JP2000187102A - Antireflection material and polarizing film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection material and a polarizing film which has a multilayered structure having a hard coating layer with high refractive index and excellent layer strength so that reflection of external light such as sun rays and light from a fluorescent lamp on a display is prevented, that each layer which constitutes the antireflection material has high strength and high wear resistance, and that when the film is used for a touch panel or the like, it has durability. SOLUTION: A hard coating layer 12 is formed directly or with other layers interposed on one or both surfaces of a transparent base body 11, and a surface layer which is extremely thin and has a lower refractive index than the refractive index of the hard coating layer 12 is formed on the surface of the hard coating layer 12. The hard coating layer 12 contains a polymer having a (meth) acrylate compd. having at least a fluorene skeleton as the polymer component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display (LCD), a plasma display (PDP),
The present invention relates to an antireflection material which is suitably used for an image display such as T, EL and the like, and is particularly excellent in antifouling property, antireflection, chemical resistance and abrasion resistance of an image portion, and a polarizing film using the same.

[0002]

2. Description of the Related Art Image display devices such as LCDs, PDPs, CRTs and ELs (hereinafter referred to as "displays") are widely used in various fields including televisions and computers, and are remarkable. Has evolved. In recent years, expectations are growing for the spread to mobile phones, PHS, and other various types of mobile terminals.

As displays for portable terminals, LCDs having features such as light weight, compactness and versatility are considered to dominate the market. However, these portable terminals are equipped with a touch panel and a plastic pen. What is operated by directly touching with a finger or a finger is becoming mainstream. 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 a strong demand for preventing reflection of external light such as sunlight or fluorescent light on a display, that is, antireflection. I have. At present, these demands are spreading not only to portable terminal devices but also to various displays ranging from small to large.

[0004]

In order to solve this problem, a high-refractive-index layer is laminated on the surface of a display, and a low-refractive-index layer is laminated thereon to form a multilayer structure. A method has been developed to reduce the reflectivity of the outermost surface. The material for the low refractive index layer is MgF or SiO _2, and the material for the high refractive index layer is Ti.
O ₂ , ZrO _{2 and the} like can be mentioned, and these materials are usually laminated by a vapor phase method such as vapor deposition or sputtering, or a sol-gel method. However, the vapor phase method is expensive in processing equipment and is not suitable for processing a large area, and the sol-gel method has a problem in economical efficiency because coating and firing are repeated. As a film forming method, there has been proposed a method of forming a film by a wet coating method. However, at present, film thickness control on the order of 10 nm required for characteristics is insufficient, and there are problems such as color unevenness (interference unevenness). Was.

On a transparent substrate such as polyethylene terephthalate (PET), a touch panel or the like operated by directly touching with a pen or a finger is provided, and an anti-reflection film provided with an anti-reflection layer as described above on this surface is attached. When used together, a high degree of wear resistance, chemical resistance, and contamination prevention are required. Usually, in order to satisfy these characteristics, the antireflection layer is provided with a hard coat layer. In order to improve the antireflection characteristics of the antireflection film, it is necessary to control the refractive index of this hard coat layer as well.

From an optical point of view, it is necessary to increase the refractive index of the hard coat layer and provide a layer having a lower refractive index than that of the hard coat layer. It is very difficult to satisfy durability such as abrasion resistance and chemical resistance as a film.

As the resin used for the hard coat layer, a transparent thermosetting resin, a thermoplastic resin, a radiation curing resin, or the like is usually used. Further, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like are added to these resins as needed. In order to increase the refractive index of the hard coat layer, it is performed by adding ultrafine particles having a high refractive index to the binder resin as a filler, or using a binder resin having a high refractive index, or using these together. It is done by that. However, when the content of the filler is increased to achieve a higher refractive index, the hardness of the hard coat layer decreases, and thus a problem occurs in durability. So, in this case,
It is desirable to use a binder resin having a low filler content and a high refractive index.

[0008] As a binder resin having a high refractive index,
Halogen atoms other than F, aromatic rings, or S, N, P
Resins containing a high refractive index component such as atoms can be used. However, while the above-mentioned resins have a high refractive index, they have a problem in stability in a paint, and are liable to be brittle, and have problems in scratch resistance, light resistance, coloring, and the like. Therefore, at present, a material suitable for forming a hard coat layer satisfying both high refractive index and durability has not been provided yet.

The present invention has been made in view of the above-mentioned circumstances in the prior art, and has a multi-layer structure including a hard coat layer having a high refractive index and excellent durability. And prevents reflection of external light such as fluorescent lamps, etc., exhibits excellent anti-reflection properties, and can provide clear images without glare without lowering image contrast, and are optically stable. The purpose of the present invention is to provide an anti-reflective material that has excellent chemical resistance, high strength of each layer constituting the anti-reflective material, excellent abrasion resistance, and durability even when used for a touch panel or the like. And 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.

