JP2002338720A - Hard coating, hard coat film and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coating having a high hardness, scarcely suffering from a crack, hardly curling, and exhibiting good image sharpness. SOLUTION: The hard coating comprises a laminated product comprising a transparent substrate and a hard coat layer formed thereon, where the film thickness of the hard coat layer is 20-200 μm. A hard coat film and an image display device are also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard coat film and a hard coat film having a transparent substrate having a cured resin layer by an active energy ray. For more information,
The present invention relates to a hard coat film and a hard coat film having excellent scratch resistance and surface hardness. INDUSTRIAL APPLICABILITY The present invention is suitable for a surface of a display such as a CRT, an LCD, a PDP, and an FED, and a protective film and a protective film such as a touch panel and a glass for home appliances. Further, a hard coat film and a hard coat film provided with a layer having a function such as antireflection, ultraviolet / infrared absorption, selective wavelength absorbing layer, electromagnetic wave shielding layer and antifouling layer on the surface thereof, and image display having these Related to the device.

[0002]

2. Description of the Related Art In recent years, plastic products have been replaced by glass products from the viewpoint of workability and weight reduction. However, since the surfaces of these plastic products are easily damaged, a hard coat film is applied for the purpose of imparting scratch resistance. Often used together. Also, for conventional glass products,
In many cases, a plastic film is bonded to prevent scattering, and a hard coat layer is widely formed on the surface of the film to enhance the hardness of the film surface.

[0003] Conventional hard coat films are usually prepared by directly coating an active energy ray polymerizable resin such as a thermosetting resin or an ultraviolet curable resin on a plastic substrate film or a primer of about 0.03 to 0.3 µm. It is manufactured by forming a thin coating film of about 3 to 10 μm through a layer.

However, in the conventional hard coat film, the plastic base film as an underlayer is deformed due to the insufficient hardness of the hard coat layer and the thin coating film thickness. In this case, the hard coat layer is deformed accordingly, and the hardness of the hard coat film as a whole is lowered, so that it is not sufficiently satisfactory. For example, a hard coat film obtained by applying an ultraviolet-curable paint to the above thickness on a polyethylene terephthalate film widely used as a plastic substrate film has a pencil hardness of 3%.
H level is common, 9H which is the pencil hardness of glass
Nothing at all.

In order to increase the hardness of the hard coat layer, a resin-forming component of the layer is made of a polyfunctional acrylate-based monomer, and a powdered inorganic filler such as alumina, silica and titanium oxide and a polymerization initiator are added thereto. The coating composition contained therein is disclosed in Japanese Patent No. 1815116. Also,
Japanese Patent No. 1416240 discloses a photopolymerizable composition containing an inorganic loading material composed of silica or alumina surface-treated with alkoxysilane or the like. Further, filling with crosslinked organic fine particles has been studied in recent years. These have the effect of slightly increasing the surface hardness of the hard coat film, but also have the problems of increased haze and brittleness, which alone can sufficiently respond to the surface hardness performance of the hard coat film required in recent years. It wasn't good.

Japanese Patent Application Laid-Open No. 2000-52472 proposes a method of satisfying curl and scratch resistance by forming a two-layer hard coat layer and adding silica as a fine particle to the first layer. Japanese Patent Application Laid-Open No. 2000-71392 discloses a hard coat layer having a two-layer structure, a lower layer using a cured resin layer made of a blend of a radical-curable resin and a cation-curable resin, and an upper layer made of only a radical-curable resin. There is a description of a hard coat film using a cured resin layer. However, these were not sufficiently satisfactory 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 m is effective for increasing the hardness. In particular, by increasing the thickness of the layer containing inorganic and organic fillers in the hard coat layer, the hardness of the hard coat film can be further improved, but by increasing the thickness, the increase in haze increases, and the hard coat layer is cracked or peeled. At the same time, the curl of the hard coat film due to curing shrinkage increases. For this reason, it has been difficult to obtain a hard coat film having good characteristics that can be practically used by the conventional technique.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hard coat film and a hard coat film which have high hardness, hardly cause cracks, have small curl, and have good image sharpness.

[0009]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the thickness of the hard coat layer has been greatly increased to a specific range and the haze has been kept low, thereby improving the surface hardness and improving image sharpness. It has been found that a hard coat film and a good hard coat film having good characteristics can be obtained, and that these good characteristics can be realized by using a specific compound. That is, the following means have been achieved. (1) A hard coat film including a hard coat layer provided on a transparent substrate, wherein the hard coat layer has a thickness of 20 to 2
A hard coat film having a thickness of 00 μm. (2) The hard coat film according to (1), wherein the primer layer is provided between the transparent substrate and the hard coat layer, and the haze of the hard coat film is 1.5% or less. (3) a hard coat layer formed by applying a curable composition containing a compound containing three or more ethylenically unsaturated groups in the same molecule and a compound containing a ring-opening polymerizable group, followed by curing. The hard coat film according to (1) or (2), which is a coat layer. (4) The compound containing a ring-opening polymerizable group is a crosslinkable polymer containing a repeating unit represented by the following formula (1) (1)
Or (3) The hard coat film according to any one of (1) to (3).

Embedded image In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. P ¹ is a monovalent group containing a ring-opening polymerizable group, and L ¹ is a single bond or a divalent linking group. (5) The hard coat film according to any one of (1) to (4), wherein the ring-opening polymerizable group is a cationic polymerizable group. (6) A hard coat film, wherein the transparent substrate in the hard coat film according to any one of (1) to (5) is a plastic film. (7) The hard coat film according to (6), wherein the curl value of the hard coat film when expressed by the following formula A has a curl in a range of plus 15 to minus 15.

(Formula A) Curl = 1 / R (R is the radius of curvature (m)) (8) The hard coat film according to any one of (1) to (5) on the image display surface, or An image display device provided with the hard coat film according to (6) or (7). (9) The hard coat film according to any one of (1) to (5) above,
An anti-reflective laminated film characterized by laminating an anti-reflection layer as a layer and an antifouling layer as an outermost layer. (10) Reflection characterized in that at least one antireflection layer and an antifouling layer as an outermost layer are laminated on the hard coat layer of the hard coat film according to (6) or (7). Anti-lamination film. (11) An image display device comprising the antireflection laminated film according to (9) or the antireflection laminated film according to (10) provided on an image display surface.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The term "hard coat film" in the present invention refers to a hard coat coating in which a hard coat layer is provided on a transparent base material. The material may be a synthetic resin film, a glass plate, or the like, and includes all hard coat coatings obtained by applying a hard coat layer to these substrates. The hard coat film of the present invention, after applying a curable composition containing both a compound containing three or more ethylenically unsaturated groups in the same molecule and a compound containing a ring-opening polymerizable group on a substrate, It has a hard coat layer formed by curing, and the hard coat layer may be a single layer or may be composed of a plurality of layers, but is preferably a simple single layer in the production process. The single layer in this case is a hard coat layer formed of the same composition, and may be formed by a plurality of coatings as long as the composition after application and drying has the same composition. On the other hand, the term “multilayer” means that a plurality of compositions having different compositions are formed. In the present invention, at least one layer includes a compound containing three or more ethylenically unsaturated groups in the same molecule and a ring-opening polymerizable group. After applying the curable composition containing both of the compounds, it is necessary to form a hard coat layer formed by curing, especially the outermost layer has three or more ethylenically unsaturated groups in the same molecule. A hard coat layer formed by applying a curable composition containing both a compound containing the compound and a compound containing a ring-opening polymerizable group and then curing the composition is preferable.

