JP2000338308A - Antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film which hardly curls, has resistance to fracture and has excellent surface hardness, scratch resistance and abrasion resistance. SOLUTION: This antireflection film is formed by providing hard coating layers comprising at least two layers on at least one side of a plastic base material sheet and, further thereon, successively laminating antireflection layers. In such a case, at least one layer of the hard coating layers includes a high molecular weight monomer and/or an acrylic polymer which has a copolymerizable unsaturated double bond at terminal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film having excellent surface hardness, abrasion resistance and scratch resistance, small curl, and excellent antireflection properties.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting an antireflection property to a plastic substrate sheet, for example, a method disclosed in
No. 01, JP-A-9-85875 and JP-A-10-728, a hard coat layer such as an actinic ray curable resin or a thermosetting resin is formed on a plastic substrate sheet, There has been proposed a method of forming an antireflection layer on a coat layer.

[0003]

However, it has been found that the above-mentioned antireflection film has the following problems.

That is, in these antireflection films, the abrasion resistance and the scratch resistance of the antireflection layer are insufficient.
In particular, when attaching an anti-reflection film to the surface of a CRT or display device, or when assembling a CRT or display device with the affixed to a device such as a display or an instrument, the reflection of the anti-reflection layer is caused by the contact of a nail or mechanical pencil. Problems such as scratching and scraping of the prevention layer occurred.

As a countermeasure, there is a method of using a composition having sufficient abrasion resistance and scratch resistance for the hard coat layer below the antireflection layer. In this method, the thickness of the hard coat layer is reduced. Need to be thicker. However, when the hard coat layer is thickened, the curl of the anti-reflective film increases due to the difference in shrinkage between the hard coat layer and the plastic substrate sheet, and the anti-reflective layer is easily cracked due to warpage, so that it is difficult to attach and assemble. There is a problem that the acceptance yield is deteriorated.

It is an object of the present invention to have abrasion resistance and scratch resistance, to reduce curling, to prevent cracking during application and assembly,
An object of the present invention is to provide an antireflection film having a high product yield.

[0007]

Means for Solving the Problems The object of the present invention is to achieve the above object, and the antireflection film of the present invention is provided on at least one surface of a plastic substrate sheet.
An anti-reflection film comprising a hard coat layer having at least two layers, and an anti-reflection layer further laminated thereon.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The plastic base sheet used in the present invention is not particularly limited, and can be appropriately selected from known plastic base sheets. As such a plastic substrate sheet,
For example, polyester, polyethylene, polypropylene, diacetate, triacetate, polystyrene, polycarbonate, polymethylpentene,
Sheets made of resin such as polysulfone, polyetherethylketone, polyimide, fluorine, nylon, and polymethacrylic resins can be used. Among these resins, polyester-based resins, triacetate-based resins and polymethacrylate-based resins are preferred from the viewpoints of optical and strength and excellent uniformity.

In particular, polyethylene terephthalate, triacetyl cellulose and polymethyl methacrylate resins are preferably used because of their excellent transparency and no optical anisotropy.

In the above plastic substrate sheet,
Those having a light transmittance at 400 to 800 nm of 40% or more and a haze of 3% or less are preferred. If the light transmittance is less than 40%, or if the haze is more than 3%, it tends to lack sharpness when used as a display member, which is not preferable. Further, from the viewpoint of exhibiting such effects, it is a practical range that the upper limit of the light transmittance is 99.5% and the lower limit of the haze is about 0.1%.

The plastic substrate sheet may be uncolored or colored.

Various surface treatments (for example, corona discharge treatment, glow discharge treatment, flame treatment, etching treatment, roughening treatment, etc.) may be applied to the plastic substrate sheet used in the present invention before the hard coat layer is provided. Alternatively, a surface coating (polyurethane-based, polyester-based, polyester acrylate-based, polyurethane acrylate-based, polyepoxy acrylate-based, titanate-based compound, or the like) for promoting adhesion may be performed. In particular, those obtained by undercoating a composition comprising a copolymer obtained by grafting an acrylic compound to a hydrophilic group-containing polyester resin and a cross-linking agent, have improved adhesiveness, and have durability such as wet heat resistance and boiling water resistance. Preferred as an excellent plastic substrate sheet.

