JPH11218604A - Antirefrlection film and image display device using the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film having an antistatic layer which is suitable for mass production and which has excellent strength by using a specified amt. of polymers having crosslinked anionic groups in the antistatic layer and finely dispersing conductive inorg. fine particles in the antistatic layer. SOLUTION: This film consists of a transparent plastic film supporting body, an antistatic layer 4 having 2 to 10 μm thickness, and a low refractive index layer having 1.20 to 1.55 refractive index successively formed in this order. The antistatic layer 4 contains 20 to 90 wt.% conductive inorg. fine particles 41 having 1 to 200 nm average particle size and 10 to 80 wt.% polymers 42 having crosslinked anionic groups. The polymers 42 in the antistatic layer 4 preferably have sulfonic acid groups and phosphoric acid groups as anionic groups, and moreover, the polymers 42 preferably have amino groups or ammonium groups. The surface resistance of the antistatic layer 4 is preferably 10<10> to 10<5> Ω/sq.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antireflection film having a transparent plastic film support and a low refractive index layer, and an image display device using the same.

[0002]

2. Description of the Related Art An antireflection film is used for a liquid crystal display (LC).
D), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT). Glasses and camera lenses are also provided with an antireflection film. As the antireflection film, a multilayer film in which a transparent thin film of a metal oxide is laminated has conventionally been commonly used. The reason for using a plurality of transparent thin films is to prevent reflection of light of various wavelengths. The transparent thin film of a metal oxide is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, in particular, a vacuum vapor deposition method which is a kind of the physical vapor deposition method.
Although a transparent thin film of a metal oxide has excellent optical properties as an antireflection film, the method of forming by vapor deposition has low productivity and is not suitable for mass production. A method of forming an antireflection film by applying inorganic fine particles instead of the vapor deposition method has been proposed.

[0003] Japanese Patent Publication No. 60-59250 discloses an antireflection layer having fine pores and fine inorganic particles. The antireflection layer is formed by coating. The micropores are formed by performing an activation gas treatment after the application of the layer, and the gas is released from the layer. JP-A-59-50
No. 401 discloses an antireflection film in which a support, a high refractive index layer, and a low refractive index layer are laminated in this order. The gazette states that
An antireflection film having a medium refractive index layer between the support and the high refractive index layer is also disclosed. The low refractive index layer is formed by applying a polymer or inorganic fine particles. JP-A-2-245
No. 702 discloses two or more types of ultrafine particles (for example, Mg
An antireflection film in which F ₂ and SiO ₂ ) are mixed to change the mixing ratio in the film thickness direction is disclosed. The refractive index was changed by changing the mixing ratio.
The optical properties similar to those of the antireflection film provided with the high refractive index layer and the low refractive index layer described in Japanese Patent No. 50401 are obtained. The ultrafine particles are formed by thermal decomposition of ethyl silicate.
Adhered by iO ₂ . In the thermal decomposition of ethyl silicate, carbon dioxide and water vapor are also generated by burning the ethyl portion. As shown in FIG. 1 of the publication, a gap is formed between the ultrafine particles due to the separation of carbon dioxide and water vapor from the layer. JP-A-5-13021 discloses that the gap between ultrafine particles existing in the antireflection film described in JP-A-2-245702 is filled with a binder. JP-A-7-48527 discloses an antireflection film containing a binder and an inorganic fine powder made of porous silica. JP-A-8-110401
JP-A-8-179123 discloses that a high-refractive-index film having a refractive index of 1.80 or more is formed by introducing high-refractive-index inorganic fine particles into plastic and applied to an antireflection film. Is disclosed.

[0004]

SUMMARY OF THE INVENTION The present inventor has studied on an antireflection film. As a result of the research, it has been found that the conventional antireflection film easily adsorbs dust in the air during the manufacturing and processing steps and during use. If dust in the air is adsorbed during the manufacturing and processing steps, defects are likely to occur in the antireflection film. If dust in the air is adsorbed during use, the visibility of the image display device provided with the antireflection film is reduced. Adsorption of dust in the air occurs when a plastic film, which is easily charged, is used as a transparent support. In order to prevent dust from adsorbing in the air, an antistatic layer may be provided on the antireflection film. As the antistatic layer, a layer containing conductive inorganic fine particles has high productivity and is suitable for mass production. However, the research of the present inventors has revealed that there is a problem to be solved in order to provide an antistatic layer containing conductive inorganic fine particles on an antireflection film. It is difficult to finely disperse the conductive inorganic fine particles and form the antistatic layer while maintaining the finely dispersed state. In order to form a layer having an excellent antistatic function, it is necessary to finely and uniformly disperse the conductive inorganic fine particles in the layer. As a means for dispersing the inorganic fine particles, use of a surfactant or a polymer for dispersion (anionic or cationic) is known. However, these dispersing means function only at the stage of forming the antistatic layer. After the formation of the antistatic layer, these dispersing means not only do not function at all, but also deteriorate the physical strength (abrasion resistance) and the chemical strength (chemical resistance) of the antistatic layer.

It is an object of the present invention to provide an antireflection film suitable for mass production. Another object of the present invention is to provide an antireflection film having an antistatic function. Still another object of the present invention is to provide an antireflection film having an antistatic layer having excellent strength. Still another object of the present invention is to provide an image display device in which reflection is prevented by appropriate means.

The object of the present invention has been attained by the following antireflection films (1) to (7) and the following image display device (8). (1) A transparent plastic film support, an antistatic layer having a thickness of 2 to 10 μm, and a refractive index of 1.20 to 1.
A low-refractive index layer having a thickness of 55 is laminated in this order, and the antistatic layer contains 20 to 90% by weight of conductive inorganic fine particles having an average particle size of 1 to 200 nm and a polymer having an anionic group crosslinked. An anti-reflection film containing 10 to 80% by weight of (2) The polymer having an anionic group of the antistatic layer,
The antireflection film according to (1), which has a phosphate group or a sulfonic group as an anionic group. (3) The polymer having an anionic group of the antistatic layer,
The antireflection film according to (1), further having an amino group or an ammonium group. (4) The surface resistance of the antistatic layer is 10 ^{10 to} 10 ⁵ Ω / s
The antireflection film according to (1), wherein q is q. (5) The antireflection film according to (1), wherein the antistatic layer is a layer formed by coating, and the polymer having an anionic group is a polymer formed by a polymerization reaction simultaneously with or after coating the layer. .

(6) The conductive inorganic fine particles of the antistatic layer are
The antireflection film according to (1), which is made of ITO or ATO. (7) The low-refractive-index layer contains 50 to 95% by weight of inorganic fine particles having an average particle diameter of 0.5 to 200 nm and 5 to 50% by weight of a polymer, and is formed by stacking at least two or more inorganic fine particles. The antireflection film according to (1), which is a layer in which microvoids are formed. (8) A transparent plastic film support, an antistatic layer having a thickness of 2 to 10 μm, and a refractive index of 1.20 to 1.
A low-refractive index layer having a thickness of 55 is laminated in this order, and the antistatic layer contains 20 to 90% by weight of conductive inorganic fine particles having an average particle size of 1 to 200 nm and a polymer having an anionic group crosslinked. Display device, wherein an antireflection film containing 10 to 80% by weight of is disposed such that the transparent plastic film support is on the image display device side.

[0008]

As a result of research conducted by the present inventors, the use of a polymer having an anionic group cross-linked in the antistatic layer in an amount of 10 to 80% by weight allows the conductive inorganic fine particles of the antistatic layer to be finely divided. Dispersed and succeeded in forming a layer while maintaining the finely dispersed state. The polymer having an anionic group functions as an excellent dispersant for the conductive inorganic fine particles in the state of the anionic monomer before the formation of the antistatic layer. Then, after forming the antistatic layer with the anionic monomer, by polymerization and crosslinking,
A polymer having crosslinked anionic groups is formed. The conductive inorganic fine particles are firmly bound by the crosslinked polymer having an anionic group, and an antistatic layer having excellent strength is obtained. Since the antistatic layer formed according to the present invention has extremely high strength, it can also function as a hard coat layer (a layer for imparting scratch resistance to a transparent plastic film support). The antireflection film having the improved antistatic layer as described above can be easily manufactured by coating and is suitable for mass production.
By using this antireflection film, reflection of light on the image display surface of the image display device can be effectively prevented.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Layer Structure of Antireflection Film) The layer structure of the antireflection film will be described with reference to FIG. FIG. 1 is a schematic sectional view showing various layer configurations of the antireflection film. FIG.
The most basic mode shown in (a) has a layer structure in the order of a transparent support (5), an antistatic layer (4), and a low refractive index layer (1). The embodiment shown in FIG. 1B has a layer structure of a transparent support (5), an antistatic layer (4), a high refractive index layer (2), and a low refractive index layer (1) in this order. As shown in (b), an antireflection film having a high refractive index layer (2) and a low refractive index layer (1) is disclosed in JP-A-59-504.
As described in JP-A-01, it is preferable that the high refractive index layer satisfies the following formula (I) and the low refractive index layer satisfies the following formula (II).

[0010]

(Equation 1)

Where m is a positive integer (generally 1, 2 or 3), n1 is the refractive index of the high refractive index layer, and d1 is the layer thickness (nm) of the high refractive index layer. .

[0012]

(Equation 2)

Where n is a positive odd number (generally 1);
n2 is the refractive index of the low refractive index layer, and d2 is the layer thickness (nm) of the low refractive index layer. The embodiment shown in FIG. 1 (c) comprises a transparent support (5), an antistatic layer (4), a medium refractive index layer (3), a high refractive index layer (2), and a low refractive index layer (1). It has an orderly layer configuration. As shown in (c), an antireflection film having a middle refractive index layer (3), a high refractive index layer (2) and a low refractive index layer (1) is described in JP-A-59-50401. As described above, it is preferable that the middle refractive index layer satisfies the following formula (III), the high refractive index layer satisfies the following formula (IV), and the low refractive index layer satisfies the following formula (V).

[0014]

(Equation 3)

In the formula, h is a positive integer (generally 1, 2 or 3), n3 is the refractive index of the medium refractive index layer, and d3 is the thickness (nm) of the medium refractive index layer. .

[0016]

(Equation 4)

Where j is a positive integer (generally 1, 2 or 3), n4 is the refractive index of the high refractive index layer, and d4 is the layer thickness (nm) of the high refractive index layer. .

