JP2003227902A - Antireflection hard coat film and image display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection hard coat film having high surface hardness and excellent antireflection performance and an image display using the same. <P>SOLUTION: The antireflection hard coat film has on a transparent support a hard coat layer in which a curable composition which cures upon irradiation with an active energy beam comprises a curable resin containing three or more ethylenically unsaturated groups in the same molecule and/or a curable resin containing three or more ring-opening polymerizable groups in the same molecule and has an antireflection layer disposed on the hard coat layer, wherein the antireflection layer has at least a low refractive index layer whose refractive index is lower than that of the hard coat layer on the top layer side. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin layer (hard coat layer) obtained by curing a transparent substrate film with active energy rays, and a low refractive index layer, a high refractive index layer and a medium refractive index in this order from the outermost layer side. The present invention relates to an antireflection hard coat film having three layers, which is excellent in high surface hardness and antireflection property. By providing the antireflection hard coat film of the present invention, it is possible to obtain a transparent substrate having reduced reflection and excellent high surface hardness. The antireflection hard coat film of the present invention is suitable for the surface of displays such as CRTs, LCDs, PDPs and FEDs, touch panels, protective films for glass, acrylic plates 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, as for conventional glass products, the number of cases in which a plastic film is attached 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 surface hardness of these films. It is being appreciated.

A conventional hard coat layer is a thermosetting resin,
Alternatively, an active energy ray-polymerizable resin such as a UV-curable resin is directly applied onto a plastic substrate or 3 μm or more and 10 μm or more via a primer layer of about 0.03 to 0.5 μm.
It is manufactured by forming a thin coating film of about 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 obtained by applying an ultraviolet curable coating material to the above thickness on a polyethylene terephthalate film which is widely used as a plastic substrate film, a pencil hardness of 3H level is generally used. 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 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. Although these have the effect of increasing the surface hardness of the hard coat layer, they also have the problems of increased haze and poor deterioration of brittleness, and this alone cannot sufficiently satisfy 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. However, there is a problem in that the thicker the hard coat layer, the larger the haze, the cracking and peeling of the hard coat layer are likely to occur, and the curling of the hard coat film due to curing shrinkage increases. 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. An antireflection function was necessary to reduce the reflection of external light. In order to prevent reflection, a multilayer film in which transparent metal oxide thin films are laminated has been conventionally used. The reason why a plurality of transparent thin films are used is to prevent reflection of light in a wavelength range as wide as possible in the visible range. The transparent thin film of metal oxide is formed by chemical vapor deposition (CVD) method, physical vapor deposition (PVD) method,
In particular, it is formed by a vacuum vapor deposition method or a sputtering method, which is a type of physical vapor deposition method. A transparent thin film of a metal oxide has excellent optical properties as an antireflection film, but has low productivity and high production cost.

In addition, provision of an antireflection layer made of alkoxysilane or the like is disclosed in JP-B-4-9281 and JP-B-2534260, but it takes a long time for the reaction and high temperature treatment is required. There are problems such as
There was a problem in productivity and selection of base material. In addition, in studying the addition of these functional layers, it was necessary to study the material and structure in consideration of the physical properties of the support.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hard coat film having a high surface hardness and an excellent antireflection property. Another object of the present invention is to
An object of the present invention is to provide an image display device provided with the above hard coat film and provided with a transparent substrate having various functionalities.

[0011]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have provided a hard coat layer composed of a curable composition which is cured by irradiation with active energy rays, whereby a good hard coat having a high surface hardness is provided. It has been found that a film can be obtained, and by further forming an antireflection film having a three-layer structure, the average reflectance in the visible wavelength region can be suppressed to 0.5% or less and the reflection by external light can be reduced. The film is completed.

