JP2002286907A - Layered antireflection film and antireflection member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a layered antireflection film and an antireflection member which uses the film having high film strength and excellent adhesion property of the film without decreasing the superior antireflection function and having excellent film strength and adhesion property particularly even when the base body is made of plastics. SOLUTION: In the layered antireflection film, a transparent low refractive index layer 4 in the multilayered structure contains a silicon alkoxide and/or its hydrolyzed products as the component having functional groups having reactivity with the functional groups in another layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated anti-reflection film and an anti-reflection member using the same, and more particularly, to a display surface of various displays such as a liquid crystal display (LCD), a portable information terminal, a portable telephone, and the like. The present invention relates to a laminated antireflection film formed on a plastic substrate, which is suitably used for a cover, a meter display section of an automobile, a cover of various instruments, and the like, and an antireflection member using the same.

[0002]

2. Description of the Related Art In recent years, with the spread of liquid crystal displays (LCDs), personal digital assistants, mobile phones, and the like, the display surfaces of these image display sections reflect external light, reflect external images, and display surfaces. Are becoming unclear. Further, in the case where a liquid crystal backlight emits light with a small battery, such as a portable information terminal or a mobile phone, a decrease in the total light transmittance due to reflection of the liquid crystal on the surface of the base material is a serious problem.

In order to solve these problems, a structure having an antireflection film formed on a display surface has been proposed and put to practical use. As a method of forming the antireflection film on the display surface, there are roughly the following two methods. One of the methods is a method of forming an antireflection film on a surface of a base material by a vapor deposition method or a sputtering method,
Another method is to form an anti-reflection film by applying an anti-reflection coating solution on the surface of the base material and drying the coating solution.

[0004]

However, the above-described methods using the conventional vapor deposition method and sputtering method are superior in the characteristics of the obtained anti-reflection film as compared with the method of applying an anti-reflection coating solution. There is a problem that manufacturing cost is high and mass productivity is poor. In addition, the method of applying and drying the antireflection coating solution is excellent in cost, but has a problem that the film is easily damaged due to low film strength, and the film is weak in adhesion and easily peeled. there were. In particular, when the substrate is plastic, there is a problem that the film forming temperature cannot be increased, so that the film strength and the adhesion of the film are inferior to those formed on a glass substrate.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has high film strength and excellent film adhesion without deteriorating an excellent antireflection function. Even in the case of (1), an object is to provide a laminated antireflection film excellent in film strength and film adhesion and an antireflection member using the same.

[0006]

In order to solve the above problems, the present invention employs the following laminated antireflection film and an antireflection member using the same. That is, the laminated antireflection film of the present invention is a multilayer antireflection film, wherein at least one layer of the multilayer structure has a functional group having reactivity with at least a functional group contained in another one layer. It is characterized by containing components.

[0007] In this laminated antireflection film, at least one layer of the multilayer structure contains a component having a functional group having reactivity with at least a functional group contained in another one layer, so that the film strength is reduced. As the height increases, the adhesion of the film also becomes excellent. This film does not impair the antireflection function.

It is preferable that the functional group having reactivity with the functional group contained in the other layer is a carboxyl group and / or an amino group. The multilayer structure preferably has a configuration in which a hard coat layer, a high refractive index layer, and a low refractive index layer are laminated. A configuration in which a middle refractive index layer is provided between the hard coat layer and the high refractive index layer may be adopted.

Preferably, the component is one selected from carboxyl group-containing monomethacrylate, carboxyl group-containing monoacrylate, and aminosilane. The hard coat layer preferably contains carboxyl group-containing monomethacrylate and / or carboxyl group-containing monoacrylate. The low refractive index layer or the middle refractive index layer preferably contains aminosilane.

The hard coat layer contains an ultraviolet curable resin and silicon dioxide, the high refractive index layer and / or the middle refractive index layer contains a metal oxide, and the low refractive index layer contains silicon dioxide. The configuration may be as follows. The hard coat layer is formed by a coating solution containing an ultraviolet curable resin and ultrafine particles of silicon dioxide, and the high refractive index layer and / or the middle refractive index layer is formed by a coating solution containing metal oxide ultrafine particles. The low refractive index layer may be formed of a coating solution containing a silicon dioxide binder.

The antireflection member of the present invention is characterized in that the laminated antireflection film of the present invention is provided on one or both surfaces of a transparent substrate. The transparent substrate is preferably a transparent resin film or a transparent resin plate. In this antireflection member, by providing the laminated antireflection film of the present invention on one or both surfaces of the transparent substrate, the antireflection film on the display surface has high film strength and excellent film adhesion. Becomes Also,
There is no risk of impairing the excellent anti-reflection function.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of a laminated antireflection film and an antireflection member using the same according to the present invention will be described with reference to the drawings. These embodiments are specifically described for better understanding of the gist of the invention, and do not limit the invention unless otherwise specified.

