JP2006178276A - Antireflection layered film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive antireflection layered film showing particularly high antistatic property and antireflection property and having high transparency, surface hardness, scratch resistance, stain resistance and chemical resistance. <P>SOLUTION: The antireflection layered film comprises a hard coat layer and an antistatic low refractive index layer, layered in this order on a transparent support, wherein the antistatic low refractive index layer comprises an actinic ray-curing resin containing a compound having at least a (meth)acryloyloxy group in the molecule and porous conductive fine particles having ≤100 nm particle size and ≤1.40 refractive index n. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is excellent in productivity, optical properties, antistatic properties, surface hardness and scratch resistance, and is provided on a display (liquid crystal display, CRT display, projection display, plasma display, EL display, etc.) provided on a transparent substrate. The present invention relates to an antireflection laminated film applied to the screen surface.

  Many displays are used in an environment where external light or the like enters regardless of whether indoors or outdoors. Incident light such as external light is specularly reflected on the display surface or the like, and the reflected image is mixed with display light to lower the display quality and make the display image difficult to see. For this reason, in order to provide an antireflection function, a multilayer film in which transparent thin films of metal oxide are laminated has been conventionally used. The transparent thin film of metal oxide is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, and in particular, is formed by a vacuum vapor deposition method which is a physical vapor deposition method. The antireflection film thus formed exhibits excellent optical characteristics, but the formation method by vapor deposition has a problem that productivity is low and it is not suitable for mass production.

  Furthermore, since the surface of a polymer material such as a plastic or a film is relatively flexible, a method of polymerizing an acrylic polyfunctional compound on the surface of the article and providing a hard coat layer is used to obtain surface hardness. . The hard coat layer thus obtained has high surface hardness, glossiness, transparency, and scratch resistance, which are properties unique to acrylic resins. On the other hand, it is easy to be charged because of its excellent insulating properties, and it can cause troubles due to contamination due to dust adhering to the surface of the product provided with a hard coat layer, or charging when used in precision machinery. I had a problem to do.

  In order to solve these problems, a conductive layer is very thin enough not to drop the surface hardness between the base material and the hard coat layer or between the hard coat layer and the low refractive index layer. There is a method of providing Moreover, the coating method is used as the formation method, and the improvement of productivity is attempted.

  Examples of the conductive agent used include metal oxide fine particles, conductive polymers, various activators, hydrophilic compounds, and ionic conductive compounds. Among them, the method using various active agents, hydrophilic compounds, and ion conductive compounds (see, for example, Patent Document 1) is highly dependent on humidity because ion conduction is performed using moisture in the outside air as a medium, and the upper layer. However, when a new layer such as an antireflection layer is formed, the performance is not stable.

On the other hand, in the technique using electron conductive fine particles that are not affected by the humidity environment, a hard coat kneading method and a method of providing a conductive layer between layers are used. In the kneading method (see, for example, Patent Document 2), the refractive index of fine particles is usually high, and the amount of fine particles is determined because of electronic conductivity, thereby reducing light interference with the substrate. It becomes difficult to achieve both conductivity. If the blending amount is too small, conductivity will not be exhibited, and if it is too large, there will be a problem that the light transmittance will decrease, and if the film thickness is reduced to increase the transmittance, the function of protecting the substrate will decrease. There is a problem. In addition, since the antireflection layer is formed on the hard coat layer, there is a problem that the antistatic performance is lowered. Conductive polymers have similar problems. In the method of providing a conductive layer between the base material and the hard coat layer (for example, see Patent Document 3), it is necessary to perform a special treatment on the upper layer in consideration of conductivity by laminating it on the upper layer of the conductive layer. In addition, the multi-layer structure causes a problem that the number of processes increases and the productivity decreases. Similarly, a method in which a conductive layer is provided between a hard coat layer and an antireflection layer (see, for example, Patent Document 4) has a problem that the number of processes increases and productivity decreases due to the multilayer structure.

Patent literature is described below.
JP 2002-40209 A JP-A-11-92750 JP-A-11-326602 JP 2001-330702 A

  The present invention has been made to solve the above-described problems, and exhibits particularly high antistatic properties and antireflection properties, and has high transparency, surface hardness, scratch resistance, antifouling properties, and chemical resistance. It is an object of the present invention to provide an antireflection laminated film that is excellent in performance at low cost.

