JP2001287308A - Plastic laminate and image display protecting film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic laminate having surface hardness, scratch resistance and abrasion resistance and suitably used as the image display protecting film of an image display apparatus of every kind. SOLUTION: The plastic laminate is constituted by laminating a hard coat layer on at least the single surface of a plastic base material and the surface hardness of the hard coat layer is 2H or more and the surface shaving index thereof is 1.0-15.0. This plastic laminate is used as the image display protecting film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic laminate having excellent surface hardness, abrasion resistance and scratch resistance. More specifically, the present invention relates to a protective film and sheet for a display section, an instrument display section and the like. The present invention relates to a plastic laminate and an image display protection film suitable for a keyboard, a nameplate, a touch panel, and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for imparting abrasion resistance and surface hardness to a plastic substrate sheet, for example, Japanese Unexamined Patent Publication No.
JP-A-162261, JP-A-8-197670 and JP-A-9-300549 propose a method of forming a hard coat layer such as an active ray-curable resin or a thermosetting resin on a plastic base sheet. Have been.

[0003]

However, it has been found that the above-mentioned plastic laminate has the following problems.

That is, in the above-described conventional plastic laminate, the hard coat layer has sufficient surface hardness and abrasion resistance, but the curl is large, so that the hard coat layer is easily cracked. Adhesion with the material is insufficient, and particularly when used for a film, there is a problem that running stability is poor and processing cannot be performed.

As a countermeasure, attempts have been made to add a filler such as silica to the hard coat layer to maintain the surface hardness and abrasion resistance and reduce the curl. However, in this method, the filler precipitates during the processing, for example, the appearance deteriorates. When an antireflection layer or the like is laminated on the hard coat layer, the adhesion to the layer on the hard coat layer is reduced. In addition, the fillers show off on the opposite surface of the base material, resulting in problems such as an increase in the defective rate in processing.

An object of the present invention is to provide a plastic laminate having surface hardness and abrasion resistance, less curl, good adhesion, and a high production yield.

Another object of the present invention is to provide an image display protection film made of such a plastic laminate and an image display device using the plastic laminate.

[0008]

As a result of intensive studies by the present inventors, the object of the present invention has been industrially advantageously achieved by the present invention having the following constitution.

[1] In a plastic laminate having a hard coat layer provided on at least one surface of a plastic substrate, the hard coat layer has a surface hardness of 2H or more and a surface scraping index of 1.0 to 15.0. And the center line average roughness (Ra) of the hard coat layer surface is 0.001 to 0.02 μm.
m, a plastic laminate.

[2] When the hard coat layer has 2
It contains a polyfunctional (meth) acrylate having at least two (meth) acryloyl groups, fine particles, and a resin composed of a high-molecular-weight monomer having an unsaturated double bond copolymerizable at a terminal and / or an acrylic polymer. The plastic laminate according to the above [1], wherein the fine particles are powdered silica or colloidal silica, and the surface of the fine particles is bonded to an organic compound via a silyloxy group.

[3] A high molecular weight monomer having a copolymerizable unsaturated double bond at a terminal is a compound having a (meth) acryloyl group at a terminal and having a number average molecular weight of 1,000 to 10,000.
[1] is a high molecular weight compound of No. 00, and the 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.
Or the plastic laminate of [2].

[4] An acrylic polymer obtained by copolymerizing (meth) acrylic acid and an alkyl (meth) acrylate as essential components.
(Meth) acrylic acid alkyl ester copolymer or styrene / acrylic copolymer obtained by copolymerizing styrene monomer and (meth) acrylic acid / (meth) acrylic acid alkyl ester copolymer as essential components And its weight average molecular weight is 5,000-100,000
And the 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, wherein the plastic laminate according to the above [1] or [2] is used. .

[5] The plastic laminate according to any one of [1] to [4], wherein the plastic substrate is made of a polyester, acetate or acrylate resin.

[6] The plastic laminate according to any one of [1] to [5], wherein an antireflection layer is provided on the hard coat layer.

[7] The plastic laminate according to the above [6], wherein the antireflection layer comprises a multilayer laminate of a metal oxide, and has a light reflectance of 2% or less at 480 to 650 nm. .

[8] An image display protection film comprising the plastic laminate according to any one of [1] to [8].

[9] The plastic laminate according to any one of the above [1] to [8] is adhered to the image display surface and / or the front plate thereof via an adhesive layer or an adhesive layer. Image display device.

[10] In a plastic laminate in which a hard coat layer and an antireflection layer are sequentially laminated on at least one surface of a plastic substrate, the hard coat layer comprises fine particles and two or more particles per molecule. A resin obtained by polymerizing and / or reacting a polyfunctional (meth) acrylate having a (meth) acryloyl group with a high molecular weight monomer having an unsaturated double bond copolymerizable at a terminal and / or an acrylic polymer. A plastic laminate characterized by containing:

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The plastic laminate of the present invention comprises:
It has a basic laminated structure consisting of a plastic substrate and a hard coat layer.

