JP2001310423A - Flaw resistant transparent support and anti-reflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a support and an anti-reflection film which show less deformation and are flaw resistant by suppressing shrinkage of a hard coat layer due to crosslinkage of a binder polymer and further to provide a flaw- resistant support and an anti-reflection film which are excellently flaw-resistant by improving mechanical properties of the hard coat layer. SOLUTION: A flaw-resistant support comprises a transparent support (1) and a hard coat layer (2) laminated on the transparent support (1) wherein the hard coat layer contains a surface treated fine inorganic particle and a crosslinked binder polymer, the surface treatment being conducted by use of an organic compound containing an anionic functional group or an organometallic compound containing one or more of aluminum, silica, titanium and zirconium each as a surface-treating agent, the binder polymer being obtained by crosslinking of a polyfunctional acrylate compound. An anti- reflection film is obtained by use of the flaw-resistant support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film in which a scratch-resistant support, a transparent support, a hard coat layer, and a low refractive index layer are laminated in this order, 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 anti-reflection film, an anti-reflection film in which a transparent thin film of a metal oxide is laminated on a transparent support 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.
Methods for forming an antireflection film by vapor deposition are described in JP-A-60-144702, JP-A-61-245449, JP-A-62-178901 and JP-A-9-197103.

In addition, there has been proposed a method of forming an antireflection film by coating instead of vapor deposition. The method by coating
Although it is slightly inferior to the method by vapor deposition in terms of optical functions, it is characterized by easy production and high productivity. In the coating method, the components of the optical functional layer (low-refractive-index layer, high-refractive-index layer, medium-refractive-index layer) are applied on a transparent support,
An anti-reflection film is formed. Methods for forming this antireflection film by coating are described in JP-B-60-59250, JP-A-59-50401, JP-A-2-245702,
5-13021, 8-110401 and 8
It is described in each publication of -179123. In both the method of providing an optical functional layer by vapor deposition and the method of providing an optical functional layer by coating, it is common to provide a hard coat layer on a transparent support before providing the optical functional layer. The hard coat layer has a function of improving the scratch resistance of the transparent support. Therefore, the hard coat layer is usually formed using a hard material such as a crosslinked binder polymer, and the binder polymer is often crosslinked after forming the hardcoat layer. However, in this method, the flatness often deteriorates when the hard coat layer is formed, which often causes a problem in forming an antireflection film. Further, as the use of the antireflection layer expands, the current hard coat may have insufficient scratch resistance, and further improvement in scratch resistance has been demanded.

[0004]

The present inventors have studied the hard coat layer and found that in many cases, the binder polymer shrinks in the crosslinking reaction, and the hard coat layer is deformed and minute cracks occur. . In addition, there was also a problem that the antireflection film was deformed due to shrinkage of the entire hard coat layer. The deformation of the antireflection film becomes a serious problem when the antireflection film is used by attaching it to the image display surface of the image display device. An object of the present invention is to provide a scratch-resistant support and an anti-reflection film in which shrinkage of a hard coat layer due to crosslinking of a binder polymer is suppressed and deformation is small. Another object of the present invention is to improve the mechanical properties of the hard coat layer and provide a support and an antireflection film having excellent scratch resistance.

[0005]

The object of the present invention is attained by the following scratch-resistant support (1) to (6), antireflection film (7) to (9) and image display device (10). Was done. (1) A scratch-resistant support having a hard coat layer provided on a transparent support, wherein the hard coat layer contains surface-treated inorganic fine particles and a crosslinked binder polymer, and the surface treatment is an anionic functional An organic compound containing a group, or an organic metal compound is performed as a surface treatment agent,
And a scratch-resistant support, wherein the binder polymer is obtained by crosslinking a polyfunctional acrylate compound. (2) the surface treating agent is a phosphate group, a phosphate monoester,
Phosphoric acid diester, sulfonic acid group, sulfuric acid monoester,
Item (1) is an organic compound having a carboxylic acid group, a salt thereof, or an acid chloride thereof, or an organic metal compound containing at least one selected from aluminum, titanium, and zirconium. 2. The scratch-resistant support according to 1. (3) The scratch-resistant support according to (1), wherein the surface treating agent is a phosphoric acid monoester-containing organic compound. (4) The inorganic fine particles are composed of particles containing at least one of silicon dioxide, zirconium oxide, aluminum oxide and titanium dioxide. (1) to (3)
Item 14. The scratch-resistant support according to any one of the above items. (5) The scratch-resistant support according to any one of (1) to (4), wherein the inorganic fine particles are made of particles containing aluminum oxide. (6) The scratch-resistant support according to item (5), wherein the hard coat layer has a thickness of 1 to 15 μm. (7) an antireflection film in which a transparent support, a hard coat layer, and a low refractive index layer having a refractive index lower than that of the transparent support are laminated in this order, wherein the transparent support and the hard coat An antireflection film, wherein the layer is formed of the scratch-resistant support according to any one of (1) to (6). (8) The transparent support, the hard coat layer, the high refractive index layer having a refractive index higher than the refractive index of the transparent support, and the low refractive index layer having a refractive index lower than the refractive index of the transparent support are arranged in this order. Wherein the transparent support and the hard coat layer are formed of the scratch-resistant support according to any one of (1) to (6). Prevention film. (9) a transparent support, a hard coat layer, a medium refractive index layer having a refractive index higher than the refractive index of the transparent support, a high refractive index layer having a refractive index higher than the refractive index of the medium refractive index layer, and transparent. A low refractive index layer having a refractive index lower than the refractive index of the support is an antireflection film laminated in this order, and the transparent support and the hard coat layer are any of (1) to (6). 1
13. An anti-reflection film formed of the scratch-resistant support described in item 8. (10) An image display device, wherein the antireflection film according to any one of (7) to (9) is formed on the image display surface.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The basic structure of an antireflection film according to 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 antireflection film. The embodiment shown in FIG. 1A has a layer structure in the order of a transparent support (1), a hard coat layer (2), a low refractive index layer (3), and an overcoat layer (4). The transparent support (1) and the low refractive index layer (3) have a refractive index satisfying the following relationship. Refractive index of low refractive index layer <refractive index of transparent support In the embodiment shown in FIG. 1B, the transparent support (1), the hard coat layer (2), the high refractive index layer (5), the low refractive index It has a layer structure of a layer (3) and an overcoat layer (4). The transparent support (1), the high refractive index layer (5) and the low refractive index layer (3) have a refractive index satisfying the following relationship. The refractive index of the low refractive index layer <the refractive index of the transparent support <the refractive index of the high refractive index layer The embodiment shown in FIG. 1 (c) is a transparent support (1), a hard coat layer (2), a medium refractive index. It has a layer structure of a layer (6), a high refractive index layer (5), a low refractive index layer (3), and an overcoat layer (4) in this order. The transparent support (1), the medium refractive index layer (6), the high refractive index layer (5) and the low refractive index layer (3) have 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 the polymer forming the plastic film 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 ( For example, 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, 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.