The compounds containing a ring-opening polymerizable group which can be used in the present invention are described below. The compound containing a ring-opening polymerizable group is a compound having a ring structure in which ring-opening polymerization proceeds by the action of a cation, anion, radical, or the like, and among them, cation ring-opening polymerization of a heterocyclic compound is preferable. Examples of such compounds include epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, cyclic lactone derivatives, cyclic carbonate derivatives, cyclic imino ethers such as oxazoline derivatives, and the like. Particularly preferred are epoxy derivatives, oxetane derivatives, and oxazoline derivatives. The compound having a ring-opening polymerizable group in the present invention is not particularly limited as long as it has the above-mentioned cyclic structure. Preferred examples of such compounds include, for example, monofunctional glycidyl ethers, monofunctional alicyclic epoxies, difunctional alicyclic epoxies, diglycidyl ethers, trifunctional or higher glycidyl ethers (trimethylolethane Glycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc., and glycidyl ethers having four or more functional groups (sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl of cresol novolac resin) Ethers, polyglycidyl ethers of phenol novolak resins, etc.) tri- or higher functional alicyclic epoxies (Eporide GT
-301, Eporide GT-401, EHPE (above,
Daicel Chemical Industries, Ltd.), phenol novolak resin polycyclohexyl epoxy methyl ether, etc.), oxetanes (OX-SQ, PNOX-1009)
(Above, manufactured by Toagosei Co., Ltd.) and the like, but the present invention is not limited thereto.

The compound having a ring-opening polymerizable group of the present invention is
It is preferable to have two or more ring-opening polymerizable groups in the same molecule, but it is more preferable to have three or more. In addition, the compound having a ring-opening polymerizable group of the present invention has 2
At least one kind may be used in combination, and in this case, a compound having one ring-opening polymerizable group in the same molecule can be used in combination, if necessary.

In the present invention, it is particularly preferable that the compound having a ring-opening polymerizable group contains a crosslinkable polymer containing a repeating unit represented by the general formula (1). Hereinafter, these crosslinkable polymers of the present invention 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, and is preferably a hydrogen atom or a methyl group. L ¹ is a single bond or a divalent linking group, preferably a single bond, —O—, an alkylene group, an arylene group and *-linked to the main chain at the * side.
COO-, * -CONH-, * -OCO-, * -NHC
O-. P ¹ is a monovalent group containing a ring-opening polymerizable group, and preferred 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, and an oxazoline ring. Of these, a monovalent group including an epoxy ring, an oxetane ring, and an oxazoline ring is particularly preferable.

The crosslinkable polymer of the present invention 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 simplest and preferable. Preferred specific examples of the repeating unit represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0015]

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[0016]

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[0017]

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The crosslinkable polymer of the present invention containing a 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), A copolymer containing a repeating unit other than the general formula (1) (for example, a repeating unit containing no 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 to control the content of the ring-opening polymerizable group of the crosslinkable polymer, a method of forming a copolymer containing a repeating unit other than the general formula (1) is preferable. It is. As a method for introducing a repeating unit other than the general formula (1), a method of introducing a corresponding monomer by copolymerization is preferable.

When a repeating unit other than the general formula (1) is introduced by polymerizing the corresponding vinyl monomer, the monomer preferably used is selected from acrylic acid and α-alkylacrylic acid (for example, methacrylic acid). Derived esters or amides (e.g., Ni-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-ylmethyl methacrylate, 3-methyl-2-norbornylmethyl methacrylate, dimethylaminoethyl methacrylate, etc., acrylic acid or α-alkylacrylic acid (acrylic acid, methacrylic acid, itacone) Acids, etc.), vinyl esters (eg, vinyl acetate), esters derived from maleic acid or fumaric acid (dimethyl maleate, dibu maleate) Le, diethyl fumarate, etc.),
Maleimides (such as N-phenylmaleimide), maleic acid, fumaric acid, sodium salts of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (eg, butadiene, cyclopentadiene, isoprene), and aromatic vinyl compounds (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, sodium methallylsulfonate, vinylidene chloride,
Examples include vinyl alkyl ethers (eg, methyl vinyl ether), ethylene, propylene, 1-butene, isobutene, and the like. These vinyl monomers may be used in combination of two or more. Vinyl monomers other than these are Research Disclosure Nos. 1955 (19
80, July) can be used. In the present invention, esters and amides derived from acrylic acid or methacrylic acid, and aromatic vinyl compounds 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 when it is desired to improve the adhesion between the 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 included. The method of forming a copolymer is preferable. The method for introducing a repeating unit having a reactive group other than the ring-opening polymerizable group is based on the corresponding vinyl monomer (hereinafter, referred to as
A method of copolymerizing a reactive monomer) is simple and preferred.

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

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

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

The preferred molecular weight range of the crosslinkable polymer containing a repeating unit represented by the general formula (1) is 1,000 to 1,000,000, more preferably 3, in number average molecular weight.
000 or more and 200,000 or less. Most preferably 5,000
It is 0 or more and 100,000 or less.

Preferred examples of the crosslinkable polymer containing a 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) mentioned above is represented by the number of the specific example described above, and the repeating unit derived from a copolymerizable monomer is described by a monomer name. The copolymer composition ratio is shown in mass%.

[0026]

[Table 1]

The hard coat layer according to the present invention comprises a curable composition containing both a compound containing three or more ethylenically unsaturated groups in the same molecule and a compound containing a ring-opening polymerizable group on a desired substrate. And then cured.

The compounds containing an ethylenically unsaturated group which can be used in the present invention are described below. Preferred types of ethylenically unsaturated groups are an acryloyl group, a methacryloyl group, a styryl group, and a vinyl ether group, and particularly preferably an acryloyl group. Compounds containing an ethylenically unsaturated group have three or more ethylenically unsaturated groups in the same molecule.
At least one, and one or two as necessary.
May be used in combination. Compounds called polyfunctional acrylate monomers having 3 to 6 acrylate groups in the molecule and urethane acrylates, polyester acrylates, epoxy acrylates having a molecular weight of several acrylate groups in the molecule, Hundreds to thousands of oligomers can be preferably used.

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

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

[0031]

Embedded image In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group. P ² is a monovalent group containing an ethylenically unsaturated group, L ² is a single bond or a divalent linking group, preferably a single bond, —O—, an alkylene group, an arylene group, and * -COO-, * linked to a chain
-CONH-, * -OCO-, * -NHCO-.
P ² is a monovalent group containing an ethylenically unsaturated group. Preferred P ^2, acryloyl group, methacryloyl group, a monovalent group containing a styryl group, most preferably a monovalent group containing an acryloyl group. The crosslinkable polymer containing a repeating unit represented by the general formula (2) may be synthesized by a method of directly introducing an ethylenically unsaturated group by polymerizing a corresponding monomer. It may be synthesized by a method of introducing an ethylenically unsaturated group into a polymer obtained by polymerization by a polymer reaction. In addition, it is also possible to combine the above methods. Examples of the polymerization reaction include radical polymerization, cationic polymerization, and anionic polymerization. When the above method is used, it is necessary to utilize the difference in polymerizability between the ethylenically unsaturated group consumed by the polymerization reaction and the ethylenically unsaturated group remaining in the crosslinkable polymer. For example,
When a monovalent group containing an acryloyl group or a methacryloyl group is used in the preferred P ² of the general formula (2), the polymerization reaction for producing a crosslinkable polymer is made to be cationic polymerization, whereby the method of the present invention is carried out by the above-mentioned method. A crosslinkable polymer can be obtained. On the other hand, when P ² is a monovalent group containing a styryl group, gelation easily proceeds in any of radical polymerization, cationic polymerization, and anionic polymerization. Combine.

