- roughened layers 12 on one or both faces of a transparent substrate 11. The transparent substrate is made of a triacetylcellulose(TAC) resin, a saponified triacetyl-cellulose(TAC) resin, a polycarbonate or an acrylic resin, while the roughened layer 12 is coated with a coating material containing methyl isobutyl ketone(MIBK) as a main solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display (LC).
D), plasma display (PDP), CRT, EL
It is preferably used for an image display body such as an antifouling property of an image portion,
The present invention relates to a technology that is excellent in antireflection, chemical resistance, and abrasion resistance, and in particular, improves durability in a high-temperature, high-humidity environment such as a vehicle-mounted image display.

[0002]

2. Description of the Related Art Many film products are used for image display devices (hereinafter referred to as displays) typified by LCDs, PDPs, CRTs, and ELs, and for optical products such as sunglasses, goggles, and helmet shields. In particular, displays include televisions, computers, mobile phones, PH
It is applied to various fields such as S and car navigation, and is expected as a large market for film products.

In this field, attention has recently been paid to antireflection films used on display surfaces of notebook computers and the like. As for the anti-reflection, conventionally, a scattered or scattered light, such as frosted glass, has been generally used for a blurred image. In order to scatter or diffuse light, it is fundamental to roughen the light incident surface, and this roughening treatment involves directly roughening the surface of the transparent substrate by sandblasting or embossing. , A method of providing a coating layer containing a filler on the surface of the transparent substrate, and a method of forming a porous film having a sea-island structure on the surface of the transparent substrate.

A method of providing a surface-roughened layer containing a filler on the surface of a transparent substrate can relatively easily control the size of the irregularities on the surface of the surface-roughened layer by controlling the particle size and the content of the filler. Currently, because of the advantages such as easy manufacturing,
It is used favorably. 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. Therefore, UV curable resins are preferably used. As an example, Japanese Patent Application Laid-Open No. HEI 1-105 having UV curable resin and silica pigment as constituents
738 and JP-A-5-162261 have been reported.

In order to further improve the antireflection effect, a layer having a lower refractive index than the roughened layer is provided on the roughened layer, or a material having a higher refractive index and a material having a lower refractive index are alternately laminated. There are known ways to do this. Mg as a material having a low refractive index
Materials having a high refractive index such as F and SiO ₂ are TiO ₂ ,
ZrO _{2 and the} like can be mentioned, and these materials are usually formed by a vapor phase method such as vapor deposition or sputtering, or a sol-gel method.

[0006]

By the way, as a material for a transparent substrate, triacetyl cellulose (hereinafter abbreviated as TAC) has conventionally been used because it is inexpensive and has excellent optical characteristics and reliability in various environments. , Polycarbonate,
Acrylic resins are frequently used, but the adhesion between these transparent substrates and the roughened layer has been a problem. That is, in recent years,
Anti-reflection films are used in car televisions, car navigation displays, and the like, which are rapidly spreading, and extremely large changes in temperature and humidity are repeated in passenger cars. However, these transparent substrates have inherently poor adhesion to the resin constituting the roughened layer, and have a TAC
Etc. have a high coefficient of thermal expansion and high hygroscopicity,
There is a drawback that the dimensions easily change due to changes in temperature and humidity. Therefore, high stress is generated between the roughened layer formed rigidly to increase the wear resistance, and serious troubles such as peeling of the roughened layer occur, which has a problem in durability. there were.

Conventionally, a resin, which is a material of a roughened layer, is dissolved in, for example, an aromatic solvent or an alcohol-based solvent to form a paint, which is applied to a transparent substrate.
It has been found that such a solvent has poor adhesion to a transparent substrate and is not suitable for use in vehicles and the like in terms of reliability. On the other hand, it is conceivable to use a highly polar solvent such as methyl ethyl ketone or ethyl acetate in order to enhance the adhesion, but such a solvent has no problem in terms of the adhesion, but the surface of the above-mentioned transparent substrate is not effective. As a result, there is a problem that the optical characteristics of the antireflection material are deteriorated.

[0008] Further, as the resolution of the display has been improved, the height and spacing of the unevenness of the roughened layer have also been required to be more dense. 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 antireflection properties and no glare, first, the height and spacing of the unevenness must be controlled to be small and uniform.

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 has been a problem that the fillers in the layer stick to each other to cause agglomeration (orange peel) and a sufficient resolution cannot be obtained. In particular, for the purpose of densifying irregularities on the surface of the roughened layer, increasing the content of the filler, or diluting the coating material of the roughened layer with a solvent or the like in order to control the thickness of the roughened layer. Was particularly remarkable.