[0018]

(Equation 5)

Where k is a positive odd number (generally 1),
n5 is the refractive index of the low refractive index layer, and d5 is the thickness (nm) of the low refractive index layer. An antistatic layer improved according to the present invention is used for the antireflection film having the above-described layer configuration.

(Transparent Support) In the present invention, a plastic film is used as a transparent support. Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate) , Poly-1,4
-Cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethyl) Pentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethylmethacrylate and polyetherketone.
Triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred. The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, more preferably 1.0% or less.
The refractive index of the transparent support is preferably from 1.4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support. The amount of infrared absorber added
The content is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight of the transparent support. As a slipping agent, particles of an inert inorganic compound may be added to the transparent support. Examples of inorganic compounds include SiO
_{2, TiO 2, BaSO 4,} CaCO 3, talc and kaolin. The transparent support may be subjected to a surface treatment. Examples of surface treatments include chemical treatment, mechanical treatment,
Corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment are included. Glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

(Antistatic Layer) FIG. 2 is a schematic sectional view of the antistatic layer. The low refractive index layer is on the upper side of the antistatic layer in FIG. 2, and the transparent support is on the lower side. As shown in FIG. 2, the antistatic layer (4) has no pores, and has conductive inorganic fine particles (4).
This is a layer in which the polymer (42) is filled during 1). In the antistatic layer (4), the average particle size is 1 to 200.
nm conductive inorganic fine particles (41) are stacked.
The polymer (42) having a crosslinked anionic group is filled between the conductive inorganic fine particles (41). The thickness of the antistatic layer is 2 to 10 μm. The thickness of the antistatic layer is preferably 3 to 7 μm, more preferably 4 to 7 μm. The surface resistance of the antistatic layer is preferably from 10 ¹⁰ to 10 ⁵ Omega / sq, more preferably 10 ⁹ to 10 ⁵ Omega / sq, most in the range of 10 ⁸ to 10 ⁵ Omega / sq preferable. The surface resistance of the antistatic layer can be measured by a four probe method. Preferably, the antistatic layer is substantially transparent. Specifically, the haze of the antistatic layer is preferably at most 10%, more preferably at most 5%, further preferably at most 3%, most preferably at most 1%. . Wavelength 5
The transmittance of 50 nm light is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more. The antistatic layer improved according to the present invention has excellent strength. The specific strength of the antistatic layer is
Pencil hardness of 1kg load (as defined in JIS-K-5400)
, Preferably at least H, more preferably at least 2H, further preferably at least 3H, most preferably at least 4H.

(Conductive Inorganic Fine Particles of Antistatic Layer) The primary particles of the conductive inorganic fine particles used in the antistatic layer preferably have a weight average diameter of 1 to 150 nm, more preferably 5 to 1 nm.
00 nm, more preferably 5 to 70 nm.
Is most preferred. The weight average diameter of the inorganic fine particles in the formed antistatic layer is from 1 to 200 nm.
The weight average diameter of the inorganic fine particles in the antistatic layer is 5 to 15
The thickness is preferably 0 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm. The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably from 10 to 400 m ² / g,
More preferably, it is 0 to 200 m ² / g.
Most preferably, it is 0 to 150 m ² / g. The conductive inorganic fine particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred. The inorganic fine particles contain oxides or nitrides of these metals as main components and may further contain other elements.
The main component means a component having the largest content (% by weight) of the components constituting the particles. Examples of other elements include T
i, Zr, Sn, Sb, Cu, Fe, Mn, Pb, C
d, As, Cr, Hg, Zn, Al, Mg, Si, P,
Includes S, B, Nb, In, V and halogen atoms. In order to enhance the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V, and a halogen atom. Tin oxide containing Sb (A
TO) and indium oxide containing Sn (ITO)
Is particularly preferred. The ratio of Sb in ATO is 3 to 20
% By weight. The ratio of Sn in ITO is preferably 5 to 20% by weight.

The conductive inorganic fine particles may be surface-treated.
The surface treatment is performed using an inorganic compound or an organic compound. Examples of the inorganic compound used for the surface treatment include alumina and silica. Silica treatment is particularly preferred.
Examples of the organic compound used for the surface treatment include a polyol, an alkanolamine, stearic acid, a silane coupling agent, and a titanate coupling agent. Silane coupling agents are most preferred. Two or more types of surface treatments may be performed in combination. The shape of the conductive inorganic fine particles is preferably a rice grain, a sphere, a cube, a spindle, or an irregular shape. Two or more kinds of conductive inorganic fine particles may be used together in the antistatic layer. The proportion of the conductive inorganic fine particles in the antistatic layer is from 20 to 90% by weight. The proportion of the inorganic fine particles is preferably from 25 to 70% by weight, more preferably from 30 to 60% by weight. The conductive inorganic fine particles are used in the form of a dispersion to form an antistatic layer. It is preferable to use a liquid having a boiling point of 60 to 170 ° C. as a dispersion medium of the conductive inorganic fine particles. Examples of dispersion media include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbon (eg, hexane, cyclohexane), halogenated hydrocarbon (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohols (eg, 1-methyl Carboxymethyl-2-propanol) are included. Particularly preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol. The conductive inorganic fine particles can be dispersed in a medium using a disperser. Examples of dispersers include sand grinder mills (eg, bead mills with pins), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. Sand grinder mills and high speed impeller mills are particularly preferred.
Further, a preliminary dispersion process may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill,
Includes kneaders and extruders.

(Binder of Antistatic Layer) The antistatic layer uses a crosslinked polymer having an anionic group as a binder. The crosslinked polymer having an anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked. The anionic group has a function of maintaining the dispersed state of the inorganic fine particles. The crosslinked structure has a function of imparting a film-forming ability to the polymer and strengthening the antistatic layer. Examples of polymer backbones include polyolefins (saturated hydrocarbons), polyethers, polyureas, polyurethanes, polyesters, polyamines, polyamides and melamine resins. The polyolefin main chain, the polyether main chain and the polyurea main chain are preferable, the polyolefin main chain and the polyether main chain are more preferable, and the polyolefin main chain is most preferable. The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. In the polyether main chain, repeating units are connected by an ether bond (-O-). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. The polyurea main chain has a urea bond (—NH—CO—N
H-) connects the repeating units. The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. In the polyurethane main chain, repeating units are bonded by a urethane bond (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). In the polyester main chain, repeating units are connected by an ester bond (—CO—O—). The polyester main chain is obtained by, for example, a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). In the polyamine main chain, repeating units are connected by an imino bond (-NH-). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. In the polyamide main chain, repeating units are connected by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). The main chain of the melamine resin has a crosslinked structure.

The anionic group is directly bonded to the main chain of the polymer, or is bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group. Examples of anionic groups include
Includes carboxylic acid groups (carboxyl), sulfonic acid groups (sulfo) and phosphoric acid groups (phosphono). Sulfonate and phosphate groups are preferred. The anionic group may be in a salt state. The cation forming a salt with the anionic group is preferably an alkali metal ion. Further, the proton of the anionic group may be dissociated.
The linking group that bonds the anionic group and the main chain of the polymer is
It is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and a combination thereof. The crosslinked structure chemically bonds (preferably covalently bonds) two or more main chains. The crosslinked structure preferably covalently bonds three or more main chains. The crosslinked structure is -CO
-, -O-, -S-, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and a divalent or higher group selected from a combination thereof. The polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably from 2 to 96% by weight,
, More preferably from 6 to 9% by weight.
Most preferably, it is 2% by weight. The repeating unit is
It may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is from 4 to 9
The content is preferably 8% by weight, more preferably 6 to 96% by weight, and most preferably 8 to 94% by weight.

The repeating unit of the polymer may have both an anionic group and a crosslinked structure. Polymers include:
Other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure) may be included. As other repeating units, a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring are preferable. The amino group or the quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, similarly to the anionic group. The same effect can be obtained even when the amino group, the quaternary ammonium group and the benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure. In the repeating unit having an amino group or a quaternary ammonium group, the amino group or the quaternary ammonium group is directly bonded to the main chain of the polymer, or is bonded to the main chain via a linking group.
The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or the quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, and more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that bonds the amino group or the quaternary ammonium group to the polymer main chain is -CO-, -NH-,
It is preferably a divalent group selected from —O—, an alkylene group, an arylene group, and a combination thereof. When the polymer contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is 0.06.
To 32% by weight, preferably 0.08 to 3% by weight.
0% by weight, more preferably 0.1 to 28% by weight.
Most preferably, it is by weight.

In the repeating unit having a benzene ring, the benzene ring is directly bonded to the main chain of the polymer, or is bonded to the main chain via a linking group. The benzene ring is
It is preferable to bond to the main chain as a side chain via a linking group. The benzene ring may have a substituent (eg, an alkyl group, a hydroxy, a halogen atom). The linking group that connects the benzene ring to the polymer main chain is -CO-,
It is preferably a divalent group selected from —O—, an alkylene group, an arylene group, and a combination thereof. When the polymer contains a repeating unit having a benzene ring, the proportion is preferably from 2 to 98% by weight, more preferably from 4 to 96% by weight, and most preferably from 6 to 94% by weight. preferable. For the most preferred polymer having a polyolefin main chain, a repeating unit having an anionic group (VI), a repeating unit having a crosslinked structure (VII), a repeating unit having both anionic group and a crosslinked structure (VIII), an amino group or Examples of the repeating unit (IX) having a quaternary ammonium group and the repeating unit (X) having a benzene ring are represented by the following formulas.

[0028]

Embedded image

In the formula, R ¹ is a hydrogen atom or methyl, L ¹ is a divalent linking group, and An is a carboxylic acid group, a sulfonic acid group or a phosphoric acid group. Equation (VI)
In the formula, L ¹ represents —CO—, —O—, an alkylene group,
It is preferably a divalent linking group selected from an arylene group and a combination thereof. The alkylene group preferably has 1 to 20 carbon atoms, and 1 to 1 carbon atom.
More preferably, it is 5 and most preferably 1 to 10. The alkylene group may have a cyclic structure. The number of carbon atoms in the arylene group is preferably from 6 to 20, more preferably from 6 to 15, and most preferably from 6 to 10. The alkylene group and the arylene group each have a substituent (eg, an alkyl group,
(Hydroxy, halogen atom). L ¹
Is shown below. The left side binds to the main chain and the right side binds to An. AL represents an alkylene group, and AR represents an arylene group.