[0010]

Means for Solving the Problems (1) Contents of antireflection material The present inventors studied a resin which is a main component of the hard coat layer in order to increase both the refractive index of the hard coat layer and the strength of the layer. As a result, it was found that it is extremely effective to use a (meth) acrylate compound having a fluorene skeleton as a polymerization component as a component contained in the resin. Therefore, the antireflection material of the present invention has been made based on the above findings, and provided on one or both surfaces of the transparent substrate, directly or via another layer, a hard coat layer, and the surface of the hard coat layer In an antireflection material provided with a surface layer having a refractive index lower than the refractive index of the hard coat layer, the hard coat layer contains at least a polymer containing a (meth) acrylate compound having a fluorene skeleton as a polymerization component. Features. Hereinafter, more preferred embodiments of the present invention will be described in detail.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Transparent substrate As the transparent substrate used for the antireflection material of the present invention, a known transparent film, glass, or the like can be used. Specific examples thereof include polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyarylate, polyimide, polyether, polycarbonate, polysulfone, polyethersulfone, cellophane, aromatic polyamide, polyethylene, polypropylene, and polyvinyl alcohol. Various resin films and glass substrates such as quartz glass and soda glass can be suitably used. When used for PDP and LCD, PET and TAC are preferred.

The higher the transparency of these transparent substrates, the better, but the light transmittance (JISC-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 desirably thin from the viewpoint of weight reduction, but in consideration of the productivity, it is 1 to 700 μm.
It is suitable to use those having a range of 25 to 250 μm.

The transparent substrate may be 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 Si vapor deposition. By doing so, the adhesiveness between the transparent substrate and the hard coat layer or another layer 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, or the like, and applying an antimony or the like to metal fine particles such as aluminum or tin or whisker or metal oxide such as tin oxide. Doped fine particles and whiskers, and fillers of charge transfer complexes formed between 7,7,8,8-tetracyanoquinodimethane and electron donors (donors) such as metal ions and organic cations are polyester. It can be provided by a method of dispersing in a resin, an acrylic resin, an epoxy resin or the like and providing by solvent coating or the like, or 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. Hard coat layer The hard coat referred to in the present invention is a pencil hardness test (JIS
K5400) showing hardness of H or more. Further, the high refractive index and the low refractive index referred to in the present invention refer to the relationship between the relative refractive indexes of adjacent layers. Next, the hard coat layer in the present invention will be described.
The resin composition of the hard coat layer of the present invention includes at least a (meth) acrylate compound having a fluorene skeleton represented by the following chemical formula 1 and / or a (meth) acrylate compound having a fluorene skeleton represented by the following chemical formula 2 (A Component) as a polymerization component, which contains a polymer obtained by polymerization using a polymerization initiator. In particular, in addition to the (meth) acrylate compound, a urethane (meth) acrylate compound represented by Chemical Formula 3 and A copolymer obtained by polymerizing a urethane (meth) acrylate compound (component B) represented by Chemical Formula 4 in combination as a copolymerization component is preferable. Less than,
These compounds will be described.

[0015]

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[0016]

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[0017]

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[0018]

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In the formula, R is a polyhydric alcohol residue, R₁Is water
Elemental atom, CH₃Or C₂H₅, R ₂Is a hydrogen atom or
CH₃, X is an isocyanate residue, Y is a polyhydric alcohol
Represents a residue. a and b are integers of 1 to 5, k is 2 to 5
An integer, l is an integer of 2-3, m is an integer of 1-2, n is 2
Represents an integer of 6.

As the (meth) acrylate compound having a fluorene skeleton of the component A, any of the compounds represented by Chemical Formula 1 or Chemical Formula 2 can be used. Particularly preferably, in formula 1, a and b are 1, and R ₁ and R ₂ are the most basic compounds of a hydrogen atom.

The urethane (meth) acrylate compound of the component B is represented by the following chemical formula (3) or (4). The urethane (meth) acrylate compound represented by Chemical Formula 3 is a compound containing a hydroxyl group (meth)
It is a compound having at least four (meth) acrylate groups in the reaction product of the acrylate compound and the polyisocyanate compound. The urethane (meth) acrylate compound of Chemical Formula 4 is a compound having at least four (meth) acrylate groups in a reaction product of a hydroxyl group-containing (meth) acrylate compound, a polyisocyanate compound, and a polyol compound. As a method for obtaining the urethane (meth) acrylate, any known method can be used.

Examples of the hydroxyl group-containing (meth) acrylate compound include glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate and the like. These can be used alone or in combination of two or more.

As the polyisocyanate compound, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethyl xylylene diisocyanate, biphenylene diisocyanate, 1,5-naphthylene diisocyanate, Polycondensation of o-tolidine diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebiscyclohexyl isocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, and burettes and nurates thereof Things can be mentioned. These can be used alone or in combination of two or more. Particularly preferred are a nulated product of tolylene diisocyanate, xylylene diisocyanate and hexamethylene diisocyanate, a nulated product of isophorone diisocyanate, and the like.