The thickness of the anchor coat layer undercoated with these compositions is usually 0.01 to ² g / m ² , preferably 0.1 to 1 g / m ² , and the thickness of the anchor coat layer is 0.1 g / m ² .
If it is thinner than 01 g / m ² , it is difficult to apply uniformly,
If it exceeds ² g / m ² , it is difficult to obtain a laminate having excellent surface hardness and abrasion resistance of the hardened layer laminated thereon, which is not preferable.

Although the thickness of the plastic substrate sheet used in the present invention is not particularly limited, it is usually 5 to 5000 μm, preferably 10 to 3000 μm from the viewpoint of mechanical strength and thermal conductivity. Further, two or more sheets may be bonded together by a known method to form a thicker plastic base sheet.

In the present invention, at least one surface of the plastic substrate sheet is provided with at least two hard coat layers.

Generally, in order to impart sufficient wear resistance and scratch resistance to the hard coat layer, it is necessary to increase the thickness of the hard coat layer. However, in the case of a single hard coat layer, if the thickness of the hard coat layer is increased, the difference in shrinkage from the plastic base sheet is different, or the hard coat layer is crosslinked between the surface in contact with the plastic base sheet and the surface in contact with the atmosphere. The problem is that the curl increases due to the difference in density, and as a result, the antireflection layer is cracked.

In the present invention, the above problem can be solved by laminating the hard coat layer on the surface in contact with the plastic substrate sheet in a thin layer.

In the present invention, the thickness of each layer of the hard coat layer is appropriately selected according to the application, but the thickness of the uppermost layer is usually 3 to 18 μm, preferably 3 to 15 μm.
More preferably, it is 5 to 10 μm.

The total thickness of each layer of the hard coat layer is preferably 5 to 23 μm, more preferably 5 to 2 μm.
The range is 0 μm. When the total thickness of each layer of the hard coat layer is less than 5 μm, the surface hardness is insufficient and the surface is easily damaged, and when the total thickness is too large, the cured film is apt to be brittle and the antireflection film is bent. Sometimes, the antireflection layer tends to crack, which is not preferable.

In at least one of the hard coat layers in the present invention, at least two (/) molecules of a high molecular weight monomer having an unsaturated double bond copolymerizable at the terminal and / or an acrylic polymer are present in one molecule. A resin obtained by polymerizing and / or reacting a compound composition containing a polymer monomer containing a polyfunctional (meth) acrylate having a (meth) acryloyl group is preferably used.

Among these resins, the high molecular weight monomer having a copolymerizable unsaturated double bond at the terminal is a high molecular compound having a (meth) acryloyl group at the terminal,
A high molecular compound having a number average molecular weight of about 1,000 to 10,000, preferably about 2,000 to 6,000 is used. The main component of the polymer portion includes a polymer composed of a methyl methacrylate polymer, a styrene polymer, a styrene / acrylonitrile polymer, a butyl acrylate polymer and a silicone polymer. Examples of the polymer compound having a (meth) acryloyl group at a terminal include a macromonomer (for example, AS
-6, AN-6, AB-6, AK-32, etc.). The use ratio of these high molecular weight monomers is desirably 5 to 50% by weight based on the total amount of resin solids.

In the present invention, the acrylic polymer is (meth) acrylic acid obtained by copolymerizing (meth) acrylic acid and its alkyl ester as essential components.
A (meth) acrylic acid alkyl ester copolymer or a styrene / acrylic copolymer obtained by copolymerizing a styrene monomer with (meth) acrylic acid and / or an alkyl ester thereof as an essential component is preferable, and its weight average The molecular weight is preferably from 5,000 to 10,000. The use ratio of these acrylic copolymers is preferably 5 to 50% by weight based on the total amount of resin solids.

When a high molecular weight monomer having an unsaturated double bond copolymerizable at the terminal and an acrylic copolymer are used in combination, the total amount of both is 5 to 5 with respect to the total resin solid content.
It is preferable to mix them so as to be 0% by weight.

In the present invention, two or more (meth) acryloyl groups per molecule (provided that “(meth)
The description of “acryloyl group” is an abbreviation of an acryloyl group or a methacryloyl group, and is the same in the claims and the description below.) A polyfunctional (meth) acrylate compound having one molecule In the polyhydric alcohol having two or more alcoholic hydroxyl groups therein, a compound in which the hydroxyl group is an esterified product of two or more (meth) acrylic acids can be used. Specifically, (a) (meth) acrylic acid diesters of alkylene glycols having 2 to 12 carbon atoms: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) )
(B) (b) (meth) acrylate diesters of polyoxyalkylene glycol such as acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol (meth) acrylate: diethylene glycol di (meth) acrylate, triethylene glycol di (C) polyhydric alcohol (meth) such as (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate Acrylic diesters: (d) addition of bisphenol A or hydride of bisphenol A with ethylene oxide and propylene oxide, such as pentaerythritol di (meth) acrylate (Meth) acrylic acid diesters: (e) diisocyanate compound such as 2,2'-bis (4-acryloxyethoxyphenyl) propane, 2,2'-bis (4-acryloxypropoxyphenyl) propane and 2 Two or more (meth) acryloyloxy groups in a molecule obtained by reacting a terminal isocyanate group-containing compound obtained by previously reacting at least two alcoholic hydroxyl group-containing compounds with an alcoholic hydroxyl group-containing (meth) acrylate (F) a compound having two or more epoxy groups in the molecule, which is reacted with acrylic acid or methacrylic acid to form two or more (meth) acryloyloxy groups in the molecule. Epoxy (meth) acrylates and the like.

In particular, a hard coat layer containing at least one kind of monomer having three or more (meth) acryloyl groups in one molecule is excellent in abrasion resistance and flexibility as well as hardness and curability. It is preferred.

A compound of a polyhydric alcohol having three or more alcoholic hydroxyl groups in one molecule, wherein the hydroxyl group is an esterified product of three or more (meth) acrylic acids.

As specific examples, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate ) Acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.

The proportion of the monomer having three or more (meth) acryloyl groups in one molecule is preferably 50 to 95% by weight based on the total amount of the resin solids. If the amount of the monomer is less than 50% by weight, it is difficult to obtain a cured film having sufficient abrasion resistance. If the amount exceeds 95% by weight, shrinkage due to polymerization is large, and It is not preferable because distortion remains in the coating film, flexibility of the coating film is reduced, and the cured film tends to curl greatly.

Further, a compound having one ethylenically unsaturated double bond in the molecule may be included. For example, methyl (meth) acrylate, ethyl (meth) acrylate,
n- and i-propyl (meth) acrylate, n-, s
ec- and t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth)
Acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-hydroxyethyl (meth)
Acrylamide, N-vinylpyrrolidone, N-vinyl-
3-methylpyrrolidone, N-vinyl-5-methylpyrrolidone, and the like. In particular, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, etc. are preferable for improving the adhesion to the plastic substrate. These monomers may be used alone or in combination of two or more.

Other resin compositions of the hard coat layer in the present invention include acrylic, melamine, urethane, and the like.
Epoxy compounds and the like are mentioned, but acrylic compounds are particularly preferable in terms of surface hardness, durability, adhesion to a substrate, and flexibility, and active ray polymerization type acrylic compounds are more preferable.

In the present invention, as a method of polymerizing and / or reacting the compound composition of the hard coat layer, a method of irradiating ultraviolet rays may be mentioned. In this case, it is desirable to add a photopolymerization initiator to the composition. .

Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-
Dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, methylbenzoylformate, p-isopropyl-
α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, carbonyl compounds such as 1-hydroxycyclohexylphenylketone, tetramethylthiuram monosulfide, tetramethylthiuram disulfide,
Examples thereof include sulfur compounds such as thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone, and peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide.

These photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is suitably from 0.01 to 10 parts by weight based on the solid content of the resin.

As another method, electron beam or radiation can be used as polymerization and / or reaction means.
Therefore, when an electron beam or radiation is used, it is not always necessary to add a polymerization initiator.