L ¹¹ : -CO-O-AL- (O-CO-A
L) _m1 - _(m1 is a positive ^{integer) L 12: -CO-O- (} AL-O) m2 -AR-AL-AR
_{- (O-AL) m3 -} (m2 and m3 are positive ^{integers) L 13: -CO-O-} AL- L 14: -CO-O-AL-O-CO- L 15: -CO-O -AL-O-CO-AR- L 16: -CO-O-AL-O-CO-AL-

The carboxylic acid group, sulfonic acid group and phosphoric acid group of An in the formula (VI) have the definitions described above. Expression (V
The repeating unit represented by I) is obtained by an addition polymerization reaction of a corresponding ethylenically unsaturated monomer. Examples of corresponding ethylenically unsaturated monomers include 2-sulfoethyl methacrylate, 2-carboxyethyl acrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrohydro Genphthalate, 2-acryloyloxypropyl tetrahydrohydrogen fumarate,
β-acryloyloxyethyl hydrogen succinate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, mono (2-acryloyloxyethyl) phosphate and mono (2-methacryloyloxyethyl) phosphate included. As these ethylenically unsaturated monomers having an anionic group, commercially available products can also be used.

[0032]

Embedded image

In the formula, R ² is a hydrogen atom or methyl, n is an integer of 2 or more, and L ² is an n-valent hydrocarbon residue. In the formula (VII), n is 2 to 20
Is more preferable, it is more preferably 2 to 10, and most preferably 3 to 6. Expression (VI
In I), L ² is preferably an aliphatic residue,
More preferably, it is a saturated aliphatic residue. An ether bond (-O-) may be contained in the aliphatic residue.
The aliphatic residue may have a branch. L ² preferably has 1 to 20 carbon atoms, and 2 to 15 carbon atoms.
Is more preferable, and most preferably 3 to 10. The repeating unit represented by the formula (VII) is
Obtained by the addition polymerization reaction of the corresponding ethylenically unsaturated monomer. Further, the corresponding ethylenically unsaturated monomer is an ester of acrylic acid or methacrylic acid with a polyhydric alcohol or polyphenol (preferably polyhydric alcohol) corresponding to L ² (—OH) _n . Examples of corresponding monomers include neopentyl glycol acrylate, 1,6-hexanediol acrylate, alkylene glycols such as propylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate. Acrylate, pentaerythritol diacrylate, bis {4- (acryloxydiethoxy) phenyl} propane, bis {4- (acryloxypolypropoxy) phenyl} propane, trimethylolpropane tri (meth)
Acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetrimethacrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate and tripentaerythritol hexatriacrylate are included. Ester of these polyhydric alcohols and acrylic acid or methacrylic acid can also use a commercial item.

[0034]

Embedded image

In the formula, R ³¹ , R ³² , R ³³ and R ³⁴ are each a hydrogen atom or methyl, and L ³¹ and L ³² are each a divalent linking group. Formula (VIII-
In a) and (VIII-b), L ³¹ and L ³² are each preferably a divalent linking group selected from —CO—, —O—, an alkylene group, an arylene group, and a combination thereof. The number of carbon atoms in the alkylene group is
It is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. The alkylene group may have a cyclic structure. The number of carbon atoms in the arylene group is preferably from 6 to 20, more preferably from 6 to 15, and most preferably from 6 to 10. The alkylene group and the arylene group may have a substituent (eg, an alkyl group, a hydroxy, a halogen atom). L ³¹ and L
Example ³² is the same as examples of L ¹ described above (L ¹¹ ~L ^16). The repeating units represented by formulas (VIII-a) and (VIII-b) are also obtained by addition polymerization of the corresponding ethylenically unsaturated monomers. Examples of ethylenically unsaturated monomers corresponding to formula (VIII-a) include bis (2-methacryloxyethyl) phosphate, bis (2-acryloyloxypropyl) phosphate and bis (2-methacryloyloxybutyl) phosphate. included. Expression (V
Examples of ethylenically unsaturated monomers corresponding to III-b) include β-acryloyloxyethyl fumarate and β
-Acryloyloxyethyl maleate. As the ethylenically unsaturated monomer, a commercially available product can also be used.

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In the formula, R ⁴¹ , R ⁴² and R ⁴³ are each a hydrogen atom or methyl, and L ⁴ , L ^4a and L ^4
4b is a divalent linking group, and Am
Is an amino group or a quaternary ammonium group. Expression (IX
-A) and (IX-b), L ⁴ , L ^4a and L
^4b is preferably a divalent linking group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and a combination thereof. The alkylene group preferably has 1 to 20 carbon atoms,
It is more preferably 1 to 15, and most preferably 1 to 10. The alkylene group may have a cyclic structure. The number of carbon atoms in the arylene group is preferably from 6 to 20, more preferably from 6 to 15, and most preferably from 6 to 10.
The alkylene group and the arylene group may have a substituent (eg, an alkyl group, a hydroxy, a halogen atom). Examples of L ⁴ , L ^4a and L ^4b are shown below. The left side binds to the main chain and the right side binds to Am. AL represents an alkylene group.

L ⁴¹ : -CO-O-AL-L ⁴² : -CO-NH-AL-L ⁴³ : -AL-

The amino and quaternary ammonium groups of Am in formulas (IX-a) and (IX-b) have the definitions given above. The repeating units represented by formulas (IX-a) and (IX-b) are obtained by an addition polymerization reaction of the corresponding ethylenically unsaturated monomer. Examples of ethylenically unsaturated monomers corresponding to formula (IX-a) include dimethylaminoethyl acrylate, dimethylaminopropyl acrylamide, hydroxypropyltrimethylammonium methacrylate chloride, ethyltrimethylammonium methacrylate chloride, dimethylaminopropyl methacrylamide and Methacrylamidopropyltrimethylammonium chloride is included. Examples of the ethylenically unsaturated monomer corresponding to the formula (IX-b) include diallyldimethylammonium chloride. Commercially available amino group or quaternary ammonium group ethylenically unsaturated monomers can also be used.

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Wherein R ⁵¹ is a hydrogen atom or methyl, R ⁵² is a hydrogen atom, carboxyl, an alkyl group having 1 to 6 carbon atoms or a halogen atom;
L ⁵ is a single bond or a divalent linking group. R of formula (X)
^{When 52} is carboxyl, R ⁵² is preferably bonded to the ortho position of the benzene ring. In the formula (X), L ⁵
Is preferably a divalent linking group selected from a combination of -CO-, -O- and an alkylene group. The number of carbon atoms of the alkylene group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 1.
Most preferably, it is 0. The alkylene group may have a cyclic structure. The alkylene group may have a substituent (eg, an alkyl group, a hydroxy, a halogen atom). Examples of L ⁵ are shown below. The left side connects to the main chain, and the right side connects to the benzene ring. AL represents an alkylene group.

L ⁵⁰ : single bond L ⁵¹ : -CO-O- (AL-O) _m4- (m4 is a positive integer) L ⁵² : -CO-O-AL-

The repeating unit represented by the formula (X) is obtained by an addition polymerization reaction of a corresponding ethylenically unsaturated monomer. Examples of corresponding ethylenically unsaturated monomers include phenoxyethyl acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxy-3-
Phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid and 2-
Acryloyloxyethyl phthalic acid is included. Commercially available ethylenically unsaturated monomers having a benzene ring can also be used. For polymers having a polyether backbone derived from an epoxy group, or ethylene group of the repeating units of the formula (-CH ₂ -) left repeating structures bound with oxygen atoms (-O-) of A unit may be used. The polymer having a crosslinked anionic group should be added as a monomer to the coating solution for the antistatic layer (the dispersion of the conductive inorganic fine particles described above) and formed by a polymerization reaction simultaneously with or after the coating of the layer. Is preferred. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The amount of the monomer having an anionic group to the inorganic fine particles is preferably in the range of 1 to 50% by weight, more preferably in the range of 5 to 40% by weight, and most preferably in the range of 10 to 30% by weight. preferable. Further, the monomer having an amino group or a quaternary ammonium group functions as a dispersing aid in the coating solution. The amount of the monomer having an amino group or a quaternary ammonium group to be used with respect to the monomer having an anionic group is preferably 3 to 33% by weight. If a polymer is formed by a polymerization reaction at the same time as or after the application of the layer, these monomers can be effectively functioned before the application of the layer.

As the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. Photopolymerization reactions are preferred. It is preferable to use a polymerization initiator for the polymerization reaction. The polymerization initiator includes acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds,
There are disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include:
2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone,
1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone.
Benzoins include benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. The phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

A commercially available polymerization initiator may be used. A polymerization accelerator may be used in addition to the polymerization initiator. The amount of the polymerization initiator and the amount of the polymerization accelerator added were 0.2% of the total amount of the monomers.
It is preferably in the range of 10 to 10% by weight. When a polymer is formed by a photopolymerization reaction, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, or a metal halide lamp can be used as a light source. Most preferably, a high-pressure mercury lamp having good irradiation efficiency is used. The coating liquid (dispersion liquid of inorganic fine particles containing a monomer) may be heated to promote polymerization of the monomer (or oligomer). Further, heating may be performed after the photopolymerization reaction after the application, and the thermosetting reaction of the formed polymer may be additionally treated. Since the polymer having an anionic group is crosslinked, it is difficult to define the molecular weight. The ratio of the polymer having a crosslinked anionic group in the antistatic layer is 1
0 to 80% by weight. The proportion of the crosslinked polymer having an anionic group is preferably from 30 to 75% by weight, more preferably from 40 to 70% by weight. The aforementioned components (inorganic fine particles, polymer, dispersion medium, polymerization initiator,
In addition to the polymerization accelerator, a polymerization inhibitor, a leveling agent, a thickener, a coloring inhibitor, an ultraviolet absorber, a silane coupling agent, an antistatic agent and an adhesion-imparting agent may be added. Examples of leveling agents include fluorinated alkyl esters (eg,
FC-430 and FC-431 of Sumitomo 3M Co., Ltd.) and polysiloxane (for example, S of General Electric Co., Ltd.)
F1023, SF1054, SF1079, Dow Cornin
g DC190, DC200, DC510, DC1
248, BYK300, BYK31 of BYK Chemie
0, BYK320, BYK322, BYK330, BY
K370).