The plastic substrate used in the present invention is not particularly limited, and can be appropriately selected from known plastic substrate sheets. Examples of such a plastic base sheet include polyester, polyethylene, polypropylene, diacetate, triacetate, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetherethylketone, and polyimide. And fluorine-based, nylon-based, and acrylate-based resins. Among these resins, polyester, acetate, and acrylate resins are more preferably used from the viewpoint of optical and strength properties and because it is easy to obtain a resin having excellent uniformity.

In particular, polyethylene terephthalate, triacetyl cellulose or polymethyl methacrylate resin is preferably used because of its excellent transparency and no optical anisotropy.

The plastic substrate is preferably in the form of a sheet, and preferably has a light transmittance at 40 to 800 nm of 40% or more and a haze of 5% or less.
When the light transmittance is less than 40%, or when the haze is more than 5%, when used as a display member, it tends to lack sharpness. 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 may be uncolored or colored.

Before providing a hard coat layer on the plastic substrate used in the present invention, various surface treatments (for example, corona discharge treatment, glow discharge treatment, flame treatment, etching treatment, surface roughening treatment, etc.), adhesion, etc. Surface coating (polyurethane, polyester, polyester acrylate, polyurethane acrylate, polyepoxy acrylate, titanate compounds, etc.) for accelerating may be performed. In particular, a plastic base material coated with a composition comprising a copolymer obtained by grafting an acrylic compound to a hydrophilic group-containing polyester resin and a cross-linking agent improves the adhesiveness and has durability such as wet heat resistance and boiling water resistance. It is preferably used as a plastic substrate sheet having excellent properties.

When these compositions are used as an undercoat layer on a plastic substrate, the thickness of the layer is usually 0.01 to 2 g / m 2.
^2, more preferably 0.1 to 1 g / m ^2, it is difficult to thickness of the undercoat layer is uniformly coated with thinner than 0.01 g / m ^2, when it exceeds 2 g / m ^2, laminated onto this It is difficult to obtain a laminate having excellent surface hardness and abrasion resistance of the hard coat layer, which is not preferable.

The thickness of the plastic substrate used in the present invention is usually from 5 to 500 in view of mechanical strength and thermal conductivity.
0 μm, preferably 10 to 3000 μm. Also, 2
More than one plastic sheet can be bonded together by a known method to form a thicker plastic substrate.

The components constituting the hard coat layer in the present invention include thermosetting resins such as acryl, epoxy, polyester, polyurethane and polysiloxane, monomers such as polyfunctional acryl, urethane, polyester and epoxy, prepolymers and the like. An actinic radiation-curable resin obtained by crosslinking a polymer with an electron beam, ultraviolet light, radiation or the like can be used.

In particular, an actinic ray-curable resin obtained by crosslinking with an electron beam, ultraviolet rays or radiation is preferably used.
Two or more (meth) acryloyl groups in one molecule (however,
In the present invention, a “(meth) acryloyl group” is an abbreviation of an acryloyl group and a methacryloyl group), and a polyfunctional (meth) acrylate compound having the same can be used. Among them, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule, fine particles, a high molecular weight monomer having a copolymerizable unsaturated double bond at a terminal and / or an acrylic monomer A hard coat layer comprising a resin containing a polymer, wherein the fine particles are powdered silica or colloidal silica, and the surface of the fine particles is treated and bonded via an organic compound and a silyloxy group, has a surface hardness and resistance. It is more preferably used because it is excellent in abrasion, has small curl, and hardly causes cracks.

Examples of the polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule include polyhydric alcohols having two or more alcoholic hydroxyl groups in one molecule. Compounds that are esterified products 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) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, etc. b) (Meth) acrylate diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene (C) (meth) acrylic acid diesters of polyhydric alcohols such as glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate: pentaerythritol di (meth) Acrylate such as, (d) hydride of bisphenol A or bisphenol A ethylene oxide or propylene oxide adduct (meth)
Acrylic acid diesters: (e) a diisocyanate compound and two or more alcohols, such as 2,2'-bis (4-acryloxyethoxyphenyl) propane and 2,2'-bis (4-acryloxypropoxyphenyl) propane Urethane (meth) having two or more (meth) acryloyloxy groups in the molecule obtained by reacting an isocyanate group-containing compound obtained by previously reacting a hydroxyl group-containing compound with an alcoholic hydroxyl group-containing (meth) acrylate A) acrylates and (f) epoxy compounds having two or more (meth) acryloyloxy groups in the molecule obtained by reacting acrylic acid or methacrylic acid with a compound having two or more epoxy groups in the molecule; And acrylates.