FIG. 1 is a sectional view showing a laminated anti-reflection film according to a first embodiment of the present invention. In the figure, reference numeral 1 denotes a transparent base material, and 2 denotes a transparent substrate. The transparent hard coat layer laminated on one surface of the substrate 1, 3 is a transparent high refractive index layer laminated on the transparent hard coat layer 2, and 4 is a transparent low refractive layer laminated on the transparent high refractive index layer 3. A transparent hard coat layer 2 to a transparent low refractive index layer 4
The laminated antireflection film 5 has a layer structure.

The transparent substrate 1 is not particularly limited as long as it has transparency. For example, silicate glass such as synthetic quartz glass, soda-lime glass, and zero-expansion glass (7059, manufactured by Corning Incorporated) Asahi Glass AL, A
N, AX, LE30 manufactured by HOYA, 79 manufactured by Corning
71), glass such as non-silicate glass, borosilicate glass and phosphate glass, and plastic such as acrylic, polycarbonate and polypropylene. The thickness is not particularly limited, and a thickness of about 0.2 to 20 mm can be used.

The transparent hard coat layer 2 is not particularly limited as long as it has transparency. Examples thereof include a melamine-based, urethane-based, alkyd-based, fluorine-containing resin-based, acrylic radical-based, acrylic silicon-based, and organo-based. The resin can be appropriately selected from an alkoxysilane-based resin, a silicate-based resin, and the like, and among them, an ultraviolet-curable resin (UV resin) is easily available at low cost. This UV-curable resin is preferably used when the substrate is a plastic because it has excellent adhesion and does not undergo thermal deformation due to heating during curing.

The UV-curable resin may be any UV-sensitive resin used in a coating method (wet coating method), such as polyester acrylate, epoxy acrylate, urethane acrylate, silicon acrylate, and polybutadiene. Acrylates and the like are preferably used for reasons such as improvement in productivity due to rapid hardening, resource / energy saving, high occupational safety and appearance, and abrasion resistance.

The transparent hard coat layer 2 is obtained by applying a transparent hard coat layer forming paint containing at least the above-mentioned resin and an organic solvent on the transparent substrate 1 and drying it. As the organic solvent, for example, alcohols, glycols, acetates, ketones and the like can be appropriately selected, and these may be used alone.
It may be used as a mixture of two or more.

As a coating method, a commonly used coating method such as a spray method, a spin coating method, a dipping method and a flow coating method can be appropriately selected. The drying temperature is preferably from 40 to 80 ° C. If the drying temperature exceeds 80 ° C, thermal deformation may occur depending on the transparent plastic substrate used such as an acrylic plate, which is not preferable.

When an ultraviolet-curable resin is used, the resin is crosslinked by irradiation with ultraviolet light to form a transparent hard coat layer 2.
The thickness of the transparent hard coat layer 2 is 1.0 to 4.0 μm.
m is preferred. The reason is that if the film thickness is less than 1.0 μm, it is not possible to obtain a sufficient hardness development, while 4.0
When the thickness exceeds μm, irregularities are generated on the transparent hard coat layer 2,
It is not preferable because it causes interference unevenness when forming the antireflection film.

Further, in order to improve the adhesiveness with the binder component contained in the transparent low refractive index layer 4 impregnating the transparent high refractive index layer 3, the function of the component contained in the transparent low refractive index layer 4 is improved. It is preferable that a component containing a functional group reactive with a group is contained in the transparent hard coat layer 2.

The high-refractive-index material contained in the transparent high-refractive-index layer 3 is not particularly limited as long as it has a function of increasing the refractive index, such as ultrafine metal oxide particles. It can be appropriately selected from yttrium oxide, zirconium oxide, niobium oxide, titanium oxide, tin oxide, ruthenium oxide, indium oxide, cerium oxide, tantalum oxide, and the like. In particular, any of zirconium oxide, titanium oxide, tin oxide, and indium oxide is preferable in terms of easy formation of ultrafine particles, low cost, and formation of a highly transparent film.

The transparent high refractive index layer 3 is prepared by treating these ultrafine metal oxide particles with a surfactant as required, dispersing the particles in an organic solvent, and applying and drying on the transparent hard coat layer 2. It is formed. As a coating method, a commonly used coating method such as a spray method, a spin coating method, a dipping method, and a flow coating method can be appropriately selected. The drying temperature is from room temperature to 80 ° C., and the film thickness is from 50 to 15
0 nm is preferred. The reason is that if the film thickness exceeds 150 nm or less than 50 nm, the required antireflection effect cannot be obtained, which is not preferable.

