JPH11295503A - Multilayered antireflection film and image display device using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain easy production comparable to that in the case where all layers are formed as coating layers and to obtain a multilayered antireflection film having excellent optical function by forming a high refractive index layer as a coating layer and disposing a low refractive index layer as a vapor-deposited layer on the high refractive index layer. SOLUTION: The antireflection film has a layer structure comprising a transparent substrate 1, a barrier layer 2, a high refractive index layer 3 and a low refractive index layer 4. The barrier layer 2 and the high refractive index layer 3 are coating layers and the low refractive index layer 4 is a vapor-deposited layer. The relation of (the refractive index of the low refractive index layer 4)<(the refractive index of the substrate 1)<(the refractive index of the high refractive index layer 3) is satisfied. The high refractive index layer 3 is formed by coating a coating soln. contg. inorg. fine particles and an ethylenically unsatd. monomer and polymerizing the monomer. The low refractive index layer 4 is formed by vapor-depositing silicon dioxide or magnesium fluoride on the high refractive index layer 3. A medium refractive index layer 5 may be disposed between the substrate 1 and the high refractive index layer 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer antireflection film having a transparent support, a high refractive index layer 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). As the antireflection film, a multilayer antireflection film in which a transparent thin film of a metal oxide is laminated has been conventionally 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 can be formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method. Usually, it is formed by a vacuum evaporation method, which is a kind of physical evaporation method. The multilayer vapor-deposited film of metal oxide has excellent optical properties as an antireflection film. A method for forming a multilayer antireflection film by vapor deposition is disclosed in
-144702, 61-245449, 62-
178901 and JP-A-9-197103.

However, the method of forming a multilayer antireflection film by vapor deposition has low productivity and is not suitable for mass production. In order to manufacture a multilayer anti-reflective coating, it is necessary to repeat the deposition process with the number of layers precisely controlled according to the relationship between the refractive index and the layer thickness of each layer that has been optimally designed in advance. There is. The repetition of the deposition process was a complicated and low productivity method. A method has been proposed in which a multilayer antireflection film is formed by coating instead of vapor deposition. Tokiko Showa 60-5
Japanese Patent No. 9250 discloses an antireflection layer having fine pores and a particulate inorganic substance. 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-59-50401 discloses a multilayer antireflection film in which a support, a high refractive index layer and a low refractive index layer are laminated in this order. This publication also discloses a multilayer antireflection film having a medium refractive index layer between a support and a high refractive index layer. The low refractive index layer is formed by applying a polymer or inorganic fine particles.

Japanese Patent Application Laid-Open No. 2-245702 discloses an antireflection film in which two or more kinds of ultrafine particles (for example, MgF ₂ and SiO ₂ ) are mixed and the mixing ratio is changed in the thickness direction. I have. By changing the refractive index by changing the mixing ratio, the same optical properties as the multilayer antireflection film provided with the high refractive index layer and the low refractive index layer described in JP-A-59-50401 are obtained. It has gained. JP-A-5-130
Japanese Patent Laid-Open No. 21 discloses that the gap between ultrafine particles existing in the antireflection film described in Japanese Patent Application Laid-Open No. 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-8-11
Nos. 0401 and 8-179123 disclose that a high refractive index film having a refractive index of 1.80 or more is formed by introducing inorganic fine particles having a high refractive index into a plastic and applied to an antireflection film. Is disclosed.

[0005]

The productivity is higher when the multilayer antireflection film is produced by coating than when it is produced by vapor deposition. However, from the viewpoint of optical functions, the multilayer antireflection film manufactured by vapor deposition is superior to the multilayer antireflection film manufactured by coating. An object of the present invention is to provide a multilayer antireflection film that is suitable for mass production and has excellent optical functions.

[0006]

The object of the present invention has been attained by the following multilayer antireflection films (1) to (5) and the following image display device (6). (1) A transparent support, a high refractive index layer and a low refractive index layer are provided in this order, and the transparent support, the high refractive index layer and the low refractive index layer have a refractive index of the low refractive index layer <the transparent support. A multilayer antireflection film having a refractive index that satisfies the relationship of the refractive index of the high refractive index layer, wherein the high refractive index layer is a coating layer and the low refractive index layer is a vapor deposition layer. Characteristic multilayer anti-reflective coating. (2) The multilayer antireflection film according to (1), wherein the high refractive index layer is a coating layer formed by applying a coating liquid containing inorganic fine particles and an ethylenically unsaturated monomer and polymerizing the ethylenically unsaturated monomer. . (3) The multilayer antireflection film according to (1), wherein the low refractive index layer is a deposited layer formed by depositing silicon dioxide or magnesium fluoride on the high refractive index layer.