The present invention has been made in view of the above-mentioned circumstances in the prior art, and has a high adhesion to TAC, PC, and acrylic resin films, and does not affect the film surface. The purpose is to provide a coating method for coating. In addition, the present invention has a high adhesion strength between the transparent substrate and the roughened layer, has sufficient reliability for use in vehicles, and reflects external light such as sunlight and fluorescent lights on a display. By exhibiting excellent anti-reflective properties, and without deteriorating the image contrast, it is possible to obtain a clear image free of glare and the like, which is optically stable and exhibits excellent chemical resistance. It is intended to provide an anti-reflective material. Further, an 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]

A. Means for Solving the Problems First, the inventors of the present invention have repeatedly studied the solvent of the paint in order to increase the adhesion strength between the TAC transparent substrate and the paint to be applied thereto. As a result, the solvent of the paint was methyl isobutyl. In the case of ketone (hereinafter, abbreviated as MIBK), it has been found that the surface of the transparent substrate is slightly affected, and there is no influence on optical characteristics, and that the adhesion strength is greatly increased. The present inventor has focused on such characteristics of MIBK and has studied other transparent substrates as a result. As a result, a transparent substrate composed of polycarbonate and acrylic resin,
Furthermore, it has been found that the same effect can be obtained also when the transparent substrate is saponified.

The present invention has been made based on the above findings, and is directed to a transparent substrate made of a TAC-based, polycarbonate or acrylic-based resin, and a paint for coating the transparent substrate obtained by saponifying the transparent substrate. It is characterized in that the solvent of the paint is mainly made of MIBK. The solvent may be MIBK alone, or a mixture of MIBK with one or more aromatic solvents such as toluene and xylene, and alcoholic solvents such as methanol, ethanol, isopropanol, ethyl cellosolve and butyl cellosolve. Is also good. However, in order to obtain the desired adhesion to the film, the content of MIBK in the solvent must be 10% or more by weight, preferably 40% or more. Further, it is preferable not to mix a solvent having a large polarity such as methyl ethyl ketone or ethyl acetate. Transparent substrate is TA
In the case of C, saponified TAC, the effects of the present invention are further exhibited because of high thermal expansion coefficient and high hygroscopicity. Hereinafter, a preferred embodiment of the coating material for film coating according to the present invention will be described with reference to a coating material for forming a roughened layer of an antireflective material.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as a transparent substrate on which a roughened layer is applied, a transparent film composed of a TAC-based, polycarbonate, or acrylic-based resin is used. Specifically, TAC films such as TAC and saponified TAC, polycarbonate films, and acrylic or homo- or copolymers of acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, acrylonitriles, etc. System film. Various resins can be used for the surface roughening layer, but they do not require heating during coating and have excellent durability such as abrasion resistance, heat resistance and chemical resistance. Resins are preferably used. Transparent substrate is saponified T
In the case of AC, it is more effective to include an ultraviolet curing resin containing an epoxy compound and a cationic photopolymerization initiator in the resin which is a main component of the paint. 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 advantage of forming a roughened layer by using such an ultraviolet-curable resin in a coating is as follows when compared with the case of using a conventional radical-reaction-type ultraviolet-curing resin in a coating.

Good adhesion to the transparent substrate. In particular, since the conventional resin system for forming a roughened layer has excellent adhesion to a saponified TAC substrate, which hardly adheres, a laminate in which a polarizing substrate, a transparent substrate, and a roughened layer are firmly adhered. You can get the body. Less oxygen inhibition. Very little cure shrinkage. Excellent pigment dispersibility.

Examples of the epoxy compounds include glycidyl ethers such as tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether, and 2-hydroxy-glycidyl 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.

[0016]

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.

[0018]

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 hardening of the roughened layer using the ultraviolet-curable resin is 20
% Is desirable. When the volumetric shrinkage is more than 20%, the curl becomes remarkable when the transparent substrate is a thin film, and when the transparent substrate is a thick and rigid film or a rigid plate-like transparent substrate such as glass, a roughened layer is formed. Of the adhesive decreases.

[0022]

## 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. The transparency of the antireflection material is affected by the refractive index of the ultraviolet curable resin, but the refractive index is 1.4.
The range of 5 to 1.70 is preferable, and if it exceeds this range, the antireflection effect is impaired.