The above problem can be solved by the following means. That is,
The invention according to claim 1 is an antireflection laminated film in which a hard coat layer and an antistatic low refractive index layer are laminated in this order on a transparent support.
The antistatic low refractive index layer includes an active energy ray-curable resin containing at least a compound having a (meth) acryloyloxy group in the molecule, and a porous conductive material having a particle size of 100 nm or less and a refractive index n of 1.40 or less. It is an antireflection laminated film characterized by comprising conductive fine particles.

  In the invention according to claim 2, the antistatic low refractive index layer is represented by the general formula (A) nd = λ / 4 (where n is the refractive index of the layer, d is the layer thickness, and λ is the wavelength of light). And an integer satisfying 450 ≦ λ ≦ 650).

  The invention according to claim 3 is the antireflection laminated film characterized in that the hard coat layer is made of a polymer containing a polyfunctional monomer having a (meth) acryloyloxy group as a main component.

The invention according to claim 4 is the hard coat layer according to claim 3, further comprising the general formula (B) R ′ _y Si (OR) _4-y (wherein R represents an alkyl group, R ′ represents The terminal represents an unreactive functional group such as an alkyl group or a fluorinated alkyl group, or a reactive functional group such as a vinyl group, an epoxy group, an aryl group or a (meth) acryloyl group, and y is an integer satisfying 1 ≦ y ≦ 3 The anti-reflection laminated film is characterized by comprising an organosilicon alkoxide represented by the formula (1) and a hydrolyzate thereof.

  The invention according to claim 5 is the antireflection laminated film, wherein the hard coat layer according to claim 4 further contains a filler having an average particle diameter of 0.5 μm or more and 10 μm or less.

  According to the present invention, it is possible to provide an antireflection laminated film having excellent hard coat properties, antifouling properties, antireflection properties, transparency, chemical resistance and antistatic properties, and at a low cost.

  Hereinafter, embodiments of the present invention will be described in detail. As the plastic film serving as the transparent support, films or sheets made of various organic polymers can be used. The base material usually used for optical members such as displays is a polyolefin-based (polyethylene) considering optical properties such as transparency and refractive index of light, as well as various physical properties such as impact resistance, heat resistance and durability. , Polypropylene, etc.), polyester-based (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), cellulose-based (triacetylcellulose, diacetylcellulose, cellophane, etc.), polamide-based (nylon-6, nylon-66, etc.), acrylic Organic polymers such as (polymethyl methacrylate, etc.), polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, ethylene vinyl alcohol are used. In particular, polyethylene terephthalate, triacetyl cellulose, polycarbonate, and polymethyl methacrylate are preferable. Furthermore, known additives such as ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants, etc. are added to these organic polymers to add functions. it can. In addition, the base material may be a single substance or a laminate or mixture of a plurality of substances. Moreover, the thickness of a base material can be suitably selected according to the use which uses a surface protection film, and 25-300 micrometers is preferable. However, the present invention is not limited to this. In addition, surface treatment can be performed for the purpose of improving the adhesion to the surface protective layer provided on the substrate. As this surface treatment method, for example, surface roughening treatment such as sandblasting or solvent treatment, or surface oxidation treatment such as corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, etc. Can be mentioned.

  The hard coat layer of the present invention is laminated on the plastic film, and the hard coat layer is an ultraviolet ray and an electron beam curable resin alone, or an organic silicon alkoxide and a hydrolyzate thereof in the cured product, It contains a filler.

  Ultraviolet and electron beam curable resin compounds used in hard coat layers for the purpose of surface modification of base materials, scratch resistance by steel wool rubbing test, surface hardness by pencil scratch test, adhesion by cello tape (registered trademark) peel test The resin can be selected and used so as to satisfy the specifications required for various properties such as the properties and cracking properties by the minimum bending test. This compound contains a photopolymerizable prepolymer, a photopolymerizable monomer, a photopolymerization initiator, and the like.

  Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These photopolymerizable prepolymers may be used alone or in combination of two or more.

Examples of the photopolymerizable monomer include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. Moreover, although these refractive indexes are around 1.5, monomers having a high refractive index include those having a cyclic group and / or those containing halogen atoms other than fluorine atoms and atoms such as S, N and P. Can be mentioned. The cyclic group includes an aromatic group, a heterocyclic group and an aliphatic ring group. Examples thereof include bis (4-methacryloylthiophenoxy) sulfide, bisphenoxyethanol full orange acrylate, and tetrabromobisphenol A diepoxy acrylate. In particular, in the present invention, it is preferable to use urethane acrylate as a prepolymer and dipentaerythritol hexa (meth) acrylate, bisphenoxyethanol full orange acrylate, or the like as a monomer.