Specifically, the present inventors have the following means.
It has been found that the above problems can be achieved more. 1. Curable composition that cures by irradiation with active energy rays
The product contains three or more ethylenically unsaturated groups in the same molecule
Curable resin and / or ring-opening polymerizable group in the same molecule
The hard coat layer, which is a curable resin containing three or more, is transparently supported.
It is provided on a holder and an antireflection layer is provided on the hard coat layer.
This antireflection layer is formed on the outermost layer side from the hard coat layer.
It has at least a low refractive index layer with a low refractive index.
Anti-reflective hard coat film, 2. Curable composition that cures by irradiation with active energy rays
The product contains three or more ethylenically unsaturated groups in the same molecule
Curable resin and / or ring-opening polymerizable group in the same molecule
The hard coat layer, which is a curable resin containing three or more, is transparent
It is provided on a holder and an antireflection layer is provided on the hard coat layer.
The antireflection layer is formed from the outermost layer side in order of the hard coating.
Layer having a lower refractive index than the hard coat layer
Higher refractive index layer, between the hard coat layer and high refractive index layer
Refractive index of substantially three layers of the medium refractive index layer having a refractive index of between
2. The antireflection hard as described in 1 above, which is formed of different layers.
Coat film, 3. The middle refractive index layer is below the design wavelength λ of the antireflection function.
Formula (I), the high refractive index layer is represented by the following formula (II), low refractive index layer
Are described in the above 1 or 2 respectively satisfying the following formula (III):
Anti-reflective hard coat film,   lλ / 4 × 0.80 <n₁d₁<Lλ / 4 × 1.00 (I)   mλ / 4 × 0.75 <n_Twod_Two<Mλ / 4 × 0.95 (II)   nλ / 4 × 0.95 <n_Threed_Three<Nλ / 4 × 1.05 (III) (In the formula, l, m, and n represent an integer of 1 or more, and n₁Is
Indicates the refractive index of the medium refractive index layer, d₁Is the thickness of the medium refractive index layer
(Nm) and n_TwoIs the refractive index of the high refractive index layer, and d
_TwoIs the layer thickness (nm) of the high refractive index layer, and n_ThreeHas a low refractive index
Indicates the refractive index of the layer, d_ThreeIs the layer thickness (nm) of the low refractive index layer
is there. ) In addition, as a design wavelength, the visible center region (450 to 650 n
When λ = 500 nm is selected as the representative wavelength of m),
In the formula, l is 1, n₁Is the refractive index of the medium refractive index layer, d ₁Is inward
It is the layer thickness (nm) of the folding ratio layer, and m is 2, n_TwoHas a high refractive index
Refractive index of the layer, d _TwoIs the layer thickness (nm) of the high refractive index layer,
n is 1, n_ThreeIs the refractive index of the low refractive index layer, d _ThreeIs a low refractive index layer
Is the layer thickness (nm). 4. The curable resin containing a ring-opening polymerizable group has the following general formula
A crosslinkable polymer containing a repeating unit represented by (1)
The antireflection hard as described in any one of 1 to 3 above
Coat film, general formula (1)

[Chemical 1] (In the formula, R ¹ is a hydrogen atom or 1 to 4 carbon atoms.
Represents an alkyl group. P ¹ represents a monovalent group containing a ring-opening polymerizable group. L ¹ represents a single bond or a divalent or higher valent connecting group. ) 5. 5. The hard coat film as described in any one of 1 to 4 above, wherein the ring-opening polymerizable group is a cationically polymerizable group. The surface elastic modulus of the hard coat layer is 4 GPa to 10 G
6. The hard coat film according to any one of 1 to 5 above, which is Pa. 7. The antireflection hard coat film according to any one of 1 to 6 above, wherein the surface of the low refractive index layer has antifouling properties, or an antifouling layer is laminated as the outermost layer. An image display device provided with the antireflection hard coat film as described in any one of 1 to 7 above.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The antireflection hard coat layer of the present invention will be described in detail below. In order to prevent scratches due to the pencil hardness test, which is one of the scratch resistance tests, it is preferable that the hardness of the hard coat layer itself is large to some extent,
The surface elastic modulus of the hard coat layer is about 4.0 GPa or more,
It is preferably at least 4.5 GPa. Surface elastic modulus is 4.
With a hard coat layer of less than 0 GPa, sufficient pencil hardness cannot be obtained. When the surface elastic modulus is expressed by universal hardness, the value is about 250 N / mm ² or more, preferably 300 N / mm ² or more. 250 N / mm ²
If the hard coat layer is less than the above, sufficient pencil hardness cannot be obtained. It has been widely practiced to increase the surface elastic modulus by adding inorganic fine particles, but if the amount of inorganic fine particles added is increased, the brittleness deteriorates, and the surface elastic modulus is 10 GP.
It is a or less, preferably 9.0 GPa or less. It is more preferably 4.0 to 10 GPa, and particularly preferably 4.5 to 9.0 GPa.

The elastic modulus in the present invention is a value obtained by using a micro surface hardness meter (Fischer Scope H100VP-HCU manufactured by Fisher Instruments Co., Ltd.). Specifically, a diamond quadrangular pyramid indenter (tip facing angle; 136 °) is used, and the indentation depth is 1μ.
It is an elastic modulus obtained by measuring the indentation depth under an appropriate test load within a range not exceeding m and changing the load and displacement during unloading. Further, the surface hardness can be obtained as a universal hardness by using the above-mentioned minute surface hardness meter. Universal hardness is a value obtained by measuring the indentation depth of a quadrangular pyramid indenter under a test load and dividing the test load by the surface area of the indentation calculated from the geometric shape of the indentation generated by the test load. It is known that there is a positive correlation between the surface elastic modulus and the universal hardness.