(Low Refractive Index Layer) FIG. 3 is a schematic sectional view of a preferred low refractive index layer. The upper side of the low refractive index layer in FIG. 3 is the surface of the antireflection film, and the lower side is the image display device or lens. As shown in FIG. 3, the low refractive index layer (1) is preferably a porous layer. In the porous low refractive index layer (1), the inorganic fine particles (1) having an average particle size of 0.5 to 200 nm are used.
1) are stacked at least two or more (three in FIG. 1). Microvoids (12) are formed between the inorganic fine particles (11). The low refractive index layer (1)
It further contains the polymer (13) in an amount of 5 to 50% by weight. The polymer (13) adheres the inorganic fine particles (11) but does not fill the microvoids (12). As shown in FIG. 1, the microvoids (12) are preferably closed (not open) by the polymer (13) and the inorganic fine particles (11). The refractive index of the low refractive index layer is
1.20 to 1.55. The refractive index is preferably from 1.30 to 1.55, and is preferably from 1.30 to 1.50.
Is more preferable, and most preferably 1.35 to 1.45. The thickness of the low refractive index layer is preferably 50 to 400 nm, and 50 to 200 n.
m is more preferable. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The low refractive index layer improved according to the present invention has excellent strength. Specifically, the strength of the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more at a pencil hardness of 1 kg load.

(Inorganic Fine Particles in Low Refractive Index Layer) The average particle size of the inorganic fine particles in the low refractive index layer is preferably 0.5 to 200 nm. When the particle diameter increases, forward scattering increases, and when the particle diameter exceeds 200 nm, scattered light becomes colored. The average particle size is more preferably from 1 to 100 nm, further preferably from 3 to 70 nm, and most preferably from 5 to 40 nm. The particle diameter of the inorganic fine particles is preferably as uniform (monodispersed) as possible. The inorganic fine particles of the low refractive index layer are preferably made of a metal oxide, a nitride, a sulfide or a halide, more preferably a metal oxide or a metal halide, and more preferably a metal oxide or a metal fluoride. Most preferably. As metal atoms, Na, K,
Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, S
n, In, W, Y, Sb, Mn, Ga, V, Nb, T
a, Ag, Si, B, Bi, Mo, Ce, Cd, Be,
Pb and Ni are preferred, and Mg, Ca, B and Si
Is more preferred. An inorganic compound containing two kinds of metals may be used. Particularly preferred inorganic compounds are alkali metal fluorides (eg, NaF, KF), alkaline earth metal fluorides (eg, CaF ₂ , MgF ₂ ) and silicon dioxide (SiO ₂ ).

The inorganic fine particles of the low refractive index layer are preferably amorphous. The inorganic fine particles are directly dispersed as a dispersion by a sol-gel method (described in JP-A-53-112732 and JP-B-57-9051) or a precipitation method (described in APPLIED OPTICS, 27 , p. 3356 (1988)). Can be synthesized. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available inorganic fine particles (for example, silicon dioxide sol) may be used. The inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium for forming a low refractive index layer. As the dispersion medium, water, alcohol (eg, methanol, ethanol, isopropyl alcohol) and ketone (eg, methyl ethyl ketone, methyl isobutyl ketone) are preferable. The amount of the inorganic fine particles is 50 to 95% by weight based on the total amount of the low refractive index layer. The amount of the inorganic fine particles is preferably 50 to 90% by weight, more preferably 60 to 90% by weight, and most preferably 70 to 90% by weight.

(Microvoids in Low Refractive Index Layer) In the low refractive index layer, it is preferable to form microvoids between the fine particles by stacking at least two or more inorganic fine particles. The porosity of the low refractive index layer is preferably from 3 to 50% by volume, more preferably from 5 to 35% by volume. When spherical particles having the same particle size (perfectly monodispersed) are closest packed, voids having a porosity of 26% by volume are formed between the particles. When spherical particles having the same particle size are simply cubic-filled, voids having a porosity of 48% by volume are formed between the particles. In an actual low-refractive-index layer, there is a certain degree of distribution of the particle size of the fine particles, so that the porosity is a lower value than the above. Increasing the porosity (the size of the microvoids) lowers the refractive index of the low refractive index layer. In the present invention, since the microvoids are formed by stacking the inorganic fine particles, by adjusting the particle diameter of the inorganic fine particles, the size of the microvoids is also moderate (does not scatter light, and there is no problem in the strength of the low refractive index layer. ) Easy to adjust value. Furthermore, by making the particle size of the inorganic fine particles uniform, a low refractive index layer having a microvoid having an optically uniform size can be obtained. Thus, the low refractive index layer can be a microvoid-containing porous film microscopically, but can be an optically or macroscopically uniform film. By forming microvoids, the macroscopic refractive index of the low refractive index layer becomes a value lower than the total refractive index sum of the fine particles and the polymer constituting the low refractive index layer. The refractive index of a layer is the sum of the refractive indices per volume of the components of the layer. The refractive index of the fine particles and the polymer is greater than 1, whereas the refractive index of air is 1.00.
Therefore, a low refractive index layer having a very low refractive index can be obtained by forming microvoids. The microvoids are preferably closed in the low refractive index layer by inorganic fine particles and a polymer. The closed void is
There is an advantage that light is less scattered on the surface of the low-refractive-index layer as compared with an opening opened on the surface of the low-refractive-index layer.

(Polymer of Low Refractive Index Layer)
It is preferred to include the polymer in an amount of 5 to 50% by weight. The polymer has a function of adhering the inorganic fine particles and maintaining the structure of the low refractive index layer containing microvoids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the microvoids. The amount of the polymer is preferably 10 to 30% by weight based on the total amount of the low refractive index layer. In order to bond the inorganic fine particles with the polymer, (1) bonding the polymer to the surface treating agent of the inorganic fine particles, (2) forming a polymer shell around the inorganic fine particles as a core, or (3) It is preferable to use a polymer as a binder between the inorganic fine particles. The polymer to be bonded to the surface treatment agent of (1) is
The shell polymer of (2) or the binder polymer of (3) is preferable. It is preferable that the polymer (2) is formed around the inorganic fine particles by a polymerization reaction before preparing the coating liquid for the low refractive index layer. The polymer of (3) is preferably formed by adding a monomer to the coating liquid for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. (1) to (3) are preferably carried out in combination of two or three kinds, and carried out in two combinations of (1) and (3) or in a combination of three kinds of (1) to (3). It is particularly preferred to do so.
(1) Surface treatment, (2) Shell and (3) Binder will be described sequentially.

(1) Surface Treatment It is preferable to perform a surface treatment on the inorganic fine particles to improve the affinity with the polymer. Surface treatment includes physical surface treatment such as plasma discharge treatment and corona discharge treatment,
It can be classified as chemical surface treatment using a coupling agent. It is preferable to carry out only a chemical surface treatment or a combination of a physical surface treatment and a chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, a titanium coupling agent, a silane coupling agent) is preferably used. When the inorganic fine particles are made of silicon dioxide, surface treatment with a silane coupling agent can be particularly effectively performed. Preferred silane coupling agents are represented by the following formulas (XI-a) and (XI-b).

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In the formula, R ⁶¹ , R ⁶⁵ and R ⁶⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 2 to 1 carbon atoms.
0 is an alkenyl group, an alkynyl group having 2 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁷ and R ⁶⁸ are each independently a carbon atom An alkyl group having 1 to 6 atoms or an acyl group having 2 to 6 carbon atoms. In the formulas (XI-a) and (XI-b), R ⁶¹ , R ⁶⁵ and R ⁶⁶ are preferably an alkyl group, an aryl group, an alkenyl group or an aralkyl group, and are preferably an alkyl group, an aryl group or an alkenyl group. Is more preferable, and an alkyl group or an alkenyl group is most preferable. The alkyl group, the aryl group, the alkenyl group, the alkynyl group and the aralkyl group may have a substituent. Examples of the substituent include glycidyl group, glycidyloxy group, alkoxy group, halogen atom, acyloxy group (eg, acryloyloxy, methacryloyloxy), mercapto, amino, carboxyl, cyano, isocyanato, and alkenylsulfonyl groups (eg, vinylsulfonyl) ) Is included. In the formulas (XI-a) and (XI-b), R ⁶² ,
R ⁶³ , R ⁶⁴ , R ⁶⁷ and R ⁶⁸ are preferably an alkyl group. The alkyl group may have a substituent. Examples of the substituent include an alkoxy group. The silane coupling agent has a double bond in the molecule, and is preferably bonded to the polymer by a reaction of the double bond. The double bond is represented by R ⁶¹ in formulas (XI-a) and (XI-b),
It is preferably present in the substituent of R ⁶⁵ or R ⁶⁶ . Particularly preferred silane coupling agents are represented by the following formula (X
These are indicated by II-a) and (XII-b).

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In the formula, R ⁷¹ and R ⁷⁵ are each independently a hydrogen atom or methyl, and R ⁷⁶ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, An alkenyl group having 2 to 10 carbon atoms,
An alkynyl group having 2 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, wherein R ⁷² , R ⁷³ , R
⁷⁴ , R ⁷⁷ and R ⁷⁸ are each independently an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms, and L ⁷¹ and L ⁷² are each independently a divalent It is a linking group. In the formula (XII-b), R ⁷⁶ represents R ⁶¹ , R ⁶⁵ and R ^{66 in the} formulas (XI-a) and (XI-b).
Has the same definition as In the formula (XII-a) and the formula (XII-b), R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁷ and R ⁷⁸ are represented by the formula (XI-
a) and R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁷ and R ^{68 in} formula (XI-b). Formula (XII-a) Formula (XII-
In b), L ⁷¹ and L ⁷² are preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, and 1 to 6 carbon atoms.
Most preferably, the alkylene group is The formula (XI−
Examples of the silane coupling agent represented by a) include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxy Silane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-
Acryloyloxypropyltrimethoxysilane, γ-
Methacryloyloxypropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β- And cyanoethyltriethoxysilane.