The antireflection effect can be improved by adding a filler to the paint and roughening the surface of the formed roughened layer. 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.
In the range of 0 μm, 5% by weight or less, 15.0 μm <D
Is desirably 1% by weight or less. Further, the particles satisfying 15.0 μm <D 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 or more, glare occurs in the image on the display. The amount of the filler is preferably in the range of 0.5 to 30% in terms of the total solids weight ratio of the roughened layer. In particular, a range of 1 to 15% is preferable. The blending amount is 0.
If it is 5% or less, the antireflection effect becomes insufficient. If it is 30% or more, not only the transparency and the contrast of the image are deteriorated, but also the durability such as abrasion resistance and environmental resistance is deteriorated. Also,
Refractive index of filler (B method according to JIS K-7142)
Is preferably equivalent to an ultraviolet curable resin. When the refractive index of the filler is different from the refractive index of the ultraviolet 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 a refractive index equivalent to that of the ultraviolet 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 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. 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.

B. Content of Coating Method The method of applying a coating material to the film of the present invention includes a transparent substrate composed of TAC, polycarbonate or acrylic resin, and a saponification treatment of such a transparent substrate. It is characterized by using a paint mainly composed of isobutyl ketone. Specifically, the solvent of the present invention and a filler such as cross-linked acrylic beads are mixed into the above-described ultraviolet-curable resin, if necessary, and the mixture is paint shaker, sand mill, pearl mill, ball mill, attritor, roll mill. , Dispersed by a high-speed impeller disperser, jet mill, high-speed impact mill, ultrasonic disperser, etc. into a paint or ink, which is then coated with air doctor, blade, knife, reverse, transfer roll, gravure roll, Kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, electrodeposition coating, dip coating,
One or both sides of the transparent substrate by a printing method such as coating such as die coating, letterpress printing such as flexographic printing, intaglio printing such as direct gravure printing, offset gravure printing, lithographic printing such as offset printing, and stencil printing such as screen printing. In the case where a solvent is contained in a single layer or a multilayer, a method of obtaining a coating layer or a printing layer by curing the coating layer or the printing layer by irradiating ultraviolet rays through a heat drying step may be used. 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 coating suitability or printing suitability of the paint, if necessary, a leveling agent such as silicone oil, polyethylene wax, carnauba wax, oils and fats such as higher alcohols, bisamides and higher fatty acids, and curing agents such as isocyanates and the like. , Calcium carbonate or silica sol,
Additives such as ultrafine particles of 0.1 μm or less such as 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 exemplified in the description of the antistatic layer described below can be applied as they are.

When the coating is applied as a roughened layer, the thickness in a dry state is in the range of 0.5 to 10 μm, preferably 1 to 5 μm. When the surface roughening layer is thinner than 0.5 μm, the abrasion resistance of the surface roughening layer deteriorates, and curing failure occurs due to 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.

C. Contents of Antireflective Material The antireflective material of the present invention can be obtained by applying the above-mentioned paint to one or both surfaces of a transparent substrate. The higher the transparency of the transparent substrate, the better, but the light transmittance (JISC-6714) is preferably 80% or more, more preferably 90% or more. The thickness of the transparent substrate is desirably thin from the viewpoint of weight reduction. However, in consideration of productivity, it is preferable to use a transparent substrate having a thickness of 1 μm to 5 μm. Further, it is preferable that the transparent substrate is subjected to a surface treatment such as a corona treatment, a plasma treatment, a fluorine treatment and a sputtering treatment, or 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. Specifically, 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 adhering electrostatically 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.

In the present invention, a surface layer can be provided on the roughened layer as needed in order to obtain a better antireflection function. The surface layer may be provided as a single layer or a plurality of layers. In the case of a single layer, a material having a lower refractive index than that of the roughened layer is used, and when a plurality of layers are laminated, a material having a higher refractive index and a material having a lower refractive index than the roughened layer are alternately formed on the roughened layer. Provided. A layer made of a material having a low refractive index is called a low refractive index layer, and a layer made of a material having a high refractive index is called a high refractive index layer. Hereinafter, these layers will be described in detail.

(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 resin, polyether resin, acrylic resin, epoxy resin, alkyd resin, polybutadiene resin, spirol acetal resin, urethane resin and polyhydric alcohol. 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, acetylenones, benzophenones, α-amyloxime ester, Michler benzoyl benzoate, tetramethylthiuram monosulfide, thioxanthone, and the like are used as photopolymerization initiators. 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), TiO2 (n = 2.3-2.
7) By containing fine particles of CeO2 (n = 1.95), an effect of shielding ultraviolet rays can be obtained. Also,
By containing fine particles of SnO2 (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 Al2O3
(N = 1.63), La2O3 (n = 1.95), Zr
O2 (n = 2.05), Y2O3 (n = 1.87) and the like can be mentioned. 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.