The average particle diameter of the metal oxide ultrafine particles is 5 to 5.
It is 100 nm, preferably 10 to 50 nm. The reason is that if the average particle size is less than 5 nm, the crystallinity of the particles is low, and the refractive index of the obtained film is low. On the other hand, if it exceeds 100 nm, Mie scattering occurs and This is because whitening occurs, which is not preferable. As the surfactant, for example, sulfonate type, sulfosuccinate type, anionic type such as phosphate ester type, alcohol-ethylene oxide type, fatty acid ester type, amide type, nonionic type such as polyethylene glycol type,
The solvent can be appropriately selected from cations such as quaternary cations, and the organic solvent can be appropriately selected from hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, and the like.

The transparent low-refractive-index layer 4 is made of a transparent low-refractive-index layer-forming coating material containing, for example, silicon alkoxide and / or a hydrolysis product thereof, a water repellent, a modifier, and an organic solvent. It is obtained by coating on the rate layer 3 and drying. From the viewpoint of film strength, it is preferable to use silicon alkoxide and / or a hydrolysis product thereof. The organic solvent can be appropriately selected from, for example, halogenated hydrocarbons, alcohols, ketones, and esters. In addition, as a coating method, a commonly used coating method such as a spray method, a spin coating method, a dipping method, and a flow coating method can be appropriately selected.

The refractive index of the transparent low refractive index layer 4 preferably has a large difference from the refractive index of the transparent high refractive index layer 3. It shows the prevention. The silicon alkoxide used for the coating material for forming the transparent low refractive index layer can be appropriately selected from tetraalkoxysilane-based compounds, alkyltrialkoxysilane-based compounds, and the like.

Then, the above-mentioned coating material for forming a transparent low refractive index layer is applied on the transparent high refractive index layer 3, and dried at room temperature to 80 ° C. The reason for setting the drying temperature to 80 ° C. or less is that the drying temperature is 8
If the temperature exceeds 0 ° C., it is not preferable because it causes thermal deformation depending on a transparent plastic substrate used such as an acrylic plate. Regarding film thickness, the refractive index of each layer,
It is preferable that the target wavelength and the reflectance are determined by simulation, and usually 50 to 150 nm.

When the above-mentioned transparent low refractive index layer forming coating material is applied on the transparent high refractive index layer 3, the silicon alkoxide contained in the transparent low refractive index layer forming coating material and / or its hydrolyzate is formed. The material is impregnated into the transparent high refractive index layer 3 as a binder component, and is brought into contact with the transparent hard coat layer 2 to form a strong laminated antireflection film having excellent film strength and adhesion when cured. it can.

Usually, the transparent high refractive index layer 3 is formed by using a paint containing ultrafine metal oxide particles and a binder component. In this case, the refractive index is reduced due to the influence of the binder component. The problem described above occurs. On the other hand, when the transparent high-refractive index layer 3 is formed of a paint containing no binder, the film strength and adhesion are inferior and cannot be put to practical use.

On the other hand, a transparent low refractive index layer coating material is applied on the transparent high refractive index layer 3 and dried to form the transparent low refractive index layer 4.
In the configuration described above, since the transparent high refractive index layer 3 can be formed without using a binder component, a high refractive index can be obtained, and the transparent low refractive index layer formed on the transparent high refractive index layer 3 can be obtained. Since the transparent high refractive index layer 3 is impregnated with the binder component contained in 4 and comes into contact with the transparent hard coat layer 2, a laminated antireflection film having excellent film strength and adhesion can be formed.

In the present invention, in addition to the above, in order to form a strong laminated antireflection film having further excellent film strength and adhesion, the transparent hard coat layer 2 and the transparent low refractive index layer 4 have a reactive functional group. Each component having a group is contained.
That is, the transparent hard coat layer 2 contains ultra-fine particles of silica, and a silica-based binder of silicon alkoxide and / or a hydrolysis product thereof is used as a binder component contained in the transparent low refractive index layer 4,
When the carboxyl group-containing monomethacrylate or monoacrylate is contained in the transparent hard coat layer 2 and the aminosilane is contained in the transparent low refractive index layer 4, the carboxyl group is contained in the transparent hard coat layer 2 and the low refractive index layer 4
Contains an amino group, and the functional groups react with each other, so that a laminated antireflection film having more excellent film strength and adhesion can be formed.

[Second Embodiment] FIG. 2 is a sectional view showing a laminated antireflection film according to a second embodiment of the present invention. The difference from the laminated anti-reflection film of the first embodiment is that
In contrast to the transparent hard coat layer 2, the transparent high refractive index layer 3, and the transparent low refractive index layer 4, the laminated antireflection film 5 having a three-layer structure is formed. That is, a laminated antireflection film 13 having a four-layer structure is formed by the refractive index layer 11, the transparent high refractive index layer 12, and the transparent low refractive index layer 4.