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

As the polyfunctional (meth) acrylate compound having three or more (meth) acryloyl groups in one molecule, the polyhydric alcohol having three or more alcoholic hydroxyl groups in one molecule has three hydroxyl groups. Examples of the above compounds which are esterified (meth) acrylic acids are mentioned.

Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and 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 desirably 50 to 95% by weight based on the total solid content of the resin. If the proportion of the monomer is less than 50% by weight, it is difficult to obtain a cured film having sufficient abrasion resistance. The amount is 95
If the amount is more than 10% by weight, there is a problem that shrinkage due to polymerization is large, distortion remains in the cured film, flexibility of the film is reduced, and curling is greatly caused on the cured film side.

Further, in the present invention, 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-, sec-, 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, in order to improve the adhesion to the plastic substrate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
N-vinylpyrrolidone and the like are preferred. These monomers may be used alone or in combination of two or more.

In the hard coat layer of the present invention, a high molecular weight monomer having a copolymerizable unsaturated double bond at the terminal can be used. For example, a high molecular compound having a (meth) acryloyl group at the terminal and having a number average molecular weight of preferably 1,000 to 10,000, more preferably about 2,000 to 6,000 is preferable. The polymer portion is mainly composed of, for example, a methyl methacrylate polymer, a styrene polymer, a styrene / acrylonitrile polymer, a butyl acrylate polymer, and a silicone polymer. Examples of such a polymer compound having a (meth) acryloyl group at a terminal include macromonomers (AS-6, AN-6, AB-6, and AK-3).
2 etc .: manufactured by Toagosei Co., Ltd.). It is desirable that the usage ratio of these high molecular weight monomers is 5 to 50% by weight based on the total amount of resin solids. More preferably, it is 5 to 30% by weight.

The acrylic polymer used in the present invention is, for example, a copolymer of (meth) acrylic acid / alkyl (meth) acrylate obtained by copolymerizing (meth) acrylic acid and its alkyl ester as essential components. And a styrene / acrylic copolymer obtained by copolymerizing a styrene monomer and (meth) acrylic acid and / or an alkyl ester thereof as an essential component. The weight average molecular weight is 5,000 or more and 100 or more. , 00
It is preferably 0 or less. The use ratio of these acrylic polymers is preferably 5 to 5% based on the total amount of resin solids.
50% by weight.

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 desirable to mix them so as to be 0% by weight.

Examples of the fine particles used in the present invention include a silicon compound, a metal compound, a polymer compound, and a mixture thereof. Examples of the silicon compound include wet silica, dry silica, and colloidal silica as silica particles. Examples of the metal compound include alumina, titania, and zirconia. Examples of the polymer compound include polymethyl (meth) acrylate resin. In addition, conductive fine particles such as tin oxide, indium oxide, cadmium oxide, and antimony oxide can also be used.

Among these fine particles, silica particles are preferably used in terms of transparency and hard coat property.
The specific surface area of the silica particles is preferably 0.1 to 3000.
In m ² / g, more preferably 10~1500m ² / g.

These silica particles can be used in the form of powder in a dry state, or dispersed in water or an organic solvent. In particular, colloidal silica is preferred in order to require transparency. Colloidal silica is obtained by dispersing fine silica particles in water or an organic solvent as a colloidal dispersion, for example, Snowtex 20, methanol silica sol, IPA-ST, DMAC-ST, XBA-ST.
(All manufactured by Nissan Chemical Industries, Ltd.). Examples of the powdery silica include Aerosil 130 and Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.).

Further, in terms of stability, dispersibility, transparency, abrasion resistance, scratch resistance, adhesion and the like of the silica particles in the hard coat layer, the silica particles are powdered silica or colloidal silica. More preferably, the reactive silica particles are bonded to an organic compound via a silyloxy group. Reactive silica particles are prepared by mixing an organic compound containing a polymerizable unsaturated group, a hydrolyzable silyl group, an isocyanate group and a thioisocyanate group in a molecule with silica particles selected from powdered silica or colloidal silica, It is obtained by causing a decomposition reaction and chemically bonding the organic compound and silica particles.

The polymerizable unsaturated group is a component that chemically crosslinks between molecules via addition polymerization by an active radical species. Examples of the polymerizable unsaturated group include an acryloxy group, a methacryloxy group, a vinyl group, a propenyl group, a butadienyl group and a styryl group.

The hydrolyzable silyl group is a component that binds to a silanol group present on the surface of the silica particles by a hydrolysis and condensation reaction. Examples of the hydrolyzable silyl group include an alkoxysilyl group, an acetoxysilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.