The high refractive index layer is made of, for example, Zn as described above.
After the high refractive material such as O is vapor-phase method such as CVD, sputtering and vapor deposition, or the high refractive material is diluted in a solvent and provided on the roughened layer by a method such as spin coater, roll coater, printing, and then dried. It can be provided directly on the surface-roughened layer by a method of curing with heat, radiation or the like (in the case of ultraviolet rays, the above-mentioned photopolymerization initiator is used). In this case, the thickness of the high refractive index layer after drying is 0.05 to 0.15.
The coating thickness is adjusted so as to be μm. When the thickness of the high refractive index layer is out of this range, the antireflection effect is 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. The composition of the low refractive index layer is not particularly limited, but it is preferable that the composition is such that the 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. Materials having these characteristics include, for example, LiF (refractive index n = 1.4), MgF 2 (n
= 1.4), 3NaF.AlF3 (n = 1.4), Al
F3 (n = 1.4) Na3AlF6 (n = 1.33) S
Inorganic materials such as iO2 (n = 1.45) are made into fine particles, and inorganic low-reflection materials, fluorine- or silicone-based organic compounds, thermoplastic resins, and thermosetting resins are contained in acrylic resins and epoxy resins. Organic low-reflection materials such as resins and radiation-curable resins can be used. Among them, a fluorine-based fluorinated material is particularly preferable in terms of preventing contamination.

Examples of the fluorine-containing material include vinylidene fluoride copolymers, fluoroolefin / hydrocarbon olefin copolymers, fluorine-containing epoxy resins, and fluorine-containing epoxy acrylates 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 obtained by mixing 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 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
It contains a solid content of 0.5 to 50% by weight as iO2. 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, alkoxysilanes, hydrolysates of metal alkoxides and metal salts, fluorine-modified polysiloxanes, 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 an acrylic resin, 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 surface layer to exhibit a good antireflection function can be calculated by a known formula. Known literature (Science Library, Physics 9
According to “Optics” on pages 70 to 72), when incident light is perpendicularly incident on the surface layer, the surface layer does not reflect light, and
It is considered that the condition for transmitting 0% should satisfy the following relational expression. In the formula, N _O indicates the refractive index of the surface layer, Ns indicates the refractive index of the roughened layer, h indicates the thickness of the surface layer, and λ _O indicates the wavelength of light.

[0046]

N _O = Ns ^1/2 Equation (1) N _O h = λ _O / 4 Equation (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 the formula, 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 55.
0 nm (standard of visibility), and these values are referred to in the above (2).
By substituting into the equation, it is calculated that the optimal thickness of the surface layer is about 0.1 μm, preferably in the range of 0.10 ± 0.01 μm.

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.

[0049]

Haze value = Hd / Ht × 100

D. Contents of Polarizing Film The polarizing film of the present invention can be obtained by laminating a protective material via a polarizing substrate on the other surface of the antireflective material having the above structure, on which the roughening layer of the transparent substrate is not provided. it can. The polarizing substrate is made of a material having transparency,
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 PVA film is uniaxially
PV stretched about 4 times and stretched into higher-order iodine ions
A polarizing substrate can be obtained by impregnating the A film.

The PVA film obtained above has the disadvantage 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. A transparent substrate and a protective material of the 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.

As the protective material, a transparent polymer compound film, for example, a cellulose 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. In addition, by using a gelling agent such as boric acid in these films, or by performing a heat treatment or formalization,
It is preferable to improve the water resistance of the film. Also,
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 is 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. 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, in which a transparent substrate 21 and a roughened layer 2 are provided on one surface of a polarizing substrate 24.
2 is provided, and the polarizing substrate 2 is provided.
4 shows that the protective material 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 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 back light source, both surfaces of the polarizing substrate 24 are protected by an antireflection material 23 having a roughened layer 22 and a protective material 25 shown in FIG. Polarizing film 36, and on the back light source side,
The liquid crystal panel 31 is formed by attaching the polarizing film 37 without the 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 crosslinked acrylic beads, MIBK, and toluene in a sand mill for 30 minutes, and a coating obtained by stirring and mixing the following base coating with a disper for 15 minutes, Thickness 80
Saponified TA, which is a transparent substrate having a transmittance of 92%
On one side of C, apply by reverse coating method,
After drying at 100 ° C for 2 minutes, UV lamp output 120w / c
m using a single condensing high-pressure mercury lamp with an 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 UV lamp on the coating substrate side) of 5 m / min. The coating was cured. Thus, a roughened layer having a thickness of 2.5 μm and a HAZE value of 16.5 was formed. Thereafter, a surface layer paint having the following composition was applied on the surface-roughened layer by reverse gravure coating.
After drying and curing at 20 ° C. for 6 hours, a surface layer having a thickness of 0.1 μm was formed to obtain an antireflection material of the present invention.