Vinyl trimethoxy silane having a double bond in the molecule, vinyl triethoxy silane, vinyl triacetoxy silane, vinyl trimethoxy ethoxy silane,
γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane are preferable, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane represented by the formula (XII-a) are particularly preferable. Examples of the silane coupling agent represented by the formula (XI-b) include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, γ- Glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercap Topropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,
Methyl vinyl dimethoxy silane and methyl vinyl diethoxy silane are included. Γ with a double bond in the molecule
-Acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, Formula (XII
Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane represented by -b) are particularly preferred.

Two or more coupling agents may be used in combination. In addition to the silane coupling agents represented by the formulas (XI-a) and (XI-b), other silane couplings may be used. Other silane coupling agents include alkyl esters of orthosilicic acid (eg, methyl orthosilicate,
(Ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, t-butyl orthosilicate) and hydrolysates thereof. The surface treatment with the coupling agent can be carried out by adding the coupling agent to the dispersion of the inorganic fine particles and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (eg, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (eg, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid) or a salt thereof (eg, metal salt, ammonium salt) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as a main chain. Polymers containing a fluorine atom in the main chain or side chain are preferred, and polymers containing a fluorine atom in the side chain are more preferred. Polyacrylates or polymethacrylates are preferred, and esters of fluorine-substituted alcohols with polyacrylic or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to reduce the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by weight of fluorine atoms, and more preferably 45 to 75% by weight of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of the ethylenically unsaturated monomer containing a fluorine atom include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Includes esters of fluorinated vinyl ethers and fluorinated alcohols with acrylic acid or methacrylic acid. The polymer containing a fluorine atom is represented by the following formula (XII
It is particularly preferred to have a fluorine-containing repeating unit represented by I).

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In the formula, R ⁸¹ is a hydrogen atom, a fluorine atom or methyl, p is 0 or a positive integer, and n is a positive integer. The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit containing no fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of the ethylenically unsaturated monomer containing no fluorine atom include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylates (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethylhexyl), methacrylate (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (eg, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether),
Vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (eg, N-tertbutylacrylamide, N-cyclohexylacrylamide), methacrylamide, and acrylonitrile are included.

When a binder polymer of (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer, and the shell polymer and the binder polymer may be chemically bonded by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer,
It is easy to maintain microvoids in the low refractive index layer. However, if the Tg is higher than the temperature at the time of forming the low refractive index layer, the fine particles may not be fused and the low refractive index layer may not be formed as a continuous layer (as a result, the strength may be reduced). In this case, it is desirable to use the binder polymer of (3) described later in combination and to form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the inorganic fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain a core composed of inorganic fine particles in an amount of 5 to 90% by volume, and more preferably 15 to 80% by volume. The polymer shell is
It is preferably formed by a radical polymerization method. The radical polymerization method is described in Takatsu Otsu and Masayoshi Kinoshita, Experimental Methods for Polymer Synthesis, Doujin Kagaku (1972) and Takayuki Otsu, Lecture Polymerization Reaction Theory 1 Radical Polymerization (I), Kagaku Dojin (1971) . Specifically, the radical polymerization method is preferably performed by an emulsion polymerization method or a dispersion polymerization method. Emulsion polymerization is described in Soichi Muroi, Chemistry of Polymer Latex, Polymer Publishing Association (1970). For the dispersion polymerization method,
Barrett, Keih EJ, Dispersion Polymerization in O
rganic Media, JOHN WILLEY & SONS (1975).

Examples of the polymerization initiator used in the emulsion polymerization method include inorganic peroxides (eg, potassium persulfate, ammonium persulfate), azonitrile compounds (eg, sodium azobiscyanovalerate), azoamidine compounds (eg, 2, 2 '
-Azobis (2-methylpropionamide) hydrochloride),
Cyclic azoamidine compound (eg, 2,2′-azobis [2
-(5-methyl-2-imidazolin-2-yl) propane hydrochloride), an azoamide compound (eg, 2,2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2) -Hydroxyethyl] propionamide). Inorganic peroxides are preferred, potassium persulfate and ammonium persulfate are particularly preferred. Examples of the polymerization initiator used in the dispersion polymerization method include azo compounds (eg, 2,
2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-
2,2′-azobis (2-methylpropionate), dimethyl-2,2′-azobisisobutyrate) and organic peroxides (eg, lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate) ) Is included. In the dispersion polymerization method, it is preferable to add a polymer dispersant to the surface-treated inorganic fine particles, dissolve the monomer and the polymerization initiator, and carry out the polymerization reaction in a polymerization medium in which the produced polymer is insoluble. Examples of polymerization media include water, alcohols (eg, methanol, ethanol, propanol, isopropanol, 2-methoxy-1-propanol, butanol, t-butanol, pentanol, neopentanol, cyclohexanol, 1-methoxy-2 -Propanol), methyl ethyl ketone, acetonitrile, tetrahydrofuran, ethyl acetate. Water, methanol, ethanol and isopropanol are preferred.
Two or more polymerization media may be used in combination.

In the emulsion polymerization method or the dispersion polymerization method, a chain transfer agent may be used. Examples of chain transfer agents include halogenated hydrocarbons (eg, carbon tetrachloride, carbon tetrabromide, ethyl dibromide acetate, ethyl tribromide acetate, ethyl dibromide benzene, ethane dibromide, ethane dichloride) , Hydrocarbons (eg, benzene, ethylbenzene, isopropylbenzene), thioethers (eg, diazothioether), mercaptans (eg, t-dodecylmercaptan, n-dodecylmercaptan, hexadecylmercaptan, n-octadecylmercaptan, thioglycerol), disulfide (Eg, diisopropylzantogen disulfide), thioglycolic acid and derivatives thereof (eg, thioglycolic acid, 2-ethylhexyl thioglycolate, butyl thioglycolate, methoxybutyl thioglycolate, trimethylolpropane tris (thioglycolate)) Contains It is. Two or more types of core-shell fine particles may be used in combination. Also, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as a main chain.
More preferably, the polymer has a saturated hydrocarbon as a main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as a main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of the monomer having two or more ethylenically unsaturated groups include esters of a polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol Tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and derivatives thereof (eg 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. . The polymer having a polyether as a main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound.

Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by a reaction of a crosslinkable group.
Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. Vinyl sulfonic acid, acid anhydride, cyanoacrylate derivative, melamine,
Etherified methylols, esters and urethanes can also be used as monomers to introduce the crosslinked structure. A functional group that exhibits crosslinkability as a result of a decomposition reaction, such as a block isocyanate group, may be used. Further, in the present invention, the cross-linking group is not limited to the above-mentioned compound, but may be one which shows reactivity as a result of decomposition of the above-mentioned functional group. When used in combination with the shell polymer (2), the glass transition temperature (Tg) of the binder polymer is preferably lower than the Tg of the shell polymer. The temperature difference between the Tg of the binder polymer and the Tg of the shell polymer is preferably 5 ° C. or higher, more preferably 20 ° C. or higher. The binder polymer is preferably formed by adding a monomer to the coating liquid for the low refractive index layer and performing a polymerization reaction (and, if necessary, a crosslinking reaction) simultaneously with or after the coating of the low refractive index layer. The polymerization initiator is the same as the polymerization initiator used for the synthesis of the shell polymer described above. Even if a small amount of polymer (eg, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

[High Refractive Index Layer and Medium Refractive Index Layer] As shown in FIG. 1B, a high refractive index layer may be provided between the antistatic layer and the low refractive index layer. Further, as shown in FIG. 1C, a middle refractive index layer may be provided between the antistatic layer and the high refractive index layer. The refractive index of the high refractive index layer is preferably from 1.65 to 2.40, and is preferably from 1.70 to 2.20.
Is more preferable. The refractive index can be determined by measurement using an Abbe refractometer or estimation from the reflectance of light from the layer surface. The refractive index of the middle refractive index layer is adjusted so as to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer.
It is preferably from 65 to 1.85. The thickness of the high refractive index layer and the middle refractive index layer is preferably from 20 nm to 500 nm, more preferably from 30 nm to 300 nm, and most preferably from 40 nm to 200 nm. The haze of the high refractive index layer and the middle refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the middle refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more at a pencil hardness of 1 kg load. The high refractive index layer and the middle refractive index layer are preferably formed using a polymer having a relatively high refractive index. Examples of high refractive index polymers include polystyrene, styrene copolymers, polycarbonates, melamine resins, phenolic resins, epoxy resins, and polyurethanes obtained by reacting cyclic (alicyclic or aromatic) isocyanates with polyols. . Other polymers having a cyclic (aromatic, heterocyclic, alicyclic) group and polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. A polymer may be formed by a polymerization reaction of a monomer capable of radical curing by introducing a double bond. Further, the polymer having an anionic group used for the antistatic layer may be used for the high refractive index layer and the medium refractive index layer.
Inorganic fine particles having a high refractive index may be dispersed in the polymer. When inorganic fine particles having a high refractive index are used, a polymer having a relatively low refractive index, such as a vinyl polymer (including an acrylic polymer), a polyester polymer (including an alkyd polymer), a cellulosic polymer, or a urethane polymer However, it can be used for stably dispersing the inorganic fine particles. An organically substituted silicon compound may be added to the high refractive index layer and the medium refractive index layer. As the silicon compound, a silane coupling agent or a hydrolyzate thereof used for the surface treatment of the inorganic fine particles in the low refractive index layer is preferably used.

As the inorganic fine particles, oxides of metals (eg, aluminum, titanium, zirconium, antimony) are preferable. A powder or colloidal dispersion of inorganic fine particles is mixed with the above-mentioned polymer or organosilicon compound and used. The average particle size of the inorganic fine particles is 10 to 20.
It is preferably 0 nm. The high refractive index layer and the medium refractive index layer may be formed from an organometallic compound having a film forming ability. It is preferable that the organometallic compound can be dispersed in an appropriate medium or is in a liquid state. Examples of organometallic compounds include metal alcoholates (eg, titanium tetraethoxide,
Titanium tetra-i-propoxide, titanium tetra-n-
Propoxide, titanium tetra-n-butoxide, titanium tetra-sec-butoxide, titanium tetra-tert-butoxide, aluminum triethoxide, aluminum tri-i-propoxide, aluminum tributoxide, antimony triethoxide, antimony tributoxide,
Zirconium tetraethoxide, zirconium tetra-
i-propoxide, zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirconium tetra-te
rt-butoxide), chelate compounds (eg, di-isopropoxytitanium bisacetylacetonate, di-butoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, bisacetylacetone zirconium, aluminum acetylacetonate, aluminum di- n-butoxide monoethyl acetoacetate, aluminum di-i-propoxide monomethyl acetoacetate, tri-n-butoxide zirconium monoethyl acetoacetate), organic acid salts (eg,
Active inorganic polymers based on zirconium carbonate and zirconium). Alkyl silicates, hydrolysates thereof, and finely divided silica, particularly silica gel dispersed in a colloidal form, may be added to the high refractive index layer and the medium refractive index layer.