  Furthermore, examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like.

  Further, n-butylamine, triethylamine, poly-n-butylphosphine and the like can be mixed and used as a photosensitizer.

In the hard coat layer of the present invention, an organosilicon alkoxide and a hydrolyzate thereof can be further added. The organosilicon alkoxide satisfies the general formula (B) R ′ _y Si (OR) _4-y . In the formula, R represents an alkyl group, and R ′ represents an unreactive functional group such as an alkyl group or a fluorinated alkyl group at the terminal, or a reactivity such as a vinyl group, an amino group, an epoxy group, an aryl group, or a (meth) acryloyl group. A functional group is shown, and y is an integer satisfying 1 ≦ y ≦ 3. For example, octyltrimethoxysilane, octadecyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 1H, 1H, 2H, 2H-purple cyclohexyl trimethoxysilane, 1H, 1H, 2H, 2H-purple oro Decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy B pills triethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane and the like.

  In the hard coat layer of the present invention, a filler having an average particle size of 0.5 μm or more and 10 μm or less can be added to newly impart antiglare properties to the antireflection film. If it is 0.5 μm or less, the antiglare property is hardly exhibited, and if it is 10 μm or more, the particle diameter is too larger than the thickness of the hard coat layer, so that it is difficult to laminate the upper antistatic low refractive index layer. As the filler, inorganic fillers such as silica, alumina, zirconia and the like, and composite oxide fillers of these two or more types, organic fillers such as acrylic, styrene, urethane, melamine, and benzoanamin, and copolymer fillers of these two or more types can be used. . The filler may be used alone or in combination of two or more. In order to improve the strength of the hard coat layer, colloidal particles having an average particle diameter of 0.5 μm or less can be added. The colloidal particle diameter is preferably 0.1 μm or less from the viewpoint of transparency. Examples of the colloidal particles include silica, alumina, and zirconia. These may be used alone, or may be two or more kinds of complex oxides or a mixture of two or more kinds.

  The hardness of the hard coat layer is preferably H or higher in pencil hardness, and can have scratch resistance necessary for the antireflection laminated film.

  In preparing the hard coat agent for forming the hard coat layer, there is no particular limitation on the blending order of the components, and ultraviolet rays, electron beam curable resin compounds, and the like are added and mixed in various solvents.

Solvents include, but are not limited to, ketones such as methyl ethyl ketone, acetone, and methyl isoptyl ketone, esters such as methyl acetate, ethyl acetate, and butyl acetate, aromatic compounds such as toluene and xylene, diethyl ether And ethers such as tetrahydrofuran and alcohols such as methanol, ethanol and isopropanol. Moreover, well-known additives, such as an antifoamer and a leveling agent, can be mix | blended with this hard-coat agent if desired. There is no restriction | limiting in particular about solid content concentration of a hard-coat agent, The range of 10 to 70 weight% is preferable from surfaces, such as coating property, drying property, economical efficiency, and the range of 30 to 50 weight% is especially suitable.

  There are no particular restrictions on the method of applying the hard coating agent to the substrate, and a bar coating method, a micro gravure method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or the like can be used. The thickness of the hard coat layer can be controlled by calculating the required amount of hard coat agent applied from the solid content concentration of the hard coat agent and the density of the hard coat layer after curing. A thickness of 2 μm to 8 μm is preferable, and a thickness of 3 μm to 6 μm is particularly preferable.

  Alternatively, the coating layer after drying may be cured by irradiation with ultraviolet rays and electron beams in an atmosphere purged with nitrogen to form a hard coat layer with less surface damage and high surface hardness.

There is no restriction | limiting in particular about the ultraviolet irradiation apparatus used for hardening, For example, the well-known ultraviolet irradiation apparatus using a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp etc. can be used. The amount of ultraviolet irradiation is usually about 100 to 800 mJ / cm ² . There is no restriction | limiting in particular about an electron beam irradiation apparatus, and an acceleration voltage is 50-300 kV normally.

  The hard coat film thus obtained has a hard coat layer and hard coat layer molding excellent in adhesion to the substrate, surface hardness, flexibility, scratch resistance, transparency or antiglare property on the surface of the article. Articles can be provided.