[Blending of dispersion liquid] 9 parts of crosslinked acrylic beads (trade name: MX150, particle size 1.5 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 100 parts of MIBK 110 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

[0061]

Embedded image

• 5 parts of isopropyl alcohol [Blending of surface layer paint] • 10 parts of silica sol (ethanol dispersion containing 30% by weight of silica particles as SiO ₂ with a particle diameter of 15 nm) • 15 parts of film forming agent (tetra Hydrolysis product of ethoxysilane: 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 was obtained.

[Blending of dispersion liquid] 14 parts of crosslinked acrylic beads (trade name: MX300, particle size 3.0 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 210 parts of MIBK

[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 roughened layer was changed as follows, and the thickness was 3.8 μm.
An antireflection material having a roughened layer having an AZE value of 13.0 was obtained.

[Blending of Dispersion] Crosslinked acrylic beads (trade name: MX300, particle size 1.5 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 5 parts (trade name: MX300, particle size 3.0 μm ± 0. 5, manufactured by Soken Chemical Co., Ltd.) 5 parts ・ MIBK 100 parts ・ IPA 50 parts ・ Toluene 50 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 was obtained.

[Blending of dispersion] Cross-linked 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 ・ MIBK 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 was obtained.

[Blending of Dispersion] 3 parts of crosslinked acrylic beads (trade name: MX300, particle size 1.5 μm ± 0.5, manufactured by Soken Kagaku) ・ 80 parts of MIBK ・ 60 parts of ethyl cellosolve ・ 60 parts of xylene

[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 Polymerization initiator 2 parts (trade name: MPI03, manufactured by Midori Kagaku) ・ Isopropyl alcohol 5 parts

Example 6 Saponified TAC as Transparent Substrate
In the same manner as in Example 1 except that a polycarbonate film was used in place of the above, an antireflection material was obtained.

Example 7 Saponified TAC as Transparent Substrate
An antireflection material was obtained in exactly the same manner as in Example 1 except that an acrylic resin (methyl methacrylate-styrene copolymer) film was used instead of the above.

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 anti-reflection material having a roughened layer having an AZE value of 11.0 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> A 4.2 μm-thick H layer was prepared in the same manner as in Example 1 except that the composition of the roughened layer was changed as follows.
An antireflection material having a roughened layer having an AZE value of 17.5 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 A film having a thickness of 3.0 μm and a thickness of 3.0 μm was prepared in the same manner as in Example 5 except that the composition of the roughened layer was changed as follows.
An antireflection agent having a roughened layer having an AZE value of 13.0 was obtained. [Blending of dispersion liquid] 2 parts of crosslinked acrylic beads (trade name: MX300, particle size 3.0 μm ± 0.5, manufactured by Soken Chemical Co., Ltd.) 100 parts of cyclohexanone

[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 methyl ethyl ketone

Using the anti-reflection material 10 obtained in Examples 1 to 7 and Comparative Examples 1 to 4, 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. The image size of each of these liquid crystal displays is, for example, 10.
The image contrast, the image glare, and the anti-glare property were evaluated by the following methods with a 4-inch resolution of, for example, 800 dots × 600 dots.
The anti-reflective material was also evaluated for heat cycle resistance, wear resistance, and chemical resistance 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, a liquid crystal display was connected to a personal computer so that the opening screen of the paint brush of Windows version 3.1 could be displayed. Was evaluated by visual judgment. The case where less than 3 people felt glare was evaluated as ○, the case where 3 or more and less than 7 people felt glare, and the case where 7 or more people felt glare was evaluated 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.

Regarding the adhesion, after immersion in hot water at 60 ° C. for 500 hours, a cross cut test (JIS K-540) was conducted.
0), and observe whether or not the transparent substrate and the roughened layer are in close contact with each other. When there is no peeling (100/100), ○, when 99/100 to 90/100, Δ, 89 / 1
00 or less was evaluated as x.