The transparent medium refractive index layer 11 is coated on the transparent hard coat layer 2 using a transparent medium refractive index layer forming paint containing at least a binder component, metal oxide ultrafine particles, and an organic solvent. -It is formed by drying. The content of the ultrafine metal oxide particles in the transparent medium refractive index layer 11 is preferably in the range of 30 to 90% by weight, particularly 50 to 80% by weight. That is, when the content of the metal oxide ultrafine particles exceeds 90% by weight, the amount of the metal oxide ultrafine particles becomes excessive, and the strength of the resulting transparent medium refractive index layer 11 and the adhesion to the transparent hard coat layer 2 are reduced. At the same time, a whitening phenomenon occurs in the transparent medium refractive index layer 11. On the other hand, when the content of the metal oxide ultrafine particles is less than 30% by weight, the refractive index of the transparent medium refractive index layer 11 becomes almost the same as the refractive index of the transparent hard coat layer 2, and the transparent medium refractive index layer This is because the effect of introducing 11 is reduced.

The ultrafine metal oxide particles used in the transparent medium refractive index layer 11 include, for example, aluminum oxide, yttrium oxide, zirconium oxide, niobium oxide, titanium oxide, tin oxide, ruthenium oxide, indium oxide, cerium oxide, Transparent high refractive index layer 12 made of tantalum or the like
Can be appropriately selected in consideration of the relationship with the metal oxide ultrafine particles used in the method.

The ultrafine metal oxide particles used in the transparent medium refractive index layer 11 preferably have a particle diameter of 5 to 100 nm. The reason is that if the average particle diameter is smaller than 5 nm, the crystallinity of the particles will be low, and the refractive index of the obtained film will be reduced. This is because the transparent medium refractive index layer 11 remarkably irregularly reflects light due to Mie scattering and looks white, and the transparency is reduced.

Further, examples of the binder component include silicon alkoxide and / or a hydrolysis product thereof. This silicon alkoxide and / or its hydrolysis product has a low refractive index, is preferably used because it has good dispersibility with the above-mentioned metal oxide ultrafine particles, and has good curability at low temperatures. .

Examples of the coating material for forming a transparent medium refractive index layer include silicon alkoxide, metal oxide ultrafine particles, water, and a hydrolysis catalyst (acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or β). An organic solvent-based paint obtained by mixing and dispersing a monodiketone salt) and a dispersant in an organic solvent using an ultrasonic disperser, a homogenizer, a sand mill or the like is preferably used. The silicon alkoxide can be appropriately selected from a tetraalkoxysilane-based compound, an alkyltrialkoxysilane-based compound, and the like. The organic solvent can be appropriately selected from alcohols, glycols, acetates, ketones and the like. These may be used alone or as a mixture of two or more.

Then, the coating material for forming a transparent medium refractive index layer is applied on the transparent hard coat layer 2 and dried at room temperature to 80 ° C. to form a film. The film thickness is preferably determined by simulating the refractive index of each layer, the target wavelength and the reflectance, but is usually preferably 50 to 150 nm. The reason for setting the drying temperature at room temperature to 80 ° C. is that if the drying temperature exceeds 80 ° C., thermal deformation may be caused depending on a transparent plastic substrate used such as an acrylic resin. In addition, as a coating method, various coating methods can be applied, and for example, can be appropriately selected from a spray method, a spin coating method, a dipping method, a flow coating method, and the like.

The transparent high refractive index layer 12 has a higher refractive index than that of the transparent medium refractive index layer 11, and the metal oxide ultrafine particles used in the transparent high refractive index layer 12 have a refractive index of There is no particular limitation as long as it has a function of increasing, but for example, appropriately selected from aluminum oxide, yttrium oxide, zirconium oxide, niobium oxide, titanium oxide, tin oxide, ruthenium oxide, indium oxide, cerium oxide, tantalum oxide, and the like can do. In particular, zirconium oxide, considering that it is easy to form ultrafine particles, that it is inexpensive, and that a highly transparent film can be formed,
Any of titanium oxide, tin oxide and indium oxide is preferred.

The transparent high refractive index layer 12 is subjected to a surface treatment of the above-mentioned metal oxide ultrafine particles with a surfactant if necessary,
It is formed by dispersing in an organic solvent to form a transparent high-refractive-index-layer-forming coating material, applying it on the transparent medium-refractive-index layer 11, and drying it. As a coating method, a commonly used coating method such as a spray method, a spin coating method, a dipping method, and a flow coating method can be appropriately selected. Also,
The drying temperature is preferably from room temperature to 80 ° C., and the film thickness is preferably from 50 to 150 nm. The reason is that if the thickness exceeds 150 nm or is less than 50 nm, the required antireflection effect cannot be obtained.