(4) Between the transparent support and the high refractive index layer,
The multilayer antireflection film according to (1), further comprising a barrier layer having a thickness of 1 to 15 μm and having a function of preventing a component of the transparent support from moving to the high refractive index layer. (5) A medium refractive index having a refractive index between the transparent support and the high refractive index layer that satisfies the relationship of refractive index of the transparent support <refractive index of the medium refractive index layer <refractive index of the high refractive index layer. The multilayer antireflection film according to (1), wherein the layer is provided as a coating layer. (6) A transparent support, a high refractive index layer and a low refractive index layer are provided in this order, and the transparent support, the high refractive index layer and the low refractive index layer have a refractive index of the low refractive index layer <the transparent support. Having a refractive index that satisfies the relationship of the refractive index of the high refractive index layer, the high refractive index layer is a coating layer, and the low refractive index layer is a vapor deposited layer. Is adhered to a display surface.

[0008]

In a material having a multilayer structure such as a multilayer anti-reflection film, it is considered that the highest productivity is obtained in principle by forming all the functional layers by the same method. Therefore, in the multilayer antireflection film having a vapor deposition layer, all the optical functional layers have been formed by vapor deposition except for the hard coat layer which needs to be formed by coating. In the multilayer antireflection film having a coating layer, all the optical functional layers were similarly formed by coating. That is, it was thought that switching the layer forming method during the manufacturing process would lower the productivity. However, the present inventor has studied and found that, surprisingly, when a high refractive index layer is used as a coating layer and a low refractive index layer is provided thereon as a vapor deposited layer, all layers are formed as coating layers. It turned out to be as easy to produce as. Production by coating is higher in productivity than production by vapor deposition, but it is technically difficult to produce a multilayer antireflection film by the multilayer simultaneous coating method, which has the highest productivity. Therefore, even in the production by coating, after the step of forming the high refractive index layer is completed, it is necessary to start the next step of forming the low refractive index layer. On the other hand, the method of forming a multilayer antireflection film by vapor deposition has low productivity because, as described above, it is difficult to control vapor deposition conditions in repeated vapor deposition processes. According to the study of the present inventor, if only the low refractive index layer is used as a vapor-deposited layer and the remaining layer is used as a coating layer, it is possible to manufacture a multilayer antireflection film with the same productivity as the case where all the coating layers are used There was found.

[0009] Under the same conditions, the refractive index of the deposited layer is higher than the refractive index of the coating layer. Therefore, if a vapor deposition layer and a coating layer are combined, it seems that it is desirable from the viewpoint of optical function to form a high refractive index layer as a vapor deposition layer and a low refractive index layer as a coating layer. However, the present inventor has studied and found that, surprisingly, when a high refractive index layer is used as a coating layer and a low refractive index layer is provided thereon as a vapor deposition layer, all the layers are formed as vapor deposition layers. It has been found that a multilayer antireflection film having an excellent optical function can be obtained. According to the study of the present inventors, the optical function of the antireflection film manufactured by vapor deposition is superior to that of the multilayer antireflection film manufactured by coating because of the difference in the optical function of the low refractive index layer. Was the cause. The low refractive index layer
It is provided on the surface side of the multilayer antireflection film. Therefore, if slight thickness unevenness occurs in the low refractive index layer, the color of reflected light becomes uneven. In the coating, a step-like coating unevenness and a wind ripple are easily generated, and it is difficult to form a low refractive index layer having a uniform thickness.
On the other hand, the high refractive index layer provided between the transparent support and the low refractive index layer does not have the above-mentioned problem, and the high refractive index layer formed by coating can be used for the high refractive index layer formed by vapor deposition. Comparable optical functions are obtained. According to the study of the present inventor, if only the low refractive index layer is a vapor deposited layer and the remaining layer is a coating layer, a multilayer antireflection film having the same excellent optical function as the case where all are vapor deposited layers Was obtained.