As described above, the method utilizing the polymer reaction described above can obtain a crosslinkable polymer regardless of the type of the ethylenically unsaturated group introduced into the general formula (2). Useful. In the polymer reaction, for example, I) a polymer containing a functional group in which an ethylenically unsaturated group is converted into a precursor, such as the elimination of hydrochloric acid from a 2-chloroethyl group, is converted into a functional group (elimination reaction, oxidation reaction). ,
A method of deriving an ethylenically unsaturated group by a reduction reaction or the like) and II) after forming a polymer containing an arbitrary functional group, a bond forming reaction with a functional group in the polymer proceeds,
A method of reacting a compound having both a functional group capable of forming a covalent bond and an ethylenically unsaturated group (hereinafter, referred to as a reactive monomer) is exemplified. These methods I) and II) may be performed in combination. As used herein, the bond formation reaction can be used without particular limitation as long as it is a reaction that forms a covalent bond among bond formation 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 gelled, the reaction proceeds at a temperature as low as possible (preferably 60 ° C. or lower, particularly preferably room temperature or lower). Are preferred. Further, a catalyst may be used for the purpose of accelerating the progress of the reaction, and a polymerization inhibitor may be used for the purpose of suppressing gelation.

Examples of combinations of functional groups in which a preferred polymer bond forming reaction proceeds will be described below, but the present invention is not limited thereto.

The combination of the functional groups which undergo the reaction at heating or at room temperature includes (a) an epoxy group, an isocyanate group, an N-methylol group, a carboxyl group, an alkyl halide, an acid anhydride, an acid chloride with respect to the hydroxyl group. An active ester group (eg, a sulfate ester),
Formyl group, acetal group, hydroxyl group, mercapto group, amino group, carboxyl group, N-methylol group for (ii) isocyanate group, epoxy group, isocyanate group, amino group for (c) carboxyl group,
N-methylol group, (d) N-methylol group,
For isocyanate group, N-methylol group, carboxyl group, amino group, hydroxyl group, and (e) epoxy group, hydroxyl group, amino group, mercapto group, carboxyl group, N-methylol group, and (f) vinyl sulfone group On the other hand, a sulfinic acid group, an amino group, a hydroxyl group, a mercapto group, an active methylene group for (to) formyl group, a formyl group, a vinyl group (allyl group, acrylic group, etc.) for (thio) mercapto group, For an epoxy group, an isocyanate group, an N-methylol group, a carboxyl group, an alkyl halide, an acid anhydride chloride, an active ester group (for example, a sulfate ester), and a (li) amino group,
Formyl group, vinyl group (allyl group, acrylic group, etc.),
Examples include combinations of an epoxy group, an isocyanate group, an N-methylol group, a carboxyl group, an alkyl halide, an acid anhydride, an acid chloride, an active ester group (for example, a sulfate ester), and the like.

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

Hydroxyl group-containing vinyl monomers (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomers (eg,
Isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N-methylol group-containing vinyl monomers (for example, N-methylol acrylamide, N-
Methylol methacrylamide, etc.), epoxy group-containing vinyl monomers (for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, C
YCLOMER-M100, A200 (manufactured by Daicel Chemical Industries, Ltd.), a carboxyl group-containing vinyl monomer (for example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate), an alkyl halide-containing vinyl monomer (for example, chloro Methyl styrene, 2-hydroxy-3-chloropropyl methacrylate), acid anhydride-containing vinyl monomer (eg, maleic anhydride), formyl group-containing vinyl monomer (eg, acrolein, methacrolein), sulfinic acid group-containing vinyl monomer (eg, styrene) Active methylene-containing vinyl monomer (eg, acetoacetoxyethyl methacrylate), vinyl group-containing vinyl monomer (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. Alternatively, it can be obtained by polymerizing a precursor monomer having low reactivity, such as polyvinyl alcohol obtained by modifying polyvinyl acetate, and then performing a functional group conversion. As a polymerization method in these cases, radical polymerization is the simplest and preferable.

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

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The crosslinkable polymer of the present invention containing a 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). A copolymer containing a repeating unit other than the general formula (2) (for example, a repeating unit containing no ethylenically unsaturated group) may be used. In particular, when it is desired to control the Tg or hydrophilic / hydrophobic property of the crosslinkable polymer, or for the purpose of controlling the content of the ethylenically unsaturated group in the crosslinkable polymer, a method of forming a copolymer containing a repeating unit other than the general formula (2) is preferable. It is. As a method for introducing a repeating unit other than the general formula (2), a) a method of directly introducing a corresponding monomer by copolymerization may be used. You may use the technique of introducing by reaction. Further, the methods a) and b) can be introduced in combination.

When a repeating unit other than the general formula (2) is introduced by polymerizing the corresponding vinyl monomer by the method a), the monomer preferably used is acrylic acid or α-alkylacrylic acid (for example, methacrylic acid). Esters, etc.)
Or amides (e.g., Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide,
N-methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride,
Methacrylamide, diacetone acrylamide, acryloylmorpholine, N-methylol acrylamide, 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, ethyl carbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octa Fluoropentyl 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-norbornyl methyl methacrylate, 5-
Norbornen-2-ylmethyl methacrylate, 3-methyl-2-norbornylmethyl methacrylate, dimethylaminoethyl methacrylate, etc., acrylic acid or α-alkylacrylic acid (acrylic acid, methacrylic acid, itaconic 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), aroma Group vinyl compounds (eg, styrene, p-chlorostyrene, t-butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylformamide, N-vinylformamide -Vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide,
1-vinylimidazole, 4-vinylpyridine, vinylsulfonic acid, sodium vinylsulfonate, sodium allylsulfonate, sodium methallylsulfonate, vinylidene chloride, vinyl alkyl ethers (eg, methyl vinyl ether), ethylene, propylene,
-Butene, isobutene and the like. These vinyl monomers may be used in combination of two or more. Vinyl monomers other than these are Research Disclosure Nos. 1955 (July 1980) can be used. In the present invention, esters and amides derived from acrylic acid or methacrylic acid, and aromatic vinyl compounds are particularly preferably used vinyl monomers.

When the repeating unit represented by the general formula (2) is introduced by a polymer reaction as described above and the reaction is not completed, a functional group having an ethylenically unsaturated group as a precursor or a reactive functional group may be used. A copolymer having a repeating unit containing is used in the present invention without any particular limitation.

Most of the repeating units not containing an ethylenically unsaturated group derived from the vinyl monomers mentioned above are mostly introduced by b) by polymerizing a precursor monomer capable of converting a functional group and conducting a polymer reaction. Is also possible. On the other hand, the crosslinkable polymer containing a repeating unit represented by the general formula (2) of the present invention may contain a repeating unit other than the general formula (2) that can be introduced only by a polymer reaction. Typical examples include polyvinyl alcohol obtained by modifying polyvinyl acetate, polyvinyl butyral obtained by acetalization of polyvinyl alcohol, and the like. Specific examples of these repeating units are shown below, but the present invention is not limited thereto.

[0048]

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In the crosslinkable polymer containing a repeating unit represented by the general formula (2) of the present invention, the proportion of the repeating unit represented by the general formula (2) is from 1% by mass to 100% by mass, It is preferably from 30% by mass to 100% by mass, particularly preferably from 50% by mass to 100% by mass.

The preferred molecular weight range of the crosslinkable polymer containing a repeating unit represented by the general formula (2) is 1,000 to 1,000,000 in number average molecular weight, and more preferably 3,
000 or more and 200,000 or less. Most preferably 5,000
It is 0 or more and 100,000 or less.

Preferred examples of the crosslinkable polymer containing a 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 described above, are represented by the numbers of the specific examples described above, and the repeating unit derived from a copolymerizable monomer. Indicates the monomer name and the copolymer composition ratio in mass%.