(Other Layers) The antireflection film further includes
A hard coat layer, a moisture-proof layer, an undercoat layer and a protective layer may be provided. The hard coat layer is provided for imparting scratch resistance to the transparent support. The hard coat layer also has a function of enhancing the adhesion between the transparent support and the layer thereon. However, since the antistatic layer formed according to the present invention has excellent strength, it can also function as a hard coat layer, and the hard coat layer is not essential. On the transparent support, an adhesive layer, a shield layer, a sliding layer and an antistatic layer may be provided in addition to the antistatic layer. The shield layer is provided to shield electromagnetic waves and infrared rays. A protective layer may be provided on the low refractive index layer. The protective layer functions as a slip layer or an antifouling layer.

Examples of the slipping agent used in the slipping layer include polyorganosiloxane (eg, polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, alkyl-modified polydimethylsiloxane), natural wax (eg, carna Uba wax,
Candelilla wax, jojoba oil, rice wax, wood wax, beeswax, lanolin, whale wax, montan wax), petroleum wax (eg, paraffin wax, microcrystalline wax), synthetic wax (eg, polyethylene wax, Fischer-Tropsch wax) ), Higher fatty acid amides (eg, stearamide, oleinamide, N, N′-methylenebisstearamide), higher fatty acid esters (eg, methyl stearate, butyl stearate, glycerin monostearate, sorbitan monooleate), higher Fatty acid metal salts (eg, zinc stearate) and fluorine-containing polymers (perfluoro main chain type perfluoropolyether, perfluoro side chain type perfluoropolyether, alcohol-modified perfluoropolyether, isocyanate-modified Perfluoropolyether). A fluorinated hydrophobic compound (eg, fluorinated polymer, fluorinated surfactant, fluorinated oil) is added to the stain prevention layer. The thickness of the protective layer is preferably 20 nm or less so as not to affect the antireflection function. The thickness of the protective layer is preferably 2 to 20 nm, more preferably 3 to 20 nm, and most preferably 5 to 10 nm.

(Production and Use of Antireflection Film) Each layer of the antireflection film is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrusion coating method ( According to U.S. Pat. No. 2,681,294), it can be formed by coating. Two or more layers may be applied simultaneously. For the method of simultaneous coating, see U.S. Pat. Nos. 2,761,791 and 2,918,898 and 3,508.
Nos. 947 and 3526528, and in Yuji Harazaki, Coating Engineering, page 253, Asakura Shoten (1973). The lower the reflectance of the antireflection film, the better.
Specifically, the average reflectance in the wavelength region of 450 to 650 nm is preferably 2% or less, more preferably 1% or less, and most preferably 0.7% or less. The haze of the antireflection film (when the following antiglare function is not provided) is preferably 3% or less, and 1% or less.
%, And most preferably 0.5% or less. The strength of the antireflection film is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher at a pencil hardness of 1 kg load. The anti-reflection film may have an anti-glare function for scattering external light. The anti-glare function is obtained by forming irregularities on the surface of the antireflection film. FIG.
In the low refractive index layer using fine particles as shown in (1), irregularities can be formed on the surface of the antireflection film by the fine particles. If the anti-glare function obtained by the fine particles is not sufficient, a small amount (0.1 to 2 μm) of relatively large particles (particle size: 50 nm to 2 μm) is added to the low refractive index layer, high refractive index layer, medium refractive index layer or antistatic layer. To 50% by weight). When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 30%, and preferably 5 to 20%.
%, More preferably 7 to 20%. The anti-reflection film is a liquid crystal display (LC
D), an image display device such as a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT). The antireflection film adheres the transparent support side to the image display surface of the image display device. The antireflection film can be further used for a case cover, an optical lens, a spectacle lens, a window shield, a light cover and a helmet shield.

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[Example 1] (Preparation of ATO dispersion) ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2Ω · c)
m) 20 parts by weight, 3 parts by weight of the following anionic monomer (1), 3 parts by weight of the following anionic monomer (2) and 74 parts by weight of cyclohexanone were dispersed by a sand grinder mill to prepare an ATO dispersion.

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The weight average diameter of ATO in the obtained dispersion was evaluated with a Coulter counter. The results are shown in Table 1.

(Preparation of coating solution for antistatic layer) Dipentaerythritol hexaacrylate (D
PHA, manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), methyl ethyl ketone and cyclohexanone to prevent charge A coating solution for a layer was prepared. The amount of addition was such that the weight ratio of the total amount of the monomers (total amount of dipentaerythritol hexaacrylate, the anionic monomer (1) and the anionic monomer (2)) to ATO was 65/35, the photopolymerization initiator and the photoinitiator The weight ratio of the total amount of the photopolymerization initiator and the photosensitizer to the total amount of the monomers is 6/100, and the weight ratio of the methyl ethyl ketone and the cyclohexanone is 1/1.
/ 1. ATO in the obtained coating solution
Was evaluated by a settling test. After 100 hours from the standing of the coating solution, A was given if no supernatant appeared, and B was given if it appeared. The results are shown in Table 1.

(Formation of Antistatic Layer) A polyethylene undercoat layer was provided on a polyethylene terephthalate film. The coating solution for the antistatic layer was uniformly applied on the undercoat layer with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, an antistatic layer having a thickness (dry film thickness) of 6 μm was formed. Measure the haze of the antistatic layer with a haze meter (NDH
-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.), and the surface resistance was measured by a four-point probe method (Loresta AP, manufactured by Mitsubishi Yuka Co., Ltd.). Further, the pencil hardness of the antistatic layer was measured according to JIS-K-5.
It measured according to 400. The results are shown in Table 1.

(Formation of Low Refractive Index Layer)
A 300% by weight methanol dispersion (methanol silica sol, manufactured by Nissan Chemical Co., Ltd.) was added to a silane coupling agent (K
BM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)
3 g of 1N hydrochloric acid was added, and the mixture was stirred at room temperature for 5 hours and then left at room temperature for 5 days to obtain a dispersion of silane-coupled silica fine particles. Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907,
Ciba Geigy), photosensitizer (Kayacure DET)
X, Nippon Kayaku Co., Ltd.), isopropyl alcohol and diacetone alcohol were added to prepare a coating solution for a low refractive index layer. The addition amount is such that the refractive index of the low refractive index layer is 1.40.
It was adjusted to be. Specifically, the weight ratio of the surface-treated silica fine particles to dipentaerythritol hexaacrylate was 83.7 / 16.3, the weight ratio of the photopolymerization initiator to the photosensitizer was 2/1, and the photopolymerization was started. The weight ratio of the total amount of the agent and the photosensitizer to the total amount of the monomers is 6/100, and the weight ratio of methanol, isopropyl alcohol and diacetone alcohol in the silica dispersion is 15/65 /.
Adjusted to 20. The coating solution was applied on the antistatic layer using a bar coater, and cured by irradiating ultraviolet rays to form a low refractive index layer having a dry film thickness of 95 nm and containing microvoids. Thus, an antireflection film was formed. The haze and pencil strength of the formed antireflection film were evaluated in the same manner as the antistatic layer. Further, the average reflectance (wavelength range of 450 to 650 nm) of the antireflection film is measured with a reflectometer (V
-550, ARV-474, manufactured by JASCO Corporation). Furthermore, the transparent support side of the anti-reflection film was adhered to the CRT surface, and the room where dust of 0.5 μm or more was 1 to 2 million per 1 ft ³ (cubic foot) was used.
Used for 4 hours. The number of adhered dust per 100 cm ^{2 of the} antireflection film was measured.
B from 49 to 49, C from 50 to 199
The case of 200 or more was evaluated as D. The results are shown in Table 1.

Example 2 ITO (tin-containing indium oxide, specific surface area: 40 m ² / g, powder specific resistance: 0.1 Ω ·
cm) 20 parts by weight, 3 parts by weight of the anionic monomer (1) used in Example 1, 3 parts by weight of the anionic monomer (2) used in Example 1, and 74 parts by weight of cyclohexanone were dispersed by a sand grinder mill. , An ITO dispersion was prepared. Except for using the obtained ITO dispersion,
An antireflection film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2 Ω · c
m) 20 parts by weight and 80 parts by weight of cyclohexanone
The mixture was dispersed by a sand grinder mill to prepare an ATO dispersion. Except that the obtained ATO dispersion was used, an antireflection film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2 Ω · c
m) 20 parts by weight, 6 parts by weight of a surfactant (Brenol A-17, manufactured by Yoshimura Oil Chemical Co., Ltd.) and 7 parts of cyclohexanone
4 parts by weight were dispersed with a sand grinder mill,
A TO dispersion was prepared. Using the obtained ATO dispersion,
Same as Example 1 except that the weight ratio of the total amount of the photopolymerization initiator and the photosensitizer used for the antistatic layer to the total amount of the surfactant and dipentaerythritol hexaacrylate was adjusted to 6/100. An antireflection film was prepared and evaluated. The results are shown in Table 1.

Comparative Example 3 An antireflection film was prepared and evaluated in the same manner as in Example 1 except that the ATO dispersion was not added to the antistatic layer coating solution. The results are shown in Table 1.