Examples of the polyol compound include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolpropane, and carboxylic acid-containing polyols, ethylene oxide of various bisphenols and propylene. An aromatic polyhydric alcohol such as an oxide reactant, an ethylene oxide and a propylene oxide reactant of bisphenolfluorene, and a (meth) acryloyl group in a molecule represented by Chemical formula 2 regardless of an aliphatic or aromatic compound Polyol. Particularly preferred are dimethylolpropionic acid, dimethylolbutanoic acid, bisphenoxyethanolfluorene and the like.

In addition to the compounds described above, acryloyl, methacryloyl, acryloyloxy and methacryloyloxy groups are used to control the properties of paints and coatings such as viscosity, crosslink density, heat resistance and chemical resistance. Monomers, oligomers having isomerizable unsaturated bonds,
A composition obtained by appropriately mixing a prepolymer can also be used. Examples of the monomer include styrene, methyl acrylate, cyclohexyl acrylate, lauryl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl acrylate. Monofunctional acrylates such as hydroxypropyl acrylate and 2-hydroxy-3-phenoxy acrylate, ethylene glycol diacrylate, 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, methyl methacrylate, 2-ethylhexyl methacrylate, n-stearyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, methoxypolyethylene methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxybutyl methacrylate; 6-hexanediol dimeta Relate, trimethylolpropane trimethacrylate, mention may be made of methacrylic acid derivatives, such as polyfunctional methacrylate such as glycerol dimethacrylate. As oligomers and prepolymers,
Examples include acrylates such as polyester acrylate, epoxy acrylate, polyether acrylate, Alkit acrylate, melamine acrylate, and silicone acrylate, unsaturated polyester, epoxy resin, and the like. These may be used alone or in combination. It is preferable to use a monofunctional (meth) acrylate-based monomer in order to lower the crosslinking density and to reduce the crosslink density, if the flexibility of the cured film is required. When severe durability such as heat resistance, abrasion resistance and solvent resistance is required for the film,
It is preferable to increase the amount of the monomer and use a trifunctional or higher functional (meth) acrylate monomer.

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

The refractive index of the resin for forming the hard coat layer can be increased by increasing the ratio of the component A. However, when the component B is used in combination, more excellent scratch resistance can be obtained. However, in order to improve the scratch resistance, B
Increasing the ratio of the components lowers the refractive index. For this reason,
The mixing ratio of the component A and the component B is preferably 20 to 90 parts by weight of the component A and 80 to 10 parts by weight of the component B when the total of both components is 100 parts by weight. Particularly preferably, 50 to 80 parts by weight of component A and 50 to 80 parts by weight of component B
0 parts by weight is good.

As the polymerization initiator, any one can be used without particular limitation as long as it generates an active radical by heat or energy rays such as visible light and ultraviolet rays. Specific examples include azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and organic peroxides such as benzoyl peroxide and lauroyl peroxide. Those which generate an active radical by energy rays include 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone,
Hydroxy-2-methyl-1-phenylpropane-1-
Acetophenones such as on, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin ethers such as benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-
4'-methyl-diphenyl sulfide, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-
Benzophenones such as propenyloxy) ethyl] benzenemethananium bromide and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2,4-diethylthioxanthone and 1-chloro-4-dichlorothioxanthone; -Trimethylbenzoyldiphenylbenzoyl oxide. These can be used alone or in combination of two or more. In addition, as an accelerator (sensitizer),
Amine compounds such as N, N-dimethylparatoluidine and 4,4′-diethylaminobenzophenone can be mixed and used. Further, stabilizers (thermal polymerization inhibitors) such as hydroquinone, p-benzoquinone, and t-butylhydroquinone may be added. The addition amount of these accelerators and stabilizers is 0.1 to
A range of 5.0% by weight is preferred.

In the resin for forming the hard coat layer, the ratio of the polymerization initiator is such that the total amount of the component A and the component B is 1
When the total amount is 100 parts by weight,
It is preferably 0.01 to 5 parts by weight, particularly preferably 1 to 3 parts by weight.
Parts by weight. If the amount of the polymerization initiator is too large, unreacted decomposition products of the polymerization initiator may cause a decrease in the strength of the layer or cause coloring of the resin. Conversely, if the amount is too small, the resin does not solidify. Further, in the case of a polymerization initiator using energy rays such as visible light and ultraviolet rays, a filler having absorption in the wavelength range of irradiation energy rays may be used. In this case, it is necessary to increase the ratio of the polymerization initiator. .