The compound composition used in the present invention contains hydroquinone, hydroquinone monomethyl ether, 2,5,5 in order to prevent thermal polymerization during production and dark reaction during storage.
It is desirable to add a known thermal polymerization inhibitor such as -t-butylhydroquinone. The addition amount of the thermal polymerization inhibitor is preferably 0.005 to 0.05% by weight based on the solid content of the resin.

An organic solvent can be added to the compound composition used in the present invention for the purpose of improving workability during coating and controlling the coating film thickness within a range not to impair the purpose of the present invention. .

The organic solvent has a boiling point of 50 to 150 ° C.
Are easy to use in terms of workability during coating, polymerization, and / or drying before and after the reaction. As a specific example,
Alcohol solvents such as methanol, ethanol, and isopropyl alcohol; acetate solvents such as methyl acetate, ethyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; aromatic solvents such as toluene; and cyclic ethers such as dioxane Solvents and the like can be mentioned. These solvents can be used alone or in combination of two or more.

Various additives can be added to the compound composition used in the present invention, if necessary, as long as the object of the present invention is not impaired. For example, an antioxidant, a leveling agent, an antistatic agent and the like can be mentioned.

In the present invention, polymerization of the compound composition and / or
Or, for the reaction, ultraviolet rays, electron beams, radiation (α rays,
β rays, γ rays, etc.) can be used, but ultraviolet rays are simpler and more preferred. Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and a carbon arc lamp. On the other hand, electron beam or radiation is advantageous in that the apparatus is expensive and requires operation under an inert gas, but it is not necessary to include a photopolymerization initiator or a photosensitizer in the coating layer. .

Further, a coloring agent such as a pigment or a dye may be added to the composition of the hard coat layer. When a coloring agent is contained, it is desirable that the antireflection film has a light transmittance of 40 to 80% at a wavelength of 550 nm.

In the present invention, an antireflection layer made of a metal oxide is further formed on the hard coat layer formed on the plastic substrate sheet. In the anti-reflection layer,
Lamination of high and low refractive index compounds or inorganic substances such as magnesium fluoride and silicon oxide can be used. In particular, there are various configurations of the anti-reflection film, but a configuration that includes at least a light absorption layer is practical. For example, it can be formed using a vacuum thin film forming technique such as vapor deposition or sputtering in the following multilayer structure including at least a dielectric layer, a conductor layer, and a light absorbing layer.

As the material of the high refractive index film, TiO ₂ , Zr
O ₂ , ITO, SnO ₂ , Y ₂ O ₃ , ZnO and the like can be mentioned. Examples of low refractive index film materials include SiO ₂ and MgF ₂ . In addition, ITO, SnO ₂ , ZnO, and the like can serve both as a conductive film and a high refractive index film.

As the light absorbing film, TiNx, Au, A
It is also possible to interpose a film such as g, NiOx or the like as a component when forming a λ / 2 film and λ / 4 as a composite film, and various film configurations are conceivable. The effects of the present invention are not impaired.

In the present invention, a wide range of visible light,
Specifically, it is desirable that the reflectance be 2% or less at least within the wavelength range of 480 nm to 650 nm. For this reason, by sticking the plastic substrate sheet on which the above-described anti-reflection layer is formed to the surface of a character or display member component such as a CRT, it is possible to reduce reflected light of light incident on the component.

In a preferred embodiment of the present invention, a transparent layer of a water-repellent / oil-repellent layer having a contact angle of water of 90 deg or more with a thickness of 1 to 20 nm is further provided on the antireflection layer. No. The purpose of this is to protect the antireflection layer and enhance the antifouling performance, as long as it meets the required performance. As a material of the water-repellent layer, a compound having a hydrophobic group is preferable, and examples thereof include perfluorosilane and fluorocarbone. Depending on the material, a coating, a physical vapor deposition method such as evaporation or sputtering, or a chemical vapor deposition method such as CVD can be used.

Next, a method for producing the antireflection film of the present invention will be described, but the present invention is not limited thereto.