As described above, the multilayer antireflection film of the present invention has the same high productivity as the case where all of the coating layers are used as coating layers.
In addition, it has the same excellent optical function as the case where all are formed as vapor deposition layers. By using such a multilayer antireflection film, light reflection on the image display surface of the image display device can be effectively prevented.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The basic structure of a multilayer antireflection film of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a main layer configuration of the multilayer antireflection film. The embodiment shown in FIG. 1A has a layer structure of a transparent support (1), a barrier layer (2), a high refractive index layer (3), and a low refractive index layer (4) in this order. Barrier layer (2) and high refractive index layer (3) are coating layers, and low refractive index layer (4) is a vapor deposited layer. The transparent support (1), the high refractive index layer (3) and the low refractive index layer (4) have a refractive index satisfying the following relationship. Refractive index of low refractive index layer <refractive index of transparent support <refractive index of high refractive index layer

In the embodiment shown in FIG. 1B, a transparent support (1), a barrier layer (2), a medium refractive index layer (5), a high refractive index layer (3), and a low refractive index layer (4) are used. )). Barrier layer (2), medium refractive index layer (5) and high refractive index layer (3) are coating layers, and low refractive index layer (4) is a vapor deposited layer. The transparent support (1), the medium refractive index layer (5), the high refractive index layer (3) and the low refractive index layer (4)
It has a refractive index satisfying the following relationship. Refractive index of low refractive index layer <refractive index of transparent support <refractive index of medium refractive index layer <refractive index of high refractive index layer

[Transparent Support] As the transparent support, a plastic film is preferably used. Examples of plastic film materials include cellulose esters (eg,
Triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamide, polycarbonate, polyester (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, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide,
Includes polymethyl methacrylate and polyether ketone. Triacetyl cellulose, polycarbonate and polyethylene terephthalate are preferred. The light transmittance of the transparent support is preferably 80% or more,
More preferably, it is 86% or more. The haze of the transparent support is preferably 2.0% or less, and is 1.0% or less.
% Is more preferable. The refractive index of the transparent support is preferably from 1.4 to 1.7.

[Barrier layer] The components (gas,
When air, a solvent, and a plasticizer move to the high refractive index layer, the low refractive index layer deposited on the high refractive index layer is easily peeled off, or the deposition of the low refractive index layer becomes difficult. Therefore,
Between the transparent support and the high refractive index layer, a barrier layer having a thickness of 1 to 15 μm having a function of preventing the components of the transparent support from moving to the high refractive index layer may be provided as a coating layer. preferable. The barrier layer preferably has a dense structure in order to prevent the components of the transparent support from moving to the high refractive index layer. In order to make the structure of the layer dense, the layer preferably contains a crosslinked polymer. The barrier layer containing the crosslinked polymer can be formed by applying a coating solution containing a polyfunctional monomer and a polymerization initiator on a transparent support and polymerizing the polyfunctional monomer. The polyfunctional monomer is preferably an ester of a polyhydric alcohol and acrylic acid or methacrylic acid.
Examples of polyhydric alcohols include ethylene glycol, 1,4
-Cyclohexanol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol, 1,2,4-cyclohexanol, polyurethane polyols and polyester polyols. Trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyols are preferred.

Polyfunctional monomers are commercially available (for example, Aronix M-210, 215, 2
20, 233, 240, 245, 260, 270, 30
5, 309, 310, 315, 320, 350, 40
0, 1100, 1200, 1310, 1600, 610
0, 6200, 6250, 6400, 6500, 710
0, 8030, 8060, 8100, 9050, KAYARAD R-526 of Nippon Kayaku Co., Ltd., HDDA, N
PGDA, TPGDA, PEG400DA, MAND
A, R-551, R-712, R-604, R-16
7, R-684, PET-30, GPO-303, TM
PTA, THE-330, Sartomer SR-268, S
R-349, SR-295, SR-355, SR-45
4, SR-205, SR-206, SR-252, Viscort # 195, # 230 of Osaka Organic Chemical Industry Co., Ltd.
# 260, # 215, # 335HP, # 310HP, #
312, # 700, # 295, # 300, # 360, G
PT, 3PA, # 400, V # 540, NK ester 1G, 2G, 4G, 9G, 23 of Shin-Nakamura Chemical Co., Ltd.
G, BG, HD, NPG, A-200, A-600, A
-HD, A-NPG, TMPT, A-TMPT, AT
MM-3, ATMMT) may be used. Two or more polyfunctional monomers may be used in combination.