In the abrasion resistance test, a steel wool # 0000 of Nippon Steel Wool was attached to a paperboard abrasion tester (manufactured by Kumagaya Riki Kogyo Co., Ltd.), and the roughened layer of the anti-reflective material was subjected to a load of 200 g. And reciprocated 50 times. afterwards,
Change δH of the HAZE value of that part (based on the following calculation)
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,
The measurement of the HAZE value was performed using the antireflection material alone. Also,
The change in HAZE value δH was calculated by dividing the HAZE value before the test from the HAZE value after the test. HAZE value change δH = HAZE value after test-H before test
AZE value

The chemical resistance was measured in the case where the surface of the roughened layer was remarkably changed, such as peeling off, after rubbing 50 times with a cotton swab (manufactured by Johnson Corporation) containing isopropyl alcohol. ×, no change was evaluated as ○, and the middle was evaluated as Δ.

[0094]

[Table 1]

As is clear from Table 1, MI was used as the solvent.
In Examples 1 to 5 using BK, even after the heat cycle test, the transparent substrate and the roughened layer were in close contact with each other, and the optical properties such as anti-glare properties and the durability were good. On the other hand, in Comparative Examples 1 and 3, since the solvent for the paint was only toluene, the roughened layer was all separated from the transparent substrate. In Comparative Example 4, although the peeling of the roughened layer did not occur,
The image contrast was degraded because the transparent substrate was affected by methyl ethyl ketone. In Comparative Examples 1 and 3, the dispersion of the filler was poor, causing a glare problem. In Comparative Examples 3 and 4, a problem occurred in the chemical resistance.

The coating material of the present invention is not limited to the above-mentioned antireflection materials, but can be applied to various transparent films such as photographic films and animation moving images.

[0097]

As described above, according to the coating material for film coating of the present invention, the adhesion strength to the transparent substrate can be increased, and the film has high reliability even under severe conditions of high temperature and high humidity. It is. Further, according to the antireflection material and the polarizing film of the present invention, in addition to such effects, excellent antireflection properties are exhibited by preventing reflection of external light such as sunlight and fluorescent lights on the display. In addition, a clear image without glare can be obtained without lowering the image contrast, and excellent effects such as optically stable and excellent abrasion resistance and chemical 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: roughening layer, 23: antireflection material, 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, 60 light source, 61 liquid crystal panel, 62 photometer.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification code FI C09D 5/00 C09D 5/00 C C09J 133/00 C09J 133/00 169/00 169/00 G02B 1/11 G02B 5/02 B 5/02 5/30 5/30 G02F 1/1335 G02F 1/1335 G09F 9/30 312Z G09F 9/30 312 314A 314 317 317 317 G02B 1/10 A

Claims (7)

[Claims] 1. A film coating paint characterized in that a paint applied to a transparent substrate composed of a triacetyl cellulose, polycarbonate or acrylic resin contains at least methyl isobutyl ketone. 2. A coating method for coating a transparent substrate composed of a triacetylcellulose, polycarbonate or acrylic resin, wherein a coating containing at least methyl isobutyl ketone is used. Coating method. 3. An antireflection material having at least one surface roughening layer on one or both sides of a transparent substrate, wherein the transparent substrate is made of a triacetylcellulose-based, polycarbonate-based or acrylic-based resin. The layers are
An anti-reflection material, which is coated with a paint containing at least methyl isobutyl ketone. 4. The transparent substrate is made of saponified triacetyl cellulose, and the surface roughening layer contains an ultraviolet curing resin containing an epoxy compound and a cationic photopolymerization initiator. 4. The anti-reflection material according to 3. 5. The anti-reflection material according to claim 3, wherein the surface roughening layer comprises the ultraviolet curable resin and a spherical filler. 6. The particle diameter D of the spherical filler is 0.5
60% by weight or more of particles in the range of μm ≦ D ≦ 6.0 μm;
Less than 20% by weight of particles in the range of 6.0 μm <D ≦ 10.0 μm, less than 5% by weight of particles in the range of 10.0 μm <D ≦ 15.0 μm, and 1.0% The anti-reflective material according to claim 5, having a particle size distribution of not more than% by weight. 7. A protective material is laminated via a polarizing substrate on the other surface of the anti-reflection material according to claim 3 on which the roughening layer is not provided. The polarizing film characterized by the above-mentioned.