The thickness of the hard coat layer of the present invention varies depending on the pencil hardness required as a product, but the pencil hardness is 3
In case of H, 10 μm or more is preferable, and pencil hardness is 4
In the case of H, 20 μm or more is preferable. Further, when a hard coat having a high surface elastic modulus is used, the film thickness can be made thinner than the intended film thickness, but when a hard coat having a low surface elastic modulus is used, it must be made thicker than the intended film thickness. When the transparent substrate is a film, increasing the thickness of the hard coat layer improves the pencil hardness, but it becomes difficult to bend the film and cracks due to bending are more likely to occur. Therefore, 60 μm or less, and further 50 μm or less are preferable. preferable. The thickness is preferably 10 to 60 μm, more preferably 20 to 50 μm. 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 coated with a curable composition which is cured by irradiation with active energy rays,
It is formed by curing by irradiation with the active energy ray.
The curing shrinkage of the curable composition upon irradiation with active energy rays is 0 to 15%, preferably 0 to 13%, more preferably 0 to 11%. The curing shrinkage ratio is obtained by calculating the density of the curable composition before irradiation with the active energy rays 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 calculated value. The density is MULTIVOLUME manufactured by Micrometrics.
It is a value measured by PYCNOMETER (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 both a curable resin containing three or more ethylenically unsaturated groups in the same molecule and a curable resin containing a ring-opening polymerizable group. The hard coat layer is
Although it may be composed of a single layer or a plurality of layers, it is preferably a single layer which is simple in the manufacturing process. The single layer in this case refers to a hard coat layer formed of the same curable composition, the composition after coating and drying is the same composition,
It may be formed by coating a plurality of times. 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 general formula (1). Hereinafter, these crosslinkable polymers will be described in detail. In 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—,
Alkylene group, arylene group and * -COO-, * -CONH-, * -OCO-, *-linked to the main chain at * side
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 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.

[0023]

[Chemical 2]

[0024]

[Chemical 3]

[0025]

[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 It may be a copolymer containing a repeating unit other than the general formula (1) (for example, a repeating unit containing no ring-opening polymerizable 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 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, acrylic acid or α-alkylacrylic acid (eg methacrylic acid) is preferably used as a monomer. 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 Bornyl methyl methacrylate, 5-norbornen-2-ylmethyl methacrylate, 3-methyl-2-norbornyl methyl methacrylate, dimethylaminoethyl methacrylate, etc., acrylic acid or α-alkyl acrylic acid (acrylic acid, methacrylic acid, itacone) Acid, etc.), vinyl esters (eg vinyl acetate), esters derived from maleic acid or fumaric acid (dimethyl maleate, dib maleate) Le, 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 resin ( For example, 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 and amides derived from acrylic acid or methacrylic acid, and aromatic vinyl-curable resins 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 adhesion 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 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 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 to 1,000,000, 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 below in Table 1.
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%.

[0034]

[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 if necessary, one or two monomers or oligomers may be used in combination. . 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 also 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)

[0040]

[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 * * -COO-, * -CONH-, * -O linked to the main chain at the side
CO- and * -NHCO-. 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, and ii) an arbitrary functional group. You may synthesize | combine by the method of introduce | transducing an ethylenically unsaturated group to the polymer obtained by superposing | polymerizing the monomer which has. Also i)
It is also possible to synthesize by combining the methods of ii) and ii). 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, when a monovalent group containing an acryloyl group or a methacryloyl group is used among the preferred P ^{2 in} the general formula (2), the method of ii) above is carried out by converting the polymerization reaction for forming a crosslinkable polymer into cationic polymerization. The crosslinkable polymer of the present invention can be obtained by 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 by heating or at room temperature include (a) hydroxyl group, epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride, acid chloride , An active ester group (eg sulfate),
For formyl group, acetal group, (b) isocyanate group, hydroxyl group, mercapto group, amino group, carboxyl group, N-methylol group, (ha) carboxyl group, 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, sulfinic acid group, amino group, (to) formyl group, hydroxyl group, mercapto group, active methylene group, (thi) mercapto group Formyl group, vinyl group (allyl group, acrylic group, etc.), epoxy group, isocyanate group, N-methylo group Group, a carboxyl group,
Alkyl halide, acid anhydride acid chloride, active ester group (for example, sulfuric acid ester), (ri) amino group, formyl group, vinyl group (allyl group, acrylic group, etc.), epoxy group, isocyanate group, N-methylol Group, carboxyl group, alkyl halide, acid anhydride, acid chloride, active ester group (for example, sulfate ester),
And the like.

Specific 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 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 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.