In the polymerization reaction of the polyfunctional monomer, it is preferable to use a photopolymerization initiator. Examples of photopolymerization initiators include
Includes acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime esters, tetramethylthiuram monosulfide and thioxanthones. A photosensitizer may be used in addition to the photopolymerization initiator. Examples of photosensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. The photopolymerization initiator was added in an amount of 0.1 to 100 parts by weight of the polyfunctional monomer.
It is preferably used in the range of 1 to 15 parts by weight, more preferably in the range of 1 to 10 parts by weight.
The photopolymerization reaction is preferably performed by ultraviolet irradiation after coating and drying of the barrier layer.

It is preferable to add a filler to the barrier layer. The filler has the function of increasing the hardness of the barrier layer, suppressing the curing shrinkage of the polyfunctional monomer, and decreasing the permeability of the gas component. It is preferable to use inorganic fine particles or organic fine particles as the filler. Examples of the inorganic fine particles include silicon dioxide particles, titanium dioxide particles, aluminum oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc, kaolin and calcium sulfate particles. Examples of organic fine particles include methacrylic acid-methyl acrylate copolymer powder, silicon resin powder, polystyrene powder, polycarbonate powder, acrylic acid-styrene copolymer powder, benzoguanamine resin powder, melamine resin powder, polyolefin powder, polyester powder, polyamide powder, polyimide Powder and polyfluoroethylene powder. The average particle size of the fine particles used as the filler is preferably 0.01 to 2 μm,
More preferably, the thickness is from 02 to 0.5 μm. The barrier layer or its coating solution may further include a colorant (pigment,
Dyes), defoamers, thickeners, leveling agents, flame retardants, ultraviolet absorbers, antioxidants and modifying resins may be added.

[High Refractive Index Layer and Medium Refractive Index Layer] As shown in FIG. 1A, a high refractive index layer is provided between a transparent support and a low refractive index layer. Further, as shown in FIG. 1B, a middle refractive index layer may be provided between the transparent support and the high refractive index layer. The high refractive index layer and the medium refractive index layer are coating layers. The refractive index of the high refractive index layer is preferably from 1.65 to 2.40, and more preferably from 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is 1.55 to 1.7.
It is preferably 0. The thickness of the high refractive index layer and the middle refractive index layer is preferably from 5 nm to 100 μm, more preferably from 10 nm to 10 μm, and most preferably from 30 nm to 1 μm. 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 medium refractive index layer preferably contain inorganic fine particles and a polymer.

The inorganic fine particles used in the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The weight average diameter of the primary particles of the inorganic fine particles is preferably from 1 to 150 nm, more preferably from 1 to 100 nm, and most preferably from 1 to 80 nm. The weight average diameter of the inorganic fine particles in the coating layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, and more preferably 10 to 100 nm.
nm, more preferably 10 to 80 nm. The specific surface area of the inorganic fine particles is 1
Preferably 0 to 400m ² / g, more preferably from 20 to 200m ² / g, and most preferably from 30 to 150m ² / g.

The inorganic fine particles are preferably formed from a metal oxide or sulfide. Examples of metal oxides or sulfides include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Titanium oxide, tin oxide and indium oxide are particularly preferred. The inorganic fine particles contain oxides or sulfides 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 Ti, Zr, Sn, Sb, Cu, F
e, Mn, Pb, Cd, As, Cr, Hg, Zn, A
1, Mg, Si, P and S. The 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, silica, zirconium oxide, and iron oxide. Alumina and silica are preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents.
Silane coupling agents are most preferred. Two or more types of surface treatments may be performed in combination. The processing may be performed by combining the above. The shape of the inorganic fine particles is
It is preferably a rice grain, a sphere, a cube, a spindle, or an irregular shape. Two or more kinds of inorganic fine particles may be used together in the high refractive index layer and the medium refractive index layer.