The antireflection film of the present invention is produced by applying a hard coat layer to a plastic substrate sheet (film), polymerizing and / or reacting the same, and further forming an antireflection layer film thereon.

As means for applying the hard coat layer of the present invention, brush coating, dip coating, knife coating, spray coating,
Normally applied coating methods such as flow coating and spin coating (such as spinner) can be easily applied. Each method has its own characteristics, and the method of application is appropriately selected depending on the required characteristics of the laminate and the intended use. The polymerization of the compound composition forming the hard coat layer, and / or as a reaction method,
Examples thereof include a method using a heat source such as steam, gas or electricity, and a method of irradiating active energy rays such as ultraviolet rays and electron beams.

The means for forming the anti-reflection layer of the present invention includes a vacuum film forming method such as vapor deposition and sputtering, and a coating method such as spray coating, dip coating, flow coating and spin coating.

The antireflection film of the present invention has a high surface hardness, excellent abrasion resistance, and has antireflection properties, so that it can be used for a wide range of applications. Specifically, it can be used in fields where antireflection properties are required, such as filters for CRTs, membrane switches, displays, nameplates, and instrument covers.

As described above, by laminating at least two hard coat layers on one surface of the plastic substrate sheet and further laminating the antireflection layer thereon, the reflected light of light incident on the member is reduced. As a result, a laminate in which scratches on the surface are less likely to be obtained is obtained.

[Method for Measuring Characteristics and Method for Evaluating Effects] The method for measuring characteristics and the method for evaluating effects in the present invention are as follows.

(1) Abrasion Resistance The sheet surface was rubbed with steel wool # 0000, and the degree of scratching was evaluated according to the following criteria.

○: hardly scratched even if strongly rubbed △: slightly scratched if considerably rubbed ×: scratched even if weakly rubbed (2) Pencil hardness HEIDON (manufactured by Shinto Kagaku Co., Ltd.) was used. JIS K
Measured according to -5400.

(3) Scratch resistance The sheet surface was rubbed with a 1 kg load using a touch pen, and the degree of scratches was evaluated according to the following criteria.

：: No scratches Δ: Slightly scratched X: Clearly visible scratches (4) Curl A sheet cut to a size of 10 × 10 cm is placed on a flat place with an antireflection layer on top. Then, the floating state of both ends was observed, and the height from the plane was measured.

(5) Curvature of Crack Generation A sheet cut into a size of 10 × 2 cm was wound around a circular cylinder with the antireflection layer facing upward, and the state of occurrence of surface cracks was observed.

(6) Durability At a temperature of 40 ° C. and 90 ° C., the sheet cut into a size of 20 × 5 cm is wound around a 50φ column with the antireflection layer facing upward.
After standing in a constant temperature / humidity chamber of 24% RH for 24 hours, it was attached to a CRT display and the appearance was evaluated.

：: No change in appearance. 画像: Image looks slightly glare.

×: The image looks glaring on the entire surface. (7) Reflectance The reflectance at 550 nm was measured using a spectrophotometer (Hitachi, Ltd.).

[0061]

Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

(Examples 1 to 7) A polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries, Inc.) having a thickness of 188 μm was used as a plastic substrate sheet, and a hard coat layer was formed on one surface thereof using various bar coaters. Coating liquids A to F having the following compositions were applied to the first and second layers so that the desired hard coat layer thickness was obtained, with the combination and coating thickness of the coating liquid compositions shown in Table 1. Multi-layer coating was performed. The first layer is the lowest layer closest to the plastic base sheet,
The second layer is a layer laminated on the first layer.

The coating layer on the obtained plastic substrate sheet was left to dry in a hot air drier for 60 seconds to evaporate the solvent, and then the coating layer was set from a height of 12 cm to 80 W / 5 cm under a high-pressure mercury lamp having an intensity of 5 cm
The film was passed at a speed of m / min to polymerize and / or react the coating film to form a hard coat layer.

Further, an antireflection film having the following structure was formed on a plastic sheet provided with a hard coat layer using a vacuum evaporation apparatus.