[0052]

[Table 2]

Examples of the compound having a ring-opening polymerizable group that can be used in the present invention include a polymer containing both repeating units represented by the general formulas (1) and (2). In this case, preferred repeating units of the general formulas (1) and (2) are the same as those described above. Further, even a copolymer containing a repeating unit other than the general formulas (1) and (2) is a copolymer containing a repeating unit having a reactive group other than an ethylenically unsaturated group and a ring-opening polymerizable group. Is also good.

In the crosslinkable polymer containing both repeating units represented by the general formulas (1) and (2),
The proportion of the repeating unit represented by the formula is from 1% by mass to 99% by mass, preferably from 20% by mass to 80% by mass, particularly preferably from 30% by mass to 70% by mass, and represented by the general formula (2) ) Is contained in an amount of 1% by mass or more and 99% by mass or less, preferably 2% by mass or less.
It is from 0% by mass to 80% by mass, particularly preferably from 30% by mass to 70% by mass.

The preferred molecular weight range of the crosslinkable polymer containing both repeating units represented by the general formulas (1) and (2) is from 1,000 to 1,000,000, more preferably from 3,000 to 20, in number average molecular weight. Less than 10,000. 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, but the present invention is not limited to these. The repeating units represented by the general formulas (1) and (2) and the repeating units such as polyvinyl alcohol are represented by the numbers of the specific examples described above, and are derived from copolymerizable monomers. For the repeating unit to be used, the monomer name was described, and the copolymer composition ratio was added in mass%.

[0057]

[Table 3]

The hard coat layer according to the present invention comprises a curable composition containing both a compound containing three or more ethylenically unsaturated groups in the same molecule and a compound containing a ring-opening polymerizable group on a desired substrate. And then cured. In the present invention, the preferred mixing ratio of the compound containing three or more ethylenically unsaturated groups in the same molecule and the compound containing the ring-opening polymerizable group varies depending on the type of the compound used, and is not particularly limited. The proportion of the compound containing a group is preferably from 30% by weight to 90% by weight, more preferably from 50% by weight to 80% by weight.

In the present invention, it is preferable that the crosslinking reaction of both the compound containing an ethylenically unsaturated group and the compound containing a ring-opening polymerizable group proceeds. A preferred crosslinking reaction of the ethylenically unsaturated group is a radical polymerization reaction, and a preferred crosslinking reaction of the ring-opening polymerizable group is a cationic polymerization reaction. In any case, the polymerization reaction can be advanced by the action of heat and / or light. A method in which a small amount of a radical generator or a cation generator (or an acid generator), which is usually called a polymerization initiator, is added, and these are decomposed by heat and / or light to generate radicals or cations, thereby promoting polymerization. Is common. Although the radical polymerization and the cationic polymerization may be performed separately, it is preferable to proceed simultaneously. There is also a method of simply heating as a method of causing the crosslinking reaction to proceed without adding a radical generator,
A method of irradiating an electron beam is preferably used.

In the present invention, when a plastic film is used as the base material, when the plastic film itself is cured by heating because of its low heat resistance, it is preferable to cure at as low a temperature as possible. The heating temperature in that case is 14
The temperature is 0 ° C or lower, more preferably 100 ° C or lower. On the other hand, curing by the action of light is often used because the crosslinking reaction often proceeds at a low temperature. Further, radiation, gamma rays, alpha rays, electron beams, a method utilizing active energy rays such as ultraviolet rays are preferable, and among them, a method of adding a polymerization initiator which generates radicals or cations by ultraviolet rays and curing by ultraviolet rays is particularly preferable. .
In some cases, curing can be further promoted by heating after irradiation with ultraviolet rays, which is preferably used. The preferred heating temperature in this case is 140
It is below ° C.

Examples of the photoacid generator that generates cations by ultraviolet rays include ionic compounds such as triarylsulfonium salts and diaryliodonium salts, and nonionic compounds such as nitrobenzyl esters of sulfonic acids. Materials Research Society, “Organic Materials for Imaging”, published by Bunshin Publishing Company (1997)
Various known photoacid generators such as the compounds described in the above can be used. Among them, a sulfonium salt or an iodonium salt is particularly preferred.
_{^{6 -, SbF 6 -, AsF}} 6 -, B (C 6 F 5) 4 - and the like are preferable.

Examples of polymerization initiators that generate radicals by ultraviolet rays include acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide, and thioxanthone. Further, as mentioned above, sulfonium salts, iodonium salts, and the like, which are usually used as photoacid generators, also act as radical generators when irradiated with ultraviolet light, and therefore may be used alone in the present invention. A sensitizer may be used in addition to the polymerization initiator for the purpose of increasing the sensitivity.
Examples of sensitizers include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone, and the like.

The polymerization initiators may be used in combination with each other, or may be used alone such as in the case of a compound which generates both a radical and a cation by itself. The polymerization initiator is used in an amount of 0.1 to 15% by mass based on the total mass of the ethylenically unsaturated group-containing compound and the ring-opening polymerizable group-containing compound contained in the curable composition. It is preferably used in an amount of 1 to 10% by mass.

In the present invention, a crosslinkable polymer having a repeating unit represented by the general formula (1) or a crosslinkable polymer having a repeating unit represented by the general formula (2)
These are collectively referred to as the polymer of the present invention).
It becomes a solid or a highly viscous liquid and is difficult to apply alone. When the polymer is water-soluble or in the form of an aqueous dispersion, it can be applied in an aqueous system, but is usually applied after being dissolved in an organic solvent. Any organic solvent can be used without particular limitation as long as it can make the polymer of the present invention soluble. Preferred organic solvents include ketones such as methyl ethyl ketone, alcohols such as isopropanol, and esters such as ethyl acetate. Further, when the monofunctional or polyfunctional vinyl monomer or the compound having a monofunctional or bifunctional or trifunctional or higher functional ring-opening polymerizable group is a low molecular weight compound, when these are used in combination,
The viscosity of the curable composition can be adjusted, and the composition can be applied without using a solvent.

In the present invention, fine particles may be added to the curable composition. Addition of the fine particles is preferable because the amount of curing shrinkage of the hard coat layer can be reduced, so that the adhesion to the substrate can be improved and the curl can be reduced when the substrate is a plastic film. 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, and aluminum oxide particles. Such inorganic crosslinked fine particles are generally hard, and when filled in a hard coat layer, not only can the shrinkage during curing 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 on the basis of the balance of each necessary property.

In general, inorganic fine particles have a low affinity for organic components such as the polymer of the present invention and polyfunctional vinyl monomers, and therefore, when they are simply mixed, aggregates are formed, or when the hard coat layer after curing tends to crack. There is. 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 high affinity for the organic component in the same molecule. Examples of the compound having a functional group capable of binding to or adsorbing to the inorganic fine particles include metal alkoxide compounds such as silane, aluminum, titanium, and zirconium, and phosphate groups, sulfate groups, sulfonic acid groups, and anionic groups such as carboxylic acid groups. Is preferred. Further, the functional group having a high affinity for the organic component may be simply a combination of the organic component and the hydrophilic / hydrophobic property, but a functional group capable of chemically bonding to the organic component is preferable, particularly an ethylenically unsaturated group, Alternatively, a ring-opening polymerizable group is preferable. In the present invention, a preferable inorganic fine particle surface modifier is a compound having a metal alkoxide or an anionic group and an ethylenically unsaturated group or a ring-opening polymerizable group in the same molecule.

Representative examples of these surface modifiers include the following coupling agents containing an unsaturated double bond, organic compounds containing a phosphoric acid group, organic compounds containing a sulfuric acid group, and organic compounds containing a carboxylic acid group. _{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 OPO (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 H2C = 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 the inorganic fine particles are mechanically finely dispersed, a surface modifier is present together, or after the inorganic fine particles are finely dispersed, the surface modifier is added and stirred, or before the inorganic fine particles are finely dispersed. The surface may be modified (if necessary, heated or dried and then heated or the pH may be changed), followed by fine dispersion. As a solution for dissolving the surface modifier,
Highly polar organic solvents are preferred. Specific examples include known solvents such as alcohols, ketones, and esters.

The organic fine particles are not particularly limited, but polymer particles comprising a monomer having an ethylenically unsaturated group, for example, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, polyethylene, Polypropylene, polystyrene, etc.
And polymer particles of the general formulas (1) and (2) of the present invention are preferably used. In addition, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, polycarbonate, nylon, polyvinyl alcohol, polytetrafluoroethylene And resin particles such as polyethylene terephthalate, polyvinyl chloride, acetylcellulose, nitrocellulose, and gelatin. These particles are preferably crosslinked. As a fine particle dispersing machine, it is preferable to use an ultrasonic wave, a disper, 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 the dispersion medium, the above-mentioned solvent for surface modification is preferably used.

The filling amount of the fine particles of the present invention is preferably 40 to 2% by volume, more preferably 25 to 3% by volume, most preferably 15 to 5% by volume, based on the volume of the hard coat layer after filling.

The hard coat layer of the present invention can be made thicker than the conventional hard coat layer even if the thickness is increased in order to increase the pencil hardness, since there are few disadvantages associated therewith.
To 200 μm, more preferably 25 to 150 μm, and most preferably 30 to 100 μm.

The haze of the hard coat film of the present invention is 0.0
It is preferably from 1% to 1.5%, and
% Or less, and most preferably 1.0% or less. The haze of the hard coat film described in the present invention means a haze of a hard coat film in which a hard coat layer is applied to a base material, and a haze in a state where various functional layers applied thereon are not included. When the thickness of the support used in the present invention is 80 to 200 μm, the haze of the support is preferably 1.0 to 0%, more preferably 0.8 to 0%. Further, in the case of a laminate in which a primer layer having a thickness of 0.03 to 0.3 μm is applied on one surface of a support having the above thickness, 1.2 to 0% is preferable, and
0 to 0% is more preferable.

In the hard coat film of the present invention, the value of the curl represented by the following formula A is preferably in the range of plus 15 to minus 15;
The range of 0 to minus 10 is more preferred, and the range of plus to minus 5 is more preferred. The measurement direction of the curl in the sample at this time is measured in the application line direction.

[0074]

(Formula A) Curl = 1 / RR R is the radius of curvature (m)

This is a characteristic necessary in the production, processing, and handling in the market of the hard coat film so as not to cause cracking and peeling of the film. The curl value is preferably in the above range, and the compatibility between the curl and the film hardness was made possible by appropriate use of the compound of the present invention. The curl measurement method referred to in the present invention is a method in which the curl is measured using the curl measurement template of Method A in JIS K7619-1988, “Measurement Method of Curl of Photographic Film”. Test condition is 2
5 ° C., relative humidity 60% RH. In the present invention, a positive curl means a curl in which the hard coat layer coating side of the film is inside the curve, and a negative curl means a curl in which the coated side is outside the curve.

The elastic modulus E of the hard coat layer of the present invention is 3
It is preferably in the range of ６6 GPa. If it exceeds 6 GPa, the brittleness and curl increase, and if it is less than 3 GPa, the pencil hardness decreases, and the practical performance deteriorates. Compatibility of elasticity, brittleness and curl was made possible by appropriate use of the compounds of the present invention.

The substrate used in the present invention may be a transparent substrate, such as a flexible substrate such as a plastic film.
Examples include non-flexible substrates such as glass.
In the present invention, mainly a plastic film can be preferably used. As a material, a film such as polyester such as polyethylene terephthalate and polyethylene naphthalate, and a cellulose resin such as polycarbonate, triacetyl cellulose and diacetyl cellulose is preferable. If the thickness of the film is too thin, the film strength is weak,
If the thickness is too large, the stiffness becomes too large.
00 μm is preferable, and 80 to 200 μm is more preferable.

The active energy ray-curable coating liquid is prepared by dissolving the above polyfunctional monomer and polymerization initiator in an organic solvent such as a ketone, alcohol, or ester. Further, the dispersion is prepared by adding a surface-modified hard inorganic fine particle dispersion and a soft fine particle dispersion.

The hard coat film of the present invention is prepared by coating the active energy ray-curable coating material on a transparent substrate by a known thin film forming method such as a dipping method, a spinner method, a spray method, a roll coater method, a gravure method, and a wire bar method. And apply
It can be manufactured by drying and irradiating with active energy rays.

Further, for the purpose of improving the adhesion of the hard coat layer to the transparent substrate, one or both
Surface treatment can be performed by an oxidation method, a roughening method, or the like. Examples of the oxidation method include a corona discharge treatment, a glow discharge treatment, a chromic acid treatment (wet method), a flame treatment, a hot air treatment, and an ozone / ultraviolet irradiation treatment. Further, one or more primer layers can be provided. Examples of the material for the primer layer include copolymers or latex of vinyl chloride, vinylidene chloride, butadiene, (meth) acrylate, vinyl ester, and the like, and water-soluble polymers such as low molecular weight polyester and gelatin. The thickness of the primer layer is preferably 0.01 to 1 μm,
It is more preferably from 2 to 0.5 μm, most preferably from 0.03 to 0.3 μm.

The hard coat layer may be composed of a plurality of layers, and may be formed by appropriately laminating.

On these prepared hard coat layers,
Films having functions such as an antireflection layer, an ultraviolet / infrared absorbing layer, a selective wavelength absorbing layer, an electromagnetic wave shielding layer and an antifouling layer can be provided, and are provided as a high-hardness functional film. These functional films can be formed by applying a solution of a known material, or by vacuum film formation such as sputtering or vapor deposition. As the antireflection layer and the antifouling layer used in the antireflection laminated film of the present invention, for example,
JP-A-1-164991, JP-A-4-338901
And preferred ranges such as surface resistivity, average reflectance and antifouling property are the same as those described in the publication.

The reflectance (specular reflectance) of the antireflection layer of the present invention
Is preferably 3.0% or less, more preferably 1.8% or less. As the antireflection layer, a low refractive index layer is usually provided, but it is also preferable to laminate a high refractive index layer as a lower layer of the low refractive index layer.In the present invention, all these layers are collectively referred to as an antireflection layer To tell. The low refractive index layer has a refractive index lower than that of a layer provided thereunder. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, and more preferably 1.20 to 1.50. The thickness of the low refractive index layer is 50 to 400 nm.
And more preferably 50 to 200 nm. Examples of the low refractive index layer include a layer made of a fluoropolymer having a low refractive index (JP-A-57-34526).
And JP-A-3-130103 and 6-115023.
And JP-A-8-313702 and JP-A-7-168004), and a layer obtained by a sol-gel method (Japanese Unexamined Patent Publication No.
No. 208811, No. 6-299091, No. 7-168
003) or a layer containing fine particles (Japanese Patent Publication No. 60-59250, JP-A-5-13021, JP-A-6-56478, JP-A-7-92306, and 9-288).
No. 201). In the layer containing fine particles, as microvoids between or within the fine particles,
Voids can be formed in the low refractive index layer. The layer containing fine particles preferably has a porosity of 3 to 50% by volume, more preferably 5 to 35% by volume.