  The antistatic low refractive index layer provided on the hard coat layer uses porous conductive fine particles and an active energy ray curable resin, while exhibiting the antistatic properties, and the antistatic low refractive index layer. The refractive index n can be lowered. By adding porous conductive fine particles to the active energy ray curable resin as a binder component, air in the fine particle pores (n = 1.0) can lower the refractive index of the layer.

  Porous conductive fine particles have a refractive index n of 1.40 or less, inorganic fine particles such as antimony pentoxide, tin oxide, zinc oxide, ITO (indium tin oxide), ATO (antimony tin oxide), polypyrrole, polyaniline Organic fine particles such as polythiophene and polyfluorene can be used. These fine particles can be used alone or in combination of two or more kinds of mixed fine particles, or these two or more kinds of composite fine particles can be used. Further, it is possible to use mixed fine particles with other metal compounds such as silica and magnesium fluoride, or composite fine particles.

  The composite fine particles may be fine particles having a core-shell structure. Specifically, it has porous metal compound fine particles with a low refractive index in the core part. By using a crystalline film having conductivity as the shell portion, porous conductive fine particles having a low refractive index are obtained. Examples of the metal compound fine particles having a low refractive index include metal compounds such as silica and magnesium fluoride, and examples of the material for the crystalline film having conductivity include antimony pentoxide, tin oxide, zinc oxide, and ITO (indium). Tin oxide) and ATO (antimony tin oxide).

  In addition, the core-shell may be reversed, that is, a conductive material may be used for the core portion and a metal compound having a low refractive index may be used for the shell portion. It may become.

The amount of the porous conductive fine particles added is not particularly limited, but is preferably in the range of 20 to 80% by weight, particularly preferably in the range of 30 to 70% by weight from the viewpoint of antistatic properties and refractive index adjustment. In order to improve the dispersibility of the porous conductive fine particles in the matrix, a dispersant can be used in the matrix. There is no restriction | limiting in particular as a dispersing agent, It is preferable to use a silicone type dispersing agent.

  In addition, by using porous conductive fine particles having a particle size of 100 nm or less, it is possible to form a conductive layer that exhibits high conductivity, lowers transmittance, and has no coloring of the layer. When the particle size exceeds 100 nm, light is remarkably reflected by Rayleigh scattering, the film becomes white and a decrease in transparency is observed, and when it is less than 2 nm, it is difficult to form fine particles, the conductivity is deteriorated, In addition, problems such as film non-uniformity due to aggregation between particles occur.

  The active energy ray-curable resin contained in the antistatic low refractive index layer is not particularly limited, and can be appropriately selected from conventionally known ones. This active energy ray-curable resin contains a photopolymerizable prepolymer, a photopolymerizable monomer, a photopolymerization initiator, and the like. Examples of the photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate, and the like. These photopolymerizable prepolymers may be used alone or in combination of two or more. Examples of the photopolymerizable monomer include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. For these prepolymers and monomers, compounds introduced with a perfluoroalkyl group, a perfluoroethylene oxide group or an alkyl group can be used for the purpose of imparting antifouling properties. Since this compound may reduce the strength of the layer, the addition amount is appropriately adjusted according to the balance between strength and antifouling property.

  By using an active energy ray-curable resin having a (meth) acryloyloxy group as the binder for the antistatic low refractive index layer, an antireflection laminated film having excellent adhesion to the hard coat layer can be obtained. Furthermore, it can be set as the antireflection laminated film excellent in chemical resistance, such as an alkali, an acid, alcohol, and ketones.

  In preparing the coating solution for forming the antistatic low refractive index layer, there is no particular limitation on the blending order of the components, and the active energy ray-curable resin and porous conductive fine particles are added and mixed in the various solvents described above. To do.

  As a method for forming the antistatic low refractive index layer, coating is performed by the above-described various coating methods so as to satisfy the general formula (A) nd = λ / 4 (range of 450 ≦ λ ≦ 650), followed by a drying treatment. After carrying out, ultraviolet rays and electron beam irradiation are carried out. By controlling the layer thickness d in the range of 450 ≦ λ ≦ 650, more preferably in the range of 500 ≦ λ ≦ 600, an antireflection laminated film having a low luminous reflectance can be obtained. The dried coating layer may be cured by irradiation with ultraviolet rays and electron beams in an atmosphere purged with nitrogen to form an antistatic low-refractive index layer having less surface damage and high surface hardness.