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[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, the methods of a) and b) can be introduced in combination.

When a repeating unit other than the general formula (2) is introduced by polymerizing a corresponding vinyl monomer by the method of a), acrylic acid or α-alkyl acrylic acid (eg methacrylic acid) is preferably used as a monomer. Acids, etc.)-Derived esters,
Or amides (for example, N-i-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide,
N-methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride,
Methacrylamide, diacetone acrylamide, acryloyl morpholine, 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-ylmethylmethacrylate, 3-methyl-2-norbornylmethylmethacrylate, dimethylaminoethylmethacrylate, 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), aromatic Group vinyl curable resin (for example, 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 Beam, sodium methallyl sulfonate, vinylidene chloride, vinyl alkyl ethers (e.g. 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. What was described in 1955 (July, 1980) can be used. In the present invention, esters derived from acrylic acid or methacrylic acid,
And amides and aromatic vinyl curable resins are vinyl monomers that are particularly preferably used.

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 or a reactive group obtained by converting an ethylenically unsaturated group into a precursor 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 vinyl monomers mentioned above 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.

[0058]

[Chemical 11]

In the present invention, the proportion of the repeating unit represented by the general formula (2) in the crosslinkable polymer containing 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 preferred molecular weight range of the crosslinkable polymer containing the repeating unit represented by the general formula (2) 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 (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%.

[0062]

[Table 2]

The curable resin having a ring-opening polymerizable group that can be used in the present invention is represented by the general formulas (1) and (2).
Polymers containing both repeating units represented by In this case, preferable 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, Good.

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

The number average molecular weight of the crosslinkable polymer containing the repeating units represented by the general formulas (1) and (2) is preferably 1,000 or more and 1,000,000 or less, more preferably 3,000 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 both repeating units represented by the general formulas (1) and (2) are shown in Table 3, but the present invention is not limited thereto. In addition, 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%.

[0067]

[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 using ultraviolet rays 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 140 ° 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 esters 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. Among them, sulfonium salts or iodonium salts are particularly preferable, and PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like are preferable as the counter ion.

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. Further, a sensitizer may be used in addition to the polymerization initiator for the purpose of increasing sensitivity. 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 capable of generating both radicals and cations by itself, they 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) (in the present invention, these are collectively referred to as " When referred to as "the polymer of the present invention"), the polymer of the present invention usually becomes a solid or high-viscosity liquid and is difficult to apply alone, and when the polymer is water-soluble or when it is made into an aqueous dispersion. Although it can be applied in an aqueous system, 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, difunctional, or trifunctional or more 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 curing shrinkage of the hard coat layer can be reduced, so that the adhesion with 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 component such as the polymer of the present invention and the polyfunctional vinyl monomer, they are liable 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. Examples of the surface modifier having a functional group capable of binding to or adsorbing to the inorganic fine particles include metal alkoxide surface modifiers such as silane, aluminum, titanium, and zirconium, and phosphoric acid groups, sulfuric acid groups, sulfonic acid groups, carboxylic acid groups, and the like. Surface modifiers having anionic 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 that can be chemically bonded to the organic component is preferable,
Particularly, an ethylenically unsaturated group or 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 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 H ₂ C = C (X) COOC ₅ H ₁₀ COOH S-8 _{CH 2 CH (O) CH 2} OC 3 H 6 Si (OCH 3) 3 ( in the above formula S-1~S-8, X represents 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 fine inorganic particles are finely dispersed. Surface modification may be performed (if necessary, heating or drying and then heating, or pH change is performed), followed by fine dispersion. 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 that can be added to the curable composition are not particularly limited, but polymer particles composed of a monomer having an ethylenically unsaturated group, for example, polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate. , Polybutyl acrylate, polyethylene, polypropylene, polystyrene, and the like, and polymer particles comprising the general formulas (1) and (2) in the present invention are preferably used. In addition, polysiloxane, melamine resin,
Benzoguanamine resin, polytetrafluoroethylene,
Polycarbonate, nylon, polyvinyl alcohol,
Examples thereof include resin particles such as polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, acetyl cellulose, nitrocellulose and gelatin. These particles are preferably crosslinked. As a fine particle disperser, ultrasonic waves, dispersers, homogenizers, dissolvers, polytrons, paint shakers,
It is preferable to use a sand grinder, a kneader, an Eiger mill, a dyno mill, a coball mill, or the like. Also,
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 during 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 coated side of the film is inside the curve, and the minus is a curl in which the coated side is outside the curve. Further, the hard coat film of the present invention has a relative humidity of 80% and 10% based on the above curl measurement 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 handleability, peeling and cracking when a film is attached under various humidities.