The average particle diameter of the fine particles in the present invention is preferably from 0.001 to 20 μm. The preferred particle size for forming a transparent cured composition is 0.001-2 μm
m, more preferably 0.001 to 0.1 μm.
Examples of the shape include a spherical shape, a porous shape, a hollow shape, a plate shape, and an irregular shape. In the present invention, spherical and hollow fine particles are preferably used from the viewpoint of transparency.

The addition amount of the fine particles is 5 to 50% in the solid content of the resin.
% By weight is preferred. If the addition amount is less than 5% by weight, it is difficult to obtain a sufficient hardness, and if it exceeds 50% by weight, there are problems such as missing particles and reduced transparency of the coating film.

In the present invention, as a method of polymerizing and / or reacting the compound composition of the hard coat layer, there is a method of irradiating ultraviolet rays. 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 0.01 to 10 in the solid content of the resin.
Parts by weight are appropriate.

As another method, electron beam or radiation can be used as polymerization and / or reaction means. When electron beams or gamma rays are used, it is not always necessary to add a polymerization initiator.

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

The compound composition used in the present invention may contain an organic solvent 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. it can.

As the organic solvent, an organic solvent having a boiling point of 50 to 150 ° C. is easily used from the viewpoint of workability during coating and drying before and after curing. Specific examples include 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; and aromatic solvents such as toluene. And cyclic ether solvents such as dioxane.
These solvents may 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. Such additives include, for example, antioxidants, leveling agents, and antistatic agents.

For polymerization and / or reaction of the compound composition used in the present invention, ultraviolet rays, electron beams, radiation (α
Rays, β rays, γ rays, etc.), but the use of ultraviolet rays is 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. In addition, the electron beam or radiation method is advantageous in that the apparatus is expensive and needs to be operated under an inert gas, but it is not necessary to include a photopolymerization initiator or a photosensitizer in the coating layer. is there.

Further, a coloring agent such as a pigment or a dye may be blended with the composition constituting the hard coat layer. When a colorant is contained, the plastic laminate has a light transmittance at a wavelength of 550 nm of 40 to 80.
% Is desirable.

The thickness of the hard coat layer is appropriately selected depending on the application, but is usually 3 μm to 50 μm, more preferably 5 μm to 30 μm. When the thickness of the hard coat layer is less than 3 μm, the surface hardness is insufficient and the surface is easily damaged. On the other hand, if it exceeds 50 μm, the cured film becomes brittle, and the cured film tends to crack when the plastic substrate provided with the hard coat layer is bent.

The pencil hardness of the hard coat layer in the present invention needs to be 2H or more, and is usually about 3 to 4H. If the pencil hardness is less than 2H, sufficient hardness cannot be obtained, which is not preferable.

The hard coat layer in the present invention needs to have a surface abrasion index in the range of 1.0 to 15.0. The value of the scraping index is a parameter indicating the precipitation of the filler contained in the hard coat layer. If the abrasion index is larger than the above range, the abraded white powder adheres to the film surface and is transferred to, for example, an antireflection layer further laminated on a hard coat layer, which causes a decrease in adhesion. The smaller this value is, the better the improvement in adhesion is.
However, in order to reduce the abrasion index, it is necessary to reduce or eliminate the filler addition amount, in this case,
Undesirably, the curl of the hard coat layer becomes large and cracks are easily generated.

Next, the surface average roughness (Ra) of the hard coat layer in the present invention needs to be in the range of 0.001 to 0.02 μm, preferably 0.001 to 0.01 μm. When Ra is larger than this range, the film surface looks distorted, and when an antireflection layer is laminated thereon, the adhesion is undesirably reduced. Also, R
On the other hand, if a is small, the film surface slips unfavorably.

In the present invention, an antireflection layer made of a metal oxide can be further formed on the hard coat layer formed on the sheet-like plastic substrate. For the antireflection layer, a laminate of a high-refractive index compound and a low-refractive index compound, or an inorganic substance such as magnesium fluoride or silicon oxide can be used. In particular, there are various types of configurations of the antireflection film. At least a dielectric layer and a multilayer structure including a conductor layer as described below are formed using a vacuum thin film forming technique such as evaporation or sputtering. You can also.

TiO ₂ , Zr
O ₂ , ITO, SnO ₂ , Y ₂ O _3, ZnO and the like can be mentioned. Examples of the low refractive index film material include SiO ₂ and MgF ₂
And the like. In addition, ITO, SnO ₂ and Zn
O and the like can have both a role as a conductive film and a role as a high refractive index film.

In the present invention, TiNx, Au, Ag, Ni
It is also possible to insert a light absorbing film such as Ox as a component, and various film configurations are conceivable.

In the plastic laminate of the present invention,
Wide range of visible light, specifically at least wavelength 480
It is preferable that the reflectance be 0 to 2% in the range of nm to 650 nm because the reflection of external light is reduced and the visibility is improved. In particular, a reflectance of 1% or less is particularly preferable to minimize fatigue of human eyes and mind. As a result, reflected light of light entering the component can be reduced by affixing the plastic laminate to characters such as a display and the surface of a display member component.