[Hard coat layer] The hard coat layer has a function of imparting scratch resistance to the transparent support. The scratch-resistant support in the present invention has a specific hard coat layer on a transparent support. The hard coat layer includes a crosslinked binder polymer. The hard coat layer containing the crosslinked binder 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. As a functional group,
Preferred are polymerizable unsaturated double bond groups. Examples of the polymerizable unsaturated double bond group include an acrylate group, a methacrylate group, and a vinyl group. An acrylate group is preferably used from the viewpoint of reactivity. 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-cyclohexanediol, pentaerythritol, trimethylolpropane, trimethylolethane, dipentaerythritol,
Includes 1,2,4-cyclohexanetriol, polyurethane polyols and polyester polyols.
Trimethylolpropane, pentaerythritol, dipentaerythritol and polyurethane polyols are preferred. Two or more polyfunctional monomers may be used in combination. By adding inorganic fine particles to the hard coat layer, the crosslinking shrinkage as a film can be improved and the flatness of the coating film can be improved. In general, inorganic fine particles are harder than organic substances,
Does not shrink due to UV irradiation or the like. Therefore, by adding inorganic fine particles to the hard coat layer, the entire layer is hardened, the scratch resistance is improved, the shrinkage of the hard coat layer due to the crosslinking reaction is suppressed, and the deformation of the antireflection film can be prevented. However, since the inorganic fine particles have low affinity with the binder polymer, even if the inorganic fine particles are added as they are, the inorganic fine particles / the binder polymer are easily broken, and it is difficult to improve the scratch resistance and deformation. Therefore, the affinity between the inorganic fine particles and the binder polymer is improved by subjecting the inorganic fine particles to a surface treatment with a coupling agent having a high affinity for the fine particles, an anionic group-containing organic compound, or the like. If the surface treating agent has a residue having a carbon-carbon double bond capable of co-crosslinking with the binder, for example, a (meth) acrylate group, the affinity between the binder polymer and the inorganic particles is increased and the strength of the hard coat layer is increased. It was confirmed that no reduction occurred. This effect is further enhanced if the acrylate compound contains a phosphorus atom having a high affinity for a metal.

As the inorganic fine particles, those having high hardness are preferable. For example, silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc,
Kaolin and calcium sulfate particles are included. Among them, silicon dioxide, titanium dioxide, aluminum oxide and zirconium oxide particles are particularly preferred. The average particle diameter of the inorganic fine particles is preferably 1 to 2000 nm,
The thickness is more preferably 2 to 1000 nm, still more preferably 5 to 500 nm, and 10 to 20 nm.
Most preferably, it is 0 nm. The addition amount of the inorganic fine particles is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, still more preferably 20 to 80% by mass, and more preferably 40 to 80% by mass of the total amount of the hard coat layer. Most preferably, it is 60% by mass.