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 from being caused by handling such as application, processing, cutting, and sticking of the hard coat film.

The substrate used in the present invention is preferably a transparent plastic film, sheet or plate. Specifically, polyethylene terephthalate, polyester such as polyethylene naphthalate, cellulose resin such as triacetyl cellulose and diacetyl cellulose, polycarbonate, polymethyl methacrylate, polycarbonate,
Films and sheets of polysulfone, polyether sulfone, polyarylate, cycloolefin polymer and the like are preferable. The thickness of the film is preferably 20 to 300 μm, more preferably 80 to 200 μm. 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 in the range that does not impair transparency, and a sheet having a thickness of 300 μm or more and several mm can be used.
In the present invention, the term “transparent” when referred to as a transparent support or a transparent film means that the transmittance at a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more.

The active energy ray-curing coating liquid is prepared by mainly dissolving the above-mentioned polyfunctional monomer and polymerization initiator in a ketone-based, alcohol-based or ester-based 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 may 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 the layers in order of hardness.

In the present invention, at least a low-refractive index layer is formed on these prepared hard coat layers, and preferably the hard coat layer side has a medium-refractive index layer, a high-refractive index layer and a low-refractive index reflection layer. By providing the antireflection layer, an antireflection hard coat film having high surface hardness can be obtained.

(Formation of Antireflection Film) FIG. 1 is a schematic sectional view showing a preferred layer structure of the antireflection hard coat film used in the present invention. A hard coat layer (2), a medium refractive index layer (3), a high refractive index layer (4) and a low refractive index layer (5) were sequentially laminated on one surface of the transparent support (1). It has a layered structure. In such an antireflection film having a three-layer structure, the optical film thickness of each of the medium refractive index layer, the high refractive index layer, and the low refractive index layer, that is, the product of the refractive index and the film thickness is nλ with respect to the design wavelength λ. It is preferably about / 4 or a multiple thereof.
This is as described in the publication. Further, it is also possible to adopt a configuration in which only the low refractive index layer (5) is laminated without the middle refractive index layer (3) and the high refractive index layer (4). Further, in order to realize the reflectance characteristics in which the reflectance is low and the tint of reflected light is reduced, in the present invention, the medium refractive index layer has the following formula (I) and the high refractive index layer has The following formula (II)
The low refractive index layer needs to satisfy the following formula (III).

Lλ / 4 × 0.80 <n ₁ d ₁ <lλ / 4 × 1.00 (I)

Mλ / 4 × 0.75 <n ₂ d ₂ <mλ / 4 × 0.95 (II)

Nλ / 4 × 0.95 <n ₃ d ₃ <nλ / 4 × 1.05 (III)

In the formula, l, m and n are integers of 1 or more,
n ₁ is the refractive index of the medium refractive index layer, d ₁ is the layer thickness (nm) of the medium refractive index layer, n ₂ is the refractive index of the high refractive index layer, and d ₂ is the high refractive index layer. Is the layer thickness (nm) of the refractive index layer, n ₃ is the refractive index of the low refractive index layer, and d ₃
Is the layer thickness (nm) of the low refractive index layer. It should be noted that the above design wavelength λ can be considered as a typical value of 500 nm when considering the visible region of 450 to 650 nm, and when designing the present invention at λ = 500 nm, l =
A combination of 1, m = 2 and n = 1 is preferable. When the material of the medium refractive index layer, the high refractive index layer or the low refractive index layer having a refractive index satisfying the above formula cannot be selected, a layer having a refractive index higher than the set refractive index and a low refractive index are set. It is known that a layer which is substantially optically equivalent to a medium refractive index layer or a high refractive index layer having a set refractive index can be formed by using the principle of an equivalent film obtained by combining a plurality of layers having the reflective film of the present invention. It can also be used to achieve rate characteristics. The “substantially three layers” described in the present invention also includes four or five antireflection layers using such an equivalent film. It is also necessary to consider the difference in the refractive index between the antireflection structure in which the above refractive index layers are combined and the object to be mounted. Further, in the case of mounting on a conventional thin hard coat layer, the refractive index of the support must be taken into consideration. Moreover, since the refractive index of the support is typically 1.43 for TAC (triacetyl cellulose) to about 1.6 for PET (polyethylene terephthalate), it is necessary to change the design each time. The present invention provides an antireflection hard coat film which is attached on a thick hard coat layer and therefore is not affected by the refractive index of a support by only considering the difference in refractive index between the hard coat layer and the antireflection structure. be able to.

The medium refractive index layer and the high refractive index layer are formed by coating a coating composition containing inorganic fine particles having a high refractive index, a heat or ionizing radiation curable monomer, an initiator and a solvent, drying the solvent, heat and / or heat. Alternatively, it is formed by curing with ionizing radiation. As the inorganic fine particles, Ti, Zr, I
It is preferable to use at least one metal oxide selected from oxides of n, Zn, Sn, and Sb. The medium-refractive index layer and the high-refractive index layer thus formed are excellent in scratch resistance and adhesion as compared with those obtained by coating and drying a polymer solution having a high refractive index. In order to secure the stability of the dispersion and the film strength after curing, etc., JP-A-11-153
A polyfunctional (meth) acrylate monomer and an anionic group-containing (meth) acrylate dispersant, as described in US Pat. No. 703, US Pat. No. 6,210,858 B1, etc., may be contained in the coating composition. preferable.

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

The phrase "mainly composed of a curable resin" means that the curable resin is contained in an amount of 50% by mass or more and other components which do not adversely affect the curing of the resin may be contained. As the curable resin that 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.

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. The surface modifier having a functional group capable of binding or adsorbing to the inorganic fine particles, silane, aluminum, titanium, metal alkoxide curable resin such as zirconium, or a phosphoric acid 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.

As typical examples of these surface modifiers, the compounds exemplified for the inorganic fine particles added to the hard coat layer can be used.

The method of surface modification of these inorganic fine particles is also as follows.
The method is the same as that for the inorganic fine particles added to the hard coat layer.

The average particle size of the inorganic fine particles used in the antireflection layer is preferably 1 to 100 nm as measured by the Coulter counter method. If it is 1 nm or less, the specific surface area is too large, and the stability in the dispersion is poor, which is not preferable. At 100 nm or more, visible light scattering occurs due to the difference in refractive index with the binder,
Not preferable. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less, and more preferably 1% or less.

In the present invention, for the curing of the medium refractive index layer and the high refractive index layer, active energy rays such as radiation, gamma rays, alpha rays, electron rays and ultraviolet rays are used.
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.

As examples of the polymerization initiator and sensitizer that generate radicals by ultraviolet rays, the radical polymerization initiator and sensitizer for the hard coat layer can be used.

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.

For the low refractive index layer, a fluorine-containing compound which is cured by heat or active energy rays is used. The dynamic friction coefficient of the cured product is preferably 0.03 to 0.15, and the contact angle with pure water is preferably 100 to 120 °. If the coefficient of kinetic friction is higher than 0.15, scratches are likely to occur when the surface is rubbed, which is not preferable. Further, if the contact angle to pure water is less than 100 °, fingerprints, oil stains, and the like tend to adhere, which is not preferable from the viewpoint of antifouling property. As the curable fluorine-containing polymer compound, a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-
1,1,2,2-tetradecyl) triethoxysilane)
In addition to the above, there may be mentioned a fluorine-containing copolymer having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as constitutional units.
Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), Partially or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical Co., Ltd.) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like. Among them, hexafluoropropylene is particularly preferable from the viewpoint of low refractive index and easy handling of the monomer. Examples of the monomer for imparting a crosslinkable group include a (meth) acrylate monomer having a crosslinkable functional group in advance in the molecule such as glycidyl methacrylate, as well as a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, and the like (meth ) Acrylate monomers (eg (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth))
Acrylate, allyl acrylate, etc.).
The latter is capable of introducing a cross-linking structure after copolymerization. JP-A-10-25388 and JP-A-10-14773.
No. 9, which is particularly preferable.

Further, not only a polymer having the above-mentioned fluorine-containing monomer as a constitutional unit, but also a copolymer of the above-mentioned fluorine-containing monomer and a monomer containing no fluorine atom may be used. The copolymerizable monomer unit is not particularly limited, and examples thereof include olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic acid esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid). 2-ethylhexyl), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers ( Methyl vinyl ether, etc.),
Vinyl esters (vinyl acetate, vinyl propionate,
(Vinyl cinnamate, etc.), acrylamides (N-tert-butyl acrylamide, N-cyclohexyl acrylamide, etc.), methacrylamides, acrylonitrile derivatives and the like, and JP-A-10-25388 and JP-A-10-147739. Is disclosed in.

Further, as a means for lowering the dynamic friction coefficient in order to impart scratch resistance, it is possible to introduce a copolymerized unit capable of improving slidability. A method for introducing a polydimethylsiloxane segment into the main chain is disclosed in JP-A-11-228.
It is disclosed in Japanese Patent No. 631 and is particularly preferable.

The fluorine-containing resin used for forming the low refractive index layer is preferably added with ultrafine Si oxide particles in order to impart scratch resistance. From the viewpoint of antireflection property, the lower the refractive index, the more preferable, but as the refractive index of the fluororesin is lowered, the scratch resistance deteriorates. Therefore, by optimizing the refractive index of the fluorine-containing resin and the addition amount of the Si oxide ultrafine particles, it is possible to find the best balance between scratch resistance and low refractive index. As Si oxide ultrafine particles,
The silica sol dispersed in a commercially available organic solvent may be added to the coating composition as it is, or various commercially available silica powders may be dispersed in an organic solvent and used.

For these medium-refractive index layer, high-refractive index layer and low-refractive index layer, the active energy ray- or heat energy-curable coating liquid is applied on a hard coat layer to form a high-refractive-index layer, a medium-refractive-index layer and a low-refractive-index layer. It can be prepared by coating the refractive index layers in this order by a known thin film forming method such as a spinner method, a gravure method, a wire bar method, drying, irradiation with active energy rays or heat treatment and curing.

The reflectance (regular reflectance) of the antireflection layer is
It is preferably 1% or less, more preferably 0.5% or less.

In the antireflection hard coat layer of the present invention, an antifouling layer may be provided on the low refractive index layer in order to further improve the antifouling property of the antireflection layer. The material is preferably a low surface energy curable resin containing a fluorine atom.
6, JP-A-2-19801, JP-A-3-17901.
Examples of the silicone-curable resin containing a fluorinated hydrocarbon group, polymers containing a fluorinated hydrocarbon group, and the like described in Japanese Patent Publication No. 1993-242242.

The antireflection hard coat layer of the present invention can be laminated together with another layer having a function such as an ultraviolet and / or infrared ray absorbing layer, a coloring layer, a selective wavelength absorbing layer, an electromagnetic wave shielding layer, It is used as a high hardness functional film. In addition, in the present invention, "on" on the transparent support means
This shows that the transparent support and the hard coat layer are laminated, and the presence of the layer having the above-mentioned function between the transparent support and the hard coat layer is not hindered.

(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.

(Preparation 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 so as to have a thickness of 00 nm to form an undercoat layer with an antistatic layer, the above coating solution for hard coat layer is applied by an extrusion method so as to have a thickness shown in Table 1.
After drying and irradiating with ultraviolet rays (700 mJ / cm ² ), Table 4
A hard coat film having the thickness described in 1. was produced.

(Preparation of titanium dioxide dispersion) Ultrafine titanium dioxide particles (TTO-55B, manufactured by Ishihara Techno Co., Ltd.) 3
0 parts by weight, carboxylic acid group-containing monomer (Aronix M-
6300 parts by weight of 5300 Toagosei Co., Ltd. and 63 parts by weight of cyclohexanone were dispersed by a sand grinder until the average particle diameter measured by the Coulter method was 42 nm to prepare a titanium dioxide dispersion.

(Preparation of Coating Solution for Medium Refractive Index Layer) 0.15 parts by weight of a photopolymerization initiator (IRGACURE 184, manufactured by Ciba Geigy) was dissolved in 75 parts by weight of cyclohexanone and 19 parts by weight of methyl ethyl ketone. Further, 3.1 parts by weight of titanium dioxide dispersion and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)
After adding 1 part by weight and stirring at room temperature for 30 minutes, the pore size was 3μ
m polypropylene filter (PPE-03) to prepare a medium refractive index layer coating solution.

(Preparation of coating liquid for high refractive index layer) 0.13 parts by weight of a photopolymerization initiator (IRGACURE 184, manufactured by Ciba Geigy) was dissolved in 54 parts by weight of cyclohexanone and 18 parts by weight of methyl ethyl ketone. Further, 26.4 parts by weight of titanium dioxide dispersion and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)
After adding 1.6 parts by weight and stirring at room temperature for 30 minutes, a polypropylene filter (PPE-03) having a pore size of 3 μm
And filtered to prepare a coating liquid for high refractive index layer.

(Preparation of coating liquid for low refractive index layer) Refractive index 1.
42, a 6 wt% solution of thermally crosslinkable fluoropolymer in methyl ethyl ketone (JN-7228, JS
R (manufactured by R Co., Ltd.) was subjected to solvent substitution to obtain a polymer solution containing a solid content of 10% by weight in a mixed solvent of 85% by weight of methyl isobutyl ketone and 15% by weight of 2-butanol. In 70 parts by weight of this polymer solution, MEK-ST (average particle size: 10 to 20 nm, solid content: 30% by weight of SiO ₂
Methyl ethyl ketone dispersion of sol, manufactured by Nissan Chemical Co., Ltd.
10 parts by weight, 42 parts by weight of methyl isobutyl ketone and 28 parts by weight of cyclohexanone were added, and after stirring,
Polypropylene filter with a pore size of 3 μm (PPE-0
It filtered by 3) and prepared the coating liquid for low refractive index layers.

Similarly, the coating liquid was adjusted so that the film thickness and the refractive index of each layer would be the values shown in Table 4, to prepare an antireflection hard coat film. The properties of these films are shown in Table 4.

(4) Image Display Device with Film Attached with Antireflection Hard Coat Layer An acrylic adhesive was attached to the surface of the hard coat film on which the hard coat layer was not provided in Examples and Comparative Examples, and Table 5 was given. It was laminated on the display device of No. 1 and the surface characteristics were examined. Each image cover device is a PDP: Hitachi 42-inch plasma display (CMP4121HDJ), CRT: Matsushita Corporation 28-inch flat television (TH-28FP2).
0), LCD: 15-inch TFT liquid crystal monitor (RDT151A) manufactured by Mitsubishi Corporation, touch panel: Zaurus (MI-L1) manufactured by Sharp Corporation.

[0121]

[Table 4]

[0122]

[Table 5]

Each evaluation method was carried out by the following method. Surface elastic modulus; Micro surface hardness tester (Fisher Instruments Co., Ltd .: Fisher Scope H100V)
P-HCU), using a diamond quadrangular pyramid indenter (tip facing angle; 136 °), and measuring the indentation depth under an appropriate test load within a range where the indentation depth does not exceed 1 μm. , Is the elastic modulus obtained from the change in load and displacement during unloading. Pencil hardness test: The hardness of the pencil scratching test is performed by conditioning the prepared hard coat film under the conditions of a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, and then using a test pencil specified by JIS-S-6006. According to the pencil hardness evaluation method defined by JIS-K-5400, it is the pencil hardness value in which no scratch is observed under a load of 9.8N. Adhesion test; using a cutter on the hard coat surface, 1
Scratch was made at intervals of 1 mm x 1 mm, and 100 pieces of squares were covered with cellotape (registered trademark No405; manufactured by Nichiban Co., Ltd.).
After 30 seconds from application, the cellophane tape was peeled off, and the number of squares peeled off or lacking in edges was observed. The case where 100 squares remained was evaluated as ◯, the case where some of the squares were missing was evaluated as Δ, and the case where a plurality of squares were peeled off was evaluated as x. Measurement of surface reflectance: A sample was prepared by rubbing the back surface with sandpaper and applying black magic to prevent reflection on the back surface. Using a spectrophotometer (manufactured by JASCO Corporation), 4
The surface reflectance of specular reflection at 5 ° of incident light in the wavelength range of 50 to 650 nm was obtained. Antifouling property: Evaluation of quick-drying oil-based ink (Zebra, "Mckey" (registered trademark)) written on the film surface, rubbed several times with "Toraysee" (registered trademark) manufactured by Toray Industries, Inc. (○ is a state where the written mark is completely wiped off, △ is a state where a part is not wiped off, and × is a state where most of the mark is left). External light reflection: The visibility of the reflection of the fluorescent lamp was visually evaluated (○: the reflection was difficult to see, ×: the reflection was clearly visible, Δ: intermediate). Soil wiping ability: Ease of removal when fingerprints on the surface were wiped off using "Toraysee" (registered trademark) manufactured by Toray Industries, Inc. was evaluated (○ means light force can be removed several times, × means It can be removed by rubbing it with force, and △ is the middle one). Steel Wool Test: The scratches when rubbing while applying a load of 1.96 N / cm ² using # 0000 steel wool were evaluated visually (◯: no scratch, Δ: slightly visible, ×: visible scratch).

[0124]

The antireflection hard coat film of the present invention has a high pencil hardness and is hard to be scratched on the surface, and has excellent antireflection. Further, by sticking 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 surface scratches. A film having such various functionalities is suitably used for protecting image display devices, plastics, and glass.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing the basic layer structure of an embodiment of the antireflection hard coat film of the present invention.

[Explanation of symbols]

1: Support 2: Hard coat layer 3: Middle refractive index layer 4: High refractive index layer 5: Low refractive index layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuhiro Nakamura             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F term (reference) 2H091 FA37X FC02 FD06 GA16                       LA02                 2K009 AA06 AA15 CC03 CC09 CC24                       DD02

Claims (2)

[Claims] 1. A curable composition which is cured by irradiation with active energy rays has an ethylenically unsaturated group of 3 in the same molecule.
Has a hard coat layer which is a curable resin containing one or more and / or a curable resin containing three or more ring-opening polymerizable groups in the same molecule on a transparent support, and an antireflection layer on the hard coat layer. The antireflection hard coat film, wherein the antireflection layer is provided with at least a low refractive index layer having a refractive index lower than that of the hard coat layer on the outermost surface side. 2. An image display device having a transparent base material provided with the antireflection hard coat film according to claim 1.