In order to prevent reflection in a wide wavelength range,
As a lower layer of the low refractive index layer, a layer having a high refractive index (a middle / high refractive index layer) is preferably laminated. The refractive index of the high refractive index layer is preferably from 1.65 to 2.40, and is 1.7.
More preferably, it is 0 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 low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.90. During·
The thickness of the high refractive index layer is preferably 5 nm to 100 μm, more preferably 10 nm to 10 μm, and most preferably 30 nm to 1 μm. The haze of the middle / high refractive index layer is preferably 5% or less, more preferably 3% or less, and more preferably 1%.
It is most preferred that: The middle / high refractive index layer can be formed using a polymer having a relatively high refractive index. Examples of high refractive index polymers include polystyrene, styrene copolymers, polycarbonates, melamine resins, phenolic resins, epoxy resins, and polyurethanes obtained by reacting cyclic (alicyclic or aromatic) isocyanates with polyols. . Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups, and polymers having a halogen atom other than fluorine as a substituent,
High refractive index. A polymer may be formed by a polymerization reaction of a monomer capable of radical curing by introducing a double bond.

In order to obtain a higher refractive index, inorganic fine particles may be dispersed in a polymer binder. The refractive index of the inorganic fine particles is preferably from 1.80 to 2.80. The inorganic fine particles are preferably formed from a metal oxide or sulfide. Examples of metal oxides or sulfides include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide. Titanium oxide, tin oxide and indium oxide are particularly preferred. The inorganic fine particles contain oxides or sulfides of these metals as main components and may further contain other elements. The main component means a component having the largest content (% by mass) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn,
Pb, Cd, As, Cr, Hg, Zn, Al, Mg, S
i, P and S are included. Inorganic materials that are film-forming and can be dispersed in a solvent or are themselves liquid, such as alkoxides of various elements, salts of organic acids, and coordination compounds (eg, chelate compounds) combined with coordination compounds Alternatively, a medium / high refractive index layer can be formed using an active inorganic polymer. Specific examples of the low, middle and high refractive index layers are disclosed in
No. 153703.

The antireflection layer on the outermost surface (usually a low refractive index layer)
A lubricating layer may be formed thereon. The lubricating layer has a function of imparting lubricity to the surface of the antireflection layer and improving scratch resistance. The lubricating layer can be formed using polyorganosiloxane (eg, silicone oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or a derivative thereof. The thickness of the lubricating layer is preferably from 2 to 20 nm. An antifouling layer can also be provided on the outermost antireflection layer. The antifouling layer lowers the surface energy of the antireflection layer and makes it less likely to adhere to hydrophilic or lipophilic stains. The antifouling layer can be formed using a fluoropolymer. The thickness of the antifouling layer is preferably 2 to 100 nm, more preferably 5 to 30 nm. Alternatively, the antireflection layer can also serve as an antifouling layer by containing a fluorine-containing polymer in the outermost antireflection layer.

The hard coat film, the hard coat film, the antireflection laminated film and the antireflection laminated film of the present invention can be used as cathode ray tube display (CRT), liquid crystal display (LC)
D), a display such as a plasma display panel (PDP) and a field emission display (FED), a touch panel for home electric appliances and the like, and a protective film such as glass.

Hereinafter, synthesis examples of the polymer of the present invention will be shown, but the present invention is not limited thereto. (Synthesis Example 1) Synthesis of Exemplified Compound K-1 After stirring 275 ml of methyl ethyl ketone (MEK) at 60 ° C for 1 hour under a nitrogen stream, 0.5 g of V-65 (a polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was added. The whole dissolved in 8.3 ml of MEK was added. Thereafter, glycidyl methacrylate (50 g) was added dropwise over 2 hours. After completion of the addition, a solution of V-65 (0.5 g) in MEK (8.3 ml) was added, and the mixture was reacted for 2 hours. Thereafter, the reaction temperature is raised to 80
The reaction was carried out at a temperature of 2 ° C. for 2 hours. The obtained reaction solution was added dropwise to 10 L of hexane over 1 hour, and the precipitate was dried under reduced pressure at 35 ° C. for 8 hours.
45 g was obtained.

Synthesis Example 2 Synthesis of Exemplified Compound P-1

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1b (3.0 mol) was dissolved in 1400 ml of tetrahydrofuran (THF), and the reactor was cooled to 5 ° C. There, 1a (3.15 mol) was dripped over 1 hour, and it was made to react after that for 6 hours. The obtained reaction solution was concentrated under reduced pressure at 30 ° C., and then distilled under reduced pressure. 1.0mm
A fraction at 118 to 121 ° C. was collected under reduced pressure of Hg, and purified by silica gel column chromatography (eluent: acetone / hexane = 5/95 (volume ratio)).
2 g were obtained. Next, 275 m of methyl ethyl ketone (MEK)
After stirring for 1 hour at 60 ° C. under a nitrogen stream, 0.5 g of V-65 (polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was added to MEK8.
The whole dissolved in 3 ml was added. Then 1c
(50 g) was added dropwise over 2 hours. After completion of the addition, V-6 was added.
5 (0.5 g) in MEK (8.3 ml) solution was added,
The reaction was performed for 2 hours. Thereafter, the reaction temperature was set to 80 ° C. and 2
The reaction was carried out for an hour, and after the reaction was completed, the mixture was cooled to room temperature. The obtained reaction solution was added dropwise to 10 L of hexane over 1 hour,
The precipitate was dried under reduced pressure at 35 ° C. for 8 hours to obtain 43 g of 1d. Next, 1d (43 g) was dissolved in acetone (390 ml) and cooled to 5 ° C. There triethylamine (39
0 mmol) was added dropwise over 1 hour, and after completion of the addition, the mixture was reacted at room temperature for 24 hours. Thereafter, the reaction vessel was cooled to 5 ° C., and 29.3 ml of a 6N aqueous hydrochloric acid solution was added dropwise over 1 hour, and after the addition was completed, the mixture was stirred for 1 hour. Ethyl acetate (1 L) and a 10% by mass aqueous sodium chloride solution (1 L) were added to the obtained reaction solution, and after stirring, the aqueous layer was separated. Further, the organic layer was treated with a 10% by mass aqueous solution of sodium chloride (1 L).
, And 100 g of sodium sulfate was added. After drying for 1 hour, sodium sulfate was separated by filtration. After concentrating the obtained solution to 500 ml, it was added dropwise to 10 L of hexane over 1 hour, and the precipitate was dried under reduced pressure at 20 ° C. for 8 hours to obtain 33 g of Exemplified Compound P-1.

(Synthesis Example 3) Synthesis of Exemplified Compound P-19 Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-10)
5: saponification degree 98.5%) was dissolved in dimethyl sulfoxide (1000 ml), pyridine (200 ml) and nitrobenzene (10 ml) were added, and the mixture was cooled to 10 ° C. Thereafter, 100 ml of acrylic acid anhydride was added dropwise over 1 hour, and after completion of the addition, the mixture was reacted at room temperature for 24 hours. The obtained reaction solution was added dropwise to 20 L of water over 1 hour to precipitate 1
L in ethyl acetate, 2N hydrochloric acid aqueous solution (1L)
Was washed twice. Further, it was washed twice with a 10% by mass aqueous sodium chloride solution (1 L), and 100 g of sodium sulfate was added.
After adding and drying for 1 hour, sodium sulfate was filtered off. After concentrating the obtained solution to 500 ml, hexane 1
The solution was added dropwise to 0 L over 1 hour, and the precipitate was dried under reduced pressure at 20 ° C. for 8 hours to obtain 28 g of Exemplified Compound P-19.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Example 1 <Preparation of Inorganic Crosslinked Fine Particle Dispersion> The following amounts of each reagent were measured in a ceramic-coated vessel. Methyl isobutyl ketone 234 g Anionic functional group-containing surface treating agent S-6 (X = H) 36 g Alumina fine particles (average particle size: 15 nm) 180 g Fineness of the above mixed solution in a sand mill (1 / 4G sand mill) at 1600 rpm for 10 hours Dispersed. Media is 1
1400 g of zirconia beads having a diameter of mmΦ was used. After the dispersion, the beads were separated to obtain a surface-modified inorganic crosslinked fine particle dispersion.

<Preparation of Curable Composition> An ethylenically unsaturated group-containing compound, a ring-opening polymerizable group-containing compound and a radical polymerization initiator (Irgacure 184)
(Manufactured by Ciba Geigy) and a cationic polymerization initiator (UV
After dissolving I-6990 (manufactured by Union Carbide Japan Co., Ltd.) in a mixed solution of methyl isobutyl ketone / methyl ethyl ketone (1/1), organic cross-linked fine particles were added, and
Stir for a minute, add a mixture of inorganic crosslinked fine particle dispersion,
The mixture was stirred for 30 minutes to obtain a curable composition. The types of the ethylenically unsaturated group-containing compound and the ring-opening polymerizable group-containing compound were selected from the combinations shown in Table 4, and the mixing ratio of the crosslinked fine particles was adjusted so as to be the ratio shown in Table 4. As the polymerization initiator, 2.9% by mass of a radical polymerization initiator and 2.9% by mass of a cationic polymerization initiator were added to the total mass of the compound containing an ethylenically unsaturated group and the compound containing a ring-opening polymerizable group. When no compound containing a ring-opening polymerizable group was contained, only 5.8% by mass of a radical polymerization initiator was added. In addition,
Details of the additives other than the inorganic fine particles are as follows.
Organic crosslinked fine particles have a core / shell ratio of 70/30% by mass.
Latex (average particle diameter: 110 nm) was dried by a spray drying method and used as it was (core: butyl acrylate / ethylene glycol dimethacrylate (9)
0/10 mass ratio), shell: copolymer of methyl methacrylate / acrylic acid / ethylene glycol dimethacrylate (90/3/7 mass ratio). DPHA: mixture of dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) TMPTA: trimethylolpropane triacrylate (manufactured by Aldrich) UV-6300: urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) DTPTA: ditrimethylolpropane tetraacrylate (manufactured by Aldrich) PETA: pentaerythritol triacrylate (A
ECMECC: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate:
(Manufactured by Aldrich) CHDMDV: 1,4-cyclohexanedimethanol divinyl ether (manufactured by Aldrich) GT-301: trifunctional epoxy compound (manufactured by Daicel Chemical Industries, Ltd.) GT-401: 4-functional epoxy compound (manufactured by Daicel Chemical Industries, Ltd.) )

[0095]

[Table 4]

<Hard coat film sample (Sample 101)
-137) Preparation> After performing glow discharge treatment on a 188 μm polyethylene terephthalate film as a transparent substrate, apply the curable composition prepared above with a wire bar to a film thickness shown in Table 4; Dried for a minute,
After irradiating with 750 mj / cm ² of ultraviolet light, the film was heated at 120 ° C. for 10 minutes to produce a hard coat film. The samples 109 and 130 were applied and cured after the lower layer was applied and cured, and the following evaluation was performed after the upper layer was applied.

The evaluation method of the sample was performed by the following method. (Evaluation Method of Pencil Hardness) After the prepared hard coat film sample was left for 2 hours at a temperature of 25 ° C. and a relative humidity of 60% RH, a pencil specified by JIS K5400 was used using a test pencil specified by JIS S6006. According to the hardness evaluation method, scratching was repeated 5 times with a pencil of each hardness using a 1 kg weight, and the number of times that no scratch was observed was represented. Note that the scratches defined in JIS K5400 are tearing of the coating film and scratches of the coating film, and it is described that dents of the coating film are not targeted. It was judged.

(Evaluation Method of Haze) The haze was measured using a turbidity meter “NDH-1001DP” manufactured by Nippon Denshoku Industries Co., Ltd. Haze = (diffuse light / total transmitted light) × 100 (%)
The value automatically measured as was used as it was.

(Evaluation Method of Image Sharpness) After the hard coat film was attached to the surface of the CRT, the sharpness of the image when the image was projected and visually observed was evaluated in the following three steps with respect to the image without attachment: And evaluated. ：: No difference from no pasting. Δ: The image is slightly blurred with respect to no pasting, but is not bothersome. X: The image is clearly blurred with respect to no pasting. The image sharpness needs to be ○ or △.

(Evaluation Method of Film Peeling) 100 pieces of 1 mm × 1 mm cross hatches (squares) were put on the surface of the hard coat film with a cutter at a temperature of 25 ° C. and a relative humidity of 60.
After leaving for 2 hours under the condition of% RH, a cellophane tape (manufactured by Nichiban Co., Ltd.) was stuck thereon, and the number of squares in which the cured film was peeled off from the film substrate when the cellophane tape was peeled off was counted. evaluated.

(Evaluation method of curl) JIS K7619-1
Method A in 988 "Measurement method of curl of photographic film"
Was measured using a curl measurement template. Test conditions are 25
° C and relative humidity 60% RH. In the present invention, a positive curl means a curl in which the hard coat layer coating side of the film is inside the curve, and a negative curl means a curl in which the coated side is outside the curve. The larger the value, the more remarkable the curl.

(Evaluation Method of Crack) A hard coat film sample was cut into a size of 35 mm × 140 mm, and a temperature of 25 ° C.
After leaving it for 5 hours under the condition of a relative humidity of 60% RH, it was rolled into a cylindrical shape with the hard coat layer coating side outside, and the curvature diameter at which cracking began to be generated was determined. Further, the cracks at the edge portion were visually evaluated, and those having no crack at all were evaluated as ○, those having an average crack of less than 1 mm as Δ, and those having an average crack of 1 mm or more as x.

From Table 4, it can be seen that the filling of the inorganic fine particles improves the pencil hardness (102 and 103 with respect to the comparative sample 101). However, at the same time, it can be seen that the filling of the inorganic fine particles does not have a large effect of improving the hardness, and conversely, the haze increases greatly. On the other hand, an increase in the film thickness is effective for improving the pencil hardness, but this shows that the haze increases and the image sharpness deteriorates particularly in the sample filled with inorganic fine particles (105 relative to the comparative sample 102). Also, it can be seen that haze must be suppressed to about 1.5% or less in order to allow image sharpness. Therefore, even if the pencil hardness is improved by increasing the film thickness, the haze increases and the image sharpness is degraded. I understand. On the other hand, when the crosslinkable group-containing compound of the present invention is used (samples 110 to 1 of the present invention).
37) Even if the sample has a large thickness, the increase in curl is very small and the hardness of 5H can be exhibited (thickened sample). Therefore, the curl can be reduced and the hardness can be obtained without filling with inorganic fine particles. It can be seen that haze-up due to the filling of inorganic fine particles can be prevented, so that image sharpness is not impaired. Further, it can be seen that the sample of the present invention significantly improves the surface and edge cracking and film peeling. The filling of the fine particles is effective for improving the pencil hardness (119 to 121 with respect to the inventive sample 116). It can be seen that the organic cross-linked fine particles have the effect of improving the hardness without increasing the haze.
These effects were first clarified by the present invention.

Example 2 (Preparation of Coating Solution-1 for High Refractive Index Layer) 30% Iron (II) Sulfate F
preparing _{eSO 4 · 7H 2 O, 40} % citric acid solution, mixed, held at 20 ° C., while stirring it at 10% of the silver nitrate and (those that have been mixed in the molar ratio 9/1) palladium nitrate solution 200ml / Min at a rate of 3 min / min.
Was added to obtain a silver-palladium colloidal dispersion. As a result of TEM observation, the particle size of the silver colloid particles was about 9 to 12 nm. As a result of measurement by ICP, the ratio of silver to palladium was the same as the charging ratio of 9/1. I-Propyl alcohol was added to 100 g of this silver colloid dispersion, ultrasonically dispersed, and filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating liquid-1 for a high refractive index layer.

(Preparation of Coating Solution-2 for High Refractive Index Layer) 125.2 g of cyclohexanone and methyl ethyl ketone
To 2 g, 0.07 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and a photosensitizer (Kayacure D)
0.02 g of ETX, manufactured by Nippon Kayaku Co., Ltd.). Further, 13.4 g of the prepared titanium dioxide dispersion and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA,
0.76 g of Nippon Kayaku Co., Ltd.) was added, and the mixture was stirred at room temperature for 40 minutes, and then filtered with a polypropylene filter having a pore size of 1 μm to prepare a coating solution-2 for a high refractive index layer.

(Preparation of Low Refractive Index Layer Coating Solution-1) 2 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) and a photopolymerization initiator (Irgacure 90)
7, 80 mg of Ciba Geigy) and 30 mg of a photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 38 g of methyl isopropyl ketone, 38 g of 2-butanol,
It was added to and dissolved in a mixture of 19 g of methanol. 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 low refractive index layer coating solution-1.

(Preparation of Coating Solution-2 for Low Refractive Index Layer) Reactive fluoropolymer (JN-7219, manufactured by JSR Corporation)
1.5 g of t-butanol was added to 50 g, stirred at room temperature for 10 minutes, and filtered with a 1 μm polypropylene filter to prepare a coating solution-2 for a low refractive index layer.

(Preparation of Coating Solution for Antifouling Layer) Isopropyl alcohol was added to a thermally crosslinkable fluoropolymer (JN-7214, manufactured by Nippon Synthetic Rubber Co., Ltd.) to prepare a 0.2% by mass crude dispersion. . The coarse dispersion was further ultrasonically dispersed to prepare an antifouling layer coating liquid.

(Films 201 to 237 with antireflection layer)
Formation of Hard Coat Film 10 Produced in Example 1
After applying a corona treatment to the hard coat layers Nos. 1 to 137, the high refractive index layer coating solution-1 of Example 2 was applied using a bar coater so that the coating amount became 70 mg / m ² , and 40 ° C.
And dried. The silver colloid-coated surface is sprayed with water fed by a pump, and after removing excess water with an air knife, a heat treatment is performed for 5 minutes while transporting in a heating zone of 120 ° C. to perform a high refractive index layer. Was formed. The low refractive index layer coating solution-1 of Example 2 was applied on each of the high refractive index layers using a bar coater, dried at 120 ° C., and then heated to 160 W
/ Cm2 air-cooled metal ride lamp (manufactured by Eye Graphics Co., Ltd.) to irradiate ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to cure the coating layer, and to have a low refractive index of 60 nm in thickness. A rate layer was formed. On each of the low refractive index layers, a coating solution for an antifouling layer was applied with a wire bar so that the coating amount after drying was 5 mg / m ² , followed by drying and heat treatment at 120 ° C. Films 201 to 237 with an antifouling layer were formed.

(Films 301 to 337 with antireflection layer
Formation of Hard Coat Film 10 Produced in Example 1
The high-refractive-index layer coating solution-2 prepared in Example 2 was applied on a hard coat layer of Nos. 1 to 137 using a bar coater, dried at 120 ° C., and then air-cooled with a 160 W / cm metal ride lamp ( Illumination 400 mW / cm ² , irradiation amount 300 mJ / cm
^The coating layer is cured by irradiating ultraviolet rays of ² to a thickness of 60 nm.
Was formed. On each of the high refractive index layers, the low refractive index layer coating solution-2 of Example 2 was applied using a bar coater, dried at 120 ° C., and then cooled with a 160 W / cm air-cooled metal ride lamp (Eye Graphics). Illuminance 400 mW / cm ² , irradiation amount 300 mJ / c
m ² ultraviolet rays to cure the coating layer, and a thickness of 60 n
m low refractive index layer was formed. A coating solution for an antifouling layer was applied on each of the low refractive index layers with a wire bar so that the coating amount after drying was 5 mg / m ² , followed by drying and heat treatment at 120 ° C. Films with antifouling layer 301-33
7 was formed.

Samples 201 to 237 and 301 to 337
Was evaluated as follows. (1) Average reflectance 450 to 6 using a spectrophotometer (manufactured by JASCO Corporation)
Average reflectance of specular reflection in incident light 5 ° in a wavelength region of 50 nm. (2) Antifouling property Evaluation of the state where a fingerprint was attached to the film surface and wiped off using Toray's Toraysee Co., Ltd. Left without any changes).

As a result of the evaluation, any one of the film samples 201 to 237 and 301 to 337 having the antireflection layer and the antifouling layer had good average reflectance in the range of 0.5 to 0.9%. The antifouling property was ○.

[0113]

According to the present invention which does not increase haze even when the film thickness is increased, a hard coat film and a hard coat film excellent in image sharpness while maintaining a high surface hardness can be provided. This is because even if the thickness of the hard coat layer is increased to improve the hardness, the curl (and brittleness) is small and the high hardness is maintained by using the crosslinkable group-containing compound of the present invention. This is because the amount can be reduced, thereby reducing the haze. As a result, an excellent hard coat film and a hard coat film for a functional film on the surface of the image display device could be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a configuration of a hard coat film according to an embodiment of the present invention.

FIG. 2 is a schematic diagram of a configuration of an antireflection laminated film according to one embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent base material 2 Primer layer (coating as needed) 3 Hard coat layer 4 High refractive index layer 5 Medium refractive index layer 6 Low refractive index layer 7 Antifouling layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 26/06 C08F 26/06 G02B 1/10 C08L 101: 00 1/11 G02B 1/10 Z // C08L 101: 00 A (72) Inventor Akihiro Matsufuji 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2K009 AA02 AA15 CC03 CC09 DD05 4F006 AA02 AA35 AA36 AB12 AB16 AB24 BA02 CA05 CA08 4F100 AA19A AK01BAKA AK53A AR00A AT00B BA02 BA07 CA30A CC02A GB07 GB41 JA20A JK09 JK12 JK12A JL04 JN01B JN06A YY00A 4J100 AB07P AL08P AL10P AM21P AQ15P BA02P BA03P BA15P BC53P BC54P CA01 CA31 HA53 HE20 HE44 JA01

Claims (8)

[Claims] 1. A hard coat film comprising a hard coat layer provided on a transparent substrate, wherein the hard coat layer has a thickness of 20 to 200 μm. 2. The hard coat film according to claim 1, wherein the hard coat film has a primer layer provided between the transparent substrate and the hard coat layer, and the haze of the hard coat film is 1.5% or less. film. 3. The hard coat layer is formed by applying a curable composition containing a compound containing three or more ethylenically unsaturated groups in the same molecule and a compound containing a ring-opening polymerizable group, followed by curing. The hard coat film according to claim 1 or 2, which is a hard coat layer. 4. The hard coat film according to claim 1, wherein the compound containing a ring-opening polymerizable group is a crosslinkable polymer containing a repeating unit represented by the following formula (1). Embedded image In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. P ¹ is a monovalent group containing a ring-opening polymerizable group, and L ¹ is a single bond or a divalent linking group. 5. The hard coat film according to claim 1, wherein the ring-opening polymerizable group is a cationic polymerizable group. 6. The hard coat film according to claim 1, wherein the transparent substrate in the hard coat film is a plastic film. 7. When the curl value of the hard coat film is represented by the following mathematical formula A, the value is from plus 15 to minus 15
The hard coat film according to claim 6, which has a curl in the range of. (Formula A) Curl = 1 / R (R is radius of curvature (m)) 8. An image display device comprising a hard coat film according to claim 1 or a hard coat film according to claim 6 provided on an image display surface. .