The proportion of the inorganic fine particles in the high refractive index layer and the medium refractive index layer is 5 to 65% by volume. The proportion of the inorganic fine particles is preferably from 10 to 60% by volume,
More preferably, it is from about 55% by volume to about 55% by volume. The inorganic fine particles are used in the form of a dispersion to form a high refractive index layer and a medium refractive index layer. It is preferable to use a liquid having a boiling point of 60 to 170 ° C. as a dispersion medium of the inorganic fine particles in the high refractive index layer and the medium refractive index layer. 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). Particularly preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol. The inorganic fine particles can be dispersed in the 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 dispersing group used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader and an extruder.

The polymer used for the high refractive index layer and the medium refractive index layer is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer. The polymerization of the ethylenically unsaturated monomer is preferably carried out after applying the high refractive index layer and the medium refractive index layer. It is particularly preferred that the polymer is a crosslinked anionic polymer. The crosslinked anionic polymer 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 to strengthen the high refractive index layer and the medium refractive index 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. The polyether main chain is
Repeat units are linked by an ether bond (-O-). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are connected by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has a urethane bond (—NH—CO—O
The repeating units are linked by-). The polyurethane main chain includes, for example, an isocyanate group and a hydroxyl group (N
-Containing a methylol group). The polyester main chain has an ester bond (—CO—O
The repeating units are linked by-). 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 4 to 94% by weight, and most preferably from 6 to 92% by weight. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is preferably from 4 to 98% by weight, more preferably from 6 to 96% by weight,
Most preferably, it is 8 to 94% by weight. The repeating unit of the polymer may have both an anionic group and a crosslinked structure. The polymer may contain another repeating unit (a repeating unit having neither an anionic group nor a crosslinked structure). 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 benzene ring has a function of increasing the refractive indices of the high refractive index layer and the medium refractive index layer. 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 bonded directly 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 a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and a combination thereof. Preferably, there is. When the polymer contains a repeating unit having an amino group or a quaternary ammonium group, the proportion is preferably 0.06 to 32% by weight, more preferably 0.08 to 30% by weight, and Most preferably, it is from 0.1 to 28% 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, the repeating unit (I) having an anionic group, the repeating unit (II) having a crosslinked structure, the repeating unit (III) having both anionic group and crosslinked structure, an amino group or Examples of the repeating unit (IV) having a quaternary ammonium group and the repeating unit (V) having a benzene ring are shown 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. Formula (I)
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-AL) _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 (I) have the above-mentioned definitions. The repeating unit represented by the formula (I) is obtained by an addition polymerization reaction of a corresponding ethylenically unsaturated monomer. Examples of corresponding ethylenically unsaturated monomers include bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate, 2-sulfoethyl methacrylate, monohydroxyethyl acrylate phthalate, dimer acrylate, 2-acryloyloxyethyl hydro Genphthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2-acryloyloxypropyl tetrahydrohydrogen phthalate, β-acryloyloxyethyl hydrogen succinate, β-methacryloyloxyethyl hydrogen hydrogen Allate, β-methacryloyloxyethyl hydrogen succinate, mono (2-acryloyloxyethyl) acid Dohosufeto and mono include (2-methacryloyloxyethyl) acid phosphate. As these ethylenically unsaturated monomers having an anionic group, commercially available products can also be used.

[0031]

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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 (II), n is 2 to 20
Is more preferable, it is more preferably 2 to 10, and most preferably 3 to 6. The formula (I
In I), L ² is preferably an aliphatic residue, and more preferably 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, more preferably 2 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms.

The repeating unit represented by the formula (II) is obtained by an addition polymerization reaction of a corresponding ethylenically unsaturated monomer. Furthermore, the corresponding ethylenically unsaturated monomers are esters of polyhydric alcohols or polyhydric phenols (preferably polyhydric alcohol) and acrylic acid or methacrylic acid corresponding to L ² (-OH) _n. Examples of the corresponding monomers include alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol acrylate, propylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, and 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-cyclohexanetetramethacrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (Di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol 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]

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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 (III-
In a) and (III-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 (III-a) and (III-b) are also obtained by addition polymerization of the corresponding ethylenically unsaturated monomers. Examples of the ethylenically unsaturated monomer corresponding to the formula (III-a) include a reaction product of a 6-hexanolide adduct of 2-hydroxyethyl methacrylate with phosphoric anhydride, bis (methacryloxyethyl) phosphate , 2-acryloyloxyethyl acid phosphate and 2-methacryloyloxyethyl acid phosphate. Formula (III-
Examples of ethylenically unsaturated monomers corresponding to b) include β
-Acryloyloxyethyl hydrogen fumarate and β-acryloyloxyethyl hydrogen maleate. As the ethylenically unsaturated monomer, a commercially available product can also be used.