In general, inorganic fine particles have a poor affinity for a binder polymer, so that the interface is easily broken simply by mixing the two, and it is difficult to crack as a film and to improve the scratch resistance. By treating the inorganic fine particles with a surface treating agent containing an organic segment, the affinity between the inorganic fine particles and the polymer binder is improved, and this problem can be solved. The surface treatment agent must be able to form bonds with the metal particles on the one hand and have a high affinity for the binder polymer on the other hand. As the functional group capable of forming a bond with a metal, a metal alkoxide is preferable, and in practice, compounds such as aluminum, titanium, and zirconium can be mentioned. Alternatively, a compound having an anionic group is preferable, and a phosphate group, a phosphate monoester, a phosphate diester, a sulfonic acid group, a sulfate monoester, a carboxylic acid group, a salt thereof,
Or it is more preferable to have these acid chlorides. It is preferable that the surface treatment agent is chemically bonded to the binder polymer, and it is preferable that the surface treatment agent has a vinyl polymer group or the like introduced at a terminal. For example, when a binder polymer is synthesized from a monomer having an ethylenically unsaturated group as a polymerizable group and a crosslinkable group, it is preferable that the metal alkoxide compound or the anionic compound has an ethylenically unsaturated group at a terminal. . In this surface treatment method, it is preferable that the inorganic fine particles are coated with the above-mentioned surface treatment agent, and after the addition to the binder polymer, the coated surface treatment agent is cured and crosslinked simultaneously with the crosslinking of the binder polymer.

Examples of surface treating agents for organometallic compounds a) Examples of aluminum-containing organic compounds a-1H₂C = CHCOOC_FourH₈Al (OC_FourH₉)_Two  a-2H₂C = CHCOOC₃H₆Al (OC₃H₇)_Two  a-3H₂C = CHCOOC₂H₄Al (OC₂H₅)_Two  a-4H₂C = CHCOOC₂H₄OC₂H₄Al (OC₂H₄OC₂H₅)_Two  a-5H₂C = C (CH_Three) COOC_FourH₈Al (OC_FourH₉)_Two  a-6H₂C = CHCOOC_FourH₈Al (OC_FourH₉) C_FourH₈COOCH = CH₂  a-7H₂C = CHCOOC₂H₄Al ｛O (1,4-ph) CH_Three｝_Two 

B) zirconium-containing organic compound b-1H₂C = CHCOOC_FourH₈Zr (OC_FourH₉)_Three  b-2H₂C = CHCOOC₃H₆Zr (OC₃H₇)_Three  b-3H₂C = CHCOOC₂H_FourZr (OC₂H₅)₃  b-4H₂C = C (CH_Three) COOC_FourH₈Zr (OC_FourH₉)₃  b-5 @CH₂= C (CH_Three) COOC_ThreeH₆｝_TwoZr (OC_FourH₉)_Two  c) Titanium-containing organic compound c-1 @ H₂C = C (CH_Three) COOC_ThreeH₆｝₃TiOCH_Three  c-2 Ti ｛H₂C = C (CH_Three) COOC_ThreeH₆｝_TwoTiOCH_Three  c-3H₂C = CHCOOC_FourH₈Ti (OC_FourH₉)_Three  c-4H₂C = CHCOOC₃H₆Ti (OC₃H₇)_Three  c-5H₂C = CHCOOC₂H_FourTi (OC₂H₅)₃  c-6H₂C = CHCOOC₃H₆Ti (OCH_Three)_Three  c-7H₂C = C (CH_Three) COOC_FourH₈Ti (OC_FourH₉)₃

Examples of anionic functional group-containing surface treatment agents d) Examples of phosphoric acid monoesters, phosphoric diesters, and phosphoric acid group-containing organic compounds d-1H₂C = C (CH_Three) COOC₂H_FourOPO (OH)_Two  d-2H₂C = C (CH_Three) COOC₂H_FourOCOC_FiveH_TenOPO (OH)_Two  d-3H₂C = CHCOOC₂H_FourOCOC_FiveH_TenOPO (OH)_Two  d-4H₂C = C (CH_Three) COOC₂H_FourOCOC_FiveH_TenOPO (OH)_Two  d-5H₂C = C (CH_Three) COOC₂H_FourOCOC_FiveH_TenOPOCl_Two  d-6H₂C = C (CH_Three) COOC₂H_FourCH @ OPO (OH)_Two)_Two  d-7H₂C = C (CH_Three) COOC₂H_FourOCOC_FiveH_TenOPO (ONa)_Two  d-8H₂C = CHCOOC₂H_FourOCO (1,4-ph) C_FiveH_TenOPO (OH)_Two  d-9 (H₂C = C (CH_Three) COO)_TwoCHC₂H_FourOCOC_FiveH_TenOPO (OH)_Two  d-10H₂C = CHPO (OH)_Two 

E) Examples of organic compounds containing sulfuric acid monoester or sulfonic acid group e-1 H ₂ C ＝ C (CH ₃ ) COOC ₂ H ₄ OSO _{3 He} e-2H ₂ C ＝ C (CH ₃ ) COOC ₃ H _{6 SO 3 H e-3 H} 2 C = C (CH 3) COOC 2 H 4 OCOC 5 H 10 OSO 3 H e-4 H 2 C = CHCOOC 2 H 4 OCOC 5 H 10 OSO 3 H e-5 H 2 _{C = CHCOOC 12 H 24 (1,4} -ph) SO 3 H e-6 H 2 C = C (CH 3) COOC 2 H 4 OCOC 5 H 10 OSO 3 Na

F) Example of carboxylic acid group-containing organic compound f-1 H ₂ C ＝ CHCOO (C ₅ H ₁₀ COO) ₂ H f-2 H ₂ C ＝ CHCOOC ₅ H ₁₀ COOH f-3 H ₂ C ＝ CHCOOC _{2 H 4 OCO (1,2-ph)} COOH f-4 H 2 C = CHCOO (C 2 H 4 COO) 2 H f-5 H 2 C = C (CH) COOC 5 H 10 COOH f-6 H 2 C = CHCOOC ₂ H ₄ COOH where ph represents a phenylene group.

For the crosslinking reaction of the binder polymer (polymerization reaction of the polyfunctional monomer), it is preferable to use a photopolymerization initiator. Examples of photopolymerization initiators include acetophenones,
Includes 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,
Includes tri-n-butylphosphine, Michler's ketone and thioxanthone. The photopolymerization initiator is preferably used in an amount of 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the polyfunctional monomer. The photopolymerization reaction is preferably carried out by irradiating ultraviolet rays after applying and drying the hard coat layer.

The hard coat layer or its coating solution further contains a colorant (pigment, dye), an antifoaming agent, a thickener, a leveling agent, a flame retardant, an ultraviolet absorber, an antioxidant and a modifying resin. It may be added. The coating solution for the hard coat layer is preferably prepared using an organic solvent as a medium. Examples of organic solvents include 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 hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (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-methoxy-2-propanol).
Two or more organic solvents may be used in combination. The thickness of the hard coat layer is preferably 1 to 15 μm.

[High Refractive Index Layer and Medium Refractive Index Layer] As shown in FIG. 1B, a high refractive index layer may be provided between the hard coat layer and the low refractive index layer. Also, FIG.
As shown in (1), a middle refractive index layer may be provided between the hard coat layer and the high refractive index layer. The refractive index of the high refractive index layer is:
It is preferably from 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 preferably from 1.55 to 1.80. However, the difference between the refractive index of the high refractive index layer and the refractive index of the middle refractive index layer is preferably 0.1 or more. 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 hardness of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in pencil hardness at a load of 1 kg. The high refractive index layer and the medium refractive index layer preferably contain inorganic fine particles and a polymer.

The inorganic fine particles (hereinafter referred to as high refractive inorganic fine particles) used for the high refractive index layer and the medium refractive index layer have a refractive index of 1.80.
To 2.80, preferably 1.90 to 2.80.
More preferably, it is 80. The mass average diameter of the primary particles of the high refraction 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 mass average diameter of the high refractive inorganic fine particles in the coating layer is from 1 to 200.
nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and most preferably 10 to 80 nm. The specific surface area of the high refractive inorganic fine particles is 10 to 400.
is preferably m ² / g, 20 to 200 meters ² /
g, more preferably 30 to 150 m ² / g.
g is most preferred.

The high refractive 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 high-refractive inorganic fine particles have an oxide or sulfide of these metals as a main component, and may further contain other elements. The main component is
It means the component having the largest content (% by mass) among the components constituting the particles. Examples of other elements include Ti, Zr, S
n, Sb, Cu, Fe, Mn, Pb, Cd, As, C
r, Hg, Zn, Al, Mg, Si, P and S are included. High refractive 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 aluminum oxide, silicon oxide, zirconium oxide, and iron oxide. Aluminum oxide and silicon oxide 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 high refractive 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 high refractive index inorganic fine particles may be used in the high refractive index layer and the medium refractive index layer.

The proportion of the high refractive index inorganic fine particles in the high refractive index layer and the medium refractive index layer is 5 to 65% by volume. The ratio of the high refractive inorganic fine particles is preferably from 10 to 60% by volume, and more preferably from 20 to 55% by volume. The high refractive inorganic fine particles are used in the form of a dispersion to form a high refractive index layer and a medium refractive index layer. The dispersion medium of the high refractive index inorganic fine particles in the high refractive index layer and the medium refractive index layer has a boiling point of 60.
It is preferable to use a liquid at a temperature of from 170 to 170 ° C. 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 hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (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-methoxy-2-propanol).
Particularly preferred are toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol. The high refractive inorganic fine particles can be dispersed in a medium using a dispersing machine. 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, a kneader and an extruder.

It is preferable to use a polymer having a relatively high refractive index for the middle refractive index layer and the high refractive index layer. 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.

[Low Refractive Index Layer] The refractive index of the low refractive index layer is
1.20 to 1.55, preferably 1.30
It is more preferably from 1.55 to 1.55. The thickness of the low refractive index layer is preferably 50 to 400 nm,
More preferably, it is 50 to 200 nm. The low refractive index layer preferably has a porosity of 3 to 50% by volume, and more preferably 5 to 35% by volume. The voids in the low refractive index layer can be formed as microvoids between particles or within particles using fine particles. The average particle size of the fine particles is 0.5 to 200 mm
Is preferably 1 to 100 nm, more preferably 3 to 70 nm, and most preferably 5 to 40 nm. The particle size of the fine particles is preferably as uniform (monodispersed) as possible. Further, inorganic fine particles or organic fine particles can also be used for the low refractive index layer.

The inorganic fine particles are preferably amorphous. The inorganic fine particles are preferably made of a metal oxide, nitride, sulfide or halide, more preferably a metal oxide or metal halide,
Most preferably, it consists of a metal oxide or metal fluoride. As metal atoms, Na, K, Mg, Ca, B
a, Al, Zn, Fe, Cu, Ti, Sn, In, W,
Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si,
B, Bi, Mo, Ce, Cd, Be, Pb and Ni are preferred, and Mg, Ca, B and Si are more preferred. An inorganic compound containing two kinds of metals may be used. A particularly preferred inorganic compound is silicon dioxide.

The microvoids in the inorganic fine particles can be formed, for example, by crosslinking silicon oxide molecules forming the particles. Crosslinking the silicon oxide molecules reduces the volume and makes the particles porous. The (porous) inorganic fine particles having microvoids are described by a sol-gel method (described in JP-A-53-112732 and JP-B-57-9051) or a precipitation method (APPLIED OPTICS, 27, p. 3356 (1988)). ) Can be directly synthesized as a dispersion. Further, the powder obtained by the drying / precipitation method can be mechanically pulverized to obtain a dispersion. Commercially available porous inorganic fine particles (for example, silicon dioxide sol) may be used. The inorganic fine particles having microvoids 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 organic fine particles are also preferably amorphous. The organic fine particles are preferably polymer fine particles synthesized by a polymerization reaction of a monomer (for example, an emulsion polymerization method). The polymer of the organic fine particles preferably contains a fluorine atom. The proportion of fluorine atoms in the polymer is preferably from 35 to 80% by mass, more preferably from 45 to 75% by mass. Examples of the fluorine atom-containing monomer used for synthesizing the fluorine-containing polymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1). , 3-dioxole), fluorinated alkyl esters of acrylic or methacrylic acid and fluorinated vinyl ethers. A copolymer of a monomer containing a fluorine atom and a monomer not containing a fluorine atom may be used. Examples of monomers containing no fluorine atom include olefins (eg, ethylene, propylene, isoprene,
Vinyl chloride, vinylidene chloride), acrylates (eg, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate), styrene (Eg, styrene, vinyltoluene, α-methylstyrene), vinyl ethers (eg, methyl vinyl ether), vinyl esters (eg, vinyl acetate, vinyl propionate), acrylamides (eg, N-tert-butylacrylamide, N-cyclohexylacrylamide), methacrylamides and acrylonitriles.

The microvoids in the organic fine particles can be formed, for example, by crosslinking a polymer forming the particles. Crosslinking the polymer reduces its volume,
The particles become porous. In order to crosslink the polymer forming the particles, two of the monomers for synthesizing the polymer are used.
It is preferable that 0 mol% or more be a polyfunctional monomer.
The ratio of the polyfunctional monomer is more preferably from 30 to 80 mol%, and most preferably from 35 to 50 mol%. Examples of polyfunctional monomers include dienes (eg, butadiene, pentadiene), esters of polyhydric alcohol and acrylic acid (eg, ethylene glycol diacrylate, 1,4-cyclohexanediol diacrylate, dipentaerythritol hexaacrylate). Esters of polyhydric alcohol and methacrylic acid (eg, ethylene glycol dimethacrylate,
4-cyclohexanetriol trimethacrylate, pentaerythritol tetramethacrylate), divinyl compounds (eg, divinylcyclohexane, 1,4-divinylbenzene), divinylsulfone, bisacrylamides (eg, methylenebisacrylamide) and bismethacrylamides. .

The microvoids between the particles can be formed by stacking at least two or more fine particles. When spherical particles having the same particle size (perfectly monodispersed) are closest packed, microvoids between particles having a porosity of 26% by volume are formed. When the spherical fine particles having the same particle size are simply cubically filled, microvoids between the fine particles having a porosity of 48% by volume are formed. In an actual low refractive index layer, the porosity considerably fluctuates from the above theoretical value due to the particle size distribution of the fine particles and the presence of microvoids in the particles. Increasing the porosity lowers the refractive index of the low refractive index layer. By forming microvoids by stacking the fine particles and adjusting the particle size of the fine particles, the size of the microvoids between the particles can be easily adjusted to an appropriate value (does not scatter light and does not cause a problem in the strength of the low refractive index layer). Can be adjusted. Furthermore, by making the particle diameter of the fine particles uniform, an optically uniform low refractive index layer in which the size of the microvoids between particles is also uniform 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 sum of the refractive indexes of the components 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 components of the low refractive index layer such as fine particles and polymer is a value larger than 1, while the refractive index of air is 1.00. Therefore, by forming microvoids,
A low refractive index layer having a very low refractive index can be obtained. The intergranular microvoids are preferably closed in the low refractive index layer by the fine particles and the polymer. The closed gap has 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.

The low refractive index layer preferably contains the polymer in an amount of from 5 to 50% by weight. The polymer has a function of adhering the fine particles and maintaining the structure of the low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the void. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) bonding the polymer to the surface treatment agent of the fine particles, (2) forming a polymer shell around the fine particles as a core, or (3) forming a polymer shell around the fine particles. It is preferable to use a polymer as the binder. (1)
The polymer to be bonded to the surface treatment agent is preferably the shell polymer of (2) or the binder polymer of (3). It is preferable that the polymer (2) is formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer of (3) is preferably formed by adding a monomer to the coating solution 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. The above (1) surface treatment,
(2) Shell and (3) Binder will be described sequentially.

(1) Surface Treatment The fine particles (particularly, inorganic fine particles) used in the low refractive index layer are preferably subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into a physical surface treatment such as a plasma discharge treatment or a corona discharge treatment, and a 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 alkoxy metal compound (eg, a titanium coupling agent, a silane coupling agent) is preferably used. When the fine particles are made of silicon dioxide, surface treatment with a silane coupling agent can be particularly effectively performed. Examples of the silane coupling agent 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 fine particles and leaving the dispersion at a temperature from room temperature to 60 ° C. for several hours to 10 days. To accelerate the surface treatment reaction, an inorganic acid (eg,
Sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acid (eg, acetic acid, polyacrylic acid, benzenesulfonic acid, phenol, polyglutamic acid), or these Salts (eg, metal salts, ammonium salts) 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. A polymer containing a fluorine atom in a main chain or a side chain is preferable, and a polymer containing a fluorine atom in a side chain is more preferable. 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 mass of fluorine atoms, and more preferably 45 to 75% by mass. 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 forming the shell may be a copolymer comprising 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), methacrylates (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),
Includes vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (eg, N-tertbutylacrylamide, N-cyclohexylacrylamide), methacrylamide and acrylonitrile.

When a binder polymer (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 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 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 more information on dispersion polymerization, see Barr.
ett, Keih EJ, Dispersion Polymerization in Organ
ic Media, JOHN WILLEY & SONS (1975).

The thermal polymerization initiator is used in an emulsion polymerization method and a dispersion polymerization method. Examples of the thermal 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) , Azoamide compounds (eg, 2,
2′-azobis {2-methyl-N- [1,1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}. Inorganic peroxides are preferred,
Potassium and ammonium persulfates are particularly preferred. Examples of the thermal 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 peroxide (Eg, lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate).

In the dispersion polymerization method, it is preferable to add a polymer dispersant to the surface-treated 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,
Alcohol (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 the chain transfer agent 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-
Dodecyl mercaptan, n-dodecyl mercaptan, hexadecyl mercaptan, n-octadecyl mercaptan, thioglycerol), disulfide (eg, diisopropylzantogen disulfide), thioglycolic acid and derivatives thereof (eg, thioglycolic acid, 2-ethylhexyl thioglycolate) Butyl thioglycolate, methoxy butyl thioglycolate, trimethylolpropane tris (thioglycolate)). 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-dichlorohexanediol diacrylate, pentane). Erythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth)
Acrylate, dipentaerythritol tetra (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid) 2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), 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 functional group, and may be a group which gives the above-mentioned functional group as a result of a decomposition reaction. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a photopolymerization initiator is more preferable than the thermal polymerization initiator used for the synthesis of (2) the shell polymer. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-
Diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxyethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-
Methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone are included. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone,
Includes 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

When used in combination with the shell polymer (2), the glass transition temperature (Tg) of the binder polymer is as follows:
It 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 solution for the low-refractive-index layer, and simultaneously or after the application of the low-refractive-index layer, by a polymerization reaction (and, if necessary, a crosslinking reaction). A small amount of polymer (eg, polyvinyl alcohol,
Polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) may be added.

[Anti-Reflection Film] The anti-reflection film may be provided with a layer other than those described above. For example, an adhesive layer, a shield layer, a slip layer, and an antistatic layer may be provided on the transparent support in addition to the hard coat layer. The shield layer is provided to shield electromagnetic waves and infrared rays. 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. An overcoat layer may be provided on the low refractive index layer. The overcoat layer preferably contains a fluorine-containing compound. The haze of the antireflection film is preferably 3 to 30%, and 5 to 20%.
Is more preferable, and most 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 transparent support side of the antireflection film is adhered to the image display surface of the image display device.

[0041]

EXAMPLES Example 1 (Preparation of Inorganic Particle Dispersion (M-1)) The following amounts of each reagent were measured in a ceramic-coated vessel. Cyclohexanone 337 g PM-2 (phosphate group-containing methacrylate manufactured by Nippon Kayaku Co., Ltd.) 31 g AKP-G015 (Alumina manufactured by Sumitomo Chemical Co., Ltd.) 92 g The above mixture was subjected to 1600 rpm for 10 hours by a sand mill (1/4 G sand mill). Finely dispersed. Media is 1
1400 g of zirconia beads having a diameter of mmΦ was used. The particle size of the obtained surface-treated aluminum oxide was 93 nm.

(Preparation of Coating Solution for Hard Coat Layer) 97 g of methanol, 163 g of isopropanol and 163 g of butyl acetate were added to 116 g of a 10% by mass methanol dispersion of the above-treated surface-treated alumina fine particles. To the mixture, 200 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) was added and dissolved. To the obtained solution, 7.5 g of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Geigy) and 5.0 g of a photosensitizer (trade name: Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were added. Dissolved. After stirring the mixture for 30 minutes, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a hard coat layer.

(Preparation of Titanium Dioxide Dispersion) Titanium dioxide (primary particle mass average particle diameter: 50 nm, refractive index: 2.7)
0) 30 parts by mass, 4.5 parts by mass of anionic diacrylate monomer (trade name: PM21, manufactured by Nippon Kayaku Co., Ltd.), cationic methacrylate monomer (trade name: DM)
0.3 parts by mass of AEA (produced by Kojin Co., Ltd.) and 65.2 parts by mass of methyl ethyl ketone were dispersed by a sand grinder to prepare a titanium dioxide dispersion.

(Preparation of coating liquid for medium refractive index layer) 151.9 g of cyclohexanone and 37.0 g of methyl ethyl ketone
g, 0.14 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DE)
TX, manufactured by Nippon Kayaku Co., Ltd.). Further, 6.1 g of the above titanium dioxide dispersion and 2.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added, and the mixture was stirred at room temperature for 30 minutes. The solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a medium refractive index layer.

(Preparation of coating solution for high refractive index layer) 152.8 g of cyclohexanone and 37.2 of methyl ethyl ketone
g, 0.06 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DE)
TX, manufactured by Nippon Kayaku Co., Ltd.). Further, 13.13 g of the above titanium dioxide dispersion and 0.76 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) were added, followed by stirring at room temperature for 30 minutes. The solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a high refractive index layer.

(Preparation of Coating Solution for Low Refractive Index Layer) A silane coupling agent (trade name: KBM) was added to 200 g of a methanol dispersion (methanol silica sol, manufactured by Nissan Chemical Industries, Ltd.) of silicon oxide fine particles having an average particle size of 15 nm. -503, manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 g of 1N hydrochloric acid were added, and the mixture was stirred at room temperature for 5 hours and then left for 3 days to prepare a silane-coupled silicon oxide fine particle dispersion. To 35.04 g of the above dispersion, isopropyl alcohol 5 was added.
8.35 g and 39.34 g of diacetone alcohol were added. 1.02 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure D)
25. 0.51 g of ETX, manufactured by Nippon Kayaku Co., Ltd.) is dissolved in 772.85 g of isopropyl alcohol, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 6 g was added and dissolved. 67.23 g of the resulting solution was added to a mixture of the above dispersion, isopropyl alcohol and diacetone alcohol. After the mixture was stirred at room temperature for 20 minutes, the mixture was filtered with a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

(Preparation of Coating Solution for Overcoat Layer) To a thermally crosslinkable fluoropolymer (trade name: JN-7214, manufactured by Nippon Synthetic Rubber Co., Ltd.) was added isopropyl alcohol, and a 0.6% by mass coarse dispersion was performed. A liquid was prepared. The crude dispersion is
The mixture was finely dispersed by ultrasonic waves to prepare a coating solution for an overcoat layer.

(Preparation of antireflection film) Triacetylcellulose film having a thickness of 80 μm (refractive index: 1.48, trade name: TAC-TD80U, Fuji Photo Film Co., Ltd.)
) Was provided with a gelatin undercoat layer. The above coating liquid for a hard coat layer was coated on a gelatin undercoat layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coated layer and to have a thickness of 9.0 μm. A hard coat layer was formed. On the hard coat layer, the above-mentioned coating solution for a medium refractive index layer was applied using a bar coater,
After drying at ℃, the coating layer is cured by irradiating ultraviolet rays,
Medium refractive index layer (refractive index: 1.72, thickness: 0.081μ)
m) was formed. The coating liquid for a high refractive index layer is applied on the medium refractive index layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coating layer, and the high refractive index layer (refractive index : 1.92, thickness: 0.053 µm). The coating solution for the low refractive index layer is applied on the high refractive index layer using a bar coater, dried at 120 ° C., and then irradiated with ultraviolet rays to cure the coating layer, and the low refractive index layer (refractive index : 1.40, thickness: 0.072 µm). The porosity of the formed low refractive index layer was 16% by volume. On the low refractive index layer, apply the coating solution for the overcoat layer to # 3.
And dried at 120 ° C. for 1 hour to form an antireflection film.

(Evaluation of antireflection film) The following items were evaluated for the obtained antireflection film. The results are shown in Table 1.

(1) Scratch Resistance After the antireflection film was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%, a JIS-K-5400 was used using a test pencil specified by JIS-S-6006. According to the pencil hardness evaluation method specified by, a hardness at which no flaw was observed under a load of 1 kg was measured.

(2) Curl value The antireflection film was cut into a sample of 35 mm × 3 mm.
After sandwiching between F-type curl value reading plates and controlling the humidity for 30 minutes at a temperature of 25 ° C. and a relative humidity of 60%, the curl value was read.

Example 2 The following amounts of each reagent were measured in a ceramic-coated vessel. 337 g of cyclohexanone 31 g of an aluminum-containing compound (a-3) 92 g of AKP-G015 (alumina manufactured by Sumitomo Chemical Co., Ltd.) 92 g The above mixture was finely dispersed in a sand mill (1 / 4G sand mill) at 1600 rpm for 10 hours. Media is 1
1400 g of zirconia beads having a diameter of mmΦ was used. 0.1 g of 1N hydrochloric acid was added thereto, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and the mixture was further stirred for 4 hours. The particle size of the obtained surface-treated aluminum oxide was 72 nm. An anti-reflection film was formed in the same manner as in Example 1 except that this aluminum oxide was used.

Example 3 The following amounts of each reagent were measured in a ceramic-coated vessel. Cyclohexanone 337 g Titanium-containing compound (c-4) 31 g TTO-55B (titanium oxide fine particles manufactured by Ishihara Sangyo Co., Ltd.) 92 g The above mixture was finely dispersed in a sand mill (1 / 4G sand mill) at 1600 rpm for 6 hours. Media is 1m
1,400 g of zirconia beads having a diameter of mΦ were used. Here 1
0.1 g of N hydrochloric acid was added, the temperature was raised to 80 ° C. under a nitrogen atmosphere, and the mixture was further stirred for 4 hours. The particle size of the obtained surface-treated titanium oxide was 32 nm. An anti-reflection film was formed in the same manner as in Example 1 except that this titanium oxide was used.

Comparative Example 1 Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 125
g and urethane acrylate oligomer (UV-63
00B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
It was dissolved in 0 g of industrial denatured ethanol. 7.5 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure DET) were added to the obtained solution.
X, Nippon Kayaku Co., Ltd.) in a solution of 5.0 g in 47.5 g of methyl ethyl ketone. After stirring the mixture, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for the hard coat layer. An anti-reflection film was prepared and evaluated in the same manner as in Example 1, except that the coating solution for a hard coat layer prepared as described above was used.

Comparative Example 2 Aluminum Oxide Fine Particles AK
88 g of methanol, 163 g of isopropanol and 163 g of butyl acetate were added to 125 g of a 40% by mass methanol dispersion of P-G015 (no surface treatment). A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DP
(HA, manufactured by Nippon Kayaku Co., Ltd.) and dissolved.
A photopolymerization initiator (Irgacure 907,
7.5 g of Ciba-Geigy and 5.0 g of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved. After stirring the mixture for 30 minutes, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a hard coat layer. An anti-reflection film was prepared and evaluated in the same manner as in Example 1, except that the coating solution for a hard coat layer prepared as described above was used.

Table 1Evaluation results of anti-reflective coating  Antireflection film Scratch resistance Curl value Summary ―――――――――――――――――――――――――――――――――― Example 1 3H 0. 6 Example 2 2H 0.4 Example 3 3H 0.7 Comparative Example 1 2H 2.1 Comparative Example 2 HB 1.4 Coating crack occurrence

[0057]

As described above, the scratch-resistant transparent support of the present invention has improved scratch resistance and deformation. By using this, an antireflection film can be produced by a coating method, thereby improving scratch resistance and preventing deformation. By using such an antireflection film, reflection of light on the image display surface of the image display device can be effectively prevented.

[Brief description of the drawings]

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

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent support 2 hard coat layer 3 low refractive index layer 4 overcoat layer 5 high refractive index layer 6 medium refractive index layer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) B32B 27/08 B32B 27/08 G02B 1/11 G09F 9/00 302 1/10 G02B 1/10 A // G09F 9 / 00 302 Z

Claims (10)

[Claims] Claims: 1. A scratch-resistant support having a hard coat layer provided on a transparent support, wherein the hard coat layer contains surface-treated inorganic fine particles and a crosslinked binder polymer, and the surface treatment comprises an anion. A scratch-resistant support, wherein an organic compound containing a functional functional group or an organic metal compound is used as a surface treatment agent, and the binder polymer is obtained by crosslinking a polyfunctional acrylate compound. 2. The surface treating agent is a phosphoric acid group, a phosphoric acid monoester, a phosphoric diester, a sulfonic acid group, a sulfuric acid monoester, a carboxylic acid group, a salt thereof, or an organic compound having an acid chloride thereof. 2. An organic metal compound containing at least one selected from aluminum, titanium and zirconium.
2. The scratch-resistant support according to 1. 3. The scratch-resistant support according to claim 1, wherein the surface treating agent is a phosphoric acid monoester-containing organic compound. 4. The scratch-resistant support according to claim 1, wherein said inorganic fine particles comprise particles containing at least one of silicon dioxide, zirconium oxide, aluminum oxide and titanium dioxide. body. 5. The scratch-resistant support according to claim 1, wherein the inorganic fine particles comprise particles containing aluminum oxide. 6. The scratch-resistant support according to claim 5, wherein the hard coat layer has a thickness of 1 to 15 μm. 7. An antireflection film in which a transparent support, a hard coat layer, and a low refractive index layer having a refractive index lower than that of the transparent support are laminated in this order. An antireflection film, wherein the hard coat layer is formed of the scratch-resistant support according to any one of claims 1 to 6. 8. A transparent support, a hard coat layer, a high refractive index layer having a refractive index higher than that of the transparent support, and a low refractive index layer having a refractive index lower than that of the transparent support. An antireflection film laminated in this order, wherein the transparent support and the hard coat layer are any one of claims 1 to 6.
13. An anti-reflection film formed of the scratch-resistant support described in item 8. 9. A transparent support, a hard coat layer, a medium refractive index layer having a refractive index higher than the refractive index of the transparent support, a high refractive index layer having a refractive index higher than the refractive index of the medium refractive index layer,
And an antireflection film in which a low refractive index layer having a refractive index lower than that of the transparent support is laminated in this order, wherein the transparent support and the hard coat layer are any one of claims 1 to 6. 13. An anti-reflection film formed of the scratch-resistant support described in item 8. 10. An image display device comprising the antireflection film according to claim 7 formed on an image display surface.