As 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 can be further provided on the antireflection layer. The purpose of providing the water-repellent layer is to protect the anti-reflection layer and enhance the anti-contamination performance, as long as it meets the required performance. As the material of the water-repellent layer, a compound having a hydrophobic group is preferable, and examples thereof include perfluorosilane and fluorocarbon. As a method for forming the water-repellent layer, a physical vapor deposition method such as vapor deposition and sputtering and a chemical vapor deposition method such as CVD can be used depending on the material.

In the plastic laminate of the present invention, an adhesive layer can be provided on the surface of the plastic substrate opposite to the surface having the hard coat layer. The adhesive layer is not particularly limited as long as the two objects are adhered by their adhesive action. As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, rubber-based, vinyl-polymer-based, condensation-polymerized, thermosetting resin-based, and silicone-based pressure-sensitive adhesives can be used. Among them, as a rubber-based adhesive, a butadiene-styrene copolymer system (S
BR), butadiene-acrylonitrile copolymer system (N
BR), chloroprene polymer system, isobutylene-isoprene copolymer system (butyl rubber) and the like. Acrylic resin,
Examples include styrene resin, vinyl acetate-ethylene copolymer, and vinyl chloride-vinyl acetate copolymer. Examples of the condensation polymerization-based pressure-sensitive adhesive include polyester resin-based pressure-sensitive adhesives. Examples of the thermosetting resin-based adhesive include an epoxy resin-based, urethane resin-based, and formalin resin-based adhesive. These resins may be used alone or in combination of two or more.

Further, as the pressure-sensitive adhesive, either a solvent-type pressure-sensitive adhesive or a non-solvent-type pressure-sensitive adhesive can be used. The formation of the pressure-sensitive adhesive layer is carried out by using a pressure-sensitive adhesive as described above and by using a commonly used technique such as coating. Further, a colorant may be contained in the adhesive layer. This can be easily achieved by mixing the adhesive with a coloring agent such as a pigment or a dye. When a colorant is contained, the plastic laminate has a light transmittance at 550 nm of 40 to 8;
It is desirable to be within the range of 0%.

Next, the method for producing the plastic laminate of the present invention will be described, but the present invention is not limited thereto.

The plastic laminate of the present invention is produced by applying, polymerizing, and / or reacting a hard coat layer on a plastic substrate.

As a means for applying the hard coat layer, a usual application method such as brush coating, dip coating, knife coating, spray coating, flow coating and spin coating (eg, spinner) can be used. 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. Examples of the method of polymerizing and / or reacting the compound composition for forming the hard coat layer 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 plastic laminate of the present invention has a high surface hardness and abrasion resistance, so that it can be used for a wide range of applications. For example, the plastic laminate of the present invention can be used in fields such as filters for cathode ray tubes (CRT), membrane switches, displays, nameplates and instrument covers. In particular, a film in which an antireflection layer is laminated on a hard coat layer can be preferably used as an image display protection film.

In particular, examples of the image display member include a liquid crystal display (LCD), a cathode ray tube (CRT) such as a television computer, a plasma display (PDP), and glass. An image display device can be obtained by mounting.

Means for bringing the plastic laminate produced as described above into close contact with the image display surface and / or the surface of the front plate thereof is not particularly limited. For example, an adhesive layer is applied to a display member or a plastic substrate and dried. By laminating with a pressure roller or the like so that the hard coat layer and the anti-reflection layer of the laminate become a surface layer, by bonding the display member and the plastic base material through the adhesive layer,
An image display device equipped with an image display protection film made of a plastic laminate can be obtained.

By laminating the hard coat layer on one surface of the plastic substrate as described above, a plastic laminate and an image display protection film that are hardly scratched on the surface can be obtained.

The method for measuring characteristics and the method for evaluating effects in the present invention are as follows.

(1) Shaving index Two films of 50 × 50 mm square were layered through hard coat through, sandwiched between cylinders of 10 mm × 50 mm in upper and lower thickness, fixed by applying a load of 200 g from the upper side, and the lower film was fixed. The test was performed 30 times at a speed of 50 revolutions per minute. Shaved powder appears as white spots on the surfaces of the two rotated films. The surface of this film was determined using a reflection differential interference microscope (manufactured by Nippon Kogaku Co., Ltd.), and the area of the shaved powder was determined using a micrometer including an eyepiece.

When the entire surface was shaved, the state of the shaved material was enlarged by a stereoscopic microscope, and a photograph was taken with an instant camera to make it easy to determine the amount. The total area of the shaved material seen on the photograph was counted and expressed in cm ² . The upper film was A, the lower film was B, and the sum of A + B was defined as the scraping index.