[0037]

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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. The formula (IV
-A) and (IV-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 (IV-a) and (IV-b) have the definitions given above. The repeating units represented by the formulas (IV-a) and (IV-b) are obtained by an addition polymerization reaction of a corresponding ethylenically unsaturated monomer. Examples of ethylenically unsaturated monomers corresponding to formula (IV-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 (IV-b) include diallyldimethylammonium chloride. Commercially available amino group or quaternary ammonium group ethylenically unsaturated monomers can also be used.

[0040]

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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 in formula (V)
^{When 52} is carboxyl, R ⁵² is preferably bonded to the ortho position of the benzene ring. In the formula (V), 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).

[0042] 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: repeating units represented by -CO-O-AL- formula (V) is obtained by condensation polymerization of corresponding ethylenic unsaturated monomers. 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-acryloyloxyethylphthalic acid. 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 crosslinked anionic polymer is added as a monomer to the coating liquid for the high refractive index layer or the medium refractive index layer (dispersion liquid of the above-mentioned inorganic fine particles), and the polymerization reaction is carried out simultaneously with or after the coating of the layer. Is preferably formed. 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.

For the polymerization reaction, it is preferable to use a polymerization initiator. Polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoro There are amine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-
Dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone is included. Benzoins include benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,
4-Dichlorobenzophenone and p-chlorobenzophenone are included. Phosphine oxides include 2,
4,6-trimethylbenzoyldiphenylphosphine oxide is included. A commercially available polymerization initiator may be used. A polymerization accelerator may be used in addition to the polymerization initiator. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by weight of the total amount of the monomers.

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 anionic polymers are crosslinked, it is difficult to define the molecular weight. The proportion of the polymer in the high refractive index layer and the medium refractive index layer is 35 to 95% by volume. The proportion of the polymer is between 40 and 90
%, More preferably 44 to 80% by volume.

The high refractive index layer, the medium refractive index layer and their coating liquids contain, in addition to the above-mentioned components (inorganic fine particles, polymer, dispersion medium, polymerization initiator, 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 promoter may be added. Examples of the leveling agent include fluorinated alkyl esters (for example, FC-430, FC by Sumitomo 3M Co., Ltd.)
-431) and polysiloxanes (eg, General El
ectric's SF1023, SF1054, SF10
79, DC190, DC200, D of Dow Corning Co., Ltd.
C510, DC1248, BYK3 of BYK Chemie
00, BYK310, BYK320, BYK322, B
YK330, BYK370). The high refractive index layer and the medium refractive index layer are 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 (described in US Pat. No. 2,681,294). Thereby, a coating layer is formed.

[Low Refractive Index Layer] The low refractive index layer is a vapor deposition layer provided on the high refractive index layer. The low refractive index layer preferably has a refractive index of 1.20 to 1.55.
It is more preferably 30 to 1.55, and 1.30
More preferably from 1.35 to 1.50, and most preferably from 1.35 to 1.45. The low refractive index layer preferably has a thickness of 50 to 400 nm,
More preferably, it is from 200 to 200 nm. 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 strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg load.

It is preferable to form a low refractive index layer by depositing an inorganic compound. The inorganic compound is preferably a metal oxide, nitride, sulfide or halide,
More preferably, it consists of a metal oxide or a metal halide, and most preferably, it consists of a metal oxide or a metal fluoride. As metal atoms, Na, K, M
g, 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. Preferred inorganic compounds include alkali metal fluorides (eg, NaF, KF), alkaline earth metal fluorides (eg, CaF ₂ , MgF ₂ ) and silicon dioxide (Si).
O ₂ ), the most preferred inorganic compounds being magnesium fluoride and silicon dioxide.