[0065] Next, on the antireflection layer thus formed, perfluorotrimethoxysilane was formed to a thickness of 20 nm by a CVD method to obtain an antireflection film.

The coating liquid compositions used in the examples are described below.

<Coating Liquid A> 90 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.), macromonomer AN-6S (terminal group is methacryloyl group, and high molecular weight (segment) component is styrene / acrylonitrile 20 parts by weight of a macromonomer having a number average molecular weight of 6,000 (manufactured by Toagosei Co., Ltd., solid content 40% by weight), and a photoinitiator 1-hydroxyphenyl ketone (Ciba.
Specialty Chemicals Co., Ltd.) 5 parts by weight,
50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone were stirred and mixed to prepare a coating liquid A.

<Coating Liquid B> 90 parts by weight of dipentaerythritol hexaacrylate, 25 parts by weight of macromonomer AA-2 (styrene-based macromonomer) solid content 40% by weight), 5 parts by weight of 1-hydroxyphenyl ketone, 50 parts by weight of toluene And 50 parts by weight of methyl ethyl ketone with stirring to obtain a coating liquid B.

<Coating liquid C> Dipentaerythritol hexaacrylate 80 parts by weight, macromonomer AN-6S
(Solid content 40% by weight) 16 parts by weight, styrene-acrylic copolymer (solid content 60%, weight average molecular weight 17790)
20 parts by weight, 5 parts by weight of 1-hydroxyphenyl ketone, 50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone were stirred and mixed to obtain a coating liquid C.

<Coating Liquid D> 100 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.), 5 parts by weight of photoinitiator 1-hydroxyphenyl ketone (manufactured by Ciba Specialty Chemicals, Inc.) , 50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone were stirred and mixed to prepare a coating liquid D.

<Coating liquid E> Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 20 parts by weight, macromonomer AN-6S (solid content 40% by weight) 160 parts by weight, photoinitiator 1-hydroxyphenyl 5 parts by weight of ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.), 50 parts by weight of toluene, and 50 parts by weight of methyl ethyl ketone were stirred and mixed to prepare a coating liquid E.

<Coating liquid F> Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 40 parts by weight, styrene-acrylic copolymer (solid content 60% by weight) 100 parts by weight, photoinitiator 1-hydroxy Phenyl ketone (Ciba
Specialty Chemicals Co., Ltd.) 5 parts by weight,
50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone were stirred and mixed to prepare a coating liquid F.

<Coating Liquid G> Dipentaerythritol triacrylate isophorone diisocyanate urethane prepolymer UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.) 100
5 parts by weight, 1 part by weight of a photoinitiator 1-hydroxyphenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.), 50 parts by weight of toluene, and 50 parts by weight of methyl ethyl ketone were mixed by stirring to obtain a coating liquid G.

[0074]

[Table 1] (Comparative Examples 1 to 4) A plastic sheet having a thickness of 18
An 8 μm polyethylene terephthalate film (“Lumirror” manufactured by Toray Industries, Inc.) is used as a hard coat layer on one side using various bar coaters so that a coating solution having the following composition is formed so as to have a desired hard coat layer thickness. DG
Was applied in a single layer with the thickness shown in Table 2.

A coating layer of the obtained plastic sheet was formed in the same manner as in Examples 1 to 7 to form a hard coat layer and then an antireflection film, and then the antireflection layer thus formed was formed. A 20-nm-thick perfluorotrimethoxysilane was formed thereon by CVD to obtain an antireflection film.

The coating solutions used in the comparative examples are described below.

<Coating liquid D><Coating liquid E><Coating liquid F> is the same as the coating liquid used in the examples.

<Coating liquid G> Dipentaerythritol triacrylate isophorone diisocyanate urethane prepolymer UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.) 100
5 parts by weight of a photoinitiator 1-hydroxyphenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.)
50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone were stirred and mixed to prepare a coating liquid G.

[0079]

[Table 2] Table 3 shows the results of evaluating the performance of the antireflection films obtained in Examples 1 to 7 and Comparative Examples 1 to 4.

[0080]

[Table 3] Examples 1 to 7 were good in all evaluation items.

In Comparative Example 1, the hard coat layer was a single layer and the curl was extremely large.

The hard coat layers of Comparative Examples 3 and 4, which did not use the polymer monomer, had insufficient abrasion resistance and scratch resistance.

In Comparative Example 2, the curl was slightly large because the hard coat layer was a single layer, and the abrasion resistance and the scratch resistance were insufficient due to the high content of the polymer monomer.

[0084]

According to the present invention, the surface hardness, pencil hardness, scratch resistance and abrasion resistance from the anti-reflection layer side are good.
In particular, even when the thickness of the hard coat layer is increased, a remarkable effect that curl is small is produced.

The excellent effect of the present invention is produced by providing at least two hard coat layers on a plastic substrate sheet and forming an anti-reflection layer thereon. It is promoted by using a hard coat layer containing a high molecular weight monomer for at least one hard coat layer.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 9/00 B32B 9/00 A 27/00 27/00 N 27/30 27/30 A G02B 1/10 C09D 4/00 // C09D 4/00 G02B 1/10 Z (72) Inventor Kiyonari Maeda 1-1-1, Sonoyama, Otsu-shi, Shiga F-term in Toga Co., Ltd. F-term (reference) 2K009 AA02 AA15 BB14 BB24 BB28 CC03 CC24 DD02 DD03 DD04 DD05 EE05 4D075 AE03 AE27 CB02 DA04 DB31 DC19 EB22 EB52 EB56 EC02 4F100 AA06 AA17D AA20 AA33 AK01A AK12B AK12C AK12H AK21B AK21C AK25B AK25C AK25H AK42 AL01B AL01C AR00D AS00B AS00C BA04 BA10A BA10D BA25B BA25C EH462 EH662 EJ542 GB41 JA07B JA07C JK09 JK12 JK14 JN06D YY00B YY00C 4J038 CG141 CH031 CH041 CH081 CH121 CH141 CH171 CH191 CJ271 CJ281 FA231 GA02 NA11 NA19 PA17 PB08 PC08

Claims (8)

[Claims] 1. An anti-reflection film comprising: a plastic substrate sheet having at least one surface provided with at least two hard coat layers, and an anti-reflection layer laminated thereon. 2. The thickness of the uppermost layer of the hard coat layer is 3 to 1
2. The anti-reflection film according to claim 1, comprising 8 μm. 3. The antireflection film according to claim 1, wherein the total thickness of each layer of the hard coat layer is 5 to 23 μm. 4. A method according to claim 1, wherein at least one layer of the hard coat layer has at least two (meth)-(meth) ene molecules in one molecule of a high molecular weight monomer having at least one copolymerizable unsaturated double bond and / or an acrylic polymer. The antireflection film according to any one of claims 1 to 3, comprising a resin obtained by polymerizing and / or reacting a compound composition containing a polymer monomer containing a polyfunctional (meth) acrylate having an acryloyl group. 5. A hard coat layer comprising a polymer comprising a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups per molecule in the solid content of the resin composition of the hard coat layer. 2. The composition according to claim 1, wherein the content is 95% by weight.
The antireflection film according to any one of Items 1 to 4, wherein 6. The high molecular weight monomer having a terminal copolymerizable unsaturated double bond is a high molecular compound having a (meth) acryloyl group at a terminal and having a number average molecular weight of 1,000 to 10,000, And the resin content after polymerization and / or reaction is 5 to 5 in the solid content of the resin composition of the hard coat layer.
The antireflection film according to claim 4, wherein the content is 50% by weight. 7. An acrylic polymer comprising a (meth) acrylic acid / alkyl (meth) acrylate copolymer and / or a copolymer of a styrene monomer and a (meth) acrylic acid / alkyl (meth) acrylate. A styrene / acrylic copolymer obtained by copolymerizing a copolymer with an essential component, having a weight average molecular weight of 5,000 to 100,000, and a resin content after polymerization and / or reaction. Is 5 to 50% by weight based on the solid content of the resin composition of the hard coat layer. 8. The anti-reflection film according to claim 1, wherein the anti-reflection layer comprises a multilayer laminate of metal oxides.