  By subjecting the transparent support and the hard coat layer to surface treatment, the surface tension of each surface can be changed, so that the adhesion between the hard coat layer and the antistatic low refractive index layer can be improved. As the surface treatment method, alkali treatment, plasma treatment, laser treatment, or corona treatment can be performed. By improving the adhesion between the layers and performing various surface treatments, foreign substances on the surface can be reduced. Thereby, an antireflection laminated film having no defects in appearance can be provided.

  In this way, by having a two-layer configuration of a hard coat layer and an antistatic low-refractive index layer on a transparent support, multiple functions can be realized with a small number of layers, reducing the number of processes and reducing costs. can do. Since the antistatic low refractive index layer is on the surface of the antireflection laminated film, the antistatic performance tends to be stable. Anti-static, anti-reflective, surface hardness, scratch resistance, antifouling properties due to surface hardness, flexibility, scratch resistance, transparency or anti-glare property due to hard coat layer, and anti-static low refractive index layer It is possible to provide a low-cost antireflection film that can provide a multi-function of chemical resistance and further has adhesion between layers.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The performance of the antireflection laminated film was evaluated according to the following method.

  Luminous reflectance: The luminous reflectance was measured from the spectral reflectance using an automatic spectrophotometer (Hitachi, U-4000). At the time of measurement, the surface opposite to the coated surface was matted and black paint was applied, and antireflection treatment from the back side was performed.

  Scratch resistance: Using # 0000 steel wool, 10 reciprocating surfaces were rubbed with a load of 250 g, and the presence or absence of scratches was visually evaluated.

  Total light transmittance and haze value: Measured using image clarity measuring instrument [NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.].

  Pencil hardness: Based on JIS K5400, evaluation was performed with a load of 500 g by a testing machine method.

  Surface resistance value: measured in accordance with JIS K6911.

Antifouling property: Fingerprints, magic and tissue scraps were attached to the surface, and the possibility of wiping was determined. (○: All can be wiped off, △: Some items are difficult to wipe off, ×: Some items cannot be wiped off)
Adhesiveness: After the surface of the film was cut at 100 points of 1 mm square, a peel test was performed using an adhesive cellophane tape [24 mm wide cello tape (registered trademark) manufactured by Nichiban Co., Ltd.], and the residual rate at the 100-point cut portion was evaluated.

Visual evaluation: The light of the fluorescent lamp was incident on the antistatic low refractive index layer side of the antireflection laminated film at a distance of 20 cm from the 20 W fluorescent lamp, and the color unevenness was visually evaluated. In the evaluation, a matte black paint was applied to the surface of the support that had not been coated, and an antireflection treatment from the back side was performed. (○: No color unevenness, Δ: Color unevenness is slightly recognized, X: Color unevenness is remarkably recognized)
<Example 1>
(Formation of hard coat layer)
A 80 μm thick triacetyl cellulose film (total light transmittance: 93%, haze value: 0.1%) was used as the transparent support. Moreover, the coating liquid for hard-coat layers was prepared using dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, urethane acrylate, and 3-acryloxypropyltrimethoxysilane.

This hard coat layer coating solution was applied onto a triacetyl cellulose film so as to have a dry film thickness of 5 μm, and a hard coat layer was formed by irradiating a 120 W metal halide lamp from a distance of 20 cm for 10 seconds.
(Formation of an antistatic low refractive index layer)
7 parts by weight of a mixture of pentaerythritol triacrylate and an acrylate having a perfluorooctane group as an organic functional group and 3 parts by weight of antimony pentoxide-silica composite oxide porous conductive fine particles diluted with 190 parts by weight of isopropanol The coating liquid for the low refractive index layer was prepared. This coating solution was applied to a film on which the antistatic low refractive index layer was laminated so that the dry film thickness was 100 nm, and cured by irradiating a 120 W metal halide lamp from a distance of 20 cm for 10 seconds. Curing was performed in a nitrogen purge atmosphere with an oxygen concentration of 3000 ppm or less. The refractive index of the antistatic low refractive index layer was 1.42 at a wavelength of 550 nm. The refractive index of the fine particles used was 1.40. Thus, an antireflection laminated film was prepared.

<Example 2>
In Example 1 (formation of antistatic low refractive index layer), the same procedure as in Example 1 except that 5 parts by weight of hydrolyzed oligomer and 5 parts by weight of antimony pentoxide-silica composite oxide porous conductive fine particles were used. Thus, an antireflection laminated film was prepared.