Example 3 ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2Ω · c
m) 20 parts by weight, the following anionic monomer (3), 6 parts by weight, the following cationic monomer, 1 part by weight, and cyclohexanone, 73 parts by weight, were dispersed by a sand grinder mill to prepare an ATO dispersion. Except that the obtained ATO dispersion was used, an antireflection film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

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Example 4 ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2 Ω · c
m) 20 parts by weight, 6 parts by weight of the following anionic monomer (4) and 74 parts by weight of cyclohexanone were dispersed by a sand grinder mill to prepare an ATO dispersion.
Except that the obtained ATO dispersion was used, an antireflection film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

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Example 5 ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2 Ω · c
m) 20 parts by weight, 6 parts by weight of the anionic monomer (4) used in Example 4, 1 part by weight of the cationic monomer used in Example 3, and 73 parts by weight of cyclohexanone were dispersed by a sand grinder mill, and dispersed by ATO. Was prepared. Except that the obtained ATO dispersion was used, an antireflection film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6 ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2 Ω · c
m) 20 parts by weight, 6 parts by weight of the following anionic monomer (5), 1 part by weight of the cationic monomer used in Example 3, and 73 parts by weight of cyclohexanone were dispersed by a sand grinder mill to prepare an ATO dispersion. . Except that the obtained ATO dispersion was used, an antireflection film was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

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Example 7 ATO (antimony-containing tin oxide, specific surface area: 95 m ² / g, powder specific resistance: 2Ω · c
m) 20 parts by weight, 6 parts by weight of the following anionic monomer (6), 1 part by weight of the cationic monomer used in Example 3, and 73 parts by weight of cyclohexanone were dispersed by a sand grinder mill to prepare an ATO dispersion. . ATO
In the dispersion, glycerol dimethacrylate (Blemmer GMR, manufactured by NOF Corporation), a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy), a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), methyl ethyl ketone And cyclohexanone were added to prepare an antistatic layer coating solution. The amount of addition is such that the weight ratio of the total amount of monomers (total amount of glycerol dimethacrylate, anionic monomer (6) and cationic monomer) to ATO is 65/35, and the weight of photopolymerization initiator and photosensitizer. The ratio is 3 /
1. The weight ratio of the total amount of the photopolymerization initiator and the photosensitizer to the total amount of the monomers was adjusted to 6/100, and the weight ratio of methyl ethyl ketone to cyclohexanone was adjusted to 1/1. A polyester undercoat layer was provided on a polyethylene terephthalate film, and a coating solution for an antistatic layer was uniformly applied on the undercoat layer with a bar coater, irradiated with ultraviolet rays, and further heated at 100 ° C. for 1 hour to cure the layer. .
Thus, an antistatic layer having a thickness (dry film thickness) of 6 μm was formed. A low refractive index layer having a dry film thickness of 95 nm was formed on the antistatic layer in the same manner as in Example 1 to form an antireflection film. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

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Example 8 ATO (tin oxide containing antimony, specific surface area: 95 m ² / g, powder specific resistance: 2Ω · c
m) 20 parts by weight, 6 parts by weight of the following anionic monomer (7), 1 part by weight of the cationic monomer used in Example 3, and 73 parts by weight of cyclohexanone were dispersed by a sand grinder mill to prepare an ATO dispersion. . ATO
The following epoxidized cyclohexane monomer, the following aromatic sulfonium salt (photopolymerization initiator), methyl ethyl ketone and cyclohexanone were added to the dispersion to prepare a coating solution for an antistatic layer. The amount added is the total amount of the monomers (the total amount of the epoxidized cyclohexane-based monomer, the anionic monomer (7) and the cationic monomer)
And the weight ratio of the photopolymerization initiator and the monomer was 6/100, and the weight ratio of methyl ethyl ketone and cyclohexanone was 1/1. A polyester undercoat layer was provided on a polyethylene terephthalate film, and a coating solution for an antistatic layer was uniformly applied on the undercoat layer with a bar coater, irradiated with ultraviolet rays, and further heated at 100 ° C. for 1 hour to cure the layer. . Thus, an antistatic layer having a thickness (dry film thickness) of 6 μm was formed. A low refractive index layer having a dry film thickness of 95 nm was formed on the antistatic layer in the same manner as in Example 1 to form an antireflection film. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

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Table 1 Table 1 (Configuration of antistatic layer) Sample Conductive fine particle number of antistatic layer Binder type Average particle size Dispersion stability ───────────────────────────────── １ Example 1 Anionic Crosslinking ATO 30 nm A Example 2 Anionic Crosslinking ITO 35 nm A Comparative Example 1 Crosslinking Only ATO 210 nm B Comparative Example 2 Crosslinking + Surfactant ATO 36 nm A Comparative Example 3 Crosslinking Only None--Example 3 Amphoteric crosslinked ATO 33 nm A Example 4 Anionic crosslinked ATO 39 nm A Example 5 Amphoteric crosslinked ATO 35 nm A Example 6 Amphoteric crosslinked ATO 36 nm A Example 7 Amphoteric crosslinked ATO 35 nm A Example 8 Amphoteric crosslinked ATO 37 nm A─── ─ ───────────────────────────────

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[Table 2] Table 1 (Evaluation of antistatic layer) Sample No. Haze Surface resistance Strength ──────────────────────────────────── Example 1 0.2% 1 0.3 × 10 ⁸ Ω / sq 3H Example 2 0.3% 5.1 × 10 ⁶ Ω / sq 3H Comparative Example 1 18.8% 4.2 × 10 ⁷ Ω / sq 3H Comparative Example 2 0.2% 1.5 × 10 ⁸ Ω / sq 4B Comparative Example 3 0.1% 10 ¹⁵ Ω / sq or more 3H Example 3 0.2% 1.7 × 10 ⁸ Ω / sq 3H Example 4 0.3% 1. 3 × 10 ⁸ Ω / sq 3H Example 5 0.2% 1.3 × 10 ⁸ Ω / sq 3H Example 6 0.2% 1.6 × 10 ⁸ Ω / sq 3H Example 7 0.4% 1 0.8 × 10 ⁸ Ω / sq 3H Example 8 0.4% 1.5 × 10 ⁸ Ω / sq 3H ────────────────────────────────────

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[Table 3] Table 1 (Evaluation of antireflection film) Sample No. Haze intensity Average reflectance Dust adhesion 例 Example 10 0.3% 3H 0.90% B Example 2 0.4% 3H 0.92% A Comparative Example 1 17.5% 3H Unmeasurable B Comparative Example 2 0.4% 4B 0.95% B Comparative Example 30 0.2% 3H 0.92% D Example 3 0.3% 3H 0.95% B Example 4 0.4% 3H 0.93% B Example 5 0.3% 3H 0.94% B Example 6 0.4% 3H 0.93% B Example 7 0.5% 3H 0.96% B Example 8 0.6% 3H 0.94% B ────────────── ─────────

Example 9 On the antistatic layer formed in Example 1, a low refractive index layer made of a photocrosslinkable fluoropolymer and having a thickness of 95 nm (refractive index: 1.40, pencil hardness:
2H) to form an antireflection film. The haze, pencil hardness, average reflectance, and dust adhesion of the prepared anti-reflection film were evaluated in the same manner as in Example 1. further,
To evaluate the antifouling property, the contact angle of water was measured. The results are shown in Table 2.

Comparative Example 4 On the antistatic layer formed in Comparative Example 3, a low refractive index layer was formed in the same manner as in Example 9 to form an antireflection film. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 2.

Example 10 On the low refractive index layer of the antireflection film prepared in Example 1, a fluorine-containing silane coupling agent was applied at 10 mg / m ² and heated at 100 ° C. for 1 hour. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 2.

Example 11 On the low refractive index layer of the antireflection film prepared in Example 2, a fluorine-containing silane coupling agent was applied at 10 mg / m ² and heated at 100 ° C. for 1 hour. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 2.

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[Table 4] Table 2 (Evaluation of antireflection film) Sample No. Haze intensity Average reflectance Dust adhesion Contact angle ──────────────────────────────────── Example 9 0.3% 2H 0.93% B 100 ゜ Comparative Example 4 0.2% 2H 0.93% D 100 ゜ Example 10 0.3% 3H 1.01% B 106 ゜ Example 11 0.3% 3H 1.00% A 105 ゜

Example 12 30.0 parts by weight of titanium dioxide (weight average diameter of primary particles: 30 nm), 2.25 parts by weight of the anionic monomer (1) used in Example 1, and used in Example 1 2.25 parts by weight of the anionic monomer (2),
0.3 parts by weight of the cationic monomer used in Example 3 and 65.2 parts by weight of cyclohexanone were dispersed by a sand grinder mill to prepare a titanium dioxide dispersion. The weight average diameter of titanium dioxide in the obtained dispersion was measured with a Coulter counter to be 52 nm. To the titanium dioxide dispersion, dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (Irgacure 907, manufactured by Ciba-Geigy), photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) Co., Ltd.), methyl ethyl ketone and cyclohexanone were added to prepare a coating solution for a high refractive index layer. The amount of addition was adjusted so that the refractive index of the high refractive index layer was 1.75. Specifically, the weight ratio of the total amount of the monomers (dipentaerythritol hexaacrylate, the total amount of the anionic monomer (1), the anionic monomer (2) and the cationic monomer) to titanium dioxide is 53.4.
/46.6, the weight ratio of the photopolymerization initiator to the photosensitizer is 3 /
1. The weight ratio of the total amount of the photopolymerization initiator and the photosensitizer to the total amount of the monomers was adjusted to 6/100, and the weight ratio of methyl ethyl ketone to cyclohexanone was adjusted to 1/1. The prepared coating solution for a high refractive index layer was uniformly applied on the antistatic layer formed in Example 1 with a bar coater, and irradiated with ultraviolet rays to cure the layer. Thus, a high refractive index layer having a thickness (dry film thickness) of 60 nm was formed. The coating solution for the low refractive index layer prepared in Example 1 was uniformly applied on the high refractive index layer with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, a low refractive index layer having microvoids and a thickness (dry film thickness) of 100 nm was formed. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 3.

Example 13 A high refractive index layer and a low refractive index layer were formed on the antistatic layer formed in Example 2 in the same manner as in Example 12, to form an antireflection film. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 3.

Comparative Example 5 A high refractive index layer and a low refractive index layer were formed on the antistatic layer formed in Comparative Example 3 in the same manner as in Example 12, to form an antireflection film. The prepared antireflection film was evaluated in the same manner as in Example 9. Third result
It is shown in the table.

Example 14 On the high refractive index layer formed in Example 12, a low refractive index layer made of a photocrosslinkable fluoropolymer and having a thickness of 100 nm (refractive index: 1.40, pencil hardness) : 2H) to form an antireflection film. The prepared antireflection film was evaluated in the same manner as in Example 9.
The results are shown in Table 3.