(2) Center line average roughness Using a universal surface profile measuring device (manufactured by Kosaka Laboratory), JI
It measured according to SB-0601.

(3) Abrasion Resistance Using a steel wool # 0000, the surface of a reciprocating film was rubbed with a load of 200 g for 20 reciprocations, and the degree of scratching was evaluated according to the following criteria. ：: Hardly scratched even if strongly rubbed. Δ: Slightly scratched when considerably rubbed. X: Damage occurs even with weak friction.

(4) Pencil hardness JIS K using HEIDON (manufactured by Shinto Kagaku Co., Ltd.)
It measured according to -5400.

(5) Scratch resistance The film surface was rubbed with a touch pen at a load of 1 kg, and the degree of scratches was evaluated according to the following criteria. ：: no damage. Δ: Slightly scratched. X: The scratch is clearly visible.

(6) Adhesion The film in which the antireflection layer was laminated on the hard coat layer was rubbed 20 times under a load of 1 kg with absorbent cotton impregnated with ethyl alcohol, and the surface condition was observed. ：: No change Δ: Partial surface layer peeling was observed. ×: Peeling is observed on the entire surface.

(7) Curl The film cut into a size of 10 × 10 cm was placed on a flat surface with the hard coat layer thereon, and the state of lifting at both ends was observed, and the height from the plane was measured.

(8) Crack Generation Curvature A film cut into a size of 10 × 2 cm was wound around a curved column with the hard coat layer facing upward, and the state of occurrence of surface cracks was observed.

(9) Durability With respect to a film in which an antireflection layer is laminated on a hard coat layer, a film cut into a size of 20 × 5 cm is wound around a 50φ cylinder with the antireflection layer facing up. ,
After leaving for 24 hours in a thermo-hygrostat at 40 ° C. and 90% RH,
The adhesion was evaluated. ：: No change. Δ: Partial peeling was observed. ×: Peeling is observed on the entire surface.

(10) Reflectance The reflectance at 550 nm was measured using a spectrophotometer (Hitachi, Ltd.).

[0085]

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

Reference Example 1 To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate, 223 parts of 1,3-bis (isocyanatomethyl) cyclohexane was added dropwise at 50 ° C. for 1 hour while stirring. Thereafter, the mixture was heated and stirred at 70 ° C. for 3 hours. To this, 555 parts of pentaerythritol triacrylate was added at 30 ° C. for 1 hour.
After dropwise addition over a period of time, the mixture was heated and stirred at 60 ° C. for 10 hours to obtain a silane compound.

The silane compound (30 parts) was added under a nitrogen stream.
MEK-ST (manufactured by Nissan Chemical Industries, Ltd., methyl ethyl ketone dispersed colloidal silica (average particle diameter 0.01 to 0.01)
5 μm), a mixture of 233 parts of silica concentration 30%), 5 parts of isopropyl alcohol, and 3 parts of ion-exchanged water at 80 ° C.
After stirring for 3 hours, 18 parts of orthoformic acid methyl ester was added, and the mixture was further heated and stirred at 80 ° C. for 1 hour to obtain a translucent silica dispersion.

Example 1 75 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) and macromonomer AN- were coated on one surface of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror) having a thickness of 188 μm. 6S (manufactured by Toagosei Co., Ltd., solid content 50% by weight, number average molecular weight 6,000) 10 parts by weight, silica dispersion manufactured in Reference Example 1 (solid content 37% by weight, silica content is solid) 70 parts by weight), 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. Was applied using a bar coater so that the film thickness after curing became 10 μm, to prepare a film provided with a coating layer. The film layer of the obtained film was left in a hot air drier for 30 seconds to evaporate the solvent, and then 3 m under a high-pressure mercury lamp having an intensity of 80 W / cm set on the surface of the film from a height of 12 cm. / Min. The coating was completely cured. Table 1 shows the performance evaluation test results of the obtained coating films.

