JP2003195005A - Antireflection hard coat layer, antireflection hard coat film and image display device provided with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection hard coat layer having an antireflection layer with high surface hardness and excellent in abrasion resistance, an antireflection hard coat film with the hard coat layer provided on a transparent base material, and an image display device provided with the hard coat layer or the hard coat film. <P>SOLUTION: In this antireflection hard coat layer having a hard coat layer composed of curable composition cured by the irradiation of an active energy beam and an antireflection layer composed of two layers with different refractive indexes of a high refractive index layer and a low refractive index layer, the low refractive index layer and the high refractive index layer are composed of a layer that is mainly made of a curable resin cured by the irradiation of an active energy beam or a layer that is made from a curable resin cured by the irradiation of an active energy beam and metal-oxide particulates. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent substrate film having a resin layer (hard coat layer) cured by active energy rays, having a high surface hardness, excellent scratch resistance, and antireflection property. Regarding the coat layer. By providing the hard coat layer of the present invention on a transparent substrate, a hard coat film having reduced reflection and excellent scratch resistance can be obtained. Furthermore, the antireflection hard coat layer or the antireflection hard coat layer of the present invention can be obtained. The transparent substrate (hard coat film) provided with is suitable for a surface of a display such as CRT, LCD, PDP, FED, a touch panel, a protective film such as glass, and the like.

[0002]

2. Description of the Related Art In recent years, plastic products are being replaced with glass products from the viewpoints of workability and weight reduction. However, since the surfaces of these plastic products are easily scratched, a hard coat layer is provided for the purpose of imparting scratch resistance. In many cases, a film provided with a hard coat layer is attached and used. In addition, even with conventional glass products, the number of cases in which a plastic film is laminated to prevent scattering is increasing, and it is widely practiced to form a hard coat layer on the surface of these films in order to strengthen the hardness of these films. It is being appreciated.

In the conventional hard coat layer, usually, an active energy ray-polymerizable resin such as a thermosetting resin or an ultraviolet curable resin is directly applied to a plastic substrate or 0.0.
3 to 3 or more via a primer layer of about 0.5 μm 1
It is manufactured by forming a thin coating film of about 0 μm or less.

However, when the conventional hard coat layer has insufficient hardness and the base plastic substrate is deformed due to the thin coating film thickness, the hard coat layer is hardened accordingly. The coat layer is also deformed and cracks are generated in the hard coat layer, which is not sufficiently satisfactory. For example, in a hard coat film in which a UV-curable coating material is applied on a polyethylene terephthalate film which is widely used as a plastic substrate film, the pencil hardness is generally 3H level. It does not reach the hardness of 9H at all.

In order to increase the hardness of the hard coat layer, the resin-forming component of the layer is a polyfunctional acrylic acid ester monomer, to which a powdered inorganic filler such as alumina, silica, titanium oxide and a polymerization initiator are added. The coating composition containing is disclosed in Japanese Patent No. 1815116. Further, Japanese Patent No. 1416240 discloses a photopolymerizable composition containing an inorganic charge material composed of silica or alumina surface-treated with alkoxysilane or the like. Further, filling of crosslinked organic fine particles has been studied recently. These have the effect of increasing the surface hardness of the hard coat layer,
There are also problems of increased haze and bad deterioration of brittleness, and this alone was not sufficient to meet the required performance.

Further, Japanese Unexamined Patent Publication No. 2000-52472 proposes a method of satisfying curl and scratch resistance by forming a hard coat layer into two layers and adding fine particle silica to the first layer. Further, in JP-A-2000-71392, a hard coat layer has a two-layer structure, a lower layer is a cured resin layer made of a blend of a radical curable resin and a cation curable resin, and an upper layer is made of only a radical curable resin. There is a description of a hard coat film using a cured resin layer. However, these were also not sufficiently satisfactory in hardness.

On the other hand, the thickness of the hard coat layer is usually 3 to
It is known that increasing the thickness to more than 10 μm is effective for increasing the hardness. When the thickness is increased, there is a problem that haze becomes large, cracking and peeling of the hard coat layer are likely to occur, and at the same time, curling of the hard coat film due to curing shrinkage becomes large. For this reason, it has been difficult to obtain a hard coat layer having good properties which can be practically used by the conventional technique.

Further, the reflectance of the hard coat layer provided for protecting the plastic and preventing the glass from scattering is large, and the visibility is poor due to the reflection and reflection of external light. To prevent reflection, it is recommended to provide an antireflection layer made of alkoxysilane or the like on the surface of the hard coat.
No. 2,534,260, there are problems in that the reaction takes time, high temperature treatment is required, and the like, and there are problems in productivity and selection of the base material. It is also possible to use a fluoropolymer having a low refractive index.
No. 51904 and Japanese Patent Application Laid-Open No. 7-168005, there is a problem that the scratch resistance of the surface is weak because the strength of the material itself is weak.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antireflection hard coat layer having an antireflection layer having high surface hardness and excellent scratch resistance. Another object of the present invention is to provide an antireflection hard coat film having the above-mentioned hard coat layer on a transparent substrate and having various functions. Still another object of the present invention is to provide an image display device provided with the above hard coat layer or hard coat film.

[0010]

Means for Solving the Problems As a result of earnest studies, the present inventor has found that the scratch resistance can be improved by providing a high refractive index layer and a low refractive index layer mainly composed of a curable resin which is cured by irradiation with active energy rays. It was found that it is possible to prepare an antireflection hard coat layer also provided with, and further, by setting the physical properties of the hard coat layer made of a curable composition that is cured by irradiation with active energy rays within a specific range, high surface hardness can be obtained. It was found that a good hard coat film can be obtained.

According to one aspect of the present invention, the following solution is provided. 1. In the antireflection hard coat layer having a hard coat layer composed of a curable composition which is cured by irradiation with active energy rays and an antireflection layer composed of two layers having different refractive indexes of a high refractive index layer and a low refractive index layer, a low refractive index Characterized in that the refractive index layer and the high refractive index layer is a layer mainly composed of a curable resin that is cured by irradiation with active energy rays or a layer composed of a curable resin that is cured by irradiation with active energy rays and metal oxide fine particles. Anti-reflective hard coat layer. In the present invention, the “layer mainly composed of a curable resin” means that the content of the metal oxide fine particles is less than 20% by weight based on the total weight of the curable resin and the metal oxide fine particles. The content is preferably less than 10% by weight, and more preferably contains no metal oxide fine particles. In the "layer composed of the curable resin and the metal oxide fine particles", the content of the metal oxide fine particles is preferably 20 to 80% by weight based on the total weight of the curable resin and the metal oxide fine particles. It is more preferable that it is
Most preferably, it is 50 to 70% by volume. Preferred embodiments of the antireflection hard coat layer of the present invention will be described below. 2. 2. The antireflection hard coat layer according to 1 above, wherein the low refractive index layer has a refractive index of 1.45 or more and 1.6 or less. The refractive index of the high refractive index layer is 0.
3. The antireflection hard coat layer according to 1 or 2 above, which is 2 or more larger; The thickness of the hard coat layer is more than 10μm and 60μ
4. The antireflection hard coat layer according to any one of 1 to 3 above, which is less than or equal to m. A curable composition that is cured by irradiation with active energy rays is a curable resin that contains three or more ethylenically unsaturated groups in the same molecule and / or a curable composition that contains three or more ring-opening polymerizable groups in the same molecule. 5. The antireflection hard coat layer according to any one of 1 to 4 above, which contains a resin. The antireflection hard coat layer according to the above 5, wherein the curable resin containing a ring-opening polymerizable group is a crosslinkable polymer containing a repeating unit represented by the following general formula (1), the general formula (1)

[Chemical 1] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. P ¹ represents a monovalent group containing a ring-opening polymerizable group. L ¹ represents a single bond or a divalent or higher valent group. Represents the linking group of.) 7. 7. The hard coat layer according to the above 5 or 6, wherein the ring-opening polymerizable group is a cationically polymerizable group. 8. The antireflection hard coat layer according to any one of 1 to 7 above, wherein the surface of the low refractive index layer has antifouling properties, or an antifouling layer is laminated as the outermost layer. According to another aspect of the present invention, the following solution is provided. 9. An antireflection hard coat film comprising a transparent substrate and the hard coat layer according to any one of 1 to 8 above. According to still another aspect of the present invention, the following solution is provided. 10. Any one of 1 to 8 above
An image display device provided with the antireflection hard coat layer as described in item 1 or the antireflection hard coat film as described in item 9 above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The thickness of the hard coat layer of the present invention is preferably more than 10 μm, more preferably 20 μm or more. When the transparent substrate is a film, increasing the thickness of the hard coat layer improves the pencil hardness, but it is difficult to bend the film and cracks due to bending are more likely to occur. Therefore, 60 μm or less and 50 μm or less are preferable. preferable. It is preferably more than 10 and 60 μm or less, and more preferably 20 or more and 50 μm or less. The hard coat layer is composed of at least one layer, and may have a form of two or more layers.