The average particle diameter of the ultrafine metal oxide particles is preferably from 5 to 100 nm, more preferably from 10 to 50 nm.
nm. The reason for this is that if the average particle size is smaller than 5 nm, the crystallinity of the particles will be low and the refractive index of the obtained film will be low. On the other hand, if it exceeds 100 nm, Mie scattering will occur and whitening of the film will occur. Because it happens. Examples of the surfactant include sulfonate type, sulfosuccinate type, anionic type such as phosphate ester type, alcohol-ethylene oxide type, fatty acid ester type, amide type,
It can be appropriately selected from a nonionic type such as a polyethylene glycol type and a cation type such as a quaternary cation type. As the organic solvent, a hydrocarbon type, a halogenated hydrocarbon type,
It can be appropriately selected from alcohols, ketones, esters and the like.

The transparent low refractive index layer 4 is formed by applying a coating material for forming a transparent low refractive index layer on the transparent high refractive index layer 12 and drying the coating. The silicon alkoxide and / or its hydrolysis product contained in the paint for use is impregnated into the transparent high refractive index layer 12 as a binder component and comes into contact with the transparent medium refractive index layer 11, so that the transparent low refractive index layer 4 is cured. In this case, the laminated antireflection film 13 having excellent film strength and adhesion can be obtained.

Further, in order to form a strong laminated anti-reflection film having further excellent film strength and adhesion, in the present embodiment, a functional group having a reaction in the transparent middle refractive index layer 11 and the transparent hard coat layer 2 is used. Components are contained. When the carboxyl group-containing monomethacrylate or monoacrylate is contained in the transparent hard coat layer 2 and the aminosilane is contained in the transparent medium refractive index layer 11, the transparent medium refractive index layer 11 is firmly connected to the transparent low refractive index layer 4. Tied to
It is suitable.

From the viewpoint of adjusting the refractive index of each layer, the strength and adhesion of the film, titanium oxide is used as the ultrafine metal oxide particles contained in the transparent high refractive index layer 12, and the transparent medium refractive index is used. It is preferable to use zirconium oxide as the metal oxide ultrafine particles contained in the layer 11 and to use silicon alkoxide and / or a hydrolysis product thereof as the binder component. The combination of titanium oxide and zirconium oxide has a refractive index of 1.55 to 1.9.
It can be adjusted to 5.

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

(1) Regarding a laminated antireflection film having a three-layer structure (transparent hard coat layer + transparent high refractive index layer + transparent low refractive index layer) "Example 1" Various paints were prepared as follows. -1 "Preparation of Transparent Low Refractive Index Forming Paint" 7.6 g of tetramethoxysilane, 0.23 g of 0.1 N nitric acid, 9.0 g of pure water, and methyl alcohol 7
To a solution obtained by mixing 3.02 g and performing a hydrolysis reaction, 10 g of propylene glycol monoethyl ether and silicon oil (manufactured by Toray Dow Corning: SF8427).
0.15 g was mixed. In order to enhance the adhesion to the obtained solution, N-phenyl-γ-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5
g was mixed to obtain a uniform paint using a stirrer.

-1 "Preparation of Transparent High Refractive Index Layer Forming Paint" Antimony-doped tin oxide having a particle size of 10 to 20 nm (AT
O) 5.0 g of fine powder (manufactured by Sumitomo Osaka Cement Co., Ltd.), 10 g of propylene glycol monoethyl ether, and 85.0 g of ethyl alcohol are mixed, and a surfactant (Adecacol CS141E, manufactured by Asahi Denka Kogyo KK) is added. 1 g was added and mixed, and then this solution was dispersed for 10 minutes using an ultrasonic homogenizer (manufactured by Central Chemical Co .: Sonifier-450) to obtain a uniform coating.

-1 "Preparation of Transparent Hard Coat Layer Forming Paint" 14 g of an acrylic UV-curable hard coat resin (UV-3701 manufactured by Toagosei Chemical Co., Ltd.) was added to fine silicon oxide powder (Aerosil 1200 manufactured by Nippon Aerosil Co., Ltd.). ) 2
1 g was added, and further 65 g of propylene glycol was added. In order to enhance the adhesion, 1.0 g of β-methacryloyloxyethyl hydrogen phthalate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester CB-1) was mixed, and the mixture was dispersed for 10 minutes using the above ultrasonic homogenizer. , And a uniform paint.

-1 "Coating method" An acrylic plate having a thickness of 2 mm was used as a substrate, and a coating material for forming a transparent hard coat layer was applied to the surface of the acrylic plate by dip coating, and after predrying at 70 ° C, , UV
Cured by irradiation. Next, a coating material for forming a transparent high refractive index layer was applied by a dip coating method, and dried at 70 ° C. for 10 minutes. Thereafter, a coating material for a transparent low refractive index layer was applied by a dip coating method, and dried and cured at 70 ° C. for 1 hour to prepare an acrylic plate having a laminated antireflection film formed on the surface.