Example 2 One side of a polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries, Inc.) having a thickness of 188 μm was coated with 75 parts by weight of dipentaerythritol hexaacrylate and a macromonomer AA-6 (manufactured by Toagosei Co., Ltd.). , Solid content 40% by weight, number average molecular weight 6,000
0) 12.5 parts by weight, 54 parts by weight of the silica dispersion prepared in Reference Example 1, 5 parts by weight of photoinitiator 1-hydroxyphenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.), and 50 parts by weight of toluene Then, a composition obtained by stirring and mixing 50 parts by weight of methyl ethyl ketone was applied using a bar coater so that the cured film thickness became 10 μm, to prepare a film having a coating film layer. The film layer of the obtained film was left in a hot air drier for 30 seconds to evaporate the solvent, and then 3 m under a high-pressure mercury lamp having an intensity of 80 W / cm set on the surface of the film from a height of 12 cm. / Min.
The coating was completely cured. Table 1 shows the performance evaluation test results of the obtained coating films. Example 3 On one side of a polyethylene terephthalate film ("Lumirror" manufactured by Toray Industries, Inc.) having a thickness of 188 μm, 66 parts by weight of dipentaerythritol hexaacrylate, a macromonomer AN-6S (manufactured by Toagosei Co., Ltd., solid content) 50% by weight, number average molecular weight 6,000) 10
Parts by weight, styrene-acrylic copolymer (solid content 60%,
A composition obtained by stirring and mixing 15 parts by weight of the weight average molecular weight 17,790), 54 parts by weight of the silica dispersion prepared in Reference Example 1, 5 parts by weight of 1-hydroxyphenyl ketone, 50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone was used. Was applied so that the film thickness after curing became 10 μm to prepare a film provided with a coating layer. The film layer of the obtained film was left in a hot air drier for 30 seconds to evaporate the solvent, and then set on the surface of the film from a height of 12 cm.
It passed under a high-pressure mercury lamp having an intensity of 0 W / cm at a speed of 3 m / min. The coating was completely cured. Table 1 shows the performance evaluation test results of the obtained coating films.

Example 4 One side of a polyethylene terephthalate film having a thickness of 188 μm (“Lumirror” manufactured by Toray Industries, Inc.) was coated with 68 parts by weight of dipentaerythritol hexaacrylate, a styrene-acrylic copolymer (solid content 60%, weight Average molecular weight 17,790) 20 parts by weight,
The composition obtained by stirring and mixing 54 parts by weight of the silica dispersion prepared in Reference Example 1, 5 parts by weight of 1-hydroxyphenyl ketone, 50 parts by weight of toluene, and 50 parts by weight of methyl ethyl ketone was cured to a thickness of 10 μm using a bar coater. And a film having a coating layer was prepared. The film layer of the obtained film was left in a hot air drier for 30 seconds to evaporate the solvent, and then 3 m under a high-pressure mercury lamp having an intensity of 80 W / cm set on the surface of the film from a height of 12 cm. / Min. The coating was completely cured. Table 1 shows the performance evaluation test results of the obtained coating films.

Example 5 An antireflection film was formed on the hard coat layer obtained in Example 1 by using a vacuum deposition apparatus so as to be an antireflection film having the following structure.

[0092] Next, on the antireflection layer thus formed, perfluorotrimethoxysilane was formed to a thickness of 2 nm by a CVD method to obtain a film. Table 1 shows the performance evaluation test results of the obtained coating films.

Example 6 A hard coat layer was formed on a triacetate film (“Fujitac” manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm in the same manner as in Example 1; A film having a water-repellent layer was prepared. Table 1 shows the results of the performance evaluation test of the obtained coating film.

Comparative Example 1 100 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) and 1-hydroxyphenyl ketone photoinitiator (Ciba Specialty Chemicals Co., Ltd.) Company)
5 parts by weight, toluene 50 parts by weight, methyl ethyl ketone 5
Example 1 was repeated except that a composition obtained by stirring and mixing 0 parts by weight was used.
A hard coat layer was formed in the same manner as described above. Table 1 shows the performance evaluation test results of the obtained coating films.

Comparative Example 2 The hard coat layer was composed of 90 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) and macromonomer AN-6S (solid content: 5%).
0 weight%, number average molecular weight 6,000) 20 weight parts, photoinitiator 1-hydroxyphenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 weight parts, toluene 50
A hard coat layer was formed in the same manner as in Example 1 except that a composition obtained by stirring and mixing 50 parts by weight of methyl ethyl ketone and 50 parts by weight of methyl ethyl ketone was used. Table 1 shows the performance evaluation test results of the obtained coating films.

Comparative Example 3 The hard coat layer was composed of 85 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) and macromonomer AN-6S (solid content: 5%).
0% by weight, 20 parts by weight of number average molecular weight 6,000, 5 parts by weight of silica powder (manufactured by Fuji Silysia Chemical Ltd .: Sylysia 310 (average particle size: 1.4 μm)), photoinitiator 1-hydroxyphenyl ketone (Ciba Specialty) Chemical Co., Ltd.) A hard coat layer was formed in the same manner as in Example 1, except that a composition obtained by stirring and mixing 5 parts by weight, 50 parts by weight of toluene, and 50 parts by weight of methyl ethyl ketone was used. Table 1 shows the performance evaluation test results of the obtained coating films.

[Comparative Example 4] A film having an antireflection layer and a water-repellent layer was formed on the hard coat film obtained in Comparative Example 3 in the same manner as in Example 5. Table 1 shows the results of the performance evaluation test of the obtained coating film.