The hard coat layer of the present invention is formed by applying a curable composition which is cured by irradiation with active energy rays and curing it by irradiation with the active energy rays. The cure shrinkage of the curable composition upon irradiation with active energy rays is
0 to 15%, preferably 0 to 13%, more preferably 0
~ 11%. The curing shrinkage ratio is obtained by calculating the density of the curable composition before irradiation with the active energy ray used, for example, UV light and the density of the curable composition after irradiation curing, and calculating from the value by the following (formula A). It is the value obtained by The density is MULTIVOLUME PY manufactured by Micrometrics.
It is a value measured by CNOMETER (25 ° C.). Numerical formula A: volumetric shrinkage ratio = {1- (density before curing / density after curing)} × 100 (%)

The curable composition for forming the hard coat layer preferably comprises a curable resin containing 3 or more ethylenically unsaturated groups in the same molecule and / or 3 or more ring-opening compounds in the same molecule. By containing a polymerizable group, and more preferably by setting the film thickness of the hard coat layer to a constant film thickness, it is possible to provide a hard coat film having high surface hardness and excellent scratch resistance. At the same time, when the volumetric shrinkage ratio satisfies the above range, curl after curing becomes small, and cracks are less likely to occur during handling. If the volumetric shrinkage exceeds 15%, such advantages may not occur.

The curable composition for forming the hard coat layer contains a curable resin which is cured by active energy rays. The curable resin that cures with active energy rays preferably contains a curable resin containing three or more ethylenically unsaturated groups in the same molecule and / or contains a ring-opening polymerizable group, and an ethylenically unsaturated group. It is more preferable to contain both a curable resin containing 3 or more in the same molecule and a curable resin containing a ring-opening polymerizable group. Moreover, when the curable composition has a ring-opening polymerizable group, it is preferable to contain three or more ring-opening polymerizable groups in the same molecule. The hard coat layer may be composed of a single layer or a plurality of layers, but it is preferable that the hard coat layer is a single layer which is simple in the manufacturing process. In this case, the single layer refers to a hard coat layer formed of the same curable composition, and may be formed by coating a plurality of times as long as the composition after coating and drying has the same composition. .
On the other hand, a plurality of layers means being formed of a plurality of curable compositions having different compositions.

The curable resin containing a ring-opening polymerizable group preferably used in the present invention will be described below. The curable resin containing a ring-opening polymerizable group is a curable resin having a ring structure in which ring-opening polymerization proceeds by the action of cations, anions, radicals and the like, and among these, a heterocyclic group-containing curable resin is preferable. Examples of such a curable resin include epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic imino ethers such as oxazoline derivatives, and the like, and epoxy derivatives, oxetane derivatives, and oxazoline derivatives are particularly preferable. In the present invention, the curable resin having a ring-opening polymerizable group preferably has two or more ring-opening polymerizable groups in the same molecule, more preferably 3
It is preferable to have one or more. Further, in the present invention, two or more curable resins having a ring-opening polymerizable group may be used in combination, and in this case, a curable resin having one ring-opening polymerizable group in the same molecule may be used if necessary. Can be used together.

The curable resin having a ring-opening polymerizable group referred to in the present invention is not particularly limited as long as it is a curable resin having the above-mentioned cyclic structure. Preferable examples of such a curable resin include, for example, monofunctional glycidyl ethers, monofunctional alicyclic epoxies, difunctional alicyclic epoxies, diglycidyl ethers (for example, ethylene glycol diglycidyl ether as glycidyl ethers). , Bisphenol A diglycidyl ether, trimethylolethane triglycidyl ether), trifunctional or higher functional glycidyl ethers (trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether,
Glyceryl triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.) Tetra- or higher functional glycidyl ethers (sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, cresol novolac resin polyglycidyl ether, phenol novolac resin polyglycidyl ether, etc. ), Cycloaliphatic epoxies (celoxide 2)
021P, Celoxide 2081, Epolide GT-3
01, Eporide GT-401 (above, manufactured by Daicel Chemical Industries, Ltd.), EHPE (Daicel Chemical Industries, Ltd.)
), Phenol novolac resin polycyclohexylepoxy methyl ether, etc.), oxetanes (OX-
SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.)
Etc.), but the present invention is not limited thereto.

In the present invention, it is particularly preferable that the curable resin having a ring-opening polymerizable group contains a crosslinkable polymer containing a repeating unit represented by the above general formula (1). Hereinafter, these crosslinkable polymers will be described in detail. In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. L ¹ is a single bond or a divalent or higher valent linking group, preferably a single bond, —O—, an alkylene group, an arylene group and * -COO linked to the main chain at the * side.
-, * -CONH-, * -OCO-, * -NHCO-. P ¹ is a monovalent group containing a ring-opening polymerizable group, and preferable P ¹ is a monovalent group containing an imino ether ring such as an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring or an oxazoline ring. Group is particularly preferred among these, and a monovalent group containing an epoxy ring, an oxetane ring and an oxazoline ring is particularly preferred.

In the present invention, the crosslinkable polymer containing a repeating unit represented by the general formula (1) is preferably synthesized simply by polymerizing a corresponding monomer. As the polymerization reaction in this case, radical polymerization is the most simple and preferable. Specific preferred examples of the repeating unit represented by formula (1) are shown below, but the invention is not limited thereto.

[0020]

[Chemical 2]

[0021]

[Chemical 3]

[0022]

[Chemical 4]

In the present invention, the crosslinkable polymer containing the repeating unit represented by the general formula (1) may be a copolymer composed of plural kinds of repeating units represented by the general formula (1), and A copolymer containing a repeating unit other than the general formula (1) (for example, a repeating unit not containing a ring-opening polymerizable group) may be used. In particular, when it is desired to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or for the purpose of controlling the content of the ring-opening polymerizable group of the crosslinkable polymer, a method of using a copolymer containing a repeating unit other than the general formula (1) is preferable. Is. As the method of introducing the repeating unit other than the general formula (1), a method of introducing the monomer by copolymerizing the corresponding monomers is preferable.

When a repeating unit other than the general formula (1) is introduced by polymerizing a corresponding vinyl monomer, a monomer preferably used is acrylic acid or α-alkylacrylic acid (eg methacrylic acid). Derived esters or amides (eg, N-i-propylacrylamide, Nn-
Butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, acrylamide, 2-acrylamide-
2-Methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetoneacrylamide, acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-propyl acrylate, i -Propyl acrylate, 2-hydroxypropyl acrylate, 2-methyl-2-nitropropyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, t-pentyl acrylate, 2-methoxyethyl acrylate, 2
-Ethoxyethyl acrylate, 2-methoxymethoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2-dimethylbutyl acrylate,
3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octafluoropentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, benzyl acrylate, n-octyl Acrylate, 2-ethylhexyl acrylate, 4-methyl-2-propylpentyl acrylate, heptadecafluorodecyl acrylate, n
-Octadecyl acrylate, methyl methacrylate,
2,2,2-trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec
-Butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, benzyl methacrylate, heptadecafluorodecyl methacrylate, n-octadecyl methacrylate, 2-isobornyl methacrylate, 2-nor Bornylmethyl methacrylate, 5-norbornen-2-ylmethylmethacrylate, 3-methyl-2-norbornylmethylmethacrylate, dimethylaminoethylmethacrylate, etc., acrylic acid or α-alkylacrylic acid (acrylic acid, methacrylic acid, itacone) Acid, etc.), vinyl esters (eg vinyl acetate), esters derived from maleic acid or fumaric acid (dimethyl maleate, dibutyl maleate) Diethyl fumarate etc.), maleimides (N-phenylmaleimide etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (eg butadiene, cyclopentadiene, isoprene), aromatic Group vinyl curable resin (eg styrene, p-
Chlorostyrene, t-butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylformamide, N-vinyl-N
-Methylformamide, N-vinylacetamide, N-
Vinyl-N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinylsulfonic acid, sodium vinylsulfonate, sodium allylsulfonate,
Examples thereof include sodium methallyl sulfonate, vinylidene chloride, vinyl alkyl ethers (for example, methyl vinyl ether), ethylene, propylene, 1-butene, isobutene and the like. You may use these vinyl monomers in combination of 2 or more types. Other vinyl monomers are Research Disclosure No. 1955
(1980, July) can be used. In the present invention, esters, amides, and aromatic vinyl-curable resins derived from acrylic acid or methacrylic acid are particularly preferably used vinyl monomers.

As the repeating unit other than the general formula (1), a repeating unit having a reactive group other than the ring-opening polymerizable group can be introduced. In particular, when it is desired to increase the hardness of the hard coat layer, or to improve the adhesiveness between layers when another functional layer is used on the substrate or the hard coat layer, a reactive group other than the ring-opening polymerizable group is contained. The method of using a copolymer is preferable. The method for introducing the repeating unit having a reactive group other than the ring-opening polymerizable group is the corresponding vinyl monomer (hereinafter,
A method of copolymerizing a reactive monomer) is simple and preferable.

Specific preferred examples of the reactive monomer are shown below, but the present invention is not limited thereto.

Hydroxyl group-containing vinyl monomer (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomer (eg,
Isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N-methylol group-containing vinyl monomer (eg, N-methylolacrylamide, N-
Methylol methacrylamide, etc.), carboxyl group-containing vinyl monomers (eg acrylic acid, methacrylic acid,
Itaconic acid, carboxyethyl acrylate, vinyl benzoate), alkyl halide-containing vinyl monomers (eg chloromethylstyrene, 2-hydroxy-3-chloropropylmethacrylate), acid anhydride-containing vinyl monomers (eg maleic anhydride), formyl groups Containing vinyl monomer (eg acrolein, methacrolein), sulfinic acid group containing vinyl monomer (eg potassium styrenesulfinate), active methylene containing vinyl monomer (eg acetoacetoxyethyl methacrylate), acid chloride containing monomer (eg acrylic acid chloride, methacrylic acid) Chloride), an amino group-containing monomer (eg, allylamine), an alkoxysilyl group-containing monomer (eg, methacryloyloxypropyltrimethoxysilane, acrylo) Le trimethoxysilane), and the like.

In the crosslinkable polymer containing the repeating unit represented by the general formula (1) in the present invention, the proportion of the repeating unit represented by the general formula (1) is 1% by mass or more and 1
The amount is 00 mass% or less, preferably 30 mass% or more and 100 mass% or less, and particularly preferably 50 mass% or more and 100 mass% or less.

The preferred molecular weight range of the crosslinkable polymer containing the repeating unit represented by the general formula (1) is 1,000 or more and 1,000,000 or less, more preferably 300 in terms of number average molecular weight.
It is 0 or more and 200,000 or less. Most preferably, it is 5,000 or more and 100,000 or less.

Preferred examples of the crosslinkable polymer containing the repeating unit represented by the general formula (1) are shown in Table 1 below.
The present invention is not limited to these. In addition, the repeating unit represented by the general formula (1), which is a specific example, is represented by the number of the specific example, and the repeating unit derived from a copolymerizable monomer is a monomer name. The copolymerization composition ratio was added in mass%.

[0031]

[Table 1]

As described above, in the curable composition which is cured by the active energy ray for forming the hard coat layer, the curable resin containing the ring-opening polymerizable group and the ethylenically unsaturated group are contained in the same molecule. It is preferable to contain both the curable resin containing 3 or more. Hereinafter, the curable resin containing three or more ethylenically unsaturated groups in the same molecule will be described in detail.

Preferred types of ethylenically unsaturated groups are an acryloyl group, a methacryloyl group, a styryl group and a vinyl ether group, and an acryloyl group is particularly preferred. The curable resin containing an ethylenically unsaturated group may have three or more ethylenically unsaturated groups in the same molecule, and a monomer or oligomer containing one or two ethylenically unsaturated groups may be used in combination as necessary. . Curable resin called a polyfunctional acrylate monomer having 3 to 6 acrylic acid ester groups in the molecule, urethane acrylate, polyester acrylate, epoxy acrylate, and several acrylic acid ester groups in the molecule An oligomer having a molecular weight of several hundreds to several thousands can be preferably used.

Specific examples of the curable resin having three or more acrylic groups in the same molecule include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and dipentaerythritol. Examples thereof include polyol polyacrylates such as pentaacrylate and dipentaerythritol hexaacrylate, and urethane acrylates obtained by reacting polyisocyanate with a hydroxyl group-containing acrylate such as hydroxyethyl acrylate.

In the present invention, a crosslinkable polymer containing a repeating unit represented by the general formula (2) can be preferably used as a curable resin having three or more ethylenically unsaturated groups in the same molecule. Hereinafter, the crosslinkable polymer containing the repeating unit represented by the general formula (2) will be described in detail.

General formula (2)

[Chemical 5]

In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. P ² represents a monovalent group containing an ethylenically unsaturated group, L ² represents a single bond or a divalent or higher valent linking group, preferably a single bond, —O—, an alkylene group, an arylene group and * Connect to main chain at side *
-COO-, * -CONH-, * -OCO-, * -NH
CO-. P ² is preferably a monovalent group containing an acryloyl group, a methacryloyl group or a styryl group, and most preferably a monovalent group containing an acryloyl group. The crosslinkable polymer containing the repeating unit represented by the general formula (2) may be synthesized by a method of i) polymerizing a corresponding monomer to directly introduce an ethylenically unsaturated group.
i) It may be synthesized by a method of introducing an ethylenically unsaturated group into a polymer obtained by polymerizing a monomer having an arbitrary functional group by a polymer reaction. Also, the methods of i) and ii) can be combined for synthesis. Examples of the polymerization reaction include radical polymerization, cationic polymerization and anionic polymerization. When using the above method i), it is necessary to utilize the difference in the polymerizability between the ethylenically unsaturated group consumed by the polymerization reaction and the ethylenically unsaturated group left in the crosslinkable polymer. For example, preferred P of the general formula (2)
^When a monovalent group containing an acryloyl group or a methacryloyl group is used among ² , a crosslinkable polymer of the present invention can be obtained by the method of ii) above by using a cationic polymerization as a polymerization reaction to form a crosslinkable polymer. You can On the other hand, when P ² is a monovalent group containing a styryl group, gelation is likely to proceed regardless of radical polymerization, cationic polymerization, or anionic polymerization, and thus the crosslinkability of the present invention is usually obtained by the method of ii) above. Synthesize a polymer.

As described above, the method utilizing the polymer reaction described in the above ii) makes it possible to obtain a crosslinkable polymer regardless of the kind of the ethylenically unsaturated group introduced in the general formula (2). Yes, it is useful. The polymer reaction is, for example, 2-
I) Ethylenic by functional group conversion (elimination reaction, oxidation reaction, reduction reaction, etc.) after producing a polymer containing a functional group which is a precursor of an ethylenically unsaturated group which is capable of eliminating hydrochloric acid from a chloroethyl group. (2) A method of deriving an unsaturated group, and (2) after forming a polymer containing an arbitrary functional group, a bond formation reaction with the functional group in the polymer proceeds, and a functional group capable of forming a covalent bond and an ethylenic group A method of reacting a curable resin having both unsaturated groups (hereinafter referred to as a reactive monomer) can be mentioned. The methods I) and II) may be combined. The bond forming reaction referred to here can be used without particular limitation as long as it is a reaction forming a covalent bond among bond forming reactions generally used in the field of organic synthesis. On the other hand, since the ethylenically unsaturated group contained in the crosslinkable polymer may be thermally polymerized during the reaction and gelated, the reaction proceeds at a temperature as low as possible (preferably 60 ° C or lower, particularly preferably room temperature or lower). Those that do are preferred. Further, a catalyst may be used for the purpose of promoting the progress of the reaction, and a polymerization inhibitor may be used for the purpose of suppressing gelation.

Examples of preferable combinations of functional groups in which the polymer bond-forming reaction proceeds are shown below, but the present invention is not limited thereto.

Examples of the combination of functional groups in which the reaction proceeds under heating or at room temperature include (a) hydroxyl group, epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride and acid chloride. , Active ester group (eg, sulfate ester), formyl group, acetal group, (b) isocyanate group,
For hydroxyl group, mercapto group, amino group, carboxyl group, N-methylol group, (c) carboxyl group, for epoxy group, isocyanate group, amino group, N-methylol group, (d) N-methylol group , Isocyanate group, N-methylol group, carboxyl group, amino group, hydroxyl group, (e) epoxy group, hydroxyl group, amino group, mercapto group, carboxyl group, N-methylol group, (f) vinyl sulfone group To a sulfinic acid group, an amino group, a (to) formyl group to a hydroxyl group, a mercapto group, an active methylene group,
(H) formyl group, vinyl group (allyl group, acryl group, etc.), epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride acid chloride, active ester group (for mercapto group) Formyl group, vinyl group (allyl group, acryl group, etc.), epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride, acid Combinations of chlorides, active ester groups (eg sulfates), etc. may be mentioned.

Specific preferred examples of the reactive monomer are shown below, but the present invention is not limited thereto.

Hydroxyl group-containing vinyl monomer (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomer (eg,
Isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N-methylol group-containing vinyl monomer (eg, N-methylolacrylamide, N-
Methylol methacrylamide, etc.), epoxy group-containing vinyl monomers (eg, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, C
YCLOMER-M100, A200 (manufactured by Daicel Chemical Industries, Ltd.), carboxyl group-containing vinyl monomers (for example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate), alkyl halide-containing vinyl monomers (for example, chloro). Methylstyrene, 2-hydroxy-3-chloropropylmethacrylate), acid anhydride-containing vinyl monomers (eg maleic anhydride), formyl group-containing vinyl monomers (eg acrolein, methacrolein), sulfinic acid group-containing vinyl monomers (eg styrene) Potassium sulfinate), vinyl monomer containing active methylene (eg acetoacetoxyethyl methacrylate), vinyl monomer containing vinyl group (eg allyl methacrylate, allyl acrylate), acid chloride Ride-containing monomers (e.g., acrylic acid chloride, chloride methacrylate), amino group-containing monomer (e.g. allylamine), and the like.

The polymer containing any functional group described in the above II) can be obtained by polymerizing a reactive monomer having both a reactive functional group and an ethylenically unsaturated group. It can also be obtained by polymerizing a precursor monomer having low reactivity such as polyvinyl alcohol obtained by modifying polyvinyl acetate and then converting the functional group. In these cases, radical polymerization is the most simple and preferable as the polymerization method.

Specific preferred examples of the repeating unit represented by the general formula (2) are shown below, but the invention is not limited thereto.

[0045]

[Chemical 6]

[0046]

[Chemical 7]

[0047]

[Chemical 8]

[0048]

[Chemical 9]

[0049]

[Chemical 10]

In the present invention, the crosslinkable polymer containing the repeating unit represented by the general formula (2) may be a copolymer composed of plural kinds of repeating units represented by the general formula (2), and It may be a copolymer containing a repeating unit other than the general formula (2) (for example, a repeating unit not containing an ethylenically unsaturated group). In particular, when it is desired to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or for the purpose of controlling the content of the ethylenically unsaturated group of the crosslinkable polymer, a method of using a copolymer containing a repeating unit other than the general formula (2) is preferable. Is. As a method of introducing the repeating unit other than the general formula (2), a) a method of copolymerizing the corresponding monomer and directly introducing it may be used, and b) polymerizing a precursor monomer capable of converting a functional group to obtain a polymer. You may use the method of introduce | transducing by reaction. Also, a) and b)
It is also possible to introduce a combination of the above methods.

When a repeating unit other than the general formula (2) is introduced by polymerizing a corresponding vinyl monomer by the method a), a monomer preferably used is acrylic acid or α-alkylacrylic acid (for example, methacrylic acid). Acids, etc.)-Derived esters or amides (eg, N-i-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N
-Methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetoneacrylamide, acryloylmorpholine, N-methylolacrylamide, N-
Methylol methacrylamide, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n
-Propyl acrylate, i-propyl acrylate,
2-hydroxypropyl acrylate, 2-methyl-2
-Nitropropyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, t-pentyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxymethoxyethyl acrylate, 2,2,2- Trifluoroethyl acrylate, 2,2-dimethylbutyl acrylate, 3-methoxybutyl acrylate, ethylcarbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octafluoropentyl acrylate, n-
Hexyl acrylate, cyclohexyl acrylate,
Cyclopentyl acrylate, cetyl acrylate, benzyl acrylate, n-octyl acrylate, 2-
Ethylhexyl acrylate, 4-methyl-2-propylpentyl acrylate, heptadecafluorodecyl acrylate, n-octadecyl acrylate, methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, hydroxyethyl Methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, benzyl methacrylate, heptadeca Fluorodecyl methacrylate, n-octadecyl methacrylate, 2 -Isobornyl methacrylate,
2-norbornyl methyl methacrylate, 5-norbornen-2-ylmethyl methacrylate, 3-methyl-2
-Derived from norbornyl methyl methacrylate, dimethylaminoethyl methacrylate, etc.), acrylic acid or α-alkyl acrylic acid (acrylic acid, methacrylic acid, itaconic acid, etc.), vinyl esters (eg vinyl acetate), maleic acid or fumaric acid Esters (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), maleimides (N-phenylmaleimide, etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, Dienes (eg butadiene, cyclopentadiene, isoprene), aromatic vinyl curable resins (eg styrene, p-chlorostyrene, t-butylstyrene, α)
-Methylstyrene, sodium styrenesulfonate),
N-vinylpyrrolidone, N-vinyloxazolidone, N
-Vinylsuccinimide, N-vinylformamide, N
-Vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinylsulfonic acid, sodium vinylsulfonate, sodium allylsulfonate, methallylsulfonic acid Examples thereof include sodium, vinylidene chloride, vinyl alkyl ethers (for example, methyl vinyl ether), ethylene, propylene, 1-butene, isobutene and the like. You may use these vinyl monomers in combination of 2 or more types. Other vinyl monomers are Research Disclosure N
o. What was described in 1955 (July, 1980) can be used. In the present invention, esters, amides, and aromatic vinyl-curable resins derived from acrylic acid or methacrylic acid are particularly preferably used vinyl monomers.

When the repeating unit represented by the general formula (2) is introduced by a polymer reaction as in the above ii) and the reaction is not completed, a functional group obtained by converting an ethylenically unsaturated group into a precursor or a reactive group is used. Although it is a copolymer having a repeating unit containing a functional group, it can be used in the invention without particular limitation.

Most of the repeating units containing no ethylenically unsaturated group derived from the above-mentioned vinyl monomers are introduced by polymerizing the above-mentioned b) functional group-convertable precursor monomer and polymerizing it. Is also possible. On the other hand, in the present invention, the crosslinkable polymer containing the repeating unit represented by the general formula (2) may contain a repeating unit other than the general formula (2) which can be introduced only by the polymer reaction. Typical examples include polyvinyl alcohol obtained by modifying polyvinyl acetate, polyvinyl butyral obtained by an acetalization reaction of polyvinyl alcohol, and the like. Specific examples of these repeating units are shown below, but the present invention is not limited thereto.

[0054]

[Chemical 11]

In the present invention, in the crosslinkable polymer containing the repeating unit represented by the general formula (2), the proportion of the repeating unit represented by the general formula (2) is 1% by mass or more and 1
The amount is 00 mass% or less, preferably 30 mass% or more and 100 mass% or less, and particularly preferably 50 mass% or more and 100 mass% or less.

The crosslinkable polymer containing the repeating unit represented by the general formula (2) preferably has a number average molecular weight of 1,000 or more and 1,000,000 or less, more preferably 300.
It is 0 or more and 200,000 or less. Most preferably, it is 5,000 or more and 100,000 or less.

Preferred examples of the crosslinkable polymer containing the repeating unit represented by the general formula (2) are shown in Table 2 below.
The present invention is not limited to this. In addition, the repeating unit represented by the general formula (2) and the repeating unit such as polyvinyl alcohol, which are mentioned above as specific examples, are represented by the numbers of the specific examples described above, and the repeating unit derived from a copolymerizable monomer is used. Indicates the monomer name, and the copolymerization composition ratio is additionally indicated by mass%.

[0058]

[Table 2]

Examples of the curable resin having a ring-opening polymerizable group that can be used in the present invention include polymers containing both repeating units represented by the general formulas (1) and (2). In this case, preferable repeating units of the general formulas (1) and (2) are the same as those described above. Further, it is a copolymer containing a repeating unit other than the general formulas (1) and (2), or a copolymer containing a repeating unit having a reactive group which is neither an ethylenically unsaturated group nor a ring-opening polymerizable group. May be.

The proportion of the repeating unit represented by the general formula (1) in the crosslinkable polymer containing both repeating units represented by the general formulas (1) and (2) is from 1% by mass to 99% by mass. % Or less, preferably 20% by mass or more and 80% by mass
It is particularly preferably 30% by mass or more and 70% by mass or less, and the proportion of the repeating unit represented by the general formula (2) is 1% by mass or more and 99% by mass or less, preferably 20% by mass or less.
Mass% or more and 80 mass% or less, particularly preferably 30 mass%
It is above 70 mass%.

The preferable molecular weight range of the crosslinkable polymer containing both repeating units represented by the general formulas (1) and (2) is 1,000 to 1,000,000, more preferably 3,000 to 200,000 in terms of number average molecular weight. . Most preferably, it is 5,000 or more and 100,000 or less.

Preferred examples of the crosslinkable polymer containing both repeating units represented by the general formulas (1) and (2) are shown in Table 3.
However, the present invention is not limited to these.
It should be noted that the repeating units represented by the general formulas (1) and (2) and the repeating units such as polyvinyl alcohol, which are mentioned above as specific examples, are represented by the numbers of the specific examples described above and are derived from a copolymerizable monomer. For the repeating unit to be used, the monomer name was described, and the copolymerization composition ratio was additionally indicated by mass%.

[0063]

[Table 3]

A curable resin containing three or more ethylenically unsaturated groups in the same molecule and a curable resin containing a ring-opening polymerizable group contained in a preferable curable composition for forming a hard coat layer. The preferred mixing ratio varies depending on the type of curable resin used and is not particularly limited, but the ratio of the curable resin containing an ethylenically unsaturated group is preferably 30% by mass or more and 90% by mass or less, and more preferably Is 50
It is from 80% by mass to 80% by mass.

A curable composition containing a curable resin containing an ethylenically unsaturated group and a curable resin containing a ring-opening polymerizable group (hereinafter, "curable composition" refers to both of these unless otherwise specified). Of the curable resin) is cured, it is preferable that the crosslinking reaction of both curable resins proceeds. A preferable crosslinking reaction of the ethylenically unsaturated group is a radical polymerization reaction, and a preferable crosslinking reaction of the ring-opening polymerizable group is a cationic polymerization reaction. In either case, the polymerization reaction can be advanced by the action of the active energy ray. Usually, a small amount of a radical generator and a cation generator (or an acid generator) called a polymerization initiator are added, and these are decomposed by an active energy ray to generate radicals and cations to allow polymerization to proceed. . The radical polymerization and the cationic polymerization may be performed separately, but it is preferable to proceed at the same time.

When the above curable composition is cured by irradiation with active energy rays, the crosslinking reaction often proceeds at a low temperature, which is preferable. In the present invention, radiation, gamma rays, alpha rays, electron rays, ultraviolet rays, etc. are used as the active energy rays. Among these, a method of adding a polymerization initiator that generates radicals or cations by using ultraviolet rays and curing by a ultraviolet ray is particularly preferable. Further, in some cases, it may be possible to further cure by heating after irradiation with ultraviolet rays, and this method can be preferably used. The preferable heating temperature in this case is 14
It is 0 ° C or lower.

Examples of the photoacid generator that generates cations by ultraviolet rays include ionic curable resins such as triarylsulfonium salts and diaryliodonium salts, and nonionic curable resins such as nitrobenzyl ester of sulfonic acid. "Organic Materials for Imaging", edited by Organic Electronics Materials Study Group, published by Bushin Publishing Co. (19
Various known photoacid generators such as curable resins described in 97) can be used. Of these, a sulfonium salt or an iodonium salt is particularly preferable, and the counter ion is preferably PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^−, or the like.

Examples of polymerization initiators that generate radicals by ultraviolet rays include known radicals such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoates, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide and thioxanthone. A generator can be used. In addition, as mentioned above, a sulfonium salt, an iodonium salt or the like which is usually used as a photoacid generator also acts as a radical generator upon irradiation with ultraviolet rays, and therefore, these may be used alone in the present invention. In addition, in order to increase the sensitivity, in addition to the polymerization initiator,
A sensitizer may be used. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone derivative and the like.

The polymerization initiators may be used in combination, or in the case of a curable resin which alone generates both radicals and cations, one kind may be used alone. The addition amount of the polymerization initiator is 0.1 to 15% by mass based on the total mass of the ethylenically unsaturated group-containing curable resin and the ring-opening polymerizable group-containing curable resin contained in the curable composition. It is preferably used in the range of 1 to 1
It is more preferable to use it in the range of 0% by mass.

In the present invention, a crosslinkable polymer having a repeating unit represented by the general formula (1) and a crosslinkable polymer having a repeating unit represented by the general formula (2) (hereinafter, referred to as
When these are collectively referred to as the “polymer of the present invention”), the polymer of the present invention is usually a solid or high-viscosity liquid and difficult to apply alone, and when the polymer is water-soluble or water-dispersed. When it is made into a substance, it can be applied in an aqueous system, but it is usually dissolved in an organic solvent and applied. The organic solvent can be used without particular limitation as long as it can dissolve the polymer of the present invention. Preferred organic solvents include ketones such as methyl ethyl ketone, alcohols such as isopropanol, and esters such as ethyl acetate. Further, when the above-mentioned monofunctional or polyfunctional vinyl monomer or the curable resin having a monofunctional or bifunctional or trifunctional or higher functional ring-opening polymerizable group is a low molecular weight curable resin, when these are used in combination, curability is improved. It is possible to control the viscosity of the composition, and it is also possible to apply without using a solvent.

In the present invention, fine particles may be added to the curable composition. By adding fine particles, the amount of shrinkage upon curing of the hard coat layer can be reduced, so that the adhesion to the substrate can be improved and curling can be reduced when the substrate is a plastic film, which is preferable. As the fine particles, any of inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be used. Examples of the inorganic fine particles include silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles and the like. Such inorganic crosslinked fine particles are generally hard, and by filling the hard coat layer, not only the shrinkage upon curing can be improved but also the surface hardness can be increased. However, since the fine particles generally tend to increase the haze, the filling method is adjusted in consideration of the balance of each required characteristic.

In general, since the inorganic fine particles have a low affinity with the organic components such as the polymer of the present invention and the polyfunctional vinyl monomer, they are likely to form aggregates or the hard coat layer after curing is easily cracked by simply mixing them. There are cases. In the present invention, in order to increase the affinity between the inorganic fine particles and the organic component,
The surface of the inorganic fine particles can be treated with a surface modifier containing an organic segment. The surface modifier preferably has a functional group capable of forming a bond with or adsorbing to the inorganic fine particles and a functional group having a high affinity for the organic component in the same molecule. As the surface modifier having a functional group capable of binding or adsorbing to the inorganic fine particles, silane, aluminum,
Metal alkoxide surface modifiers such as titanium and zirconium and surface modifiers having anionic groups such as phosphoric acid groups, sulfuric acid groups, sulfonic acid groups and carboxylic acid groups are preferred. Further, as the functional group having a high affinity with the organic component, it is possible to simply combine the organic component and the hydrophilicity / hydrophobicity, but a functional group capable of being chemically bonded to the organic component is preferable, and particularly an ethylenically unsaturated group, Alternatively, a ring-opening polymerizable group is preferable. In the present invention, the preferred inorganic fine particle surface modifier is a curable resin having a metal alkoxide or an anionic group and an ethylenically unsaturated group or a ring-opening polymerizable group in the same molecule.

Typical examples of these surface modifiers are the following unsaturated double bond-containing coupling agents, phosphoric acid group-containing organic curable resins, sulfuric acid group-containing organic curable resins, and carboxylic acid group-containing organic curable resins. Etc. _{S-1 H 2 C = C} (X) COOC 3 H 6 Si (OCH 3) 3 S-2 H 2 C = C (X) COOC 2 H 4 OTi (OC 2 H 5)
₃ S-3 H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H ₁₀ O
PO (OH) ₂ S-4 (H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H
₁₀ O) ₂ POOH S-5 H ₂ C = C (X) COOC ₂ H ₄ OSO ₃ H S-6 H ₂ C = C (X) COO (C ₅ H ₁₀ COO) ₂ H S-7 H ₂ C = C (X) COOC ₅ H ₁₀ COOH S-8 H ₂ C = CH (O) CH ₂ OC ₃ H ₆ Si (OCH
₃ ) ₃ (X = H or CH ₃ )

The surface modification of these inorganic fine particles is preferably performed in a solution. When mechanically finely dispersing the inorganic fine particles, a surface modifier is present together, or after the inorganic fine particles are finely dispersed, the surface modifier is added and stirred, or further before the inorganic fine particles are finely dispersed. Alternatively, the surface may be modified (if necessary, heated or dried and then heated, or pH is changed), and then finely dispersed. As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferable. Specific examples thereof include known solvents such as alcohols, ketones and esters.

The organic fine particles are not particularly limited, but polymer particles made of a monomer having an ethylenically unsaturated group, such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyethylene, Polypropylene, polystyrene, etc.
Further, polymer particles of the general formulas (1) and (2) in the present invention are preferably used, and in addition, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, polycarbonate, nylon,
Polyvinyl alcohol, polytetrafluoroethylene,
Resin particles of polyethylene terephthalate, polyvinyl chloride, acetyl cellulose, nitrocellulose, gelatin, etc. may be mentioned. These particles are preferably crosslinked. It is preferable to use an ultrasonic wave, a disperser, a homogenizer, a dissolver, a polytron, a paint shaker, a sand grinder, a kneader, an Eiger mill, a dyno mill, a coball mill or the like as a fine particle disperser. As the dispersion medium, the above-mentioned solvent for surface modification is preferably used.

The filling amount of the fine particles is preferably 2 to 40% by volume with respect to the volume of the hard coat layer after filling, and 3 to 2
5 volume% is more preferable, and 5 to 15 volume% is the most preferable.

The haze of the hard coat layer of the present invention is 1.5.
% Or less, more preferably 1.2% or less, and most preferably 1.0% or less.

The hard coat film of the present invention comprises
The value when the curl is expressed by the following formula B is minus 1.
It is preferably in the range of 5 to plus 15, more preferably in the range of minus 12 to plus 12, and even more preferably in the range of minus 10 to plus 10. The measurement direction of the curl in the sample at this time is the measurement direction of the base material in the case of coating in a web form. (Formula B) Curl = 1 / R R is the radius of curvature (m) This is an important property for preventing cracking and film peeling in the manufacture, processing and handling of the hard coat film in the market. It is preferable that the curl value is within the above range and the curl is small. Curling and high surface hardness in the above range can be achieved by setting the volumetric shrinkage ratio of the curable composition for forming the hard coat layer before and after curing to 15% or less. The curl is measured by JIS
It is carried out using the curl-measuring template of method A in "Method of measuring curl of photographic film" of K7619-1988.
The measurement conditions are 25 ° C., relative humidity of 60%, and humidity control time of 10 hours. Here, the curl being positive means a curl in which the hard coat layer coating side of the film is on the inside of the curve, and the curl being minus means a curl in which the coating side is on the outside of the curve. Further, the hard coat film of the present invention has a relative humidity of 80% and 10% based on the above-mentioned curl measuring method.
The absolute value of the difference between each curl value when changed to
0 is preferable, 15 to 0 is more preferable, and 8 to 0 is the most preferable. This is a property related to handling property, peeling and cracking when the film is attached under various humidity.

The crack resistance of the hard coat film in the present invention is preferably 50 mm or less, more preferably 40 mm or less, when the hard coat film is rounded with the hard coat layer coating side facing outward. It is preferably 30 mm or less, and most preferably 30 mm or less. Regarding the edge cracks, it is preferable that there is no crack or the length of the crack is less than 1 mm on average. The crack resistance is an important characteristic for preventing crack defects during handling such as application, processing, cutting, and sticking of the hard coat film.

The base material used in the present invention is preferably a transparent film-shaped, sheet-shaped or plate-shaped plastic. Specifically, polyesters such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as triacetyl cellulose and diacetyl cellulose, films and sheets such as polycarbonate, polymethyl methacrylate, polysulfone, polyether sulfone, polyarylate and cycloolefin polymer are preferable. . The thickness of the film is preferably 20 to 300 μm, and 80 to 200 μm
Is more preferable. If the base film is too thin, the film strength will be weak, and if it is thick, the rigidity will be too high. The thickness of the sheet may be 300 μm as long as the transparency is not impaired.
The thing of several mm or more can be used.

The active energy ray-curing coating solution is prepared by mainly dissolving the above-mentioned polyfunctional monomer and polymerization initiator in a ketone-based, alcohol-based, ester-based or other organic solvent. Further, the surface-modified hard inorganic fine particle dispersion liquid and the soft fine particle dispersion liquid can be added to prepare.

The hard coat layer of the present invention is prepared by dipping the active energy ray-curing coating liquid on a transparent substrate,
It is applied by a known thin film forming method such as a spinner method, a spray method, a roll coater method, a gravure method, a wire bar method, a slot extrusion coater method (single layer, multiple layers), and a slide coater method, dried, and irradiated with active energy rays. Then, it can be prepared by curing. Drying is preferably carried out under the conditions that the concentration of the organic solvent in the applied liquid film is 5% by mass or less after drying, more preferably 2% by mass or less, and further preferably 1% by mass or less. The drying conditions are affected by the thermal strength of the substrate, the transport speed, the length of the drying step, etc., but it is preferable that the content of the organic solvent is as low as possible in order to increase the polymerization rate.

Further, for the purpose of improving the adhesion between the transparent base material and the hard coat layer, one surface or both surfaces of the transparent base material can be subjected to a surface treatment by an oxidation method or a textured method, if desired. Examples of the oxidation method include corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Furthermore, more than one undercoat layer can be provided.
As the material of the undercoat layer, vinyl chloride, vinylidene chloride,
Examples thereof include copolymers or latexes of butadiene, (meth) acrylic acid ester, vinyl ester and the like, water-soluble polymers such as low molecular weight polyester and gelatin. Further, the undercoat layer may contain an antistatic agent such as tin oxide, a metal oxide such as tin oxide / antimony oxide composite oxide, tin oxide / indium oxide composite oxide, or a quaternary ammonium salt.

The hard coat layer may have a multi-layered structure and may be produced by appropriately laminating in order of hardness.

In the present invention, an antireflection layer having a high scratch resistance and comprising a low refractive index layer and a high refractive index layer is provided on the prepared hard coat layer to prevent reflection of a high surface hardness. It can be a hard coat layer.

The low refractive index layer and the high refractive index layer in the present invention are mainly composed of a curable resin which is cured by irradiation with active energy rays, or the low refractive index layer and the high refractive index layer are irradiated with active energy rays. It is preferable that the layer is composed of a curable resin that hardens and metal oxide fine particles.

As the curable resin which is cured by irradiation with active energy rays, a curable resin having two or more acrylic groups in the same molecule is preferable. Specific examples include ethylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol-A diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipenta. Erythritol pentaacrylate, dipentaerythritol hexaacrylate and other polyol polyacrylates, polyisocyanate curable resin and polyfunctional urethane acrylate and polyepoxy curable resin and hydroxyethyl acrylate obtained by reaction of hydroxyl group-containing acrylate such as hydroxyethyl acrylate Polyfunctional compounds obtained by the reaction of hydroxyl group-containing acrylates (methacrylates) It can be exemplified port carboxymethyl acrylate. Further, a polymer having an ethylenically unsaturated group such as A-1 to A-44 in the side chain may be used.

The metal oxide fine particles include titanium dioxide having an average particle size of 100 nm or less, preferably 50 nm or less (eg rutile, mixed crystal of rutile / anatase, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide. , Zirconium oxide particles, aluminum oxide particles and the like having a refractive index of more than 1.6. Titanium dioxide having a large refractive index is preferable because it can be added in a small amount.

In order to increase the affinity between the inorganic fine particles and the organic component, it is preferable to treat the surface of the inorganic fine particles with a surface modifying agent containing an organic segment. Those having a high affinity with the functional group that can be adsorbed to the fine particles and, on the other hand, the curable resin that is cured by irradiation with active energy rays are preferable. As the surface modifier having a functional group capable of binding or adsorbing to the inorganic fine particles, silane, aluminum, titanium, a metal alkoxide curable resin such as zirconium, a phosphate group,
A surface modifier having an anionic group such as a sulfuric acid group, a sulfonic acid group or a carboxylic acid group is preferable. Further, as the functional group having a high affinity with the organic component, it is possible to simply combine the organic component and the hydrophilicity / hydrophobicity, but a functional group that can be chemically bonded to the organic component is preferable, and an ethylenically unsaturated group is particularly preferable. preferable. The surface modifier of the metal oxide fine particles preferably used in the present invention is a curable resin having a metal alkoxide or anionic group and an ethylenically unsaturated group in the same molecule, or an acrylic acid copolymer having an anionic group such as carboxylic acid. Etc.

Typical examples of these surface modifiers are the following unsaturated double bond-containing coupling agents, phosphoric acid group-containing organic curable resins, sulfuric acid group-containing organic curable resins, and carboxylic acid group-containing organic curable resins. Etc. _{S-1 H 2 C = C} (X) COOC 3 H 6 Si (OCH 3) 3 S-2 H 2 C = C (X) COOC 2 H 4 OTi (OC 2 H 5)
₃ S-3 H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H ₁₀ O
PO (OH) ₂ S-4 (H ₂ C = C (X) COOC ₂ H ₄ OCOC ₅ H
₁₀ O) ₂ POOH S-5 H ₂ C = C (X) COOC ₂ H ₄ OSO ₃ H S-6 H ₂ C = C (X) COO (C ₅ H ₁₀ COO) ₂ H S-7 H ₂ C = C (X) COOC ₅ H ₁₀ COOH (X = H or CH ₃ )

The surface modification of these inorganic fine particles is preferably performed in a solution. When mechanically finely dispersing the inorganic fine particles, a surface modifier is present together, or after the inorganic fine particles are finely dispersed, the surface modifier is added and stirred, or further before the inorganic fine particles are finely dispersed. Alternatively, the surface may be modified (if necessary, heated or dried and then heated, or pH is changed), and then finely dispersed. As the solution for dissolving the surface modifier, an organic solvent having a large polarity is preferable. Specific examples thereof include known solvents such as alcohols, ketones and esters.

In the present invention, radiation, gamma rays, alpha rays, electron rays, ultraviolet rays, etc. are used as active energy rays for curing the high refractive index layer. Among them, a method of adding a polymerization initiator that generates radicals by using ultraviolet rays and curing by using ultraviolet rays is particularly preferable.

Examples of polymerization initiators that generate radicals by ultraviolet rays include known radicals such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide and thioxanthone. A generator can be used. In addition, as mentioned above, a sulfonium salt, an iodonium salt or the like which is usually used as a photoacid generator also acts as a radical generator upon irradiation with ultraviolet rays, and therefore, these may be used alone in the present invention. In addition, in order to increase the sensitivity, in addition to the polymerization initiator,
A sensitizer may be used. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone derivative and the like.

The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator added is
Based on the total mass of the ethylenically unsaturated group-containing curable resin and the ring-opening polymerizable group-containing curable resin contained in the curable composition,
It is preferably used in the range of 0.1 to 15% by mass, more preferably 1 to 10% by mass.

The refractive index of the high refractive index layer composed of the curable resin and metal oxide fine particles which are cured by irradiation with these active energy rays is preferably 1.6 or more, more preferably 1.65 or more. The ratio is preferably 0.2 or more.

For the low refractive index layer, a curable resin similar to the curable resin used for the high refractive index layer and cured by irradiation with active energy rays can be used. The cured resin used has a refractive index of preferably 1.6 or less, and the metal oxide fine particles are preferably silicon dioxide having a small refractive index.
The refractive index of the low refractive index layer is preferably 1.45 or more and 1.6 or less, and more preferably 1.55 or less.

These high-refractive index layer and low-refractive index layer are respectively applied in the range of 50 to 100 nm, and the optical distance (refractive index × thickness) is set to a quarter of the observed wavelength in order to increase the antireflection effect. It is preferably 1. In the present invention, the high refractive index layer and the low refractive index layer, the active energy ray-curable coating liquid on the hard coat layer, the high refractive index layer, the low refractive index layer in order of the spinner method, gravure method, wire bar method It can be produced by applying a known thin film forming method such as the above, drying, irradiating with an active energy ray, and preferably completely curing without semi-curing.

The reflectance (regular reflectance) of the antireflection layer is
It is preferably 3.0% or less, and more preferably 1.5% or less.

In the antireflection hard coat layer of the present invention, in order to improve the antifouling property of the antireflection layer, the low refractive index layer may contain a curable resin containing fluorine and / or silicon, or may have a low refractive index. A layer containing a curable resin containing fluorine and / or silicon may be provided on the refractive index layer. Examples of the curable resin to be added to the low refractive index layer include known fluorine-curable resins and silicon-curable resins, or curable resins having a block having a fluorine- and silicon-containing portion, and further resins or metal oxides. A curable resin having a segment having good compatibility with and a segment containing fluorine or silicon is preferable, and fluorine or silicon can be unevenly distributed on the surface by adding to the low refractive index layer.

Specific examples of these curable resins include block copolymers of fluorine- or silicon-containing monomers and other hydrophilic or lipophilic monomers, or graft copolymers. Examples of the fluorine-containing monomer include perfluoroalkyl group-containing (meth) acrylic acid esters represented by hexafluoroisopropyl acrylate, heptadecafluorodecyl acrylate, perfluoroalkylsulfonamidoethyl acrylate, perfluoroalkylamidoethyl acrylate, and the like. Examples of the silicon-containing monomer include a monomer having a siloxane group formed by the reaction of polydimethylsiloxane and (meth) acrylic acid. Examples of hydrophilic or lipophilic monomers include (meth) acrylic acid esters such as methyl acrylate, esters of hydroxyl group-containing polyester with (meth) acrylic acid, hydroxyethyl (meth) acrylate, and (meth) acrylic acid of polyethylene glycol. Esters and the like can be mentioned. Examples of commercially available curable resins include acrylic-based oligomer defencers MCF-300, 312, and 323 having a perfluoroalkyl chain microdomain structure, and perfluoroalkyl group / lipophilic group-containing oligomer Megafac F-1.
70, F-173, F-175, etc., Megafac F-17, an oligomer containing a perfluoroalkyl group / hydrophilic group.
1 etc. (manufactured by Dainippon Ink and Chemicals, Inc.) or a fluoroalkyl-based modiper F-200, 220, 600 which is a block polymer of a vinyl monomer consisting of a segment excellent in surface migration and a segment compatible with a resin. , 820
Etc. Silicon type modiper FS-700, 710 etc. (made by NOF CORPORATION) are mentioned.

In order to provide an antifouling layer on the low refractive index layer, a low surface energy curable resin containing a fluorine atom is preferable, and specifically, it is described in JP-A-57-34526.
No. 2, JP-A-2-19801, JP-A No. 3-17901, etc., and the silicone-curable resin containing a fluorohydrocarbon group, a fluorohydrocarbon group-containing polymer, and the like.

The antireflection hard coat layer of the present invention can be laminated together with other layers having functions such as an ultraviolet / infrared absorbing layer, a coloring layer, a selective wavelength absorbing layer and an electromagnetic wave shielding layer, and has a high hardness. It is used as a functional film.

By sticking the antireflection hard coat layer or the antireflection hard coat film of the present invention on the surface, it is possible to obtain an image display device having good visibility and suppressing the damage to the surface. As a method for attaching the antireflection hard coat layer to the image display device, the antireflection hard coat film of the present invention may be attached to the image display device, or the antireflection hard coat layer may be directly attached to the image display device. The method of attaching the antireflection hard coat film to the image display device is simple and preferable.

[0104]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to the examples. (Preparation of Hard Coat Layer Coating Solution (h-1)) Glycidyl methacrylate was dissolved in methyl ethyl ketone (MEK), and the reaction solution was reacted for 2 hours at 80 ° C. while adding a thermal polymerization initiator dropwise to hexane. Solution 10 in which polyglycidyl methacrylate (polystyrene-equivalent molecular weight: 12,000) obtained by dropping and drying the precipitate under reduced pressure was dissolved in methyl ethyl ketone to a concentration of 50% by mass.
To 0 parts by mass, 1 part of trimethylolpropane triacrylate (biscoat # 295; manufactured by Osaka Organic Chemical Industry Co., Ltd.)
50 parts by mass and a photo radical polymerization initiator (IRGACURE 18
(4, manufactured by Ciba Geigy) and 6 parts by weight of a cationic photopolymerization initiator (Rhodesil 2074, manufactured by Rhodia) dissolved in 30 parts by weight of methyl isobutyl ketone are mixed with stirring to prepare a hard coat layer coating solution. Was produced. (Preparation of coating liquid for hard coat layer (h-2)) 70 parts by mass of a solution prepared by dissolving polyfunctional epoxy-terminated epoxy resin (EHPE, manufactured by Daicel Chemical Industries, Ltd.) in methyl isobutyl ketone to a concentration of 70% by mass. In addition, 150 parts by mass of ditrimethylolpropane tetraacrylate (EB140, manufactured by Daicel Chemical Industries, Ltd.) and 6 parts by weight of a radical photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy) and a cationic photopolymerization initiator (Rhodesil 2074, manufactured by Rhodia) 6 parts by mass dissolved in 30 parts by mass of methyl isobutyl ketone were mixed with stirring to prepare a hard coat layer coating liquid.

(Production of Hard Coat Film) Thickness 17
Both sides of 5 μm PET (biaxially-stretched polyethylene terephthalate film) are corona-treated, and a latex (L-L) made of styrene-butadiene copolymer having a refractive index of 1.55 and a glass transition temperature of 37 ° C. is provided on the surface on which the hard coat layer is installed.
X407C5, manufactured by Nippon Zeon Co., Ltd. and tin oxide / antimony oxide composite oxide (FS-10D, Ishihara Sangyo Co., Ltd.)
5) by weight, and the film thickness after drying is 2
After coating to have a thickness of 00 nm to form an undercoating layer with an antistatic layer, the coating solution for the hard coat layer is applied to the thickness shown in Table 4 by an extrusion method,
It was dried and irradiated with ultraviolet rays (700 mJ / cm ² ) to prepare a hard coat film. (Preparation of Antireflection Layer) (1) Preparation of High Refractive Index Layer Coating Liquid (a-1) Titanium Dioxide Fine Particles (TTO-55B, Ishihara Sangyo Co., Ltd.)
30.0 parts by mass, carboxylic acid group-containing monomer (Aronix M-5300 manufactured by Toagosei Co., Ltd.) 4.5 parts by mass, and cyclohexanone 65.5 parts by mass are dispersed by a sand grinder mill to have a mass average diameter of 55 nm. A titanium dioxide dispersion of was prepared. Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) and a photoradical polymerization initiator (Irgacure 184, manufactured by Ciba Geigy) are added to the titanium dioxide dispersion, and the total amount of monomers (dipentaerythritol hexaacrylate, anionic 5% based on the total amount of monomers and cationic monomers)
And were mixed and adjusted so that the refractive index of the high refractive index layer was as shown in Table 4.

(2) Preparation of coating liquid (a-2) for low refractive index layer Pentaerythritol tetraacrylate (PETA,
60 parts by mass of Nippon Kayaku Co., Ltd., 2 parts by mass of a photo-radical polymerization initiator (Irgacure 184, manufactured by Ciba-Geigy),
Megafac _{531A (C 8 F 17 SO 2} N (C 3 H 7)
9 mass g of CH ₂ CH ₂ OCOCH = CH ₂ , manufactured by Dainippon Ink and Chemicals, Inc. and methyl ethyl ketone were mixed and stirred to prepare a coating liquid for the low refractive index layer. The refractive index is adjusted by 30.0 parts by mass of silicon dioxide fine particles (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) and a carboxylic acid group-containing monomer (Aronix M-5300 Toagosei Co., Ltd.).
4.5 parts by mass and 65.5 parts by mass of cyclohexanone were dispersed and adjusted by a sand grinder mill, and a silicon dioxide fine particle dispersion liquid having a mass average diameter of 12 nm was added.

(3) Formation of a hard coat film with an antifouling antireflection layer: After coating the hard coat layer of (h-1) or (h-2),
The coating liquid for a high refractive index layer of (a-1) is applied using a wire bar to a dry film thickness of 75 nm, dried, and irradiated with ultraviolet rays, and further (a-2) on the high refractive index layer. A low-refractive-index layer coating solution was applied to a dry film thickness of 90 nm, dried, and irradiated with ultraviolet rays to obtain an antireflection layer-coated hard coat film.

(4) Image display device having a film provided with an antireflection hard coat layer An acrylic adhesive was applied to the surface of the hard coat film of Example 1 and Comparative Examples 1 to 3 on which the hard coat layer was not provided. , Laminated on the plasma display front plate. The results of examining the surface characteristics are shown in Table 5.

[0109]

[Table 4]

[0110]

[Table 5]

The respective evaluation methods are as follows.
It was Pencil hardness test: The hardness of the pencil scratch test is
Apply a dry coat film at a temperature of 25 ° C and a relative humidity of 60%.
According to JIS-S-6006, after humidity control for 2 hours.
JIS-K-5400 regulates using a test pencil
According to the pencil hardness evaluation method, scratches are recognized under a load of 9.8N.
It is the value of the hardness of a pencil that cannot be folded. Adhesion test; using a cutter on the hard coat surface, 1
Scratch at an interval of 1 mm x 1 mm, and in 100 squares,
Rotape (registered trademark No 405; manufactured by Nichiban Co., Ltd.)
30 seconds after attaching, the cellophane tape was peeled off and peeled off
The number of squares with missing edges was observed. 100 boxes
○ If the eyes are left, ○
The ones were marked with Δ, and the ones in which a plurality of squares were peeled off were marked with x. Surface reflectance measurement; rub the back surface with sandpaper, and
A sample coated with Zic to prevent reflection on the back side
Using a spectrophotometer (manufactured by JASCO Corporation),
In incident light 5 ° in the wavelength range of 50 to 650 nm
The surface reflectance of regular reflection was calculated. Steel wool test; use # 0000 steel wool
Yes, 1.96 N / cm ^TwoWhen rubbing while applying the load of
The number of times the scratch became visible was determined. Eraser rub; eraser No. made by Lion Corporation. Fifty
Using a load of 9.8 N, reciprocate the surface 50 times,
The damage was evaluated visually. No scratches or changes observed
The thing was marked as ○. Antifouling property; quick-drying oil-based ink written on the film surface (Zeb
"Mckey" (registered trademark) manufactured by La Co., Ltd.
Rossi "(registered trademark) rubbed several times and wiped off
Evaluation of state (○ indicates that the written mark is completely wiped off, △ indicates
A part of it is not wiped off, and most of X is wiped off
State). External light reflection; Visually evaluate the visibility of the reflection of fluorescent lamps
(○ indicates that the reflection is difficult to see, and × indicates that the reflection is
Those that can be seen clearly, △ are those in the middle). Dirt wiping ability: Fingerprints on the surface can be removed by Toray Industries
Evaluate the ease of removal when wiped with "C" (registered trademark)
Valuable (○ is a light force that can be taken in a few times, × is a strong force)
Can be rubbed off, △ is the middle one).

[0112]

The antireflection hard coat layer of the present invention has high surface hardness and excellent scratch resistance, and the film provided with the antireflection hard coat layer of the present invention has suppressed reflection and high pencil hardness. The surface is not easily scratched. Furthermore, by sticking the antireflection hard coat layer or the antireflection hard coat film of the present invention on the surface, it is possible to obtain an image display device having good visibility and suppressing scratches on the surface. The film having such various functions is suitably used for protecting image display devices, plastics, and glass.

[Brief description of drawings]

FIG. 1 is a schematic view showing an embodiment of a hard coat film of the present invention.

[Explanation of symbols]

1 Low refractive index layer 2 High refractive index layer 3 hard coat layer 4 Transparent base material 5 Adhesive layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02F 1/1335 G02B 1/10 Z F term (reference) 2H091 FA37X FB04 FB13 FC12 FC23 FD23 GA16 LA02 LA03 2K009 AA05 AA15 BB24 CC03 CC09 CC24 CC33 DD02 DD05 DD06 DD08 EE03 EE05 4F100 AA17B AA17C AA21 AK01A AK01B AK01C AK02A AK02B AK02C AK25 AK42 AK53 AR00B AR00C AR00D BA03 BA04 BA07 DE01B DE01C GB48 JB14A JB14B JB14C JK09 JN01D JN06 JN06B JN06C JN18B JN18C YY00A YY00B YY00C 4J027 AA02 BA06 BA07 BA10 BA13 BA14 BA15

Claims (6)

[Claims] 1. An antireflection hard coat having a hard coat layer made of a curable composition that is cured by irradiation with active energy rays, and an antireflection hard coat having two layers of a high refractive index layer and a low refractive index layer having different refractive indexes. In the layer, the low-refractive index layer and the high-refractive index layer are mainly composed of a curable resin curable by irradiation of active energy rays or a layer composed of curable resin curable by irradiation of active energy rays and metal oxide fine particles. An antireflection hard coat layer characterized by being present. 2. The low refractive index layer has a refractive index of 1.45 or more.
The antireflection hard coat layer according to claim 1, which has a refractive index of 6 or less and a refractive index of the high refractive index layer is 0.2 or more higher than that of the low refractive index layer. 3. The antireflection hard coat layer according to claim 1, wherein the thickness of the hard coat layer is more than 10 μm and 60 μm or less. 4. A curable composition which is cured by irradiation with active energy rays has an ethylenically unsaturated group of 3 in the same molecule.
The antireflection hard coat layer according to any one of claims 1 to 3, which contains a curable resin containing at least 3 and / or a curable resin containing at least 3 ring-opening polymerizable groups in the same molecule. 5. An antireflection hard coat film comprising a transparent substrate and the hard coat layer according to claim 1 provided on the transparent substrate. 6. An image display device provided with the antireflection hard coat layer according to any one of claims 1 to 4 or the antireflection hard coat film according to claim 5.