Comparative Example 1 Various paints were prepared as described below. -2 "Adjustment of transparent low refractive index layer forming paint" Same as "Adjustment of transparent low refractive index layer forming paint" in Example 1 except that N-phenyl-γ-aminopropyltrimethoxysilane was not added. A paint was prepared by the method described above. -1 "Adjustment of Transparent High Refraction Layer Forming Paint" A coating material was prepared in the same manner as in "Adjustment of Transparent High Refraction Layer Forming Paint" in Example 1. -2 “Adjustment of transparent hard coat layer forming paint” Except that β-methacryloyloxyethyl hydrogen phthalate was not added, coating was performed in the same manner as in “Adjustment of transparent hard coat layer forming paint” in Example 1. Fabrication was performed. Thereafter, a laminated anti-reflection film was formed on the acrylic plate in the same manner as in Example 1 using this paint.

[Evaluation Test] The characteristics of the thus obtained laminated antireflection films of Example 1 and Comparative Example 1 were measured.
The test items were as follows. a. Surface resistivity (Ω / □): Hiresta IP manufactured by Mitsubishi Chemical Corporation b. Total light transmittance (%): Haze Met manufactured by Nippon Denshoku Industries Co., Ltd.
er NDH2000 c. Haze value (%): Haze Meter N manufactured by Nippon Denshoku Industries Co., Ltd.
DH2000 d. Pencil hardness: Pencil hardness tester manufactured by Ohira Rika Kogyo e. Taber test (ΔH): Taber abrasion tester manufactured by Tester Sangyo Co., Ltd. f. Cross cut test: JIS K 5400 compliant g. Reflectance (bottom position): V-570 manufactured by JASCO h. Appearance: Unevenness of the film surface and interference of reflection were visually observed.

Table 1 shows the results of the evaluation test.

[Table 1]

From the results shown in Table 1, it was found that the result of the Taber test in Example 1 was smaller than that of Comparative Example 1 by one digit, and the wear resistance was excellent. For test items other than the Taber test, almost the same results were obtained in both Example 1 and Comparative Example 1, and no difference was observed between Example 1 and Comparative Example 1.

(2) Regarding a laminated antireflection film having a four-layer structure (Part 1) (Transparent hard coat layer + Transparent middle refractive index layer + Transparent high refractive index layer + Transparent low refractive index layer) "Example 2" Various paints Was prepared as follows. -2 "Preparation of paint for forming transparent low refractive index layer" 7.6 g of tetramethoxysilane, 0.23 g of 0.1 N nitric acid, 9.0 of pure water, and 73.
02g, and a solution obtained by performing a hydrolysis reaction was mixed with 10g of propylene glycol monoethyl ether and silicone oil (SF8427, manufactured by Dow Corning Toray).
15 g were mixed and a uniform paint was obtained using a stirrer.

-2 "Preparation of paint for forming transparent high refractive layer" 2.0 g of fine zirconium oxide powder (manufactured by Sumitomo Osaka Cement Co., Ltd .: particle size: 10 to 30 nm), 10 g of propylene glycol monoethyl ether, and ethyl alcohol 8
8.0 g was mixed, a surfactant (Adeka Co., Ltd .: Adecacol CS141E) was added and mixed, and then the solution was dispersed for 10 minutes using the above-mentioned ultrasonic homogenizer to obtain a uniform paint. did.

-1 "Preparation of Transparent Medium Refractive Index Layer Forming Coating Material" 4.16 g of tetramethoxysilane, 0.09 g of 0.1 N nitric acid, 3.6 g of pure water, and 8.
15 g of the mixture, and the mixture was subjected to the hydrolysis reaction.
ATO fine powder of 0 to 20 nm (Sumitomo Osaka Cement Co., Ltd.)
1.8 g, propylene glycol monoethyl ether 10.0 g, and ethyl alcohol 79.6 g were added. In order to enhance the adhesion, N-phenyl-γ-
0.5 g of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM573) was mixed, and then this solution was dispersed for 10 minutes using the above-mentioned ultrasonic homogenizer to obtain a uniform coating.

-1 "Preparation of paint for forming transparent hard coat layer" The same paint as in Example 1 was used. -2 "Coating method" An acrylic plate having a thickness of 2 mm was used as a base material, and a coating material for forming a transparent hard coat layer was applied thereto by a dip coating method, preliminarily dried at 70 ° C, and then cured by UV irradiation. . Next, a coating material for forming a transparent middle refractive index layer was applied by a dip coating method, and dried and cured at 70 ° C. for 10 minutes. Next, a transparent high refractive index layer forming paint is applied by a dip coating method, and dried at 70 ° C. for 10 minutes. An acrylic plate having a laminated anti-reflection film formed on the surface was produced by drying and curing under the condition of 1 hour.

Comparative Example 2 Various paints were prepared as described below. -2 "Adjustment of paint for forming transparent low refractive index layer" A paint was prepared in the same manner as in "Adjustment of paint for forming a transparent low refractive index layer" in Example 2. -2 "Adjustment of paint for forming transparent high refractive index layer" A paint was prepared in the same manner as in "Adjustment of paint for forming a transparent high refractive index layer" in Example 2.

-2 "Adjustment of Transparent Medium Refractive Index Layer Forming Coating" Example 2 "Adjustment of Transparent Medium Refractive Index Layer Forming Coating" except that N-phenyl-γ-aminopropyltrimethoxysilane was not added. The paint was produced in the same manner as in the above. -2 “Adjustment of transparent hard coat layer forming paint” Except that β-methacryloyloxyethyl hydrogen phthalate was not added, coating was performed in the same manner as in “Adjustment of transparent hard coat layer forming paint” in Example 1. Fabrication was performed. Thereafter, a laminated antireflection film was formed on the acrylic plate in the same manner as in Example 2 using this paint.

[Evaluation Test] The characteristics of the laminated antireflection films of Example 2 and Comparative Example 2 obtained as described above were evaluated in Example 1.
And it measured by the method similar to the comparative example 1. Table 2 shows the results of the evaluation test.

[Table 2]

From the results shown in Table 2, it was found that the result of the Taber test in Example 2 was smaller than that of Comparative Example 2 by about 1/5, and the wear resistance was excellent. For test items other than the Taber test, almost the same results were obtained in both Example 2 and Comparative Example 2, and no difference was observed between Example 2 and Comparative Example 2.

(3) Regarding a laminated antireflection film having a four-layer structure (part 2) (Transparent hard coat layer + transparent medium refractive index layer + transparent high refractive index layer + transparent low refractive index layer) Was prepared as follows. -2 "Adjustment of paint for forming transparent low refractive index layer" A paint was prepared in the same manner as in "Adjustment of paint for forming a transparent low refractive index layer" in Example 2.

-3 "Preparation of Transparent High Refractive Index Layer Forming Paint" Titanium oxide fine powder (manufactured by Ishihara Sangyo Co., Ltd., product number ST-)
(01: particle size of 10 to 35 nm), 2.5 g of propylene glycol monoethyl ether, and 87.5 g of isopropyl alcohol were mixed, and a surfactant (Adekacol CS141E, manufactured by Asahi Denka Kogyo Co., Ltd.) was added.
g was added and mixed, and then this solution was dispersed using the above-described ultrasonic homogenizer for 10 minutes to obtain a uniform coating.

-3 "Preparation of Transparent Medium Refractive Index Layer Forming Paint" 4.16 g of tetramethoxysilane, 0.09 g of 0.1 N nitric acid, 3.6 g of pure water, and 8.
15 g of a mixed solution subjected to a hydrolysis reaction was added to zirconium oxide fine powder (manufactured by Sumitomo Osaka Cement Co .;
(30 nm), 1.5 g of propylene glycol monoethyl ether, and 79.9 g of ethyl alcohol were added. To increase the adhesion, N-phenyl-
0.5 g of γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM573) was mixed, and then this solution was dispersed for 10 minutes using the above-mentioned ultrasonic homogenizer to obtain a uniform coating.

-1 "Preparation of paint for forming transparent hard coat layer" The same paint as in Example 1 was used. Thereafter, a laminated antireflection film was formed on the acrylic plate in the same manner as in Example 2 using this paint.

Comparative Example 3 Various paints were prepared as described below. -2 "Adjustment of transparent low refractive index layer forming paint" A coating material was prepared in the same manner as in "Adjustment of transparent low refractive index layer forming paint" in Example 3. -3 “Adjustment of Transparent High Refractive Index Layer Forming Paint” A paint was produced in the same manner as in “Adjustment of Transparent High Refractive Index Layer Forming Paint” in Example 3.

-4 "Preparation of Transparent Medium Refractive Index Layer Forming Coating" Example 3 "Preparation of Transparent Medium Refractive Index Layer Forming Coating" except that N-phenyl-γ-aminopropyltrimethoxysilane was not added. The paint was produced in the same manner as in the above. -2 “Adjustment of transparent hard coat layer forming paint” Except that β-methacryloyloxyethyl hydrogen phthalate was not added, coating was performed in the same manner as in “Adjustment of transparent hard coat layer forming paint” in Example 1. Fabrication was performed. Then, a laminated antireflection film was formed on the acrylic plate in the same manner as in Example 3 using this paint.

[Evaluation Test] The characteristics of the laminated antireflection films of Example 3 and Comparative Example 3 obtained as described above were evaluated in Example 1.
And it measured by the method similar to the comparative example 1. Table 3 shows the results of the evaluation test.

[Table 3]

From the results shown in Table 3, it was found that the result of the Taber test of Example 3 was smaller than that of Comparative Example 3 by about 1/5, indicating that the abrasion resistance was excellent. Regarding the test items other than the Taber test, the results were almost the same in both Example 3 and Comparative Example 3, and no difference was observed between Example 3 and Comparative Example 3.

[0069]

According to the laminated antireflection film of the present invention, at least one layer of the multilayer structure contains at least one component having a functional group reactive with a functional group contained in another layer. Therefore, the film strength and adhesion can be increased, and there is no possibility that the antireflection function is impaired.

According to the antireflection member of the present invention, since the laminated antireflection film of the present invention is provided on one or both surfaces of the transparent substrate, an antireflection film having high film strength and excellent adhesion is displayed. It can be formed on a surface and does not impair the excellent antireflection function of the display surface.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a laminated antireflection film according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view illustrating a laminated antireflection film according to a second embodiment of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent substrate 2 transparent hard coat layer 3 transparent high refractive index layer 4 transparent low refractive index layer 5 laminated antireflection film 11 transparent medium refractive index layer 12 transparent high refractive index layer 13 laminated antireflection film

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/30 G02F 1/1335 G02F 1/1335 G09F 9/00 313 G09F 9/00 313 G02B 1/10 A (72) Inventor Kazuhiko Nagata 585 Tomicho, Funabashi-shi, Chiba Prefecture Sumitomo Osaka Cement Co., Ltd. (72) Inventor Katsuhiko Masaki 585 Tomimachi, Funabashi-shi, Chiba F-term (reference) 2H091 FA37X FA37Z FB02 FC01 GA01 LA02 LA16 2K009 AA05 AA06 AA15 BB02 BB14 BB24 CC03 CC09 CC35 CC35 CC35 CC42 DD02 DD05 4D075 AE03 AE19 BB42Y BB46Y CA02 CA03 CA13 CB02 CB06 DA04 DA06 DB13 DB36 DB43 DB48 DC13 DC19 DC24 EA21 EB02 EB12 EB16 EB22 EB24 EB32 EB33 EB35 EB36 EB38 EB42 EB43 EC02 EC03 4F100 AA17B AA17H AA28 AA29 AH03C AH03D AH03H AH06C AH06D AH06H AK01E AK25A AK52 AL06A AR00A AT00E BA05 BA07 BA10A CA18 CA23B CA23H CC02A CC02B GB32 GB41 GB48 JK12 JK12A JN01 JN01E JN06 JN18B JN18C JN18D 5G435 AA01 AA08 AA17 GG43 HH03 HH20 KK07

Claims (11)

[Claims] 1. An antireflection film having a multilayer structure, wherein at least one layer of the multilayer structure contains a component having a functional group having reactivity with a functional group contained in at least one other layer. A laminated anti-reflection film characterized by the above-mentioned. 2. The laminated antireflection film according to claim 1, wherein the functional group having reactivity with a functional group contained in the other one of the layers is a carboxyl group and / or an amino group. 3. The multilayer anti-reflection film according to claim 1, wherein the multilayer structure is formed by laminating a hard coat layer, a high refractive index layer, and a low refractive index layer. 4. The laminated anti-reflection film according to claim 3, wherein a middle refractive index layer is provided between said hard coat layer and said high refractive index layer. 5. The composition according to claim 1, wherein the component is a carboxyl group-containing monomethacrylate, a carboxyl group-containing monoacrylate,
The laminated antireflection film according to any one of claims 1 to 4, wherein the antireflection film is one selected from aminosilanes. 6. The laminated anti-reflection film according to claim 3, wherein the hard coat layer contains a carboxyl group-containing monomethacrylate and / or a carboxyl group-containing monoacrylate. 7. The laminated antireflection film according to claim 3, wherein the low refractive index layer or the middle refractive index layer contains aminosilane. 8. The hard coat layer contains an ultraviolet curable resin and silicon dioxide, the high refractive index layer and / or the middle refractive index layer contains a metal oxide, and the low refractive index layer contains silicon dioxide. The laminated anti-reflection film according to claim 3 or 4, wherein 9. The hard coat layer is formed of a coating solution containing an ultraviolet-curable resin and ultrafine particles of silicon dioxide, and the high refractive index layer and / or the medium refractive index layer contains ultrafine metal oxide particles. Formed by the coating liquid
5. The laminated anti-reflection film according to claim 3, wherein the low refractive index layer is formed by a coating solution containing a silicon dioxide-based binder. 10. An anti-reflection member comprising the transparent anti-reflection film according to claim 1 provided on one or both surfaces of a transparent substrate. 11. The anti-reflection member according to claim 10, wherein the transparent substrate is a transparent resin film or a transparent resin plate.