Comparative Example 6 On the high refractive index layer formed in Comparative Example 5, a low refractive index layer was formed in the same manner as in Example 14.
An anti-reflection film was formed. About the created anti-reflection film,
Evaluation was performed in the same manner as in Example 9. The results are shown in Table 3.

Example 15 On the low refractive index layer of the antireflection film prepared in Example 12, a fluorine-containing silane coupling agent was applied at 10 mg / m ² and heated at 100 ° C. for 1 hour. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 3.

Example 16 A fluorine-containing silane coupling agent was applied at 10 mg / m ² on the low refractive index layer of the antireflection film prepared in Example 13, and heated at 100 ° C. for 1 hour. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 3.

[0110]

[Table 5] Table 3 (Evaluation of antireflection film) Sample No. Haze intensity Average reflectance Dust adhesion Contact angle ──────────────────────────────────── Example 12 0.3% 3H 0.63% B 36 ゜ Example 13 0.3% 3H 0.62% A 34 ゜ Comparative Example 5 0.2% 3H 0.62% D 35 ゜ Example 14 0.3% 2H 0.62% B 101 {Comparative Example 6 0.2% 2H 0.63% D 102} Example 15 0.3% 3H 0.66% B 108 # Example 16 0.3% 3H 0.67% A 107 ゜

Example 17 Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) were added to the titanium dioxide dispersion prepared in Example 12. A photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), methyl ethyl ketone and cyclohexanone were added to prepare a coating solution for a medium refractive index layer and a coating solution for a high refractive index layer. The amount of the coating liquid for the medium refractive index layer was adjusted so that the refractive index of the medium refractive index layer was 1.66. Specifically, the weight ratio of the total amount of the monomers (dipentaerythritol hexaacrylate, the total amount of the anionic monomer (1), the anionic monomer (2) and the cationic monomer) to titanium dioxide is 71.6 / 28. 0.4, the weight ratio of the photopolymerization initiator to the photosensitizer is 3/1, the weight ratio of the total amount of the photopolymerization initiator and the photosensitizer to the total amount of the monomers is 6/100,
And it adjusted so that the weight ratio of methyl ethyl ketone and cyclohexanone might be 1/1. The amount of the high refractive index layer coating solution was adjusted so that the refractive index of the high refractive index layer was 1.95. Specifically, the weight ratio of the total amount of the monomers (total amount of dipentaerythritol hexaacrylate, anionic monomer (1), anionic monomer (2) and cationic monomer) to titanium dioxide is 2
6.0 / 74.0, the weight ratio of the photopolymerization initiator to the photosensitizer is 3/1, and the weight ratio of the total amount of the photopolymerization initiator and the photosensitizer to the total amount of the monomers is 6 / 100, and the weight ratio between methyl ethyl ketone and cyclohexanone was adjusted to be 1/1. On the antistatic layer formed in Example 1, the prepared coating solution for the middle refractive index layer was uniformly applied with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, a middle refractive index layer having a thickness (dry film thickness) of 79 nm was formed. The prepared coating solution for a high-refractive-index layer was uniformly applied on the medium-refractive-index layer with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, the thickness (dry film thickness) is 1
A 29 nm high refractive index layer was formed. On the high refractive index layer,
The coating liquid for a low refractive index layer prepared in Example 1 was uniformly applied with a bar coater, and irradiated with ultraviolet rays to cure the layer. In this way, the microvoids have a thickness (dry film thickness)
Formed a low refractive index layer having a thickness of 92 nm. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

Example 18 A medium refractive index layer, a high refractive index layer and a low refractive index layer were formed on the antistatic layer formed in Example 2 in the same manner as in Example 17, and the antireflection film was formed. It was created. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

Comparative Example 7 A medium refractive index layer, a high refractive index layer and a low refractive index layer were formed on the antistatic layer formed in Comparative Example 3 in the same manner as in Example 17, and an antireflection film was formed. Created.
The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

[Example 19] Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) were added to the titanium dioxide dispersion prepared in Example 12. A photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), methyl ethyl ketone and cyclohexanone were added to prepare a coating solution for a medium refractive index layer and a coating solution for a high refractive index layer. The amount of the coating liquid for the medium refractive index layer was adjusted so that the refractive index of the medium refractive index layer was 1.80. Specifically, the weight ratio of the total amount of the monomers (dipentaerythritol hexaacrylate, the total amount of the anionic monomer (1), the anionic monomer (2) and the cationic monomer) to titanium dioxide is 45.2 / 54. 0.8, the weight ratio of the photopolymerization initiator to the photosensitizer is 3/1, the weight ratio of the total amount of the photopolymerization initiator and the photosensitizer to the total amount of the monomers is 6/100,
And it adjusted so that the weight ratio of methyl ethyl ketone and cyclohexanone might be 1/1. The amount of the high refractive index layer coating solution was adjusted so that the refractive index of the high refractive index layer was 1.95. Specifically, the total amount of monomers (total amount of dipentaerythritol hexaacrylate, anionic monomer (1) and anionic monomer (2))
The weight ratio of the photopolymerization initiator and the photosensitizer is 3/1, the weight ratio of the photopolymerization initiator and the photosensitizer is 3/1, the total amount of the photopolymerization initiator and the photosensitizer, and the total of the monomers. Weight ratio to quantity is 6
/ 100, and the weight ratio of methyl ethyl ketone to cyclohexanone was adjusted to 1/1. On the antistatic layer formed in Example 1, the prepared coating solution for the middle refractive index layer was uniformly applied with a bar coater, and the layer was cured by irradiating ultraviolet rays. In this way, the thickness (dry film thickness)
Formed a middle refractive index layer of 78 nm. The prepared coating solution for a high-refractive-index layer was uniformly applied on the medium-refractive-index layer with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, a high refractive index layer having a thickness (dry film thickness) of 58 nm was formed. The coating solution for the low refractive index layer prepared in Example 1 was uniformly applied on the high refractive index layer with a bar coater, and the layer was cured by irradiating ultraviolet rays. Thus, a low refractive index layer having microvoids and a thickness (dry film thickness) of 95 nm was formed. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

Example 20 On the high refractive index layer formed in Example 17, a low refractive index layer made of a photocrosslinkable fluoropolymer and having a thickness of 92 nm (refractive index: 1.40, pencil hardness) : 2H) to form an antireflection film. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

Comparative Example 8 On the high refractive index layer formed in Comparative Example 7, a low refractive index layer was formed in the same manner as in Example 20.
An anti-reflection film was formed. About the created anti-reflection film,
Evaluation was performed in the same manner as in Example 9. The results are shown in Table 4.

Example 21 A fluorine-containing silane coupling agent was applied at 10 mg / m ² on the low refractive index layer of the antireflection film prepared in Example 17, and heated at 100 ° C. for 1 hour. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

Example 22 On the low refractive index layer of the antireflection film prepared in Example 18, a fluorine-containing silane coupling agent was applied at 10 mg / m ² and heated at 100 ° C. for 1 hour. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

Example 23 A fluorine-containing silane coupling agent was applied at 10 mg / m ² on the low refractive index layer of the antireflection film prepared in Example 19, and heated at 100 ° C. for 1 hour. The prepared antireflection film was evaluated in the same manner as in Example 9. The results are shown in Table 4.

[0120]

[Table 6] Table 4 (Evaluation of antireflection film) Sample No. Haze intensity Average reflectance Dust adhesion Contact angle ──────────────────────────────────── Example 17 0.3% 3H 0.34% B 36 ゜ Example 18 0.3% 3H 0.33% A 33 ゜ Comparative Example 7 0.2% 3H 0.34% D 34 ゜ Example 19 0.3% 3H 0.35% B 35 ゜ Example 20 0.3% 2H 0.37% B 101 ゜ Comparative Example 8 0.2% 2H 0.35% D 102 ゜ Example 21 0.3% 3H 0.38% B 108 ゜ Example 22 0.3% 3H 0.38% A 108 ゜ Example 23 0.3% 3H 0.39% B 106 ゜───────────────────

[0121]

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing various layer configurations of an antireflection film.

FIG. 2 is a schematic sectional view of an antistatic layer.

FIG. 3 is a schematic sectional view of a low refractive index layer.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 low refractive index layer 2 high refractive index layer 3 medium refractive index layer 4 antistatic layer 5 transparent support 11 inorganic fine particles of low refractive index layer 12 microvoids in low refractive index layer 13 binder of low refractive index layer 41 antistatic layer Conductive inorganic fine particles of 42 Binder for antistatic layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 33/14 C08L 101/02 101/02 C09D 4/00 C09D 4/00 G02B 1/10 Z

Claims (8)

[Claims] 1. A transparent plastic film support, an antistatic layer having a thickness of 2 to 10 μm, and a refractive index of 1.20.
And a low refractive index layer having an average particle diameter of 1 to 200 nm. An anti-reflection film containing 10 to 80% by weight of a polymer having the following. 2. The antireflection film according to claim 1, wherein the polymer having an anionic group of the antistatic layer has a phosphate group or a sulfonic acid group as an anionic group. 3. The antireflection film according to claim 1, wherein the polymer having an anionic group of the antistatic layer further has an amino group or an ammonium group. 4. The antistatic layer has a surface resistance of 10 ^{10 to} 10
^The antireflection film according to claim 1, wherein the resistance is ⁵ Ω / sq. 5. The reflection according to claim 1, wherein the antistatic layer is a layer formed by coating, and the polymer having an anionic group is a polymer formed by a polymerization reaction simultaneously with or after coating the layer. Prevention film. 6. The method according to claim 1, wherein the conductive inorganic fine particles of the antistatic layer are made of IT.
The anti-reflection film according to claim 1, comprising O or ATO. 7. The low-refractive-index layer contains 50 to 95% by weight of inorganic fine particles having an average particle size of 0.5 to 200 nm and 5 to 50% by weight of a polymer, and stacks at least two or more inorganic fine particles. The antireflection film according to claim 1, wherein the antireflection film is a layer in which microvoids are formed between fine particles. 8. A transparent plastic film support, an antistatic layer having a thickness of 2 to 10 μm, and a refractive index of 1.20.
And a low refractive index layer having an average particle diameter of 1 to 200 nm. An image display device comprising: an antireflection film containing 10 to 80% by weight of a polymer having the following formula: wherein the transparent plastic film support is on the image display device side.