<Example 3>
In Example 1 (formation of hard coat layer), antiglare property is imparted to 9.5 parts by weight of a mixture of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, urethane acrylate, and 3-acryloxypropyltrimethoxysilane. For the purpose, an antireflection laminate film was prepared in the same manner as in Example 1 except that 0.5 part by weight of acrylic particles having an average particle diameter of 4 μm was added to prepare a coating solution for the hard coat layer.

<Comparative Example 1>
In Example 1 (formation of an antistatic low refractive index layer), an antireflection laminated film was prepared in the same manner as in Example 1 except that 7 parts by weight of the acrylate mixture and 3 parts by weight of silica fine particles were used.

<Comparative example 2>
An antireflection laminate film was prepared in the same manner as in Example 1 except that 7 parts by weight of the acrylate mixture and 3 parts by weight of antimony pentoxide fine particles were used in (formation of an antistatic low refractive index layer).

<Comparative Example 3>
In Example 1 (formation of an antistatic low refractive index layer), an antireflection laminated film was prepared in the same manner as in Example 1 except that the dry thickness of the antistatic low refractive index layer was 74 nm.

<Comparative example 4>
In Example 1 (formation of antistatic low refractive index layer), an antireflection laminated film was prepared in the same manner as in Example 1 except that the dry thickness of the antistatic low refractive index layer was 120 nm.
Table 1 shows the evaluation results of the antireflection laminated film of the present invention obtained in Examples 1 to 3 and the antireflection laminated film obtained in Comparative Examples 1 to 4.

  In Examples 1 and 2, by satisfying claims 1 to 4, antireflection properties, highly transparent optical properties, surface hardness, scratch resistance hard coat properties, antistatic properties, wiping properties, and antifouling properties It can be seen that a multifunctional antireflection laminated film having excellent resistance can be obtained.

In Example 3, it turns out that the multifunctional anti-reflective film which further provided the glare-proof property by the filler of Claim 5 is obtained.

  In Comparative Example 1, by making the fine particles into silica particles, the surface resistance value is high and the antifouling property is inferior.

  In Comparative Example 2, when the fine particles are antimony particles having a high refractive index, the refractive index of the layer is increased, so that the luminous reflectance is high and the antireflection property is poor.

  In Comparative Example 3, since the film thickness is thinner than the range of the general formula (A), red color unevenness is recognized in the visual evaluation.

  In Comparative Example 4, since the film thickness is thicker than the range of the general formula (A), blue color unevenness is recognized in the visual evaluation.

  In the result comparison of Examples 1 to 3 and Comparative Examples 1 to 4, by satisfying claims 1 to 5, the hard coat performance such as scratch resistance and surface hardness is maintained while maintaining sufficient performance, adhesion and antistatic Property, antifouling property, high transparency, or antiglare property can be exhibited at the same time. Furthermore, since a multifunctional film can be obtained with a small number of layers, it is possible to provide a low-cost antireflection laminated film by a coating method.

It is sectional drawing which shows the antistatic hard coat film concerning one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent support 2 ... Hard-coat layer 3 ... Antistatic low refractive index layer 4 ... Antireflection laminated film

Claims (5)

In the antireflection laminated film in which a hard coat layer and an antistatic low refractive index layer are laminated in this order on a transparent support,
The antistatic low refractive index layer includes an active energy ray-curable resin containing at least a compound having a (meth) acryloyloxy group in the molecule, and a porous conductive material having a particle size of 100 nm or less and a refractive index n of 1.40 or less. An antireflective laminated film comprising a conductive fine particle.   The antistatic low refractive index layer has the general formula (A) nd = λ / 4 (where n is the refractive index of the layer, d is the layer thickness, λ is the wavelength of light, and 450 ≦ λ ≦ 650) The antireflection laminated film according to claim 1, wherein   The antireflection laminated film according to claim 1 or 2, wherein the hard coat layer is made of a polymer mainly composed of a polyfunctional monomer having a (meth) acryloyloxy group. The hard coat layer according to claim 3, further general formula _{(B) R 'y Si (} OR) 4-y ( wherein R represents an an alkyl group, R' is an alkyl group at its terminal, fluorinated alkyl A reactive functional group such as a vinyl group, an amino group, an epoxy group, an aryl group, or a (meth) acryloyl group, and y is an integer satisfying 1 ≦ y ≦ 3) An anti-reflection laminated film comprising an organosilicon alkoxide and a hydrolyzate thereof.   5. The antireflection laminate film according to claim 4, wherein the hard coat layer further comprises a filler having an average particle diameter of 0.5 μm or more and 10 μm or less.

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