The low refractive index layer is deposited by chemical vapor deposition (CVD).
This is performed by a physical vapor deposition (PVD) method. Physical vapor deposition is preferred. A vacuum deposition method, which is one of the physical vapor deposition methods, is particularly preferable. The vacuum deposition method is further classified into a sputtering method, an electron gun (EB) heating method, and an ion plating method. Electron gun heating is most preferred. In the formation of the low refractive index layer, it is important to control the thickness in the vacuum evaporation method. While monitoring with an optical film thickness meter,
It is preferable to control the vapor deposition conditions by feeding back the thickness information to the vapor deposition apparatus. Thereby, it is possible to obtain a uniform planar low refractive index layer having a thickness according to the theoretical value.

[Other Layers] The antireflection film further includes:
A moisture-proof layer, an antistatic layer, an undercoat layer and a protective layer may be provided. On the transparent support, an adhesive layer, a shield layer, a slip layer, and an antistatic layer may be provided in addition to the barrier 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), metal salts of higher fatty acids (eg, zinc stearate) and fluorine-containing polymers (eg, perfluoro main chain type perfluoro) Polyether, perfluoro side chain type perfluoropolyether, alcohol-modified perfluoropolyether, isocyanate-modified perfluoropolyether).

A fluorine-containing hydrophobic compound (eg, a fluorine-containing polymer, a fluorine-containing surfactant, a fluorine-containing oil) is added to the antifouling 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.

[Multilayer Antireflection Film] The multilayer antireflection film may have an antiglare function for scattering external light.
The anti-glare function can be obtained by forming irregularities on the surface of the multilayer antireflection film. The haze of the multilayer antireflection film is preferably 3 to 30%, and 5 to 20%.
Is more preferable, and most preferably 7 to 20%. The multilayer antireflection film is used for a liquid crystal display device (L
The present invention is applied to an image display device such as a CD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT).
The transparent support side of the multilayer antireflection film is adhered to the image display surface of the image display device.

[0054]

EXAMPLES Example 1 (Formation of Barrier Layer) 125 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) and a urethane acrylate oligomer (UV-6300)
B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Was dissolved in denatured ethanol for industrial use. In the resulting solution,
7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DETX,
A solution prepared by dissolving 5.0 g of Nippon Kayaku Co., Ltd. in 49 g of methyl ethyl ketone was added. After stirring the mixture, 1
The solution was filtered through a filter having a mesh of μm to prepare a coating solution for the barrier layer. A triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is provided with a gelatin undercoat layer, and the above barrier layer coating solution is coated on the gelatin undercoat layer using a bar coater. And dried at 120 ° C. Next, the coating layer was cured by irradiating ultraviolet rays to form a barrier layer having a thickness of 9.0 μm.

(Preparation of Titanium Dioxide Dispersion) Titanium dioxide (primary particle weight average particle diameter: 50 nm, refractive index: 2.7)
0) 30 parts by weight, the following anionic monomer (1) 3 parts by weight, the following anionic monomer (2) 3 parts by weight, the following cationic monomer 1 part by weight, and methyl ethyl ketone 63 parts by weight were dispersed by a sand grinder. , A titanium dioxide dispersion was prepared.

[0056]

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[0057]

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[0058]

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(Preparation of Coating Solution for High Refractive Index Layer) A photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) was added to 183 g of cyclohexanone and 46 g of methyl ethyl ketone.
0.085 g and a photosensitizer (Kayacure DETX,
0.028 g of Nippon Kayaku Co., Ltd.) was dissolved. further,
17.9 g of titanium dioxide dispersion and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.)
1.2 g), and stirred at room temperature for 30 minutes.
The mixture was filtered through a filter having a mesh of m to prepare a coating liquid for a high refractive index layer.

(Preparation of Multilayer Antireflection Film) A coating liquid for a high refractive index layer is applied on the barrier layer using a bar coater, dried at 120 ° C., and then the applied layer is cured by irradiating ultraviolet rays. A refractive index layer (thickness: 0.075 μm) was formed. Silicon dioxide was vapor-deposited on the high refractive index layer using a batch-type vacuum vapor deposition apparatus using electron gun (EB) heating as an evaporation energy source. The deposition conditions were controlled while measuring the thickness of the formed deposition layer online. Thus, a low refractive index layer (thickness: 0.093 μm) was formed, and a multilayer antireflection film was formed. 4 of the obtained multilayer antireflection film
The average reflectance at a wavelength of 50-650 nm is 0.9
It was 3. The surface had a pencil hardness of 2H.

(Formation of Barrier Layer) A first undercoat layer having a thickness of 0.2 μm containing SBR latex and polystyrene particles on a polyethylene terephthalate film having a thickness of 175 μm, and a thickness containing an acrylic resin and colloidal silica thereon A second undercoat layer of 0.1 μm was provided as a coating layer. Example 1 on the second undercoat layer
Was applied using a bar coater and dried at 120 ° C. Next, the coating layer was cured by irradiating ultraviolet rays to form a barrier layer having a thickness of 7.5 μm.

(Preparation of coating liquid for medium refractive index layer) A photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) was added to 172 g of cyclohexanone and 43 g of methyl ethyl ketone.
0.18 g and 0.059 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were dissolved. Further, 15.8 g of titanium dioxide dispersion and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.)
3.1 g), and stirred at room temperature for 30 minutes.
The mixture was filtered through a filter having a mesh of m to prepare a coating solution for a medium refractive index layer.

(Preparation of Multilayer Antireflection Film) A coating liquid for a medium refractive index layer was applied on the barrier layer using a bar coater, dried at 120 ° C., and cured by irradiation with ultraviolet rays. A refractive index layer (thickness: 0.081 μm) was formed. The coating solution for a high refractive index layer used in Example 1 was applied on the middle refractive index layer using a bar coater, dried at 120 ° C., and then cured by irradiating ultraviolet rays to cure the coating layer. (Thickness: 0.060 μm). Magnesium fluoride was vapor-deposited on the high refractive index layer using a batch-type vacuum vapor deposition apparatus using electron gun (EB) heating as an evaporation energy source. The deposition conditions were controlled while measuring the thickness of the formed deposition layer online. Thus, a low refractive index layer (thickness: 0.093 μm) was formed, and a multilayer antireflection film was formed. 450 to 65 of the obtained multilayer antireflection film
The average reflectance at a wavelength of 0 nm was 0.35. The pencil hardness of the surface was H.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a main layer configuration of a multilayer antireflection film.

[Explanation of symbols]

 Reference Signs List 1 transparent support 2 barrier layer (coating layer) 3 high refractive index layer (coating layer) 4 low refractive index layer (deposition layer) 5 medium refractive index layer (coating layer)

Claims (6)

[Claims] A transparent support, a high refractive index layer and a low refractive index layer are provided in this order, and the transparent support, the high refractive index layer and the low refractive index layer have a refractive index of the low refractive index layer <transparent. A multilayer antireflection film having a refractive index that satisfies the relationship of the refractive index of the support <the refractive index of the high refractive index layer, wherein the high refractive index layer is a coating layer,
A multilayer antireflection film, wherein the low refractive index layer is a vapor deposited layer. 2. The high refractive index layer is a coating layer formed by applying a coating solution containing inorganic fine particles and an ethylenically unsaturated monomer and polymerizing the ethylenically unsaturated monomer.
3. The multilayer antireflection film according to item 1. 3. The multilayer antireflection film according to claim 1, wherein the low refractive index layer is a deposited layer formed by depositing silicon dioxide or magnesium fluoride on the high refractive index layer. 4. A coating layer having a thickness of 1 to 15 μm having a function of preventing a component of the transparent support from migrating to the high refractive index layer between the transparent support and the high refractive index layer. The multilayer antireflection film according to claim 1, wherein 5. A material having a refractive index between the transparent support and the high refractive index layer that satisfies the relationship of the refractive index of the transparent support <the refractive index of the medium refractive index layer <the refractive index of the high refractive index layer. The multilayer antireflection film according to claim 1, wherein the refractive index layer is provided as a coating layer. 6. A transparent support, a high refractive index layer and a low refractive index layer in this order, wherein the transparent support, the high refractive index layer and the low refractive index layer have a refractive index of the low refractive index layer <transparent. Having a refractive index that satisfies the relationship of the refractive index of the support <the refractive index of the high refractive index layer,
An image display device, wherein a transparent support of a multilayer antireflection film having a high refractive index layer as a coating layer and a low refractive index layer as a vapor deposition layer is adhered to a display surface.