High refraction in binder resin of hard coat layer
Hard coat layer
Can be adjusted. Refractive index of the filler
Is relatively higher than the refractive index of the resin component of the hard coat layer.
High and in the range of 1.6 to 2.7
No. As a specific example of the filler, ZnO (refractive index n =
1.9), TiO₂(N = 2.3-2.7), CeO₂
(N = 1.95), Sb ₂O₅(N = 1.71), Sn
O₂(N = 1.95), ITO (n = 1.95), Y₂
O₃(N = 1.87), La₂O₃(N = 1.95),
ZrO₂(N = 2.05), Al₂O₃(N = 1.6
3), HfO₂(N = 2.0), Ta₂O₅Etc.
It is. These fillers can be used alone or as a mixture.
And become colloidal dispersed in organic solvent or water.
Is used. In particular, methanol, ethanol, iso
Propyl alcohol, methyl ethyl ketone, methyl iso
Dispersed in organic solvents such as butyl ketone and cyclohexane
Organosol is not suitable for the resin used for the hard coat layer.
Is good in terms of dispersibility, and as the particle size,
1 to 100 nm, preferably 5 to 2 nm from the viewpoint of transparency of the coating film.
Desirably, it is 0 nm. In addition, for binder resin
The content of the filler is preferably 70% or less. H
The wear resistance of the hard coat layer increases as the content of the filler increases.
And durability such as chemical resistance decrease. Therefore, the content
Preferably, it is as small as possible.

In the present invention, as a method of providing a hard coat layer on one or both surfaces of a transparent substrate directly or via another layer, a filler, water or an organic solvent may be added, if necessary, to the resin described above. The mixture is dispersed by a paint shaker, a sand mill, a pearl mill, a ball mill, an attritor, a roll mill, a high-speed impeller disperser, a jet mill, a high-speed impact mill, an ultrasonic disperser, etc. to obtain a paint or ink, and this is an air doctor. Coating, blade coating, knife coating,
Reverse coating, transfer roll coating, gravure roll coating, kiss coating,
Cast coating, spray coating, slot orifice coating, calendar coating,
Coating such as electrodeposition coating, dip coating, die coating and letterpress printing such as flexographic printing,
Direct gravure printing, intaglio printing such as offset gravure printing, lithographic printing such as offset printing, stencil printing such as screen printing, etc. are provided in a single layer or multilayer on one or both sides of the transparent substrate by a printing method, and include a solvent. In this case, a method may be used in which the coating layer or the printing layer is cured by heat or irradiation with energy rays (in the case of ultraviolet rays, a photopolymerization initiator is required) or the like after the heat drying step. If the radiation is electron beam,
50 to 10 emitted from various electron beam accelerators such as Cockloft-Walton type, Bande graph type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type, High frequency type
An electron beam having an energy of 00 KeV is used,
In the case of ultraviolet rays, ultraviolet rays emitted from light rays such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, and metal halide lamp can be used.

In order to improve the coating suitability or printing suitability of paints and inks, if necessary, a leveling agent such as silicone oil, polyethylene wax, carnauba wax, higher alcohols, bisamides, oils and fats such as higher fatty acids, isocyanates and the like may be used. 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 refractive index of the hard coat layer formed as described above is preferably in the range of 1.55 to 1.75. Further, the thickness of the hard coat layer is in the range of 1 to 10 μm, preferably 1 to 5 μm. When the hard coat layer is thinner than 1 μm, the hard coat layer is deteriorated in abrasion resistance or hardened poorly due to oxygen inhibition such as when an ultraviolet curable resin is used. If the thickness is more than 10 μm, curling may occur due to curing shrinkage of the resin, micro cracks may occur in the hard coat layer, and adhesion to the transparent substrate may be reduced.

C. Surface layer In order to obtain an anti-reflection function, a surface layer having a smaller refractive index is provided on the hard coat layer. Hereinafter, this surface layer will be described. The composition of the surface layer is not particularly limited, but it is preferable that the surface layer be configured so that its critical surface tension is 20 dyn / cm or less. When the critical surface tension is larger than 20 dyn / cm, it becomes difficult to remove dirt attached to the surface layer. Further, in order to improve the anti-reflection effect, the refractive index of the surface layer should be 1.20 to 1.4.
It is preferably 5. Materials having these characteristics include, for example, LiF (refractive index n = 1.4), MgF
₂ (n = 1.4), 3NaF.AlF ₃ (n = 1.
4), AlF ₃ (n = 1.4), Na ₃ AlF ₆ (n =
1.33), fine particles of inorganic materials such as SiO ₂ (n = 1.45), and inorganic low-reflection materials containing fluorine-based or silicone-based organic compounds contained in an acrylic resin or an epoxy-based resin. Organic low-reflection materials such as a plastic resin, a thermosetting resin, and a radiation-curable resin can be used. When a transparent substrate is made of a plastic film such as TAC or PET which is easily damaged by heat, a radiation-curable resin is preferable as the material of these surface layers. Among them, a fluorine-based fluorinated material is particularly preferable in terms of preventing contamination.

As the 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 (DuPont, refractive index n = 1.30), CYTOP (Asahi Glass Co., Ltd., n = 1.34), 17FM (Mitsubishi Rayon Co., Ltd.) N = 1.35), Opstar JN-721
2 (manufactured by Nippon Synthetic Rubber Co., Ltd., n = 1.40), LR2
01 (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-hydroxypropyl methacrylate, and other fluorinated methacrylates, 3-perfluoro Octyl-2
-Hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-
Fluorine-containing acrylates such as 9-methyldecyl) ethyl acrylate, 3-perfluorodecyl-1,2-epoxypropane, 3- (perfluoro-9-methyldecyl)
Epoxides such as -1,2-epoxypropane, radiation-curable fluorine-containing monomers such as epoxy acrylate,
Oligomer, prepolymer and the like can be mentioned. These can be used alone or in combination of two or more.

However, although these are excellent in stain resistance, they have poor wetting properties, so that depending on the composition, the problem of repelling the surface layer on the hard coat layer and the problem of the surface layer being peeled off from the hard coat layer. It is desirable to appropriately mix and use monomers, oligomers, and prepolymers having a polymerizable unsaturated bond such as an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group, which are used as the radiation-curable resin, because they may occur. .

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 can be used. The sol in which the ultrafine silica particles having a diameter of 5 to 30 nm are dispersed in water or an organic solvent may be prepared by dealkalizing alkali metal ions in the 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 replacing 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. In producing the organic solvent-based silica sol, it is not necessary to completely replace water with an organic solvent. The silica sol contains solids 0.5 to 50% strength by weight as SiO _2. Various structures such as spherical, needle-like, and plate-like structures can be used for the ultrafine silica particles in the silica sol.

As the film forming agent, alkoxysilane,
Hydrolysates of metal alkoxides and metal salts, fluorine-modified polysiloxanes, and the like can be used.
By using the above-described film forming agent, the critical surface tension of the surface layer is reduced, and the adhesion of oil can be suppressed.

Further, an antistatic agent may be added to the surface layer in order to prevent dirt such as dust which electrostatically adheres to the display surface, or an antistatic layer may be provided on the surface layer. The thickness of the antistatic layer is desirably an optical film thickness that does not affect the antireflection effect. Preferably, it is 10 nm or less. As the antistatic agent, the materials described for the antistatic layer can be applied as they are.

In the present invention, the surface layer is formed of the above-mentioned low refractive index material by a wet coating method such as roll coating or printing, or a vapor phase method such as vacuum deposition, sputtering, plasma CVD, or ion plating. Provided on the hard coat layer. When provided by a wet coating method, a leveling agent such as silicone oil, polyethylene wax, carnauba wax, a higher alcohol, a bisamide, a fatty acid such as a higher fatty acid, an isocyanate, etc., as necessary, in order to improve coating suitability or printability. And additives such as ultrafine particles of 0.05 μm or less, such as calcium carbonate, silica sol, and synthetic mica.

The thickness for the surface layer to exhibit a good antireflection function can be calculated by a known calculation 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 ₀ is the refractive index of the surface layer, Ns is the refractive index of the hard coat layer, h is the thickness of the surface layer, and λ ₀ is the wavelength of light.

[0043]

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

According to the above equation (1), the reflection of light is 100
It can be seen that in order to prevent the percentage, the material should be selected so that the refractive index of the surface layer becomes the square root of the refractive index of the lower layer (hard coat layer). 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, when the refractive index of the hard coat layer and the refractive index of the surface layer are 1.50 and 1.38, respectively, and the wavelength of light is 550 nm (standard of visibility), and these values are substituted into the above equation (2), Thickness 0.1μ
m, preferably 0.10 ± 0.01 μm
Is calculated to be optimal. As described above, the surface layer needs to be extremely thin and very evenly provided (in-plane variation in thickness causes color unevenness due to interference with the hard coat layer). Therefore, as a method of providing the surface layer, a gas phase method is preferable.

The surface layer in the present invention may be a single layer having the above composition, or may be formed as a multilayer. That is, in the case of a multi-layer, a combination in which a low-refractive-index layer is provided on a high-refractive-index layer has a structure in which one set or a plurality of layers are laminated on the hard coat layer or the surface layer of the single layer, that is, on the low-refractive index layer. be able to.

(2) Contents of Polarizing Film A protective material is laminated via a polarizing substrate on the other surface of the transparent substrate of the antireflective material having the above-mentioned structure, on which the hard coat layer and the surface layer are not provided, thereby providing a polarized light. A film can be constructed. Hereinafter, the details of the polarizing film of the present invention will be described.

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

B. Protective material The PVA film obtained above is apt to tear due to lack of strength and the like, and has a drawback of a large shrinkage ratio with respect to a change in humidity. Therefore, the protective material is laminated on one surface of the polarizing substrate. You. In addition, the transparent substrate of the anti-reflection material is bonded to the other surface of the polarizing substrate and has the same function as the protective material. The protective material and the transparent substrate are bonded 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 triacetyl cellulose, a polyester film, a polycarbonate film and the like can be used. Among them, triacetyl cellulose is particularly preferred. The thickness of the film is preferably from 10 to 2000 μm. Further, it is preferable to improve the water resistance of the films by using a gelling agent such as boric acid, or by performing a heat treatment or formalization on these films. Further, in order to improve the adhesion to the polarizing substrate, it is preferable to perform a surface treatment such as a saponification treatment or a corona treatment so that the surface energy of the bonding surface with the polarizing substrate becomes 50 dyn / 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 sectional view showing the structure of the antireflection material of the present invention. The antireflection material 10 has a structure in which a hard coat layer 12 is provided on one surface of a transparent substrate 11. The hard coat layer 12
Although a surface layer is formed on the surface of, the illustration is omitted because the surface layer is extremely thin (the same applies hereinafter). FIG. 2 is a schematic cross-sectional view showing the structure of the polarizing film 20 of the present invention.
Anti-reflective material 23 having a hard coat layer 22 on 1
Indicates that the protective member 25 is provided on the other surface of the polarizing substrate 24.

FIG. 3 shows a structure of a liquid crystal display 30 in which the antireflection property is improved by the antireflection 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 oriented by a rubbing operation, and 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 both sides of the two glass substrates of the TN liquid crystal cell opposite to the rear light source, both surfaces of the polarizing substrate 24 were protected by an antireflection material 23 having a hard coat layer 22 shown in FIG. A polarizing film 36 and a polarizing film 37 having no hard coat layer on the back light source side are provided.
Are adhered so that the polarization angles are twisted by 90 ° with each other, whereby the liquid crystal panel 31 is 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,
Light is transmitted through the liquid crystal panel 31, and an image can be displayed by giving a contrast between the light transmitting portion and the light non-transmitting portion of the liquid crystal panel 31.

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 hard coat layer, a lower polarizing film 47 having no hard coat layer and an upper polarizing film positioned outside the glass substrates 43 and 44 The anti-reflection material 10 is laminated on the reference numeral 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.

[0055]

The present invention will be described in more detail by way of examples. In the following description, “parts” means “parts by weight”. [Synthesis Example of Component A] Synthesis Example A-1 Bisphenoxyethanolfluorene (trade name BPEF, manufactured by Osaka Gas Chemical Co., Ltd.) 600 g, acrylic acid 258 g, p-toluenesulfonic acid 30 g, toluene 1
350 g, 1 g of hydroquinone monomethyl ether and 0.03 g of hydroquinone were mixed, and 100 to 11
While refluxing at 5 ° C., the dehydration esterification reaction was performed until the theoretical dehydration amount was obtained. Thereafter, the reaction solution was neutralized with alkali, and
Washing was performed with 0% saline. After washing, toluene was removed to obtain diacrylate (A-1).

Synthesis Example A-2 350 g of bishydroxyphenylfluorene, 500 g of epichlorohydrin, and 10 g of triethylbenzylammonium chloride were mixed, and 160 g of a 50% aqueous sodium hydroxide solution was added dropwise under reflux. Reacted for hours. Next, 300 g of water was added, and after standing, the organic layer was separated, adjusted with acetic acid so that the pH became 5, and then washed twice with 300 g of water. Concentration was performed to remove residual water and epichlorohydrin. The epoxy equivalent of this product was 270. Here, 80 g of toluene, 0.5 g of hydroquinone monomethyl ether,
And 95 g of acrylic acid, and heated to 100 ° C.
It reacted for about 15 hours. Diacrylate of resin oxidation 5 mgKOH / g, epoxy equivalent 7500, solid content 85% (A
-2) A solution was obtained.

[Synthesis Example of Component B] Synthesis Example B-1 A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (having a hydroxyl value of 120)
mg KOH / g, hereinafter referred to as PETA) 940 g, hexamethylene diisocyanate (hereinafter referred to as HDI) 16
8 g and a few drops of dibutyltin dilaurate (hereinafter referred to as DBTL) were mixed, and the mixture was heated to 80 ° C. and reacted for about 5 hours to obtain a urethane acrylate (B-1).

Synthesis Example B-2 Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 53 mg KOH / g, hereinafter referred to as DPPA) 2200
g, HDI 168 g, and a few drops of DBTL,
The reaction was carried out by heating to 0 ° C. for about 7 hours to obtain urethane acrylate (B-2).

Synthesis Example B-3 Synthesis was performed in the same manner as in Synthesis Example B-1 except that 174 g of 2,4-tolylene diisocyanate was used instead of 168 g of HDI, to obtain a urethane acrylate (B-3).

Synthesis Example B-4 Synthesis was performed in the same manner as in Synthesis Example B-1 except that 250 g of 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) was used instead of 168 g of HDI, and urethane acrylate (B-4) I got

Synthesis Example B-5 Synthesis was performed in the same manner as in Synthesis Example B-1 except that 188 g of xylylene diisocyanate was used instead of 168 g of HDI, to obtain a urethane acrylate (B-5).

Synthesis Example B-6 3200 g of DPPA, 666 g of a nullified product of isophorone diisocyanate, and a few drops of DBTL were mixed to give 8
The reaction was carried out by heating to 0 ° C. for about 7 hours to obtain urethane acrylate (B-6).

Synthesis Example B-7 Bisphenoxyethanol fluorene 438 g, MDI
500 g and a few drops of DBTL are mixed, heated to 80 ° C. and the reaction is allowed to proceed for about 3 hours, then 2350 g of DPPA
Was added, and the reaction was carried out at 80 ° C. for about 6 hours to obtain urethane acrylate (B-7).

Synthesis Example B-8 134 g of dimethylolpropionic acid, 500 g of MDI,
And a few drops of DBTL are mixed, heated to 80 ° C. and the reaction is allowed to proceed for about 6 hours, then 1050 g of PETA is added,
The reaction was carried out at 80 ° C. for about 6 hours to obtain urethane acrylate (B-8).

<Example 1> First, a dispersion obtained by dispersing a mixture having the following composition in a sand mill for 30 minutes and a base coating material for a hard coat layer having the following composition were mixed with a disperser. After stirring and mixing for a minute, the coating material was coated to a thickness of 80 μm, a transmittance of 92%, and a refractive index of 1.4.
9 was coated on one side of triacetyl cellulose (trade name: Fuji Tack Tack, manufactured by Fuji Photo Film Co., Ltd.) as a transparent substrate made of No. 9 by a reverse coating method.
After drying at 2 ° C. for 2 minutes, the irradiation distance (the distance from the lamp center to the coating surface) was 10 cm, and the processing speed (the speed of the coating substrate side relative to the mercury lamp) was 5 m using one condensing high-pressure mercury lamp having an output of 120 w / cm. The coating film was cured by irradiating ultraviolet rays at a rate of / min. Thus, a thickness of 5 μm and a refractive index of 1.6
No. 5 hard coat layer was formed. Next, as a coating for the surface layer, fluorinated silica sol LR201 (total solid content: 4%, solvent: ethanol / butyl cellosolve = 50)
/ 50, manufactured by Nissan Chemical Industry Co., Ltd.) and spin-coated on the hard coat layer,
After drying at ℃ for 1 minute, heat curing at 120 ℃ for 6 hours, thickness 0.1μm, refractive index 1.38, critical surface tension 16dy
An n / cm surface layer was formed to obtain an antireflection material of the present invention having a reflectance of 0.8%.

[Blending of Dispersion] Antimony Tin Oxide (ATO) (Primary Particle Diameter 10 nm) 30 parts Dispersant (trade name: A-147, manufactured by Nippon Unicar Co., Ltd.) 3 parts Methyl ethyl ketone 40 parts・ Methyl isobutyl ketone 60 parts

[Incorporation of Base Coating for Hard Coat Layer] A-1 49 parts B-1 21 parts Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy) 5 parts Isopropyl alcohol 80 parts

<Examples 2 to 13, Comparative Example 1> Examples of the present invention were prepared in the same manner as in Example 1 except that the composition of the copolymer component of the base coating material for the hard coat layer was changed to the composition shown in Table 1. 2 to 13 and Comparative Example 1 were obtained. Some of the C components other than the A and B components include DPPA or PPEA. Where DPPA
Is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 53 mgKOH / g), and PPEA is phenylphenoxyethanol acrylate.

<Example 14> An antireflection material of the present invention was obtained in the same manner as in Example 1 except that a coating material for a surface layer having the following composition was used. [Blending of paint for surface layer] Silica sol (Ethanol dispersion containing 30% by weight of silica ultrafine particles as SiO ₂ with a particle diameter of 15 nm) 10 parts Film-forming agent Hydrolysis product of tetraethoxysilane (as SiO ₂₎ Calculate the solid content 6%) 15 parts ・ Solvent ethanol 53 parts

<Comparative Example 2> An antireflection material for comparison was obtained in the same manner as in Example 1 except that the surface layer was not provided. <Comparative Example 3> Example 1 except that no hard coat layer was provided.
In the same manner as in the above, an antireflection material for comparison was obtained. <Comparative Example 4> In the same manner as in Comparative Example 1, except that a hard coat layer was formed by using only a base paint without using a dispersion liquid as a hard coat layer paint (only resin and no ATO). Thus, an antireflection material for comparison was obtained.

Using the antireflection materials 10 obtained in Examples 1 to 14 and Comparative Examples 1 to 4, the reflectance, abrasion resistance, chemical resistance, critical surface tension, and stain resistance were measured and evaluated by the following methods. did. Further, using each antireflection material 10 of Examples 1 to 14 and Comparative Examples 1 to 4, a polarizing film 20 with a hard coat layer having a configuration shown in FIG. 2 was produced. Next, the polarizing film 20 with the hard coat layer was attached to a glass substrate 33 as shown in FIG. Using each of the liquid crystal displays 30 of Examples 1 to 14 and Comparative Examples 1 to 4 thus produced, image contrast was evaluated by the following method. The image size of each of the liquid crystal displays 30 was, for example, 10.4 inches and the resolution was, for example, 800 × 600 dots, and the image contrast was evaluated.

The reflectivity was measured by using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) to measure the regular reflection at 5 ° in the wavelength range of 400 to 700 nm, and expressed as a Y value corrected for visibility according to JIS Z8701. The measurement was performed in a state where the non-measurement surface was completely blackened with black magic. The antireflection property is particularly good when it is 1% or less, and considerably deteriorates when it exceeds 4%.

The abrasion resistance was as follows. Steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. was attached to a paperboard abrasion tester (manufactured by Kumagaya Riki Kogyo Co., Ltd.), and the surface layer of the anti-reflective material was subjected to a load of 2
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. Abrasion resistance δH is 1.5
Below, it is good, and when it exceeds 5, the number of scratches increases, which is a practical problem. 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 the surface layer surface was remarkably changed, such as peeling, after rubbing the surface layer 50 times with a cotton swab (manufactured by Johnson) impregnated with isopropyl alcohol. 、, the middle was evaluated as △.

The critical surface tension is determined by the Wilhelmy method by measuring the contact angle of the surface layer of the antireflective material with water and methylene iodide, and the following formula described in Basic Science of Coating (published by Yuji Harazaki, published by Maki Shoten), pages 170 to 171. , Z
From the ismam plot, γ extrapolated to COS θ-1
It was determined from the value of the _{LV °.} 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

The stain resistance is as follows. One drop of rapeseed oil is dropped on the surface of the surface layer with a dropper, and the dropped rapeseed oil is rubbed 20 times with a Bencott made by Asahi Kasei Corporation containing ligroin. Further, after that, an SEM photograph of the wiped surface was taken, and it was confirmed whether or not the surface was scratched or the Bencott fibers were attached. When the scratches and the adhesion of Bencott fibers were remarkably observed on the hard coat layer, the result was evaluated as x, when no change was observed, and as intermediate.

The screen contrast is JIS C70721.
988, 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 is, for example, 1 cm, the distance between the liquid crystal panel 61 and the photometer 62 is, for example, 50 cm, and the aperture angle of the photometer is:
For example, it was set to 5 °. The light source used was 5 W EL, and the photometer used was LS-100 manufactured by Minolta Camera. The case where CR was 4 or more was evaluated as ◎, the case of 3 or more but less than 4 was evaluated as ○, the case of 2 or more and less than 3 was evaluated as Δ, and the case of less than 2 was evaluated as ×. Table 1 shows the evaluation results.

[0078]

[Table 1]

As is clear from the results shown in Table 1, the antireflection materials of the present invention all have good reflectance and durability and excellent characteristics, while Comparative Examples 1 to 4
In the antireflection materials of Nos. 1 and 2, both have a problem in reflectance. In addition, Comparative Examples 1 and 4 have inferior contrast, Comparative Example 2 has stain resistance and contrast, and Comparative Example 3 has
The durability was not enough for practical use.

[0080]

As described above, according to the present invention, excellent antireflection properties are exhibited by preventing the reflection of external light such as sunlight and fluorescent lights on the display, and the image contrast is reduced. Without the need to obtain clear images without glare, optically stable, excellent abrasion resistance, chemical resistance, and an anti-reflective material and polarizing film that exhibit excellent contamination resistance Obtainable.

[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]

10 anti-reflection material, 11 transparent substrate, 12 hard coat layer, 20 polarizing film with hard coat layer, 21
Transparent substrate, 22 hard coat 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, 3
4: glass substrate, 33 ', 34': transparent electrode surface, 35:
Nematic liquid crystal, 36: polarizing film, 40: liquid crystal display, 41: liquid crystal panel, 43, 44: glass substrate, 45
… Nematic liquid crystal, 46, 47… Polarized film, 60…
Light source, 61: liquid crystal panel, 62: photometer

Claims (5)

[Claims] A hard coat layer is provided on one or both sides of a transparent substrate, directly or via another layer, and a surface layer having a refractive index lower than that of the hard coat layer on the surface of the hard coat layer. In the antireflection material provided with
The anti-reflection material, wherein the hard coat layer contains a polymer having a (meth) acrylate compound having at least a fluorene skeleton as a polymerization component. 2. The antireflection material according to claim 1, wherein the polymer is a copolymer containing a urethane (meth) acrylate compound as a copolymer component. 3. The hard coat layer has a refractive index of 1.6 or more.
2. The composition according to claim 1, further comprising 2.7 fillers.
Or the antireflection material according to 2. 4. The critical surface tension of the surface layer is 20 dyn.
/ Cm or less, The anti-reflection material according to any one of claims 1 to 3. 5. A protective material via a polarizing substrate on the other surface of the anti-reflection material according to claim 1, wherein the hard coat layer and the surface layer are not provided on the transparent substrate. A polarizing film characterized by being laminated.