Example 7 In order to bond the plastic laminate obtained in Example 5 to glass, AGR-100 (manufactured by Nippon Kayaku Co., Ltd.) was used as an adhesive on the surface not provided with an antireflection layer. ), And after bonding with glass,
Curing was performed with an ultraviolet irradiation amount of 1,000 mj / cm ² .
Table 1 shows the test results.

[0099]

[Table 1] Examples 1 to 6 were good in all evaluation items.

In Comparative Example 1, since the scraping index and the center line average roughness were lower than those in the range of the present invention, the curl was large and the curvature of occurrence of cracks was large.

In Comparative Example 2, since the center line average roughness was lower than the range of the present invention, the scratch resistance was low and insufficient.

In Comparative Example 3, the wear resistance and the scratch resistance were insufficient because the abrasion index exceeded the range of the present invention.

In Comparative Example 4, the adhesion to the antireflection layer and the durability were insufficient.

Example 7 was good in all evaluation items as a display member when bonded to glass.

[Examples 8 to 10] Instead of the glass of Example 7, a 17-inch television cathode ray tube (CRT), a liquid crystal display (LCD) and a plasma display (PDP) are used.
The plastic laminate obtained in Example 1 was mounted on the front surface of the display screen in the same manner as in Example 6 to obtain an image display device. Both the abrasion resistance and the scratch resistance were free from scratches, and the reflectance was 0.6%.

[0106]

The excellent effects of the present invention are caused by optimizing the range of the surface abrasion index and the surface average roughness (Ra) of the hard coat layer. That is, according to the present invention, the pencil hardness of the hard coat layer, the scratch resistance and the abrasion resistance are good, the curl is small, and even when a film such as an anti-reflection layer is laminated on the hard coat layer, A plastic laminate having a remarkable effect of good properties and durability can be obtained. The plastic laminate is suitably used as an image display protection film for various image display devices.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 9/04 C08K 9/04 C08L 101/02 C08L 101/02 C09C 1/28 C09C 1/28 3/08 3/08 C09D 4/02 C09D 4/02 4/06 4/06 7/12 7/12 C09J 7/02 C09J 7/02 Z G02B 1/10 C09D 183/07 1/11 G02B 1/10 Z // C09D 183/07 A

Claims (10)

[Claims] 1. A plastic laminate having a hard coat layer provided on at least one surface of a plastic substrate, wherein the hard coat layer has a surface hardness of 2H or more, a surface abrasion index of 1.0 to 15.0, And the center line average roughness (Ra) of the hard coat layer surface is 0.001 to 0.02 μm
A plastic laminate, characterized in that: 2. A hard coat layer comprising a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in one molecule, fine particles, and a high molecular weight terminal having a copolymerizable unsaturated double bond at a terminal. A resin comprising a molecular weight monomer and / or an acrylic polymer, wherein the fine particles are powdered silica or colloidal silica, and the surface of the fine particles is treated and bonded to an organic compound via a silyloxy group. The plastic laminate according to claim 1, wherein 3. The high molecular weight monomer having a copolymerizable unsaturated double bond at a terminal is a high molecular weight compound having a (meth) acryloyl group at a terminal and having a number average molecular weight of 1,000 to 10,000, And the content after polymerization and / or reaction is 5% of the solid content of the resin composition of the hard coat layer.
3 to 50% by weight.
The plastic laminate according to the above. 4. A (meth) acrylic acid / alkyl (meth) acrylate copolymer obtained by copolymerizing an acrylic polymer with (meth) acrylic acid and alkyl (meth) acrylate as essential components. A styrene / acrylic copolymer obtained by copolymerizing a styrene monomer and a (meth) acrylic acid / alkyl (meth) acrylate copolymer as essential components,
Its weight average molecular weight is 5,000-100,000,
The plastic laminate according to claim 1 or 2, wherein the 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. 5. The plastic laminate according to claim 1, wherein the plastic substrate is made of a polyester, acetate or acrylate resin. 6. The plastic laminate according to claim 1, wherein an antireflection layer is provided on the hard coat layer. 7. The anti-reflection layer is composed of a metal oxide multilayer laminate, and has a light reflectance of 2% at 480 to 650 nm.
The plastic laminate according to claim 6, wherein: 8. An image display protection film comprising the plastic laminate according to claim 1. 9. An image display obtained by sticking the plastic laminate according to claim 1 on an image display surface and / or a surface of a front plate thereof via an adhesive layer or an adhesive layer. apparatus. 10. In a plastic laminate in which a hard coat layer and an antireflection layer are sequentially laminated on at least one surface of a plastic substrate, the hard coat layer is composed of fine particles and two or more ( Contains a resin obtained by polymerizing and / or reacting a polyfunctional (meth) acrylate having a (meth) acryloyl group with a high molecular weight monomer having an unsaturated double bond copolymerizable at a terminal and / or an acrylic polymer. A plastic laminate characterized by: