CN1894601A - Antireflection film, electromagnetic wave shielding light transmitting window material, gas discharge type light emitting panel, flat display panel, show window material and solar cell module - Google Patents

Abstract

An antireflection film comprising transparent base film 1 and, sequentially superimposed thereon, hard coat layer (2), high refractive index layer 3 and low refractive index layer 4. Alternatively, there is provided an antireflection film comprising a transparent base film and, sequentially superimposed thereon, a conductive high refractive index hard coat layer and a low refractive index layer. The low refractive index layer is obtained through irradiating of a coating film comprising hollow silica microparticles, a polyfunctional (meth)acrylic compound and a photopolymerization initiator with ultraviolet rays in an atmosphere of 0 to 10,000 ppm oxygen concentration so as to harden the same.

Description

Anti-reflection film, electromagnetic shielding light-transmitting window material, gas discharge type light emitting panel, flat panel display panel, window material and solar cell module

technical field

I. The first aspect relates to the coating suitable for various displays such as word processors, computers, CRTs, plasma TVs, liquid crystal displays, and organic ELs, as well as window glass for automobiles, buildings, and trains, and frame glass for paintings. Type anti-reflection film.

II. The second aspect relates to a coating-type light-absorbing antireflection film suitable for display surfaces of various displays such as word processors, computers, CRTs, plasma TVs, liquid crystal displays, and organic ELs.

III. The third aspect involves coating suitable for various displays such as word processors, computers, CRTs, plasma TVs, liquid crystal displays, and organic ELs, as well as window glass for automobiles, buildings, and trains, and frame glass for paintings. Type anti-reflection film.

IV. The fourth aspect relates to an electromagnetic-shielding light-transmitting window material and a gas discharge type light-emitting panel, and particularly to an electromagnetic-shielding light-transmitting window having a coating-type antireflection layer excellent in antireflection performance formed on the outermost surface materials and gas discharge type luminescent panels.

V. The fifth aspect relates to flat-panel displays and window materials, particularly flat-panel displays and window materials having a coating-type anti-reflection layer with excellent anti-reflection performance formed on the surface.

VI. The sixth aspect relates to a solar cell module, especially a solar cell module with low external light reflectance, high sunlight incident rate, and excellent luminous efficiency.

Background technique

I. To prevent light reflection, ensure high The light transmittance, generally use anti-reflection film.

Heretofore, as an antireflection film used for such an application, an antireflection film provided with a high-refractive-index layer and a low-refractive-index layer on the surface of a transparent base film has been provided. The anti-reflection film obtains an anti-reflection function by utilizing the difference in refractive index between the high-refractive index layer and the low-refractive index layer.

Among the existing anti-reflection films, there are many anti-reflection films formed by the dry film-forming method of laminating low-refractive-index layers such as SiO ₂ and MgF ₂ and high-refractive index layers such as TiO ₂ and ITO by vapor deposition or sputtering. film, but the dry method is very time-consuming and expensive when forming a film.

On the other hand, an antireflection film can be produced at a relatively low cost by a film-forming method using a wet method such as a microgravure coating method. As a coating type antireflection film, as shown in FIG. 1, on the surface of a transparent base film 1 formed of a synthetic resin, a hard coat layer 2, a high refractive index layer 3, and a low The anti-reflection film formed by the refractive index layer 4. There is also an antireflection film formed by forming a conductive high-refractive index hard coat layer having both a high-refractive index layer and a hard coat layer on a substrate film, and then forming a low-refractive index layer thereon.

However, in the wet method, it is difficult to lower the refractive index of the low refractive index component and to increase the refractive index of the high refractive index component, and it is difficult to obtain good antireflection performance. In particular, reducing the refractive index of the low-refractive index layer is very difficult, and various studies have been made on reducing the refractive index of the low-refractive index layer.

Generally, as a low-refractive-index layer material of a coating-type antireflection film, a fluororesin in which some hydrogen atoms of an alkyl group are replaced by fluorine atoms is often used (for example, Japanese Patent Laid-Open No. 9-203801).

Although the refractive index of the low-refractive index layer using fluororesin is low, in order to lower the refractive index, the chain length of the fluorine-substituted alkyl chain of the fluororesin must be increased. On the other hand, if the chain length of the alkyl chain is increased, Then there is a problem that the film strength of the formed low-refractive index layer decreases. For example, if a conventional low-refractive-index layer formed of a fluororesin is wiped with a plastic eraser, film peeling is very likely to occur. In the low ^- refractive index layer using fluororesin disclosed ⁱⁿ Japanese Patent Laid-Open No. 9-203801, according to the experiment of the present inventors, plastic When wiping with an eraser, rupture of the film occurs about 10 times.

As a coating-type low-refractive-index layer, a method of fixing low-refractive-index (n) microparticles with a particle diameter of 1 to 100 nm with a binder has also been proposed. Among them, although the layer in which silica fine particles (n=1.47) is immobilized by an acrylic binder has high film strength, the refractive index of silica fine particles is high (1.47), so it is impossible to make The formed low refractive index layer has a refractive index of 1.49 or less.

In addition, in the layer where MgF ₂ fine particles were immobilized by an acrylic binder (n=1.38), although the refractive index of the low-refractive index layer decreased to some extent (n=1.46), the compatibility of MgF ₂ with the acrylic binder The performance is poor, and the film strength becomes very poor.

Therefore, it has been proposed to use a fluorinated alkyl group-containing silicone component as a binder in addition to hollow silica particles (hollow silica) as fine particles with good compatibility with a binder and a low refractive index. A technical solution for improving film strength and lowering the refractive index (Japanese Patent Laid-Open No. 2003-202406, Japanese Patent Laid-Open No. 2003-202960).

However, in the antireflection film, the base film generally used is a polyethylene terephthalate (PET) film or a triacetyl cellulose film, and in the PET film, from the viewpoint of heat resistance, it cannot be Heating above 130°C. In the film-forming method by the wet method, if a silicone component that cannot be subjected to heating and sintering treatment or the like is used as a binder, chemical corrosion resistance and abrasion resistance are very poor as shown in the comparative experiment examples described later. In particular, when immersed in an alkaline aqueous solution (3% by weight NaOH) for about 30 minutes, the silicone component undergoes alkaline hydrolysis, and the film is easily dissolved. Therefore, in a system using a binder containing a silicone component and mixed with hollow silica, in the case of strongly wiping the low-refractive index layer which is the outermost layer of the antireflection film with an alkaline detergent, Due to the dissolution of the low-refractive index layer, the anti-reflection function is lost.

On the other hand, it has also been proposed to use a multifunctional acrylic resin with more than two functional groups as a binding agent to form a thin film of a low refractive index layer mixed with porous silica particles by a wet method (Japanese Patent Laid-Open No. 2003-261797 Gazette, Japanese Patent Laid-Open No. 2003-262703, Japanese Patent Laid-Open No. 2003-266602).

However, according to the research of the present inventors, it has been found that the film strength of the film obtained by mixing a polyfunctional acrylic resin with a bifunctional or higher group and porous silica particles is very poor, even if only a polyfunctional group with a bifunctional group or higher is used. Even when acrylic resin is mixed with porous silica particles, a low-refractive-index layer having abrasion resistance cannot be formed. In addition, in these patent documents, the low-refractive index layer is directly formed on the surface of the base material. However, when the low-refractive index layer is directly formed on the base material in this way, the antireflection performance, which is indispensable for an antireflection film such as the minimum reflectance, cannot be obtained. film. Moreover, in these patent documents, porous silica particles are used instead of hollow silica particles, and porous silica particles cannot sufficiently reduce the refractive index of silica, so the refractive index of the low-refractive index layer rate cannot reach a sufficiently low value.

As the uppermost low-refractive index layer of the anti-reflection film, not only low refractive index is important, but also durability such as abrasion resistance and chemical corrosion resistance is also very important, and as mentioned above, in the prior art, No coating-type antireflection film having a low-refractive index layer having excellent film properties such as abrasion resistance and chemical corrosion resistance and a low refractive index has been provided.

II. Anti-reflection film suitable for preventing light reflection and ensuring high light transmission on the display surface of various displays such as word processors, computers, CRTs, plasma TVs, liquid crystal displays, and organic EL.

Conventionally, as an antireflection film for such applications, an antireflection film in which a high-refractive index layer and a low-refractive index layer are provided on the surface of a transparent base film has been proposed. In such an antireflection film, the antireflection performance is obtained by utilizing the difference in refractive index between the high-refractive index layer and the low-refractive index layer.

Among the existing anti-reflection films, there are many anti-reflection films formed by the dry film-forming method of laminating low-refractive-index layers such as SiO ₂ and MgF ₂ and high-refractive index layers such as TiO ₂ and ITO by vapor deposition or sputtering. film, but the dry film forming method is very time-consuming and costly when forming a film.

On the other hand, an antireflection film can be produced at a relatively low cost by a film-forming method using a wet method such as a microgravure coating method.

However, in the wet method, it is difficult to lower the refractive index of the low refractive index component and to increase the refractive index of the high refractive index component, and it is difficult to obtain good antireflection performance. In particular, reducing the refractive index of the low-refractive index layer is very difficult, and various studies have been made on reducing the refractive index of the low-refractive index layer.

Generally, as a low-refractive-index layer material of a coating-type antireflection film, a fluororesin in which some hydrogen atoms of an alkyl group are replaced by fluorine atoms is often used (for example, Japanese Patent Laid-Open No. 9-203801).

Although the refractive index of the low-refractive index layer using fluororesin is low, in order to lower the refractive index, the chain length of the fluorine-substituted alkyl chain of the fluororesin must be increased. On the other hand, if the chain length of the alkyl chain is increased, Then there is a problem that the film strength of the formed low-refractive index layer decreases. For example, if a conventional low-refractive-index layer formed of a fluororesin is wiped with a plastic eraser, film peeling is very likely to occur. In the low ^- refractive index layer using fluororesin disclosed ⁱⁿ Japanese Patent Laid-Open No. 9-203801, according to the experiment of the present inventors, plastic When wiping with an eraser, rupture of the film occurs about 10 times.

As a coating-type low-refractive-index layer, a method of fixing low-refractive-index (n) microparticles with a particle diameter of 1 to 100 nm with a binder has also been proposed. Among them, although the layer in which silica fine particles (n=1.47) is immobilized by an acrylic binder has high film strength, the refractive index of silica fine particles is high at 1.47. The formed low refractive index layer has a refractive index of 1.49 or less.

In addition, in the layer where MgF ₂ fine particles were immobilized by an acrylic binder (n=1.38), although the refractive index of the low-refractive index layer decreased to some extent (n=1.46), the compatibility of MgF ₂ with the acrylic binder The performance is poor, and the film strength becomes very poor.

Therefore, it has been proposed to use a fluorinated alkyl group-containing silicone component as a binder in addition to hollow silica particles (hollow silica) as fine particles with good compatibility with a binder and a low refractive index. A technical solution for improving film strength and lowering the refractive index (Japanese Patent Laid-Open No. 2003-202406, Japanese Patent Laid-Open No. 2003-202960).

However, in the antireflection film, the base film commonly used is a polyethylene terephthalate (PET) film or a triacetyl cellulose (TAC) film. In the PET film, in terms of heat resistance, Heating above 130°C cannot be performed. In the film-forming method by the wet method, if a silicone component that cannot be subjected to heating and sintering treatment or the like is used as a binder, chemical corrosion resistance and abrasion resistance are very poor. In particular, when immersed in an alkaline aqueous solution (3% by weight NaOH) for about 30 minutes, the silicone component undergoes alkaline hydrolysis, and the film is easily dissolved. Therefore, in a system using a binder containing a silicone component and mixing it with hollow silica, in the case of strongly wiping the low-refractive index layer which is the outermost layer of the antireflection film with an alkaline detergent or the like , due to the dissolution of the low refractive index layer, the anti-reflection function is lost.

On the other hand, it has also been proposed to use a multifunctional acrylic resin with more than two functional groups as a binding agent to form a thin film of a low refractive index layer mixed with porous silica particles by a wet method (Japanese Patent Laid-Open No. 2003-261797 Gazette, Japanese Patent Laid-Open No. 2003-262703, Japanese Patent Laid-Open No. 2003-266602).

However, according to the research of the present inventors, it has been found that the film strength of the film obtained by mixing a polyfunctional acrylic resin with a bifunctional or higher group and porous silica particles is very poor, even if only a polyfunctional group with a bifunctional group or higher is used. Even when acrylic resin is mixed with porous silica particles, a low-refractive-index layer having abrasion resistance cannot be formed. In addition, in these patent documents, the low-refractive index layer is directly formed on the surface of the base material. However, when the low-refractive index layer is directly formed on the base material in this way, the antireflection performance, which is indispensable for an antireflection film such as the minimum reflectance, cannot be obtained. film. Moreover, in these patent documents, porous silica particles are used instead of hollow silica particles, and porous silica particles cannot sufficiently reduce the refractive index of silica, so the refractive index of the low-refractive index layer rate cannot reach a sufficiently low value.

In the anti-reflection film, especially in the anti-reflection film for plasma display panel and CRT, it is further required to have a low reflectance on the short wavelength side (400-450nm), be able to fully transmit blue light, and have a short wavelength. The transmittance on the wavelength side is high, and the transmitted color is not yellowish.

In the prior art, the compositions of commonly used anti-reflection films are as follows, and the reflection spectra of these anti-reflection films are shown in FIG. 3 .

Composition 1: Low refractive index layer (n=1.45)/high refractive index hard coat layer (n=1.71)/PET film

Composition 2: Low refractive index layer (n=1.45)/high refractive index hard coat layer (n=1.68)/TAC film

In the above compositions 1 and 2, the film thickness of the high refractive index layer and the low refractive index layer is 1/4 wavelength (1/4λ) of the optical film thickness. In composition 1, the anti-reflection performance is insufficient. At this time, in composition 2, the minimum reflectance is about 0.4% at a wavelength of 550nm, which is low, and the reflectance at a wavelength of 450nm is about 4.5%. There is an increase. Since the reflectance on the short-wavelength side is high in this way, in this composition 2, blue light cannot be sufficiently transmitted. In addition, if the transmittance on the short wavelength side is low, the transmitted light after passing through the film will be yellowish. Therefore, for example, in a display, when white light is generated, it will be yellowish.

Without changing the above composition 2, in order to reduce the reflectance on the short wavelength side, in composition 2, a method of slightly increasing the film thickness of the high refractive index layer and slightly reducing the film thickness of the low refractive index layer was proposed (composition 3).

That is, in composition 1, the high-refractive index layer and the low-refractive-index layer are coated with a film thickness of about 1/4λ of the optical film thickness, but in composition 3, the film thickness of the high-refractive index layer is 0.32λ, low The film thickness of the refractive index layer was 0.22λ. The reflectance spectrum of this composition 3 compared with composition 1 is shown in FIG. 4 .

When the thickness of the high-refractive index layer is increased in this way, the reflectance on the short-wavelength side decreases, and the reflectance at a wavelength of 400 nm is as high as 3.5%. In addition, the minimum reflectance is slightly increased, so even if the reflectance on the short-wavelength side decreases, the visible reflectance increases, which is a problem. In addition, although the reflectance on the short-wavelength side is lowered, 3.5% is still too high, and it is necessary to develop an antireflection film with sufficiently low minimum reflectance and visible reflectance.

Therefore, the present applicant has previously proposed a light-absorbing antireflection film in which a hard coat layer, a transparent conductive layer, a light-absorbing layer, and a low-refractive index layer are sequentially laminated on a transparent base film (Japanese Patent Application (Japanese Patent Application) No. 2002 -318349), or an anti-reflective film layered in this order on a transparent substrate film with a hard coat layer, a conductive light-absorbing layer, and a low-refractive index layer.

For example, FIG. 5 shows a film in which a hard coat layer, a transparent conductive layer, a light-absorbing layer, and a low-refractive index layer are sequentially laminated on a transparent base film, the film thickness of the hard coat layer is 5 to 10 μm, and the transparent conductive layer The thickness is 0.35λ, the film thickness of the light absorbing layer (carbon black/titanium black/acrylic resin, n=1.63, k=0.35) is 0.15λ, and the low refractive index layer (silica fine particles/acrylic fine particles, n=1.495 ) with a film thickness of 0.175λ is the reflection spectrum of a light-absorbing antireflection film (composition 4).

As shown in Figure 5, by forming a light-absorbing anti-reflection film with a special composition of a transparent conductive layer, a light-absorbing layer, and a low-refractive index layer formed on a hard coat layer, it is possible to achieve very low reflectance on the short-wavelength side anti-reflection film.

As the uppermost low refractive index layer of the antireflection film, not only its low refractive index is important, but also durability such as abrasion resistance and chemical corrosion resistance is also very important, and as mentioned above, in the prior art Among them, a coating-type antireflection film having a low-refractive index layer having excellent film properties such as abrasion resistance and chemical corrosion resistance and a low refractive index has not been provided.

Therefore, there is a need for a coating type that does not deteriorate the transparent resin film, can form a low-refractive index layer with a low refractive index on the transparent resin film, can be continuously produced, and has excellent properties such as abrasion resistance and chemical corrosion resistance. Anti-reflective film.

On the other hand, in antireflection films for plasma display panels and CRTs that require low reflectance and low transmittance on the short wavelength side, by using the above-mentioned composition 4, good effects can be obtained, but even in this composition 4 However, there are still problems to be solved.

In a conventional antireflection film (composition 1) that does not use a light-absorbing layer, even if streaks are generated in the low-refractive index layer, the transmittance hardly changes, so even a small amount of damage is not conspicuous, whereas In the case of the light-absorbing antireflection film of this composition 4, if a small amount of damage occurs in the low-refractive index layer, even the light-absorbing layer will be peeled off, and the transmittance at the peeled-off portion of the light-absorbing layer will become very high, so the damage becomes very obvious. Therefore, an antireflection film using this light-absorbing layer is required to have very high abrasion resistance with a low refractive index.

However, when the film strength of the low-refractive index layer is increased, the refractive index of the low-refractive index layer becomes very high at n=1.49, and a sufficient low-refractive index cannot be achieved. In the above-mentioned composition 4, if the refractive index of the low-refractive index layer is high, in order to obtain the minimum reflectance of 0.5% or less, the thickness of the light-absorbing layer must be increased, but if the thickness of the light-absorbing layer is increased, there is a transmission The rate decreases and becomes a problem of 70% or less.

III. Suitable for various displays such as word processors, computers, CRTs, plasma TVs, liquid crystal displays, organic EL, etc., as well as window glass of automobiles, buildings, trains, and frame glass of paintings, etc., in order to prevent light reflection and An anti-reflection film is used to ensure high light transmission.

Conventionally, as an antireflection film for such applications, an antireflection film in which a high-refractive index layer and a low-refractive index layer are provided on the surface of a transparent base film has been proposed. In such an antireflection film, the antireflection performance is obtained by utilizing the difference in refractive index between the high-refractive index layer and the low-refractive index layer.

Among the existing anti-reflection films, there are many anti-reflection films formed by the dry film-forming method of laminating low-refractive-index layers such as SiO ₂ and MgF ₂ and high-refractive index layers such as TiO ₂ and ITO by vapor deposition or sputtering. film, but the dry method is very time-consuming and expensive when forming a film.

On the other hand, an antireflection film can be produced at a relatively low cost by a film-forming method using a wet method such as a microgravure coating method. As a coating type antireflection film, as shown in FIG. 21, it is mainly used on the surface of a transparent base film 21 formed of synthetic resin, and a hard coat layer 23, a high refractive index layer 24, and a low An antireflection film for the refractive index layer 25 . In addition, there is an antireflection film in which a conductive high-refractive-index layer having both a high-refractive-index layer and a hard coat layer is formed on a base film, and a low-refractive-index layer is formed thereon.

However, in the wet method, it is difficult to lower the refractive index of the low refractive index component and to increase the refractive index of the high refractive index component, and it is difficult to obtain good antireflection performance. In particular, reducing the refractive index of the low-refractive index layer is very difficult, and various studies have been made on reducing the refractive index of the low-refractive index layer.

Generally, as a low-refractive-index layer material of a coating-type antireflection film, a fluororesin in which some hydrogen atoms of an alkyl group are replaced by fluorine atoms is often used (for example, Japanese Patent Laid-Open No. 9-203801).

Although the refractive index of the low-refractive index layer using fluororesin is low, in order to lower the refractive index, the chain length of the fluorine-substituted alkyl chain of the fluororesin must be increased. On the other hand, if the chain length of the alkyl chain is increased, Then there is a problem that the film strength of the formed low-refractive index layer decreases. For example, if a conventional low-refractive-index layer formed of a fluororesin is wiped with a plastic eraser, film peeling is very likely to occur. In the low ^- refractive index layer using fluororesin disclosed ⁱⁿ Japanese Patent Laid-Open No. 9-203801, according to the experiment of the present inventors, plastic When wiping with an eraser, rupture of the film occurs about 10 times.

As a coating-type low-refractive-index layer, a method of fixing low-refractive-index (n) microparticles with a particle diameter of 1 to 100 nm with a binder has also been proposed. Among them, the layer in which silica particles (n=1.47) are immobilized with an acrylic binder has high film strength, but the refractive index of silica particles is relatively high at about 1.47, so it is impossible to The refractive index of the formed low refractive index layer is made to be 1.49 or below.

In addition, in the layer where MgF ₂ fine particles were immobilized by an acrylic binder (n=1.38), although the refractive index of the low-refractive index layer decreased to some extent (n=1.46), the compatibility of MgF ₂ with the acrylic binder The performance is poor, and the film strength becomes very poor.

Therefore, it has been proposed to use a fluorinated alkyl group-containing silicone component as a binder in addition to hollow silica particles (hollow silica) as fine particles with good compatibility with a binder and a low refractive index. A technical solution for improving film strength and lowering the refractive index (Japanese Patent Laid-Open No. 2003-202406, Japanese Patent Laid-Open No. 2003-202960).

However, in the antireflection film, the base film commonly used is a polyethylene terephthalate (PET) film or a triacetyl cellulose (TAC) film. In the PET film, in terms of heat resistance, Heating above 130°C cannot be performed. In the film-forming method by the wet method, if a silicone component that cannot be subjected to heating and sintering treatment or the like is used as a binder, chemical corrosion resistance and abrasion resistance are very poor. In particular, when immersed in an alkaline aqueous solution (3% by weight NaOH) for about 30 minutes, the silicone component undergoes alkaline hydrolysis, and the film is easily dissolved. Therefore, in a system using a binder containing a silicone component and mixed with hollow silica, in the case of strongly wiping the low-refractive index layer which is the outermost layer of the antireflection film with an alkaline detergent, Due to the dissolution of the low-refractive index layer, the anti-reflection function is lost.

On the other hand, it has also been proposed to use a multifunctional acrylic resin with more than two functional groups as a binding agent to form a thin film of a low refractive index layer mixed with porous silica particles by a wet method (Japanese Patent Laid-Open No. 2003-261797 Gazette, Japanese Patent Laid-Open No. 2003-262703, Japanese Patent Laid-Open No. 2003-266602).

However, according to the research of the present inventors, it has been found that the film strength of the film obtained by mixing a polyfunctional acrylic resin with a bifunctional or higher group and porous silica particles is very poor, even if only a polyfunctional group with a bifunctional group or higher is used. Even when acrylic resin is mixed with porous silica particles, a low-refractive-index layer having abrasion resistance cannot be formed. In addition, in these patent documents, the low-refractive index layer is directly formed on the surface of the base material. However, when the low-refractive index layer is directly formed on the base material in this way, the antireflection performance, which is indispensable for an antireflection film such as the minimum reflectance, cannot be obtained. film. Moreover, in these patent documents, porous silica particles are used instead of hollow silica particles, and porous silica cannot sufficiently lower the refractive index of silica, so the refractive index of the low-refractive index layer A sufficiently low value cannot be reached either.

As the uppermost low-refractive index layer of the anti-reflection film, not only low refractive index is important, but also durability such as abrasion resistance and chemical corrosion resistance is also very important, and as mentioned above, in the prior art, No coating-type antireflection film having a low-refractive index layer having excellent film properties such as abrasion resistance and chemical corrosion resistance and a low refractive index has been provided.

IV. In a plasma display panel (PDP), an electromagnetic-shielding light-transmitting window (PDP front filter) is generally used for the purpose of shielding electromagnetic waves, shielding near-infrared rays, shielding neon, and the like. In addition, direct-bonded gas discharge panels for improved visibility have been continuously developed. These are provided with an anti-reflection function to the surface in order to reduce the reflection of external light.

38a is a cross-sectional view of an electromagnetic shielding light-transmitting window material 31 disclosed in Japanese Patent Laid-Open No. 2002-341779. The electromagnetic shielding light-transmitting window material 31 uses an adhesive intermediate film 34A, a transparent Adhesive 34B and adhesive 34C laminate and integrate the outermost anti-reflection film 33, the copper/PET layer etching film 40 as an electromagnetic shielding film, the transparent substrate 32, and the innermost near-infrared shielding film 35. , the end surface of the laminated body and the inner and outer edge portions close to the end surface are pasted with a conductive adhesive tape 37 to integrate them. In addition, the size of the electromagnetic shielding film 40 is almost the same as that of the transparent substrate 32, and the conductive tape 38 is attached to the edge portion so as to be wound from one surface to the other surface.

33A is a transparent base film, and 33B is an antireflection film, and is usually formed by sequentially laminating a hard coat layer, a high-refractive index layer, and a low-refractive index layer on a transparent base material. 35A is a transparent base film, and 35B is a near-infrared absorbing layer. 38A and 37A are metal foils, and 38B is an adhesive layer. 41 is a copper foil, 42 is a light absorption layer, 43 is a transparent base film, and 44 is a transparent adhesive layer.

38b shows a cross-sectional view of the gas discharge type light-emitting panel disclosed in Japanese Patent Application Laid-Open No. 2002-341781. In FIG. 38b, components that perform the same functions as those in FIG. 38a are denoted by the same symbols. This gas discharge type light-emitting panel 60 uses adhesive intermediate films 34A, 34B, and 34C as adhesives, and the outermost layer antireflection film 33, copper/PET laminated etching film 40 as an electromagnetic shielding film, and near The infrared shielding film 35 and the illuminant panel body 50 are laminated and integrated, and the end surface of the laminate and the inner and outer edges near the end surface are pasted with a conductive adhesive tape 37 to be integrated.

In addition, as the high-refractive-index layer and the low-refractive-index layer of the antireflection layer constituting the antireflection film, a large number of high-refractive-index layers and low-refractive-index layers formed by a dry film-forming method using vapor deposition or sputtering have been proposed. However, in the dry film-forming method, the film-forming process is time-consuming and expensive, so the wet film-forming method using the pattern coating method is becoming the main method.

As mentioned above, on the display surface of a PDP or the like, an anti-reflection film is generally used to reduce the reflection of external light. Especially in the case of a PDP, the anti-reflection film needs to improve the color when the light is off and the color purity when the light is on. . However, since the plasma display panel emits light by discharge of a rare gas, it is very difficult to adjust the color. Especially in the case of a coating-type antireflection film, there is a limit to lowering the refractive index of the low-refractive index layer and increasing the refractive index of the high-refractive index layer (for example, in the low-refractive index layer, the limit is n = about 1.46, and in the high refractive index layer, the limit is about n=1.68.) In addition, in order to enhance the color of the reflected color and improve the color purity, it is necessary to have a flat reflectance characteristic in the visible light region. In addition, antifouling properties are also required in the antireflection film as the outermost layer.

V. In flat display panels such as LCD, organic EL, and CRT, in order to prevent reflection of external light, an anti-reflection function is generally provided. So far, in order to impart this antireflection function, for example, in the case of a CRT, a method of directly forming an antireflection film on a glass substrate on the surface by a dry film-forming method such as a sputtering method or an evaporation method has been disclosed. A method of affixing an anti-reflection film formed by a dry method or a wet method such as a microgravure coating method on a film, etc. Among them, the method using the dry method has the disadvantages of long film forming time and high cost. Therefore, recently, the wet method is mainly used, but an antireflection film formed by the wet method is inferior in antireflection function to an antireflection film formed by the dry method, which is also a disadvantage.

In addition, in the case of LCD, an anti-glare film with fine unevenness formed on the surface by a wet method is usually used. Since LCDs were used in television applications, transparent (non-glare) anti-reflection films, A composite film having the above-mentioned anti-glare function and anti-reflection function at the same time.

In addition, since organic EL is self-luminous and has high luminance, it does not require high anti-reflection properties. However, in outdoor applications, it is required to reduce external light reflection and improve visibility.

In addition, even in touch-type display panels typified by PDAs using LCDs, in order to realize higher-quality images and improve visibility, it is required to prevent external light reflection.

On the other hand, it is also required to prevent the reflection of external light so that the color of the display itself can be clearly distinguished in the display window of artworks and decorations.

Therefore, in the prior art, for special exhibits, an anti-reflection film is usually formed on the window material by a dry film-forming method. That is, because the window materials formed by the wet film forming method cannot obtain sufficient anti-reflection function under the conventional circumstances, and there are problems in interference pattern and coloring, etc., the dry film forming method is usually used. However, the current situation is that the window materials obtained by the dry film forming method are not suitable for ordinary window materials, but are only suitable for special display window materials because of their high price.

As mentioned above, in the existing anti-reflection technology, since the anti-reflection film obtained by the dry film-forming method is expensive, it is desirable to use the wet film-forming method. However, in the wet-type film-forming method, the improvement of the anti-reflection performance is limited. That is, the reduction of the refractive index of the low refractive index layer and the increase of the refractive index of the high refractive index layer are limited (for example, the limit is n=1.46 in the low refractive index layer, and the limit is n=1.46 in the high refractive index layer. around 1.68). Therefore, further improvement in antireflection performance cannot be achieved. In addition, in order to improve color purity and improve visibility, it is necessary to have flat reflectance characteristics in the visible light range. In addition, especially in window material applications, in order to be able to distinguish the color of the display itself, it is required to reduce color change (color difference), However, existing anti-reflection films are difficult to meet these required properties. In addition, the antireflection film as the outermost layer must also have antifouling properties.

VI. In recent years, solar cells that directly convert sunlight into electrical energy have been paid more and more attention to and continue to be developed from the perspectives of efficient use of resources and prevention of environmental pollution.

A solar cell generally forms a structure as shown in FIG. 43: an ethylene-vinyl acetate copolymer (EVA) resin is passed between a surface-side transparent protection member 111 on the light-receiving side side and an inner surface-side protection member (back cover material) 112. The sealing films of the thin films 113A and 113B seal the solar cell 114 , that is, discharge elements such as silicone.

Such a solar cell module 110 is manufactured by sequentially laminating a surface-side transparent protective member 111 such as a glass substrate, an EVA film 113A for a sealing film, a solar cell member 114, an EVA resin film 113B for sealing, and a rear cover material 112, By heating and melting EVA and making it cross-linked and solidified, the adhesive is integrated.

Hitherto, glass substrates without any treatment have been used as surface-side transparent protective members of solar cell modules, and in solar cell modules using ordinary glass substrates as surface-side transparent protective members, about 4 % of the sunlight is reflected, and thus the sunlight equivalent to the reflected light cannot be converted into energy, which hinders the improvement of the power generation efficiency of the solar cell module.

It is also conceivable to apply surface processing to the surface of the glass substrate, which is a transparent protective member on the surface side of the solar cell module, for reducing the reflection of external light. Due to the advanced technology, no surface processing can be carried out.

On the other hand, in various displays such as word processors, computers, CRTs, plasma TVs, liquid crystal displays, and organic ELs, as well as window glass of automobiles, buildings, and trains, etc., in order to prevent light reflection and ensure high light transmission properties, using an anti-reflection film with a high-refractive-index layer and a low-refractive-index layer on the surface of a transparent substrate film, especially an anti-reflective film that forms a high-refractive-index layer and a low-refractive-index layer by a wet method such as a microgravure coating method It is widely used because of its low production cost.

Therefore, it can be considered that such a coating type anti-reflection film is also suitable for solar cell modules. In the existing anti-reflection film, the anti-reflection performance is not sufficient, and especially the ultraviolet rays with high solar energy are shielded. Therefore, using such an anti-reflection film The reflective film sometimes leads to a decrease in power generation efficiency.

Contents of the invention

I. The 1st aspect, the object of the present invention is to provide a kind of can not cause the degradation of transparent substrate film, can easily form the low-refractive-index layer with low refractive index, and can continuous production, abrasion resistance, chemical corrosion resistance Coating type anti-reflection film with excellent performance.

The antireflection film of the first aspect is a reflective film formed by sequentially laminating a hard coat layer, a high refractive index layer, and a low refractive index layer on a transparent base film, or sequentially laminating a highly conductive film on a transparent base film. The anti-reflection film formed by the refractive index hard coat layer and the low refractive index layer is characterized in that: the low refractive index layer is irradiated with ultraviolet rays through the coating film under an atmosphere with an oxygen concentration of 0 to 10000 ppm to make it Obtained by curing, wherein the coating film contains: hollow silica particles (hereinafter referred to as "hollow silica"), multifunctional (meth)acrylic compounds, that is, having 2 or more (methyl) Acryloyl (meth)acrylic compound, photopolymerization initiator.

The hollow silica used in the first aspect has a low refractive index and is effective as a material for the low refractive index layer. In addition, by selecting a polyfunctional (meth)acrylic compound as a binder component, abrasion resistance, chemical resistance, and stain resistance can be imparted, and a favorable low-refractive index layer can be formed. In addition, the low-refractive-index layer of the first aspect is cured by irradiating ultraviolet rays under a specific low-oxygen condition, so heating is not required, and furthermore, the transparent resin film does not deteriorate, and the low-refractive index layer can be formed in continuous production. Low refractive index layer with excellent abrasion resistance and chemical corrosion resistance.

That is, the inventors of the present invention conducted a follow-up test as shown in the comparative experiment example described later on the above-mentioned prior art, and found that when a low refractive index layer was formed by mixing a polyfunctional acrylic resin having a bifunctional or more functional group and porous silica particles, , the film strength is very low, and even if a polyfunctional acrylic resin with more than two functional groups is mixed into the hollow silica particles, the abrasion resistance cannot be improved at all. In addition, it was found that even if a low-refractive index layer is directly formed on the surface of the substrate, antireflection performance such as minimum reflectance, which is indispensable for an antireflection film, is still insufficient.

It has also been found that the refractive index of silica cannot be sufficiently lowered in porous silica fine particles, and hollow silica must be used for further lowering the refractive index.

Based on these findings, the present inventors found that, first, regarding the film composition, by forming a transparent base film/hard coat layer, a high-refractive index layer/low-refractive-index layer, or, a transparent base film/conductive high-refractive-index hard coat layer/low-refractive-index layer to improve anti-reflection performance. Also, the abrasion resistance of the low-refractive index layer is greatly improved by curing the adhesive by irradiating ultraviolet rays under the condition of very low oxygen concentration, among which, very strong abrasion resistance can be obtained only when a special acrylic resin is used as the adhesive Damage and chemical resistance, thus completing the first aspect of the anti-reflection film.

According to the first aspect, it is possible to provide a low-refractive-index layer capable of forming a low-refractive-index layer on a transparent resin film in a short period of time without deteriorating the transparent resin film, capable of continuous production, and having abrasion resistance and chemical corrosion resistance. Anti-reflective film coating with excellent properties such as anti-corrosion.

II. The object of the second aspect is to provide a low-refractive-index layer that does not cause deterioration of the transparent resin film, can form a low-refractive index layer on the transparent resin film, and can be continuously produced, and has abrasion resistance and chemical corrosion resistance. Coating type anti-reflection film with excellent performance.

In particular, the second aspect relates to an antireflection film formed by sequentially laminating a hard coat layer, a transparent conductive layer, a light absorbing layer, and a low refractive index layer on a transparent base film, or sequentially laminating a hard coat layer, a transparent conductive layer, and a low refractive index layer on a transparent base film. An anti-reflection film formed of a conductive light-absorbing layer and a low-refractive-index layer. Among them, by forming a low-refractive-index layer with a low refractive index and excellent abrasion resistance, it is possible to provide low reflectance on the short-wavelength side and sufficient transparency. Light-absorbing anti-reflection film that emits blue light, has a low transmittance on the short-wavelength side, and has no yellowish transmittance.

The anti-reflection film of the second aspect is an anti-reflection film formed by sequentially laminating a hard coat layer, a transparent conductive layer, a light-absorbing layer, and a low-refractive index layer on a transparent base film, or sequentially laminating a hard coat layer on a transparent base film. An anti-reflection film formed by a coating layer, a conductive light-absorbing layer, and a low-refractive index layer, wherein the low-refractive index layer is formed by irradiating the coating film with ultraviolet rays under an atmosphere having an oxygen concentration of 0 to 10,000 ppm. It is obtained by curing, wherein the coating film contains hollow silica particles (hereinafter referred to as "hollow silica"), multifunctional (meth)acrylic compounds, that is, having two or more (meth) An acryloyl (meth)acrylic compound, a photopolymerization initiator, and a minimum reflectance of 0.5% or less, a transmittance of 70% or more at a wavelength of 550nm, and a reflectance of 2% or more at a wavelength of 400nm the following.

The hollow silica used in the second aspect has a low refractive index and is effective as a material for the low refractive index layer. In addition, by selecting a polyfunctional (meth)acrylic compound as a binder component, abrasion resistance, chemical resistance, and stain resistance can be imparted, and a favorable low-refractive index layer can be formed. In addition, the low-refractive-index layer of the second aspect is cured by irradiating ultraviolet rays under a specific low-oxygen condition, so heating is not required, and furthermore, the transparent resin film does not deteriorate, and the low-refractive index layer can be formed in continuous production. Low refractive index layer with excellent abrasion resistance and chemical corrosion resistance. Therefore, it is possible to realize an antireflection film having a minimum reflectance of 0.5% or less, a hard coat layer with a transmittance of 70% or more at 550 nm, and a wavelength of 400 nm with a reflectance of 2% or less.

That is, the present inventors conducted follow-up experiments on the above-mentioned prior art, and found that when a low-refractive index layer is formed by mixing a multifunctional acrylic resin with more than two functional groups and porous silica particles, the film strength is very low, even if only the Even when a polyfunctional acrylic resin having more than two functional groups is mixed into the hollow silica fine particles, the abrasion resistance cannot be improved at all. In addition, it was found that even if a low-refractive index layer is directly formed on the surface of the substrate, antireflection performance such as minimum reflectance, which is indispensable for an antireflection film, is still insufficient.

It has also been found that the refractive index of silica cannot be sufficiently lowered in porous silica fine particles, and hollow silica must be used for further lowering the refractive index.

Based on these findings, the present inventors found that: first, regarding the film composition, by forming a transparent base film/hard coat layer/transparent conductive layer/light absorbing layer/low refractive index layer, or, forming a transparent base film/easy adhesion layer/hard coat layer/conductive light-absorbing layer/low refractive index layer to improve anti-reflection performance. Also, the abrasion resistance of the low-refractive index layer is greatly improved by curing the adhesive by irradiating ultraviolet rays under the condition of very low oxygen concentration, among which, very strong abrasion resistance can be obtained only when a special acrylic resin is used as the adhesive damage and chemical resistance, thus completing the second aspect of the anti-reflection film.

According to the second aspect, it is possible to provide a low-refractive-index layer capable of forming a low-refractive-index layer on a transparent resin film in a short period of time without deteriorating the transparent resin film, which can be continuously produced, and has abrasion resistance and chemical corrosion resistance. Anti-reflective film coating with excellent properties such as anti-corrosion.

In particular, according to the antireflection film of the second aspect, in the antireflection film provided with the light absorbing layer, it is possible to form a low-refractive index layer with a very low refractive index that is significantly excellent in abrasion resistance, thereby reducing light absorption. The film thickness of the layer increases the transmittance. Therefore, it is possible to achieve a minimum reflectance of 0.5% or less, a hard coat 550nm transmittance of 70% or more, a wavelength of 400nm reflectance of 2% or less, high transmittance, and low reflectance. Reflective film suitable for plasma display panels and CRT applications.

III. The object of the third aspect is to provide a low-refractive-index layer that can be easily formed without deteriorating the transparent resin film, can be continuously produced, and has excellent properties such as abrasion resistance and chemical corrosion resistance. coating type anti-reflection film.

The antireflection film of the third aspect is an antireflection film formed by sequentially laminating an easy-adhesive layer, a hard coat layer, a high refractive index layer, and a low refractive index layer on a transparent base film, or on a transparent base film. The anti-reflection film formed by stacking an easy-adhesive layer, a high-refractive-index hard coat layer and a low-refractive-index layer in sequence, is characterized in that the low-refractive-index layer is passed through an atmosphere with an oxygen concentration of 0 to 10,000 ppm. The coating film is obtained by irradiating ultraviolet rays to cure it. The coating film contains hollow silica particles (hereinafter referred to as "hollow silica"), a multifunctional (meth)acrylic compound, that is, has two or two The above (meth)acryloyl (meth)acrylic compound, photopolymerization initiator.

The hollow silica used in the third aspect has a low refractive index and is effective as a material for the low refractive index layer. In addition, by selecting a polyfunctional (meth)acrylic compound as a binder component, abrasion resistance, chemical resistance, and stain resistance can be imparted, and a favorable low-refractive index layer can be formed. In addition, the low-refractive-index layer of the third aspect is cured by irradiating ultraviolet rays under a specific low-oxygen condition, so heating is not required, and furthermore, the transparent resin film does not deteriorate, and the low-refractive index layer can be formed in continuous production. Low refractive index layer with excellent abrasion resistance and chemical corrosion resistance.

That is, the present inventors conducted follow-up experiments on the above-mentioned prior art, and found that when a low-refractive index layer was formed by mixing a polyfunctional acrylic resin with more than bifunctional groups and porous silica particles, the film strength was very low, even if only bifunctional Even when a polyfunctional acrylic resin having more than a functional group is mixed into the hollow silica fine particles, the abrasion resistance cannot be improved at all. In addition, it was found that even if a low-refractive index layer is directly formed on the surface of the base material, antireflection performance such as minimum reflectance, which is indispensable for an antireflection film, is still insufficient.

It has also been found that the refractive index of silica cannot be sufficiently lowered in porous silica fine particles, and hollow silica must be used for further lowering the refractive index.

Based on these findings, the present inventors found that, first, regarding the film composition, by forming a transparent base film/easy adhesion layer/hard coat layer, a high refractive index layer/low refractive index layer, or, forming a transparent base film/easy adhesion layer, Adhesive layer/conductive high refractive index hard coat layer/low refractive index layer to improve anti-reflection performance. In addition, the abrasion resistance of the low-refractive index layer is greatly improved by curing the adhesive by irradiating ultraviolet light under the condition of very low oxygen concentration, among which, very strong abrasion resistance can be obtained only when a special acrylic resin is used as the adhesive Damage and chemical resistance, thus completing the third aspect of the anti-reflection film.

According to the third aspect, it is possible to provide a low-refractive-index layer capable of forming a low-refractive-index layer on a transparent resin film in a short period of time without deteriorating the transparent resin film, capable of continuous production, and having abrasion resistance and chemical corrosion resistance. Anti-reflective film coating with excellent properties such as anti-corrosion.

IV. The purpose of the fourth aspect is to provide an anti-reflective performance of the outermost anti-reflection layer (reduction of external light reflection, reduction of reflected color), and a high-visibility electromagnetic device with excellent antifouling properties. Shielding light-transmitting window materials and gas discharge type light-emitting panels.

The electromagnetic shielding window material of the fourth aspect is formed by laminating and integrating at least an electromagnetic shielding layer, a transparent substrate, and an outermost antireflection layer, wherein the antireflection layer has a high refractive index layer, and The low-refractive-index layer provided on the high-refractive-index layer, the low-refractive-index layer contains hollow silica particles (hereinafter referred to as "hollow silica"), polyfunctional (meth)acrylic It is formed by the coating film of compound and photopolymerization initiator.

The gas discharge type light-emitting panel of the fourth aspect is formed by laminating and integrating the light-emitting panel body, the electromagnetic shielding layer provided on the front surface of the light-emitting panel body, and the outermost anti-reflection layer, and is characterized in that: The anti-reflection layer has a high refractive index layer, a low refractive index layer disposed on the high refractive index layer, and the low refractive index layer contains hollow silicon dioxide particles (hereinafter referred to as "hollow silicon dioxide") by photocuring. ), polyfunctional (meth)acrylic compounds, and photopolymerization initiator coatings.

The hollow silica used in the fourth aspect has a low refractive index and is effective as a material for the low refractive index layer. In addition, by selecting a polyfunctional (meth)acrylic compound as a binder component, abrasion resistance, chemical resistance, and stain resistance can be imparted, and a favorable low-refractive index layer can be formed. In addition, since the low-refractive-index layer of the fourth aspect is cured by irradiating ultraviolet rays, heating is not required, and when a transparent resin film is used as a base material, it does not deteriorate, and the low-refractive-index layer can be formed by continuous production. .

According to the fourth aspect, it is possible to provide a high-visibility electromagnetic shielding property with excellent anti-reflection performance (reduction of external light reflection, reduction of reflection color) and excellent anti-fouling properties of the outermost anti-reflection layer. Light-transmitting window materials and gas-discharge type light-emitting panels.

V. The purpose of the fifth aspect is to provide a high-resistance material with excellent anti-reflection performance (reduction in reflection of external light, reduction in reflection color, reduction in color change) of the anti-reflection layer arranged on the surface, and excellent antifouling properties. Visual flat panel display panels and window materials.

The flat display panel of the fifth aspect is a flat display panel provided with an antireflection layer on the surface, wherein the antireflection layer has a high refractive index layer and a low refractive index layer arranged on the high refractive index layer, and is characterized in that The low refractive index layer is formed by photocuring a coating film containing hollow silica particles (hereinafter referred to as "hollow silica"), a polyfunctional (meth)acrylic compound, and a photopolymerization initiator. .

The window material of the fifth aspect is a window material provided with an anti-reflection layer on the surface, wherein the anti-reflection layer has a high refractive index layer and a low refractive index layer arranged on the high refractive index layer, and is characterized in that: The low refractive index layer is formed by photocuring a coating film containing hollow silica particles (hereinafter referred to as "hollow silica"), a polyfunctional (meth)acrylic compound, and a photopolymerization initiator.

The hollow silica used in the fifth aspect has a low refractive index and is effective as a material for the low refractive index layer. In addition, by selecting a polyfunctional (meth)acrylic compound as a binder component, abrasion resistance, chemical resistance, and stain resistance can be imparted, and a favorable low-refractive index layer can be formed. Furthermore, since the low-refractive-index layer of the fifth aspect is cured by irradiating ultraviolet rays, heating is not required, and further, the low-refractive-index layer can be formed in continuous production without deterioration when using a transparent resin film as a base material.

According to the fifth aspect, an antireflection layer provided on the surface has excellent antireflection performance (reduction of reflection of external light, reduction of reflection color, reduction of color change), and a high-visibility product having excellent antifouling properties can be provided. Innovative flat panel display panels and window materials.

VI. The object of the sixth aspect is to provide a high-efficiency solar cell module with improved power generation efficiency by forming an antireflection layer on the surface with a low reflectance of external light and a high incidence rate of solar energy.

A solar cell module according to claim 6 is formed by sealing a member for solar cells between a surface-side transparent protection member and an inner surface-side protection member, and is characterized in that an antireflection layer is formed on the surface of the surface-side transparent protection member. The solar cell module, the anti-reflection layer has a high refractive index layer and a low refractive index layer arranged on the high refractive index layer, and the low refractive index layer contains hollow silicon dioxide particles (hereinafter referred to as " Hollow silica"), polyfunctional (meth)acrylic compound, photopolymerization initiator coating film.

The hollow silica used in the sixth aspect has a low refractive index and is effective as a material for the low refractive index layer. In addition, by selecting a polyfunctional (meth)acrylic compound as a binder component, abrasion resistance, chemical resistance, and stain resistance can be imparted, and a favorable low-refractive index layer can be formed. In addition, since the low-refractive-index layer of the sixth aspect is cured by irradiating ultraviolet rays, heating is not required, and even if a transparent resin film is used as a base material, it does not deteriorate, and the low-refractive-index layer can be formed by continuous production. .

According to the sixth aspect, a high-efficiency solar cell module having improved antireflection efficiency is provided by forming an antireflection layer having a low reflectance of external light and a high incidence rate of solar energy on the surface.

Description of drawings

Fig. 1 is a schematic sectional view showing the constitution of a conventional coating type antireflection film.

Fig. 2 is a schematic cross-sectional view showing the structure of a light-absorbing antireflection film.

Fig. 3 is a reflection spectrum diagram of an existing anti-reflection film.

Fig. 4 is a reflection spectrum diagram of an existing anti-reflection film.

Fig. 5 is a reflection spectrum diagram of a light-absorbing antireflection film.

Fig. 6 is a reflectance spectrum diagram of Experimental Example B-1.

Fig. 7 is a reflectance spectrum diagram of Experimental Example B-2.

Fig. 8 is a reflectance spectrum diagram of Experimental Example B-3.

FIG. 9 is a reflectance spectrum diagram of Experimental Example A-1.

Fig. 10 is a reflection spectrum diagram of Experimental Example A-2.

Fig. 11 is a reflectance spectrum diagram of Experimental Example A-3.

Fig. 12 is a reflection spectrum diagram of Experimental Example B-4.

Fig. 13 is a reflectance spectrum diagram of Experimental Example B-5.

Fig. 14 is a reflection spectrum diagram of Experimental Example B-6.

Fig. 15 is a reflectance spectrum diagram of Experimental Example B-7.

Fig. 16 is a reflection spectrum diagram of Experimental Example A-4.

Fig. 17 is a reflectance spectrum diagram of Experimental Example A-5.

Fig. 18 is a reflectance spectrum diagram of Experimental Example A-6.

Fig. 19 is a reflectance spectrum diagram of Experimental Example B-8.

Fig. 20 is a reflectance spectrum diagram of Experimental Example B-9.

Fig. 21 is a schematic sectional view showing the constitution of a conventional coating type antireflection film.

Fig. 22 is a reflectance spectrum diagram of Experimental Example b-1.

Fig. 23 is a reflectance spectrum diagram of Experimental Example b-2.

Fig. 24 is a reflectance spectrum diagram of Experimental Example b-3.

Fig. 25 is a reflectance spectrum diagram of Experimental Example a-1.

Fig. 26 is a reflectance spectrum diagram of Experimental Example a-2.

Fig. 27 is a reflection spectrum diagram of Experimental Example a-3.

Fig. 28 is a reflectance spectrum diagram of Experimental Example b-4.

Fig. 29 is a reflectance spectrum diagram of Experimental Example b-5.

Fig. 30 is a reflectance spectrum diagram of Experimental Example b-6.

Fig. 31 is a reflection spectrum diagram of Experimental Example b-7.

Fig. 32 is a reflection spectrum diagram of Experimental Example a-4.

Fig. 33 is a reflectance spectrum diagram of Experimental Example a-5.

Fig. 34 is a reflectance spectrum diagram of Experimental Example a-6.

Fig. 35 is a reflectance spectrum diagram of Experimental Example b-8.

Fig. 36 is a reflection spectrum diagram of Experimental Example b-9.

Fig. 37 is a cross-sectional view showing a configuration example of an antireflection film used in the fourth aspect.

Fig. 38a is a schematic cross-sectional view showing an example of a conventional electromagnetic shielding light-transmitting window material, and Fig. 38b is a schematic cross-sectional view showing an example of a conventional gas discharge type light-emitting panel.

Fig. 39 is a schematic cross-sectional view showing a configuration example of an antireflection film used in the fifth aspect.

Fig. 40 is a graph showing the influence of the film thickness of the high refractive index layer on the reflectance.

Fig. 41 is a graph showing the influence of the film thickness of the high refractive index layer on the reflectance.

Fig. 42 is a schematic cross-sectional view showing a surface antireflection layer of an embodiment of the solar cell module according to the sixth aspect.

Fig. 43 is a cross-sectional view showing the structure of a solar cell module.

Fig. 44 is a graph showing the influence of the film thickness of the high-refractive index layer and the low-refractive index layer on the reflectance.

Detailed ways

I. Implementation of the first aspect

Embodiments of the antireflection film according to the first aspect will be described below.

As shown in FIG. 1 , in the antireflection film according to the first aspect, a hard coat layer 2 , a high refractive index layer 3 and a low refractive index layer 4 are sequentially laminated on a transparent base film 1 . Alternatively, in FIG. 1, a conductive high-refractive-index hard coat layer is provided instead of the hard-coat layer and the high-refractive index layer.

In the first aspect, as the substrate 1, polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), acrylic Resins, polycarbonate (PC), polystyrene, cellulose triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane, Cellophane, etc., preferably transparent films of PET, PC, and PMMA.

The thickness of the base film 1 can be appropriately determined according to the properties required for the application of the obtained antireflection film (for example, strength, film properties), etc., and is usually in the range of 1 μm to 10 mm.

As the hard coat layer 2, a synthetic resin-based hard coat layer is preferable, especially an ultraviolet curable resin is preferable, and a combination of polyfunctional acrylate and silica fine particles is particularly preferable. The thickness of the hard coat layer 2 is preferably 2 to 20 μm.

The high refractive index layer 3 is preferably a synthetic resin containing metal oxide particles. The synthetic resin is particularly preferably an ultraviolet curable synthetic resin, particularly preferably an acrylic resin, an epoxy resin, or a styrene resin, and most preferably an acrylic resin. In addition, as the metal oxide fine particles, at least one selected from the group consisting of ITO, TiO ₂ , ZrO ₂ , CeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ and Ho ₂ O ₃ is preferable. or a plurality of high refractive index metal oxide particles, particularly preferably TiO ₂ particles and ITO particles.

With regard to the ratio of metal oxide particles and synthetic resin in the high refractive index layer 3, if there are too many metal oxide particles and insufficient synthetic resin, the film strength of the high refractive index layer will decrease. On the contrary, if the metal oxide particles are too small, Otherwise, the refractive index cannot be sufficiently increased. Therefore, the proportion of the metal oxide fine particles is 10 to 60% by volume, particularly preferably 20 to 50% by volume, based on the total amount of the metal oxide fine particles and the synthetic resin.

The thickness of such a high refractive index layer 3 is preferably about 80 to 100 nm. In addition, the refractive index of the high refractive index layer 3 is preferably 1.65 or more, particularly preferably 1.66 to 1.85. In this case, by controlling the refractive index of the low refractive index layer 4 to 1.39 to 1.47, the surface can be obtained. An antireflection film excellent in antireflection performance with a minimum reflectance of 1% or less. In particular, when the refractive index of the low-refractive index layer 4 is controlled to 1.45 or less, the anti-reflection property can be further improved, and an anti-reflection film having a surface reflectance with a minimum reflectance of 0.5% or less can be produced.

In the first aspect, the low refractive index layer 4 is obtained by irradiating ultraviolet rays to a coating film comprising hollow silica, polyfunctional (methyl ) a binder component formed of an acrylic compound and a photopolymerization initiator.

Hollow silica is hollow shell-shaped silica fine particles, and its average particle diameter is 10 to 200 nm, particularly preferably 10 to 150 nm. When the average particle diameter of the hollow silica is less than 10 nm, it is difficult to lower the refractive index of the hollow silica, and if it exceeds 200 nm, there is diffuse reflection of light and the surface roughness of the formed low refractive index layer increases. and so on.

Hollow silica has air with a low refractive index (refractive index = 1.0) inside the hollow, and thus, its refractive index is significantly lower than that of conventional silica (refractive index = 1.46). The refractive index of hollow silica is determined by the volume ratio of its hollow part, and usually the refractive index is preferably around 1.20-1.40.

In addition, the refractive index of hollow silica: n (hollow silica) is derived from the refractive index of silica constituting the hollow particle shell: n (silica), and the refractive index of the air inside: n (air) , calculated according to the following formula.

n (hollow silica) = n (silica) × volume percentage of silica

As mentioned above, n(silica) is about 1.47, and n(air) is very low at 1.0, so the refractive index of such hollow silica is very low.

Furthermore, the refractive index of the low-refractive-index layer of the first aspect using such hollow silica: n (low-refractive-index layer) is composed of the refractive index of hollow silica: n (hollow silica) and a binder The refractive index of the component: n (binder), calculated according to the following formula.

n (low refractive index layer) =

n(hollow silica)×volume ratio of hollow silica in the low refractive index layer+n(binder)×volume ratio of binder in the low refractive index layer.

Among them, in addition to the special fluorine-containing acrylic binder, the refractive index of the binder is usually about 1.50 to 1.55. Therefore, increasing the volume percentage of hollow silica in the low refractive index layer will reduce the refractive index of the low refractive index layer. It is important to reduce the rate.

In the first aspect, the more content of hollow silicon dioxide in the low refractive index layer, the more the low refractive index layer can be formed, and the antireflection film with excellent antireflection performance can be obtained. When the content of the agent component is relatively reduced, the film strength of the low-refractive index layer decreases, and the abrasion resistance and durability decrease. However, the reduction in membrane strength caused by the increase in the amount of hollow silica mixed can be compensated by surface treatment of hollow silica, and the membrane strength can also be supplemented by selecting the type of binder component to be mixed.

In the first aspect, the content of the hollow silica in the low refractive index layer is preferably 20 to 55% by weight, particularly 30 to 50% by weight, by surface treatment of the hollow silica and selection of binder components. , In order to realize the low refractive index of the low refractive index layer, the refractive index is about 1.39 to 1.45, and at the same time, the wear resistance is ensured.

Next, the polyfunctional (meth)acrylic compound as the binder component of the low refractive index layer of the first aspect will be described.

The polyfunctional (meth)acrylic compound is preferably a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or a 4-functional (meth)acrylic compound represented by the following general formula (II) The quasi-compound is a main component, and is preferably contained in an amount of 50% by weight or more, particularly preferably 90% by weight or more, of the entire binder component.

[chemical 1]

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

n, m, o, p, q, r each independently represent an integer of 0 to 2,

R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

[Chem 2]

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

s, t, u, and v each independently represent an integer of 0 to 2,

R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

Examples of the hexafunctional (meth)acrylic compound represented by the general formula (I) include dipentaerythritol hexaacrylate, ethylene oxide adducts of dipentaerythritol hexaacrylate, or ethylene oxide adducts. A compound in which H is substituted by F, these compounds may be used alone or in combination of two or more.

In addition, examples of the tetrafunctional (meth)acrylic compound represented by the above general formula (II) include pentaerythritol tetraacrylate, ethylene oxide adducts (1 to 8) of pentaerythritol tetraacrylate, or A compound in which H of ethylene oxide is replaced by F, these compounds may be used alone or in combination of two or more.

As a binder component, one or more 6-functional (meth)acrylic compounds represented by the above-mentioned general formula (I) and one or more 4-functional (meth)acrylic compounds represented by the above-mentioned general formula (II) can be used in combination. base) acrylic compounds.

The polyfunctional (meth)acrylic compound represented by the above general formula (I), (II), especially the hexafunctional (meth)acrylic compound represented by the above general formula (I) has high hardness and abrasion resistance It is excellent and can effectively form a low-refractive-index layer with high abrasion resistance.

In addition, in the first aspect, as the binder component, it is preferable to use a hexafunctional (meth)acrylic compound represented by the above general formula (I) and/or a tetrafunctional (meth)acrylic compound represented by the above general formula (II) base) acrylic compound, used in combination with a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) or a specific fluorine-containing multifunctional (meth)acrylic compound, by using these binding agents Component that imparts abrasion resistance and stain resistance to the low refractive index layer. In addition, these binder components have a lower refractive index than the hexafunctional (meth)acrylic compound represented by the above general formula (I) or the tetrafunctional (meth)acrylic compound represented by the above general formula (II), Therefore, even if the mixing amount of the hollow silica is reduced, a low-refractive-index layer having a low refractive index can be formed.

A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III)

(In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.)

Examples of the fluorine-containing bifunctional (meth)acrylic compound represented by the above general formula (III) include 2,2,3,3,4,4-hexafluoropentanediol diacrylate, etc., these The compounds may be used alone or in combination of two or more.

In addition, the above-mentioned specific polyfunctional (meth)acrylic compound, that is, a (meth)acrylic compound having 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or less, having 3 to 6 functional groups, and (meth)acrylic compounds having 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1,000 to 5,000 may be used alone or in combination of two or more .

It is also possible to use one or more of the above-mentioned fluorine-containing bifunctional (meth)acrylic compounds in combination with one or more fluorine-containing multifunctional (meth)acrylic compounds.

Using the fluorine-containing bifunctional (meth)acrylic compound can lower the refractive index of the low refractive index layer and improve the antifouling property, but if the compounding amount is too large, the abrasion resistance will decrease. Therefore, it is preferable to mix 5% by weight or more of the fluorine-containing bifunctional (meth)acrylic compound in the total binder components, particularly preferably 5 to 10% by weight.

In addition, although the use of the above-mentioned fluorine-containing polyfunctional (meth)acrylic compound can also achieve a low refractive index of the low refractive index layer and improve antifouling properties, but if the amount of the compound is too large, the abrasion resistance reduced sex. Therefore, it is preferable to mix the fluorine-containing polyfunctional (meth)acrylic compound in an amount of 5% by weight or more, particularly preferably 5 to 10% by weight, of the total binder components.

In addition, in the case of using a fluorine-containing bifunctional (meth)acrylic compound in combination with a fluorine-containing polyfunctional (meth)acrylic compound, it is preferable that, among the total binder components, the fluorine-containing bifunctional (meth)acrylic The compound and the fluorine-containing polyfunctional (meth)acrylic compound are mixed in a total of 5% by weight or more, particularly preferably 5 to 10% by weight.

The hollow silica used in the first aspect has a particle diameter larger than that of conventional silica particles (with a particle diameter of about 5 to 20 nm) mixed in an existing low-refractive index layer. Therefore, even in In the case of using the same binder component, the film strength of the formed low-refractive index layer tends to be weaker than in the case of mixing silica particles, and by applying appropriate surface treatment to the hollow silica , can improve the binding force with the binder component, improve the film strength of the formed low refractive index layer, and improve the wear resistance.

As the surface treatment of the hollow silica, it is preferable to use a terminal (meth)acrylic silane coupling agent represented by the following general formula (IV) to perform terminal (meth)acrylic modification on the surface of the hollow silica. sex.

[Chem 3]

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group,

^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms,

R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

Such terminal (meth)acrylic silane coupling agents include, for example, CH ₂ =CH-COO-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ , CH ₂ =C(CH ₃ )-COO -(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

In order to carry out terminal group (meth)acrylic modification on the surface of hollow silica by using such a terminal group (meth)acrylic silane coupling agent, it is preferable to couple the hollow silica with a terminal group (meth)acrylic silane coupling agent. The mixed solution of the joint agent is hydrothermally reacted at 100 to 150° C., or the mixed solution is irradiated with microwaves to cause a reaction. That is, when only the terminal (meth)acrylic silane coupling agent and hollow silica are mixed, the surface cannot be chemically modified with the terminal (meth)acrylic silane coupling agent, and the desired surface modification effect cannot be obtained. In the case of utilizing the hydrothermal reaction, if the reaction temperature is low, sufficient terminal (meth)acrylic acid modification cannot be performed. However, if the reaction temperature is too high, the reactivity will decrease instead, so the hydrothermal reaction temperature is preferably 100 to 150°C. In addition, although the hydrothermal reaction time varies depending on the reaction temperature, it is usually about 0.1 to 10 hours. On the other hand, in the case of using microwaves, if the set temperature is too low, sufficient terminal (meth)acrylic acid modification cannot be performed. Therefore, for the same reason as above, the set temperature is preferably 90 to 150 ℃. The microwave is suitable to use a microwave with a frequency of 2.5 GHz. If the microwave is irradiated, the terminal group (meth)acrylic acid modification can be carried out in a short time of about 10 to 60 minutes. In addition, as a mixed solution used in this reaction, for example, a hollow silica of 3.8% by weight and an alcohol solvent of 96% by weight (a mixed solvent of 1:4 (weight ratio) of isopropanol and isobutanol) can be cited. , 3% by weight of acetic acid, 1% by weight of water, and a reaction solution made of 0.04% by weight of silane coupling agent.

By chemically modifying the surface of hollow silica with such a terminal (meth)acrylic silane coupling agent, the hollow silica and the binder component can be firmly bonded, even when the amount of hollow silica mixed is large. Even in the case of , a low-refractive-index layer excellent in wear resistance can be formed, and the low-refractive index of the low-refractive-index layer can be achieved by increasing the blending amount of hollow silica.

In addition, the surface of the hollow silica can also be modified with a terminal fluorinated alkyl silane coupling agent represented by the following general formula (V). In this case, the terminal group The terminal group fluorinated alkyl modification carried out by the fluorinated alkyl silane coupling agent is preferably under the same conditions as when the above-mentioned terminal group (meth)acrylic acid silane coupling agent is used to carry out the terminal group (meth)acrylic acid modification , by hydrothermal method or microwave irradiation method.

[chemical 4]

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.)

In addition, examples of the terminal group fluorinated alkylsilane coupling agent include C ₈ F ₁₇ -(CH ₂ ) ₂ -Si-(OCH ₃ ) ₃ , C ₆ F ₁₃ -(CH ₂ ) ₂ -Si -(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

By chemically modifying the surface of the hollow silica using such a terminal group fluorinated alkylsilane coupling agent, the antifouling property of the formed low refractive index layer can be improved.

The low-refractive-index layer of the first aspect is formed by irradiating the above-mentioned binder component with ultraviolet light to cure it in the presence of a photopolymerization initiator. One or more of Ilugac 184, 819, 651, 1173, 907 and the like are preferably mixed in an amount of 3 to 10 phr based on the binder component. When the compounding quantity of a photoinitiator is less than this range, sufficient crosslinking hardening cannot be performed, and when it exceeds this range, the film strength of a low-refractive-index layer will fall.

The low refractive index layer of the first aspect is coated with a composition obtained by mixing hollow silica, a polyfunctional (meth)acrylic compound as a binder component, and a photopolymerization initiator in a predetermined ratio to a high refractive index layer. index layer or conductive high-refractive-index hard coat layer, which is formed by irradiating ultraviolet rays in an atmosphere with an oxygen concentration of 0 to 10,000 ppm to cure it. Damage is greatly reduced, so it is controlled to 1000 ppm or less, preferably 200 ppm or less.

The thickness of such a low refractive index layer is preferably 85 to 110 nm.

In the first aspect, in order to form the hard coat layer 2, the high refractive index layer 3 and the low refractive index layer 4 on the base film 1, or form the conductive high refractive index hard coat layer and the low refractive index layer 4, preferably An uncured resin composition (resin composition in which the above fine particles are mixed if necessary) is applied, followed by irradiation with ultraviolet rays. In this case, it may be cured after each application of one layer, or after application of three or two layers.

Specific methods of coating include a method in which a coating solution obtained by dissolving a binder component in a solvent such as toluene is coated with a gravure coater, dried, and then cured by ultraviolet rays. According to this wet coating method, there is an advantage that a film can be formed uniformly at high speed and at low cost. Curing by irradiating ultraviolet rays after coating has the effect of improving adhesion and film hardness, and can continuously produce anti-reflection films without heating.

Such an antireflection film according to the first aspect can ensure good light transmission and durability when used for front filters of PDPs of OA devices or liquid crystal panels, or windows of vehicles or special buildings.

The first aspect will be described more specifically below by listing examples and comparative examples.

In addition, in the following content, various characteristics and physical properties were evaluated according to the following methods.

<Measurement of Refractive Index>

On a PET film without an easy-adhesive layer ("Toray Lumira", film thickness 50 μm), the composition for forming a low-refractive index layer is coated at a thickness of about 1/4λ relative to the light wavelength of 550 nm and let it solidify. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm. Then, a black vinyl tape was stuck on the uncoated surface, the reflectance was measured, and the refractive index was calculated from the minimum reflectance of the reflectance spectrum.

<Measurement of abrasion resistance (rubber rubbing resistance)>

A hard coat layer ("Z7503" manufactured by JSR) is applied on a 50 μm thick TAC film ("TAC film" manufactured by Fuji Film Co., Ltd.), then dried and cured to form a film with a thickness of 5 μm and a pencil hardness of 3H or more. hard coating. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm. Next, a film-forming composition for a high refractive index layer ("Ei-3" manufactured by Dainippon Paint Co., Ltd.) containing ITO fine particles, a polyfunctional acrylic compound, and a photopolymerization initiator is applied, dried, and cured to form a film with a thickness of about 90 nm. , A high refractive index layer having a refractive index of 1.67 to 1.68. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm.

Next, the low-refractive-index layer film-forming composition was coated on the high-refractive-index layer, dried and cured to form a low-refractive-index layer with a thickness of about 95 nm. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 800 mJ/cm ² , and the oxygen concentration during curing was 150 ppm.

For the antireflection film (reflection color: purple) produced in this way, its surface (low refractive index layer surface) was reciprocally rubbed with a plastic eraser at a load pressure of about 4.9×10 ⁴ N/m ² . If the film of the low-refractive index layer is destroyed, the reflected color will gradually change from purple → red → yellow, so the number of reciprocations until the color changes first is the number of rubber rubbing resistance, and the number of rubber rubbing resistance is 100 times or 100 times. When the number of times was more than 100 times, the wear resistance was good (◯), and when it was less than 100 times, it was poor (×).

<Minimum Reflectance>

For the anti-reflection film produced by the same method as the above-mentioned evaluation method of abrasion resistance, a black tape was attached to the inner surface (the side opposite to the film-forming surface), and the reflection spectrum was measured at 5° regular reflection. The reflectance of is recorded as the minimum reflectance. This minimum reflectance is all 0.5% or less in "Examples".

<Chemical resistance>

Put tulle on the film-forming surface side of the antireflection film manufactured by the same method as the above-mentioned abrasion resistance evaluation method, and drop a few drops of 3% by weight NaOH aqueous solution, in order to prevent the water in the NaOH aqueous solution from evaporating. Cover with a disposable paper cup and place at 25°C for 30 minutes. Then, the tulle was taken away, washed with pure water, and the reflection color of the anti-reflection film was observed visually for any change. If there was no change in the reflection color, it was rated as having excellent chemical corrosion resistance (○), and if the reflection color was changed, it was marked as Chemical resistance is poor (×).

<Binder Strength>

Add 5 phr of photopolymerization initiator (Irugakuyua-184 (Irugakuyua-184) manufactured by Saiba Specialty Chemicals Co., Ltd.) to the binder component, and apply it to PET with a double-sided easy-adhesive layer manufactured by Toyobo Co., Ltd. On the film "A4300", then, in an atmosphere with an oxygen concentration of 100ppm, irradiate ultraviolet light with a metal halide lamp at a cumulative light intensity of 1000mJ/ ^cm2 to cure it, forming a bonding agent layer with a thickness of 8μm. For the agent layer, the Vickers hardness was measured at a penetration depth of 1 μm using a microhardness tester manufactured by FISHERSCOPE.

<Fouling resistance>

On the anti-reflection film produced by the same method as the above-mentioned evaluation method of abrasion resistance, draw a super-thin line (red) with a magic pen made by Zebra Co., Ltd. on the film-forming surface side. If the magic pen cannot draw a line, record it as The antifouling property was good (◯), and when a line could be drawn, it was rated as poor antifouling property (×).

In addition, as the hollow silica, hollow silica having an average particle diameter of 60 nm and a refractive index n=about 1.30 or less was used.

[Example]

Next, with respect to the antireflection film according to the first aspect, experimental examples demonstrating the effects of various aspects of performance improvement will be given.

Experimental example 1

In order to evaluate the binder components, the hardness of the binder components shown in Table 1 was measured by the method described above.

In addition, 5 phr of photopolymerization initiator "Ilgacyua-184" was added to the binder component, and hollow silica was added so that the total amount of photopolymerization initiator and binder: hollow silica = 62.5: 37.5 (weight %), to obtain the low refractive index layer film-forming composition, use this composition, detect abrasion resistance and chemical corrosion resistance by the above method, the results are shown in Table 1.

[Table 1] no Binder component Binding agent chemical resistance wear resistance type Number of functional groups molecular weight Hardness(N/mm ² ) Resistance to rubber friction times (times) evaluate 1 2-Hydroxyethyl acrylate*1 1 116 Unable to determine x 1 x 2 Dimethyloltricyclodecane diacrylate*1 2 328 318 ○ 5 x 3 Trimethylolpropane Triacrylate*1 3 296 356 ○ 20 x 4 Pentaerythritol triacrylate*1 3 298 423 ○ 30 x 5 Pentaerythritol tetraacrylate*1 4 352 419 ○ 100 ○ 6 Dipentaerythritol hexaacrylate*1 6 580 476 ○ 175 ○ 7 U-15HA※2 15 2076 473 ○ 35 x 8 EA-6320※3 3 924 291 ○ 2 x 9 U-6HPA*4 6 818 156 ○ 25 x

*1: Manufactured by Kyoei Corporation

*2: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (15 functional groups, high hardness acrylic oligomer)

*3: Manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (not high hardness type)

※4: Product made by Shin-Nakamura Chemical Industry Co., Ltd. (high hardness type urethane acrylate)

According to Table 1, it can be seen that for binder components, the more functional groups, the better. If the molecular weight increases, the number of functional groups is very large, and although the hardness increases, the wear resistance decreases. Therefore, although a large number of functional groups is good, if the molecular weight exceeds a certain level, the performance of hollow silica as a binder deteriorates.

Therefore, the hexafunctional or tetrafunctional (meth)acrylic compound represented by the above general formulas (I) and (II) is very suitable as a binder for hollow silica. In this case, all chemical corrosion resistances were good.

Experimental example 2

In order to evaluate the pretreatment of the hollow silica, the pretreatment shown in Table 2 was performed on the hollow silica by the following method. In addition, as a silane coupling agent, an acrylic modified silane compound "KBM-5103" (CH ₂ =CH-COO-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ ) manufactured by Shin-Etsu Chemical Co., Ltd. was used.

Pretreatment method (1): with 3.8% by weight of hollow silica, 96% by weight of alcohol solvent (a mixed solvent of isopropanol and isobutanol 19:81 (weight ratio)), 3% by weight of acetic acid, 1% by weight of The reaction solution made of water and 0.04% by weight of silane coupling agent was put into a pressure-resistant stainless steel container with PTFE (polytetrafluoroethylene) inside, and hydrothermally synthesized at the temperature shown in Table 2 for 4 hours.

Pretreatment method (2): put the reaction solution prepared in the same way as the above-mentioned pretreatment method (1) into a microwave generator manufactured by Tokyo Electronics Co., Ltd., and irradiate it for 15 minutes at the set temperature shown in Table 2. The frequency is 2.5 GHz microwave. Since the microwave generator reacts in an open system, the reaction solvent will boil.

Pretreatment method (3): A reaction solution was prepared in the same manner as in the above-mentioned pretreatment method (1), and then no energy was applied.

In addition, prepare non-porous silica fine particles ("IPA-ST" (particle diameter: 10-20nm) manufactured by Nissan Chemical Co., Ltd.), and pretreat the silica fine particles in the same manner as the above-mentioned pretreatment method (1). deal with.

Using non-pretreated hollow silica, pretreated hollow silica, non-pretreated silica fine particles, pretreated silica fine particles to be evaluated as wear-resistant in Experimental Example 1 The dipentaerythritol hexaacrylate with the best destructive properties is used as the binder component, and 5 phr of the polymerization initiator "Ilgacyua-184" is added to the binder component, so that the total amount of the photopolymerization initiator and the binder: microparticles (hollow carbon dioxide silicon or silica microparticles)=55:45 (weight ratio), respectively prepare low refractive index layer film-forming composition, detect refractive index and chemical corrosion resistance and abrasion resistance by above-mentioned method, the result is as shown in table 2 Show.

[Table 2] No. Particle type With or without surface treatment Surface treatment method Refractive index chemical resistance Resistance to rubber friction times (times) Overview method Set temperature(°C) 1 Silica particles none - - 1.50 ○ >500 x 2 Silica particles have (1) water heat 120 1.50 ○ >500 x 3 Hollow silica none - - 1.42 ○ 25 x 4 Hollow silica have (3) No response - 1.42 ○ 25 x 5 Hollow silica have (1) water heat 70 1.42 ○ 30 x 6 Hollow silica have (1) water heat 120 1.42 ○ 125 ○ 7 Hollow silica have (1) water heat 150 1.42 ○ 100 ○ 8 Hollow silica have (2) microwave 80 1.42 ○ 20 x 9 Hollow silica have (2) microwave 105 1.42 ○ 100 ○

It can be seen from Table 2:

No. 1 and 2 use silica particles without voids. Regardless of whether pretreatment is performed or not, the wear resistance is very good, but the refractive index does not decrease. It can be seen that silica particles without voids are not suitable as low Refractive index material.

When hollow silica is used, the refractive index of the low-refractive index layer like No. 3 is extremely low, but if the proportion of hollow silica is increased, the film strength decreases and the wear resistance deteriorates.

On the other hand, when only the silane coupling agent is added to the hollow silica, there is almost no change in the film strength as in No. 4.

Even if the hydrothermal method is used to react hollow silica with a silane coupling agent, there is almost no change in the wear resistance at a reaction temperature of 70°C like No. Very good wear resistance at ~150°C.

In addition, when using microwaves and reacting at a set temperature of 80°C, there is almost no change in wear resistance as in No. 8, but when the reaction is performed at a higher reaction temperature, the wear resistance The increase in abrasiveness is very large.

Therefore, it is known that as a method of improving the wear resistance of the low-refractive index layer using hollow silica, there is an acrylic modification method of terminal groups of hollow silica, and it can be achieved by using either a hydrothermal method or a microwave irradiation method. Significantly improved wear resistance.

In addition, chemical corrosion resistance is very good.

Experimental example 3

In order to study the antifouling effect of the fluorinated silane coupling agent, a fluorinated silane coupling agent "KBM-7803" (C ₈ F ₁₇ -(CH ₂ ) ₂ -Si-( OCH ₃ ) ₃ ) As a silane coupling agent, hollow silica was pretreated by a hydrothermal method at a reaction temperature of 120° C. as in the pretreatment method (1) of Experimental Example 2.

In addition, only the fluorinated silane coupling agent was added in the same manner as the pretreatment method (3) of Experimental Example 2 to prepare unreacted hollow silica.

Using hollow silica without pretreatment and hollow silica after pretreatment, dipentaerythritol hexaacrylate, which was evaluated as the best wear resistance in Experimental Example 1, was used as a binder component. 5 phr of the polymerization initiator "Irugacyua-184" was added to the ingredients so that the total amount of the photopolymerization initiator and binder: hollow silica = 62.5:37.5 (weight ratio), and the composition for forming a low-refractive index layer was prepared separately. , The refractive index and chemical corrosion resistance and wear resistance were detected by the above method, and the results are shown in Table 3.

[table 3] No. Hollow silica with or without surface treatment Surface treatment method Refractive index Resistance to rubber friction times (times) Antifouling chemical resistance Overview 1 none - 1.432 175 x ○ ○ 2 have (3) No response 1.428 90 ○ ○ x 3 have (2) water heat 1.428 120 ○ ○ ◎

It can be seen from Table 3 that due to the slightly reduced mixing amount of hollow silica, in No.1, the wear resistance is very good, but there is no antifouling property, and like No.2, if adding fluorinated silane coupling If there is no reaction with the agent, the antifouling property becomes good, but the film strength decreases. As in No. 3, if the hollow silica is modified by the reaction between the fluorinated silane coupling agent and the hollow silica, the membrane strength can be enhanced while imparting antifouling properties. Also, the refractive index is also improved.

In addition, chemical corrosion resistance is very good.

Experimental example 4

In order to study the effects brought by fluorine-containing bifunctional (meth)acrylic compounds and fluorine-containing multifunctional (meth)acrylic compounds, dipentaerythritol hexaacrylate, which has the best wear resistance in Experimental Example 1, will The mixed components shown in Table 4 were mixed with a mixed component: dipentaerythritol hexaacrylate = 10:90 (weight ratio) as a binder component, and 5 phr of photopolymerization initiator "Irgacyua- 184 ", make the total amount of photopolymerization initiator and binding agent: hollow silicon dioxide=70: 30 (weight ratio) (wherein, only dipentaerythritol hexaacrylate in No.1, photopolymerization initiator and binding agent The total amount of ingredients: hollow silicon dioxide=62.5: 37.5 (weight ratio)), prepare the low-refractive index layer film-forming composition, detect the refractive index, wear resistance and antifouling property by the above-mentioned method, the results are shown in Table 4 shown.

[Table 4] no mixed ingredients Refractive index Resistance to rubber friction times (times) Antifouling Overview 1 - 1.43 175 x ○ 2 CH ₂ ＝CH-COO-CH ₂ -CF ₃ 1.43 50 x x 3 CH ₂ =CH-COO-CH ₂ -C ₈ F ₁₇ 1.43 20 ○ x 4 Fluorinated bifunctional (meth)acrylic compound 1.43 125 ○ ○ 5 Bifunctional monomer (molecular weight about 300) 1.43 35 ○ x 6 Bifunctional monomer (molecular weight about 400) 1.43 5 ○ x 7 Trifunctional monomer (molecular weight about 400) 1.43 100 ○ ○ 8 Trifunctional monomer (molecular weight about 500) 1.43 100 ○ ○ 9 Four-functional monomer (molecular weight about 600) 1.43 100 ○ ○ 10 Hexafunctional monomer (molecular weight about 1000) 1.43 100 ○ ○

It can be seen from Table 4:

In No. 1 in which no compounding components were added, the abrasion resistance was sufficient, but the antifouling property was not. In Nos. 2 and 3 in which a monofunctional fluorinated acrylic monomer was mixed as a compounding component or in Nos. 5 and 6 in which a bifunctional acrylic monomer was mixed as a compounding component, the abrasion resistance decreased to a very low level. In contrast, in Nos. 4, 7 to 10 in which the fluorine-containing bifunctional (meth)acrylic compound represented by the general formula (III) or the fluorine-containing polyfunctional (meth)acrylic compound of the present invention was mixed , It is possible to obtain anti-fouling properties while improving wear resistance.

[comparative example]

Comparative experiment example 1

As in the aforementioned Japanese Patent Laid-Open No. 2003-202406 and Japanese Patent Laid-Open No. 2003-202960, a low-refractive index layer was prepared using a silicone-based binder component, and the film strength and chemical corrosion resistance at this time were measured. experiment.

The method of preparation of the binder components is described below.

First, add 356 parts by weight of methanol to 208 parts by weight of methyltriethoxysilane, ethyltriethoxysilane, or tetraethoxysilane, and then mix 18 parts by weight of water and 18 parts by weight of 0.01N hydrochloric acid ( [H ₂ O]:[OR]=0.5), stirred. The mixed solution was stirred for 2 hours in a thermostat at 25°C. Next, the silane-based binder and hollow silica were mixed to prepare a binder:hollow silica=65:35 (weight ratio). Furthermore, it diluted with isopropanol until the total solid content became 8 weight%, and this was made into the composition for film-forming low-refractive-index layers.

This low-refractive-index layer film-forming composition was applied to the high-refractive-index layer, and the chemical corrosion resistance and abrasion resistance were checked in the same manner as in the above-mentioned experimental example except for heat treatment at 120° C. for 30 minutes ( Resistance to rubber friction times), the results are shown in Table 5.

[table 5] No. Binder component chemical resistance Resistance to rubber friction times (times) Overview 1 Methyltriethoxysilane x 15 x 2 Ethyltriethoxysilane x 15 x 3 Tetramethoxysilane x 25 x

As can be seen from Table 5, when a silicone-based binder component is used, only a low-refractive index layer whose chemical corrosion resistance and abrasion resistance are significantly reduced can be formed.

Comparative experiment example 2

Next, the wear resistance when directly forming a low-refractive index layer on the base material disclosed in the above-mentioned Japanese Patent Application Publication No. 2003-261797, Japanese Patent Application Publication No. 2003-262703 and Japanese Patent Application Publication No. Performance, chemical resistance, anti-reflective properties were studied.

Firstly, a film-forming composition for a low refractive index layer is formed on a transparent substrate by the methods described in these patent documents. The film-forming composition is composed of various multifunctional acrylates and hollow silica according to the multifunctional group Acrylic ester: hollow silica = 65:35 (weight ratio) mixed. This low-refractive index layer film-forming composition was applied to PET film "A4100" with an easy-adhesive layer manufactured by Toyobo Co., Ltd., and irradiated with an ultraviolet cumulative irradiation dose of 800mJ/ ^cm2 under indoor atmosphere. This was cured to form a low refractive index layer having a film thickness of about 95 nm. The oxygen concentration at the time of curing was about 20%.

For the anti-reflection film in which the low refractive index layer was directly formed on the PET film in this way, its abrasion resistance (rubber rub resistance) and chemical corrosion resistance were checked by the above method, and the results are shown in Table 6.

In addition, when the minimum reflectance was measured by the above-mentioned method, all of them exceeded 1.0%, and it was confirmed that the antireflection performance was poor.

[Table 6] No. Binder component Resistance to rubber friction times (times) Antifouling Overview type Number of functional groups 1 Ethylene glycol diacrylate 2 <10 x Low anti-reflection performance, and lower abrasion and chemical resistance than when using silicone-based binders 2 1,6-Hexanediol diacrylate 2 <10 x 3 trimethylolpropane triacrylate 3 <10 x 4 pentaerythritol tetraacrylate 4 <10 x 5 dipentaerythritol hexaacrylate 6 <10 x

As can be seen from Table 6, the antireflection film in which the low-refractive index layer was directly formed on the surface of the base material had low antireflection performance. In addition, since the adhesiveness between the surface of the base material and the low-refractive index layer is poor, the wear resistance is lower than when a silicone-based adhesive is used. Therefore, merely mixing a multifunctional acrylic resin in hollow silica cannot ensure abrasion resistance at all, and chemical resistance is also poor.

Comparative experiment example 3

Based on the results of Comparative Experiment 2, the present inventors then conducted the following experiments by changing the film structure in order to find out whether the film structure of directly forming a low-refractive index layer on the surface of the substrate is the cause of poor performance.

A hard coat layer ("Z7503" manufactured by JSR) is applied on a TAC film with a thickness of 50 μm ("TAC film" manufactured by Fujifilm Co., Ltd.), and then dried and cured to form a hard coating with a thickness of 5 μm and a pencil hardness of 3H or more. coating. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm. Next, a film-forming composition for a high refractive index layer ("Ei-3" manufactured by Dainippon Paint Co., Ltd.) containing ITO fine particles, a polyfunctional acrylic compound, and a photopolymerization initiator is applied, dried, and cured to form a film with a thickness of about 90 nm. , A high refractive index layer having a refractive index of 1.67 to 1.68. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm.

Next, the low-refractive-index layer film-forming composition prepared in Comparative Experimental Example 2 was coated on the high-refractive-index layer, dried and cured to form a low-refractive-index layer with a thickness of about 95 nm. The curing conditions were as follows: the cumulative irradiation dose of ultraviolet rays was 800 mJ/cm ² , and the oxygen concentration during curing was about 20% of the indoor atmosphere.

The antireflection film (reflection color: purple) produced in this way was examined for abrasion resistance (rubber rubbing resistance) and chemical corrosion resistance by the above-mentioned method, and the results are shown in Table 7.

In addition, the minimum reflectance measured by the above-mentioned method was all 0.5% or less, and it was confirmed that the antireflection property was improved.

[Table 7] No. Binder component Resistance to rubber friction times (times) chemical resistance Overview type Number of functional groups 1 Ethylene glycol diacrylate 2 <10 x Anti-reflective performance has improved, but abrasion resistance and chemical resistance are still low 2 1,6-Hexanediol diacrylate 2 <10 x 3 trimethylolpropane triacrylate 3 <10 x 4 pentaerythritol tetraacrylate 4 <10 x 5 dipentaerythritol hexaacrylate 6 <11 x

As can be seen from Table 7, compared with Comparative Experiment 3 in which the low-refractive index layer is directly formed on the substrate, the anti-reflection performance is improved. In addition, although the adhesion of the low-refractive index layer is improved, the wear resistance Slightly improved, but the abrasion resistance is still far from the level of commercial products as anti-reflection film, and the chemical resistance is also poor.

From the comparison of the above experimental examples and comparative experimental examples, it can be seen that not only hollow silica is used as the microparticles, but also a bifunctional or more functional (meth)acrylic compound is used as the binder component. According to the first aspect, by adding The layer structure is made into transparent substrate film/hard coat layer/high refractive index layer/low refractive index layer, and when the low refractive index layer is cured by ultraviolet radiation under the condition of low oxygen concentration of 0-10000ppm, it can effectively improve the wear resistance. damage resistance, chemical resistance and anti-reflective properties.

II. Implementation of the second aspect

Embodiments of the antireflection film according to the second aspect will be described below.

As shown in FIG. 2, the antireflection film according to the second aspect is formed by sequentially laminating an easy-adhesive layer 12, a hard coat layer 13, a transparent conductive layer 14, a light-absorbing layer 15, and a low-refractive index layer 16 on a transparent base film 11. And formed. Alternatively, in FIG. 2, a conductive light-absorbing layer is provided instead of the transparent conductive layer and the light-absorbing layer.

In the second aspect, as the base film 11, polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), Acrylic resin, polycarbonate (PC), polystyrene, cellulose triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane , cellophane, etc., preferably PET, PC, PMMA transparent film.

The thickness of the base film 11 can be appropriately determined according to the properties required for the application of the obtained antireflection film (for example, strength, thin film properties), etc., and is usually 1 μm to 10 mm.

As the transparent base film, a PET film is particularly preferable, and in the case of the PET film, an easy-adhesive layer having a refractive index of 1.55 to 1.61 and a film thickness of 75 to 95 nm is coated on the above-mentioned hard coat side of the PET film. , the minimum reflectivity is reduced, and there is no interference, so it is preferred.

The easy-adhesive layer 12 is used to improve the adhesion of the hard coat layer 13 to the substrate film 11, and is usually mixed with SiO ₂ , ZrO ₂ , TiO ₂ , and Al ₂ in thermosetting resins such as copolyester resin and polyurethane resin. Metal oxide fine particles such as O ₃ , preferably metal oxide fine particles having an average particle diameter of about 1 to 100 nm to adjust the refractive index. In addition, it is also possible to control the refractive index to 1.58 using only resin.

The hard coat layer 13 on the transparent base film 11 can be formed by coating a common hard coat agent such as acrylic resin or silicone resin. If necessary, about 0.05 to 5% by weight of a known ultraviolet absorbing material can be mixed with this hard coat layer to impart ultraviolet shielding performance thereto. The film thickness of the hard coat layer 13 is preferably about 2 to 20 μm.

In the second aspect, the hard coat layer 13 has a refractive index of 1.48 to 1.55. In this case, when the refractive index of the easy-adhesion layer 12 is denoted as na _and the refractive index of the transparent base film 11 is When denoted as n _b , and the refractive index of the hard coat layer 13 is denoted as n _HC , when

(n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03

In particular, (n _b +n _HC )/2-0.01≤n _a ≤(n _b +n _HC )/2+0.01,

The film thickness T of the easy-adhesive layer 12 satisfies:

(550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm

in particular

The range of (550/4)×(1/n _a )-5nm≤T≤(550/4)×(1/n _a )+5nm is preferable because obviously excellent antireflection performance can be obtained.

The transparent conductive layer 14 on the hard coat layer 13 is preferably formed by the following method: ATO (antimony-doped tin oxide), ZnO, Sb ₂ O ₅ , SnO ₂ , ITO (indium tin oxide) and In ₂ At least one kind of conductive fine particles in the group consisting of _O3 is mixed with a binder component such as acrylic to form a coating liquid, and the coating liquid is applied to the easy-adhesive layer 12 formed on the transparent base film 11 On top of the hard coat layer 13 on the surface, it is preferable to photocure the obtained coating film to form a transparent conductive layer.

The mixing ratio of the conductive fine particles and the binder component in the coating liquid can be appropriately determined by the refractive index of the formed transparent conductive layer 14, etc., and it is preferable that the binder component:conductive fine particles=100:200～700 (weight ratio ).

The film thickness of such transparent conductive layer 14 is preferably 80 to 200 nm. When the film thickness of the transparent conductive layer 14 is thinner than this range, sufficient electroconductivity cannot be obtained, and the surface resistance value of the antireflection film obtained will become high. On the other hand, if the transparent conductive layer 14 is too thick, the optical performance (anti-reflection performance) will be extremely reduced.

Moreover, it is preferable that the average particle diameter of the electroconductive fine particle used for formation of the transparent conductive layer 14 is 5-100 nm.

The light-absorbing layer 15 can be formed by mixing at least one kind of light-absorbing particles preferably selected from the group consisting of metal oxides, metal nitrides, and carbon, particularly carbon black particles and titanium nitride particles. It is mixed with a binder component such as acrylic to form a coating liquid, and the coating liquid is applied on the transparent conductive layer 14, and the obtained coating film is preferably photocured to form the light absorbing layer 15.

The mixing ratio of the light-absorbing fine particles and the binder component in the coating solution can be appropriately determined according to the attenuation coefficient of the light-absorbing layer 15 to be formed. In the second aspect, by combining the light-absorbing fine particles and the When the mixing ratio of the agent component is properly adjusted in the range of binder component: light-absorbing fine particles = 100-100-700, when the complex refractive index of the light-absorbing layer is expressed as n+ik, n=1.45-1.75, A light-absorbing layer with k=0.1 to 0.35 is preferable because good antireflection properties can be obtained.

The film thickness of such a light absorbing layer 15 is preferably 20 to 100 nm. When the film thickness of the light-absorbing layer 15 is thicker than this range, the transmittance decreases. However, if the film thickness of the light-absorbing layer 15 is too thin, sufficient antireflection performance cannot be obtained, which is not preferable.

In addition, in the case of forming a conductive light-absorbing layer instead of the transparent conductive layer and the light-absorbing layer, the conductive light-absorbing layer is preferably formed by mixing conductive light-absorbing fine particles such as carbon black with a binder component such as acrylic A coating solution is formed in the coating solution, the coating solution is applied to the hard coat layer, and the obtained coating film is preferably photocured to form a conductive light-absorbing layer.

The mixing ratio of the conductive light-absorbing fine particles and the binder component in the coating liquid can be appropriately determined according to the attenuation coefficient of the formed conductive light-absorbing layer, etc. In the second aspect, by using the conductive light-absorbing The mixing ratio of the absorbent fine particles and the binder component is appropriately adjusted within the range of binder component: conductive light-absorbing fine particles = 100-100-700, when the complex refractive index of the conductive light-absorbing layer is expressed as n+ik In this case, it is preferable to form a conductive light-absorbing layer with n=1.45 to 1.75 and k=0.1 to 0.35, since good antireflection properties can be obtained.

The film thickness of such a conductive light-absorbing layer is preferably 20 to 100 nm. When the film thickness of the conductive light-absorbing layer is thicker than this range, the transmittance will decrease. However, when the thickness of the conductive light-absorbing layer is too thin, sufficient antireflection properties cannot be obtained, which is not preferable.

In the second aspect, the low refractive index layer 16 is obtained by irradiating ultraviolet rays to a coating film containing hollow silica and poly A binder component composed of a functional (meth)acrylic compound and a photopolymerization initiator.

Hollow silica is hollow shell-shaped silica fine particles, and its average particle diameter is 10 to 200 nm, preferably 10 to 150 nm. When the average particle diameter of the hollow silica is less than 10 nm, it is difficult to lower the refractive index of the hollow silica, and when it exceeds 200 nm, diffuse reflection of light occurs, or the surface roughness of the formed low refractive index layer increases. question.

Hollow silica has air with a low refractive index (refractive index = 1.0) in the hollow interior, and therefore, its refractive index is significantly lower than ordinary silica (refractive index = 1.46). The refractive index of hollow silica is determined by the volume ratio of the hollow portion thereof, and is generally preferably about 1.20 to 1.40.

In addition, the refractive index of hollow silica: n (hollow silica) is from the refractive index of silica constituting the shell part of hollow fine particles: n (silica), the refractive index of the air inside: n (air ), calculated by the following formula.

n (hollow silica) = n (silica) × volume percentage of silica

As mentioned above, n(silica) is about 1.47, and n(air) is 1.0, which is very low, so such hollow silica has a very low refractive index.

In addition, the refractive index of the low-refractive-index layer of the 2nd aspect using such hollow silica: n (low-refractive-index layer) is obtained from the refractive index of hollow silica: n (hollow silica) and the binder The refractive index of the component: n (binder), calculated according to the following formula.

n (low refractive index layer) =

n(hollow silica)×volume ratio of hollow silica in the low refractive index layer+n(binder)×volume ratio of binder in the low refractive index layer.

Among them, in addition to the special fluorine-containing acrylic binder, the refractive index of the binder is usually about 1.50 to 1.55. Therefore, increasing the volume percentage of hollow silica in the low refractive index layer will reduce the refractive index of the low refractive index layer. It is important to reduce the rate.

In the second aspect, the more content of hollow silicon dioxide in the low refractive index layer, the more the low refractive index layer can be formed, and the antireflection film with excellent antireflection performance can be obtained. When the content of the agent component is relatively reduced, the film strength of the low-refractive index layer decreases, and the abrasion resistance and durability decrease. However, the reduction in membrane strength caused by the increase in the amount of hollow silica mixed can be compensated by surface treatment of hollow silica, and the membrane strength can also be supplemented by selecting the type of binder component to be mixed.

In the second aspect, the content of hollow silica in the low refractive index layer is preferably 20 to 50% by weight, particularly preferably 25 to 50% by weight, by surface treatment of hollow silica and selection of binder components, In order to realize the lowering of the refractive index of the low refractive index layer, the abrasion resistance is ensured while the refractive index is about 1.39 to 1.45.

Next, the polyfunctional (meth)acrylic compound which is the binder component of the low-refractive-index layer of a 2nd aspect is demonstrated.

The polyfunctional (meth)acrylic compound is preferably a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or a 4-functional (meth)acrylic compound represented by the following general formula (II) The quasi-compound is the main component, and preferably contains 50% by weight or more, particularly preferably 80% by weight, of the entire binder component.

[chemical 5]

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

n, m, o, p, q, r each independently represent an integer of 0 to 2,

R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

[chemical 6]

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

s, t, u, and v each independently represent an integer of 0 to 2,

R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

Examples of the hexafunctional (meth)acrylic compound represented by the general formula (I) include dipentaerythritol hexaacrylate, ethylene oxide adducts of dipentaerythritol hexaacrylate, or ethylene oxide adducts. A compound in which H is substituted by F, these compounds may be used alone or in combination of two or more.

In addition, examples of the tetrafunctional (meth)acrylic compound represented by the above general formula (II) include pentaerythritol tetraacrylate, ethylene oxide adducts (1 to 8) of pentaerythritol tetraacrylate, or Compounds in which H of ethylene oxide is replaced by F, etc. These compounds may be used alone or in combination of two or more.

As a binding agent, one or more 6-functional group (meth)acrylic compounds represented by the above-mentioned general formula (I) can be used in combination with one or more 4-functional group ( Meth)acrylic compounds.

The polyfunctional (meth)acrylic compound represented by the above general formula (I), (II), especially the hexafunctional (meth)acrylic compound represented by the above general formula (I) has high hardness and abrasion resistance It is excellent and can effectively form a low-refractive-index layer with high abrasion resistance.

In addition, in the second aspect, as the binder component, it is preferable to use a hexafunctional (meth)acrylic compound represented by the above general formula (I) and/or a tetrafunctional (meth)acrylic compound represented by the above general formula (II) base) acrylic compound, used in combination with a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) or a specific fluorine-containing multifunctional (meth)acrylic compound, by using these binding agents Component that imparts abrasion resistance and stain resistance to the low refractive index layer. In addition, these binder components have a lower refractive index than the hexafunctional (meth)acrylic compound represented by the above general formula (I) or the tetrafunctional (meth)acrylic compound represented by the above general formula (II), Therefore, even if the mixing amount of the hollow silica is reduced, a low-refractive-index layer having a low refractive index can be formed.

A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III)

(In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.)

Examples of the fluorine-containing bifunctional (meth)acrylic compound represented by the above general formula (III) include 2,2,3,3,4,4-hexafluoropentanediol diacrylate, etc., these The compounds may be used alone or in combination of two or more.

In addition, the above-mentioned specific polyfunctional (meth)acrylic compound, that is, a (meth)acrylic compound having 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or less, having 3 to 6 functional groups, and (meth)acrylic compounds having 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1,000 to 5,000 may be used alone or in combination of two or more .

It is also possible to use one or more of the above-mentioned fluorine-containing bifunctional (meth)acrylic compounds in combination with one or more fluorine-containing multifunctional (meth)acrylic compounds.

Using the fluorine-containing bifunctional (meth)acrylic compound can lower the refractive index of the low refractive index layer and improve the antifouling property, but if the compounding amount is too large, the abrasion resistance will decrease. Therefore, it is preferable to mix 5% by weight or more of the fluorine-containing bifunctional (meth)acrylic compound in the total binder components, particularly preferably 5 to 10% by weight.

In addition, although the low refractive index of the low refractive index layer can be achieved by using the above-mentioned fluorine-containing polyfunctional (meth)acrylic compound, and the antifouling property can be improved, but if the compounding amount is too large, the wear resistance reduce. Therefore, it is preferable to mix the polyfunctional (meth)acrylic compound in an amount of 5% by weight or more, particularly preferably 5 to 10% by weight, of the total binder components.

In addition, in the case of using a fluorine-containing bifunctional (meth)acrylic compound in combination with a fluorine-containing polyfunctional (meth)acrylic compound, it is preferable that, among the total binder components, the fluorine-containing bifunctional (meth)acrylic The compound and the fluorine-containing polyfunctional (meth)acrylic compound are mixed in a total of 5% by weight or more, particularly preferably 5 to 10% by weight.

The hollow silica used in the second aspect has a particle diameter larger than that of conventional silica particles (with a particle diameter of about 5 to 20 nm) mixed in an existing low-refractive index layer. In the case of using the same binder component, the film strength of the formed low-refractive index layer tends to be weaker than in the case of mixing silica particles, and by applying appropriate surface treatment to the hollow silica , can improve the binding force with the binder component, improve the film strength of the formed low refractive index layer, and improve the wear resistance.

As the surface treatment of the hollow silica, it is preferable to use a terminal (meth)acrylic silane coupling agent represented by the following general formula (IV) to perform terminal (meth)acrylic modification on the surface of the hollow silica. sex.

[chemical 7]

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group,

^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms,

R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

Such terminal (meth)acrylic silane coupling agents include, for example, CH ₂ =CH-COO-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ , CH ₂ =C(CH ₃ )-COO -(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

In order to perform terminal (meth)acrylic modification on the surface of hollow silica by using such a terminal (meth)acrylic silane coupling agent, it is preferable to couple the hollow silica with a terminal (meth)acrylic silane The mixed solution of the agent is hydrothermally reacted at 100 to 150° C., or the mixed solution is irradiated with microwaves to cause a reaction. That is, when only the terminal (meth)acrylic silane coupling agent and hollow silica are mixed, the surface cannot be chemically modified with the terminal (meth)acrylic silane coupling agent, and the desired surface modification effect cannot be obtained. In the case of utilizing the hydrothermal reaction, if the reaction temperature is low, sufficient terminal (meth)acrylic acid modification cannot be performed. However, if the reaction temperature is too high, the reactivity will decrease instead, so the hydrothermal reaction temperature is preferably 100 to 150°C. In addition, although the hydrothermal reaction time varies depending on the reaction temperature, it is usually about 0.1 to 10 hours. On the other hand, in the case of using microwaves, if the set temperature is too low, sufficient terminal (meth)acrylic acid modification cannot be performed. Therefore, for the same reason as above, the set temperature is preferably 90 to 150 ℃. The microwave is suitable to use a microwave with a frequency of 2.5 GHz. If the microwave is irradiated, the terminal group (meth)acrylic acid modification can be carried out in a short time of about 10 to 60 minutes. In addition, as a mixed solution used in this reaction, for example, 3.8% by weight of hollow silica and 96% by weight of alcohol solvent (1:4 (weight ratio) mixed solvent of isopropanol and isobutanol) , 3% by weight of acetic acid, 1% by weight of water, and a reaction solution made of 0.04% by weight of silane coupling agent.

By chemically modifying the surface of hollow silica with such a terminal (meth)acrylic silane coupling agent, the hollow silica and the binder component can be firmly bonded, even when the amount of hollow silica mixed is large. Even in the case of , a low-refractive-index layer excellent in wear resistance can be formed, and the low-refractive index of the low-refractive-index layer can be achieved by increasing the blending amount of hollow silica.

In addition, the surface of the hollow silica can also be modified with a terminal fluorinated alkyl silane coupling agent represented by the following general formula (V). In this case, the terminal group The terminal group fluorinated alkyl modification carried out by the fluorinated alkyl silane coupling agent is preferably under the same conditions as when the above-mentioned terminal group (meth)acrylic acid silane coupling agent is used to carry out the terminal group (meth)acrylic acid modification , by hydrothermal method or microwave irradiation method.

[chemical 8]

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.)

In addition, examples of the terminal group fluorinated alkylsilane coupling agent include C ₈ F ₁₇ -(CH ₂ ) ₂ -Si-(OCH ₃ ) ₃ , C ₆ F ₁₃ -(CH ₂ ) ₂ -Si -(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

By chemically modifying the surface of the hollow silica using such a terminal group fluorinated alkylsilane coupling agent, the antifouling property of the formed low refractive index layer can be improved.

The low-refractive-index layer of the second aspect is formed by irradiating the above-mentioned binder component with ultraviolet light to cure it in the presence of a photopolymerization initiator. One or more of Ilugac 184, 819, 651, 1173, 907 and the like are preferably mixed in an amount of 3 to 10 phr based on the binder component. When the compounding quantity of a photoinitiator is less than this range, sufficient crosslinking hardening cannot be performed, and when it exceeds this range, the film strength of a low-refractive-index layer will fall.

The low refractive index layer of the second aspect is coated with a composition obtained by mixing hollow silica, a polyfunctional (meth)acrylic compound as a binder component, and a photopolymerization initiator in a predetermined ratio to a high refractive index layer. index layer or conductive high-refractive-index hard coat layer, which is formed by irradiating ultraviolet rays in an atmosphere with an oxygen concentration of 0 to 10,000 ppm to cure it. Damage is greatly reduced, so it is controlled to 1000 ppm or less, preferably 200 ppm or less.

The thickness of such a low refractive index layer is preferably 85 to 110 nm.

In the second aspect, in order to form a hard coat layer 13, a transparent conductive layer 14, a light absorbing layer 15, and a low refractive index layer 16 on the base film 11 on which the easy-adhesion layer 12 is formed, or to form a hard coat layer, The conductive light-absorbing layer and the low-refractive index layer are preferably coated with an uncured resin composition (resin composition mixed with the above-mentioned fine particles if necessary), followed by irradiation with ultraviolet rays. In this case, it may be cured after each application of one layer, or after application of three or two layers.

Specific methods of coating include a method in which a coating solution obtained by dissolving a binder component in a solvent such as toluene is coated with a gravure coater, dried, and then cured by ultraviolet rays. According to this wet coating method, there is an advantage that a film can be formed uniformly at high speed and at low cost. Curing by irradiating ultraviolet light after the coating has the effect of improving the adhesiveness and the hardness of the film, and the antireflection film can be continuously produced without heating.

Such an antireflection film according to the second aspect is suitable for a PDP of an OA device or a front filter of a liquid crystal panel, and can ensure good light transmission and durability.

The second aspect will be described in more detail below by enumerating examples, comparative examples and experimental examples.

Examples 1-4, Comparative Examples 1-3

Each layer was coated in the following order and cured by irradiating the entire layer with ultraviolet light of 800 mJ/cm ² at an oxygen concentration of 150 ppm.

First, a hard coat layer (manufactured by JSR Co. "Z7503"). The formed hard coat layer had a thickness of 8 μm and a pencil hardness of 3H. Next, a film-forming composition for a transparent conductive layer (manufactured by Dainippon Paint Co., Ltd. "Ei-3") containing ITO fine particles, urethane acrylate, and a photopolymerization initiator was applied. The formed transparent conductive layer has a thickness of about 0.35λ and a refractive index of 1.68.

Next, carbon black or titanium black (TiN is the main component, with a median diameter of 60 nm) having a median particle diameter of 90 nm as a light-absorbing layer film-forming composition, and pentaerythritol tetraacrylate and As a photopolymerization initiator, a mixture of Ilgacyua 184 and 819 manufactured by SIBA Specialty Chemicals Co., Ltd. was used. 5 phr of photopolymerization initiator was used with respect to pentaerythritol tetraacrylate. The light-absorbing layer changes the ratio of the mixture of carbon black and titanium black particles to the binder, and changes the attenuation coefficient to form a light-absorbing layer with the refractive index, attenuation coefficient and film thickness shown in Table 8. In addition, the attenuation coefficient of the light absorbing layer is at most 0.35.

In addition, the composition for a low-refractive index layer having the combination and proportion shown in Table 8 was applied to form a low-refractive index layer having the refractive index and film thickness shown in Table 8.

In addition, in Examples 1 to 4, hollow silica having an average particle diameter of 60 nm and a refractive index n=approximately 1.30 was used as the hollow silica. In addition, in Comparative Examples 1 to 3, silica fine particles ("IPA-ST" (particle diameter: 10 to 20 nm) manufactured by Nissan Chemical Co., Ltd.) without pores were used as silica. In addition, the polyfunctional acrylic type of the binder used in Examples 1-4 was pentaerythritol hexaacrylate, and the acrylic type used in Comparative Examples 1-3 was pentaerythritol tetraacrylate. As a photopolymerization initiator, 5 phr of Ilgacyua 184 was added to the binder.

The refractive index of the low-refractive index layer was changed by changing the mixing ratio of the binder and the microparticles as shown in Table 8.

On the antireflection film thus obtained, a black vinyl tape was attached to the inner surface (uncoated surface), and the minimum reflectance, the reflectance at 400 nm, and the wavelength at 550 nm were measured using a spectrophotometer "U-4000" manufactured by Hitachi, Ltd. The transmittance, the results are shown in Table 8.

In addition, if the anti-reflection film (the surface of the low-refractive index layer) is rubbed back and forth with a plastic eraser under a load of 4.9×10 ⁴ N/m ² , if the film is damaged, the reflection color will change, so the color will start to change. The number of reciprocations until the change was used as the number of times of rubber friction resistance, and the abrasion resistance was checked. The results are shown in Table 8. In addition, the target characteristics of the light-absorbing antireflection film are: the minimum reflectance is within 0.5%, the reflectance at a wavelength of 400nm is 2% or less, the transmittance at a wavelength of 550nm is within 70%, and the number of times of rubber rubbing resistance is 100 times or more.

[Table 8] example light absorbing layer low refractive index layer optical properties Resistance to rubber friction times (times) Overview Refractive index n Attenuation coefficient k film thickness particle Binding agent Binder: Microparticles (weight ratio) Refractive index n film thickness Minimum reflectance (%) Reflectance 400nm(%) Transmittance 550nm(%) Example 1 1.64 0.35 0.1λ Hollow silica Multifunctional Acrylates 65:35 1.43 0.18λ 0.21 0.7 72 >100 ○ 2 1.61 0.3 0.1λ Hollow silica Multifunctional Acrylates 65:35 1.43 0.18λ 0.37 0.53 75 >100 ○ 3 1.58 0.25 0.1λ Hollow silica Multifunctional Acrylates 65:35 1.43 0.18λ 0.28 0.45 78 >100 ○ 4 1.58 0.3 0.07λ Hollow silica Multifunctional Acrylates 65:35 1.43 0.19λ 0.21 0.61 80 >100 ◎ comparative example 1 1.64 0.35 0.14λ silica Acrylate 20:80 1.495 0.175λ 0.36 1.61 66 >100 △ 2 1.64 0.35 0.12λ silica Acrylate 20:80 1.495 0.175λ 0.5 1.2 68 >100 △ 3 1.64 0.35 0.1λ silica Acrylate 20:80 1.495 0.18λ 0.54 1.01 72 >100 △

From Table 8 we can know the following content.

That is, Comparative Examples 1 to 3 show various performances in the case of using a low-refractive-index layer with a refractive index of 1.495. In order to satisfy the rubber rub resistance of 100 times or more, the transmittance exceeds 70%, so The film thickness of the light absorbing layer must be reduced, and if the transmittance exceeds 70%, the minimum reflectance exceeds 0.5% when the absorbing layer is thinned.

In contrast, in Examples 1 to 4 in which hollow silica and a strong acrylic resin were used for the low-refractive-index layer, the eraser rubbing resistance was very good, and a low-refractive-index layer with a low refractive index could be formed. Therefore, even if the film thickness of the light-absorbing layer is reduced and the attenuation coefficient of the light-absorbing layer is reduced, the minimum reflectance is maintained at 0.5% or less, wherein the minimum reflectance can also be made to be 0.5% or less, and Anti-reflection film with transmittance over 80%.

In addition, all the antireflection films formed with this film structure have a reflectance of 2% or less at a wavelength of 400 nm.

<Experiment example>

Experimental examples are given below to show that the above-mentioned rules for specifying the film thickness and refractive index of the easily-adhesive layer

(n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03

as well as

The basis of (550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm.

If the antireflection film does not have a hard coat layer, the abrasion resistance and pencil height will be lowered, and the film will be easily damaged, so a hard coat layer is usually formed. As its structure, PET film/hard coat layer/high refractive index layer/low refractive index layer are the most common.

The hard coat layer is formed by further mixing acrylic-modified silica particles in a conventional multifunctional acrylic monomer-to-oligomer mixture in order to increase hardness. The acrylic monomer or oligomer of the hard coat layer is usually The refractive index of the hard coating is about 1.49 to 1.55, and the refractive index of silica particles is about 1.47. Therefore, the refractive index of the hard coating is about 1.49 to 1.55. On the other hand, the refractive index of the PET film is about 1.65, which is very different from the refractive index of the hard coat layer.

If a hard coat layer is formed on a base film having a very large difference in refractive index in this way, a characteristic spectrum will be produced, and the minimum reflectance will be increased when an antireflection film is produced.

In order to solve this problem, a method of lowering the minimum reflectance includes a method of controlling the film thickness and the refractive index of the easily-adhesive layer.

First, an antireflection layer having the following composition of hard coat layer/high refractive index layer/low refractive index layer was formed.

[Table 9] Refractive index Optical film thickness (λ) (at 550nm) Film thickness (nm) composition hard coat 1.50 8 2930 _SiO2 microparticles/multifunctional acrylic high refractive index layer 1.68 0.25 81 ITO particles/multifunctional acrylic low refractive index layer 1.43 0.25 96 Hollow Silica/Multifunctional Acrylic

The following experimental results show to what extent the minimum reflectance of the antireflection layer is changed by the film thickness and refractive index of the easy-adhesion layer when the antireflection layer is applied.

Hereinafter, an experimental example suitable for the second aspect will be referred to as "experimental example A", and an experimental example corresponding to the comparative example will be referred to as "experimental example B".

In addition, since the refractive index n _b of the base film is 1.65 and the refractive index n _HC of the hard coat layer is 1.50, (n _b +n _HC )/2≈1.58.

The reflectance spectrum of each experimental example is shown in FIGS. 6 to 20 , and Table 10 shows the minimum reflectance.

[Table 10] Experimental example Refractive index of the easy-adhesive layer The difference between the refractive index of the easy-adhesive layer and (n _b +n _HC )/2 Film thickness of easy-adhesive layer (nm) The difference between the film thickness of the easy-adhesive layer and (550/4)×(1/n _a ) Minimum reflectivity Overview B-1 - - - - 0.48 x B-2 1.55 -3 20 -69 0.38 x B-3 1.54 -0.04 89 ±0 0.21 x A-1 1.56 -0.02 88 ±0 0.19 ○ A-2 1.58 ±0 87 ±0 0.19 ○ A-3 1.60 +0.02 86 ±0 0.19 ○ B-4 1.62 +0.04 85 ±0 0.3 x B-5 1.64 +0.06 84 ±0 0.4 x B-6 1.58 0 57 -30 0.21 x B-7 1.58 0 67 -20 0.2 x A-4 1.58 0 77 -10 0.19 ○ A-5 1.58 0 87 ±0 0.19 ○ A-6 1.58 0 97 +10 0.19 ○ B-8 1.58 0 107 +20 0.21 x B-9 1.58 0 117 +30 0.23 x

The reflectance of Experimental Example B-1 without an easy-adhesive layer on the PET film and Experimental Example B-2 with a conventional easy-adhesive layer (refractive index 1.55, film thickness 20nm) is all high, being 0.35～0.45 %.

In Experimental Examples B-3~B~5 and Experimental Examples A-1~A-3, the optical film thickness of the easy-adhesive layer is accurately controlled at 1/4λ (0.25λ) relative to the light of 550nm, and the thickness of the easily-adhesive layer is changed. the refractive index. The fact that the optical film thickness is 0.25λ means that the film thickness of the easily bonding layer satisfies exactly (550/4)×(1/n _a ).

Change the Refractive Index of Easy Glue to 1.54, 1.56, 1.58, 1.60, 1.62. It can be seen from the reflectance spectrum of each experimental example and the minimum reflectance at this time that if the refractive index of the easy-adhesion layer is close to (n _b +n _HC )/2, the minimum reflectance decreases, especially (n _b + n _HC )/2±0.02, a very high anti-reflection effect can be observed. However, when the refractive index of the easily-adhesive layer is far from (n _b +n _HC )/2, a tendency for the minimum reflectance to also increase is observed.

Experimental Example B-3...n=1.54d=(550/4)×(1/n _a )

Experimental example A-1...n=1.56d=(550/4)×(1/n _a )

Experimental example A-2...n=1.58d=(550/4)×(1/n _a )

Experimental example A-3...n=1.60d=(550/4)×(1/n _a )

Experimental Example B-4...n=1.62d=(550/4)×(1/n _a )

Experimental Example B-5...n=1.64d=(550/4)×(1/n _a )

Experimental Examples B-6 to B-9 and Examples A-5 and A-6 show the influence of the film thickness of the easy-adhesive layer, that is, the film thickness of the easily-adhesive layer deviates from (550/4)×(1/ n _a ) situation.

Response spectra of various experimental examples in which the film thickness of the easily-adhesive layer was changed by setting the refractive index of the easily-adhesive layer to (n _b +n _HC )/2, that is, exactly 1.58, and the It can be seen from the minimum reflectivity that when the refractive index of the easy-adhesive layer is

(n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03

range, and the film thickness is in the

(550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm

, the minimum reflectivity decreases.

Experimental Example B-6...n=1.58d=(550/4)×(1/n _a )-30[nm](57nm)

Experimental Example B-7...n=1.58d=(550/4)×(1/n _a )-20[nm](67nm)

Experimental Example A-4...n=1.58d=(550/4)×(1/n _a )-10[nm](77nm)

Experimental Example A-5...n=1.58d=(550/4)×(1/n _a ) [nm](87nm)

Experimental Example B-7...n=1.58d=(550/4)×(1/n _a )+10[nm](97nm)

Experimental Example B-8...n=1.58d=(550/4)×(1/n _a )+20[nm](107nm)

Experimental Example B-9...n=1.58d=(550/4)×(1/n _a )+30[nm](117nm)

From these results, it can be seen that when a conventional hard coat layer (n=1.50) is used, very good antireflection properties can be obtained in the range of the easy-adhesion layer having a refractive index of about 1.58 and a film thickness of 77 to 97 nm. Therefore, it was confirmed that, by setting in this way, it is possible to simultaneously eliminate spotty reflection color unevenness due to the difference in refractive index between the hard coat layer and the base film.

III. Implementation of the third aspect

Embodiments of the antireflection film according to the third aspect will be described below.

As shown in FIG. 21 , the antireflection film of the third aspect is formed by sequentially laminating an easy-adhesive layer 22 , a hard coat layer 23 , a high refractive index layer 24 and a low refractive index layer 25 on a transparent base film 21 . Alternatively, in FIG. 21, a high refractive index hard coat layer is provided instead of the hard coat layer and the high refractive index layer.

In the third aspect, as the base film 21, polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), Acrylic resin, polycarbonate (PC), polystyrene, cellulose triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane , cellophane, etc., preferably PET, PC, PMMA transparent film.

The thickness of the base film 21 can be appropriately determined according to the properties required for the application of the obtained antireflection film (for example, strength, film properties), etc., and is usually in the range of 1 μm to 10 mm.

The easy-adhesive layer 22 is used to improve the adhesion of the hard coat layer 23 to the substrate film 21, and is usually used by mixing SiO ₂ , ZrO ₂ , TiO ₂ , and Al ₂ in thermosetting resins such as copolyester resins and polyurethane resins. Metal oxide fine particles such as O ₃ , preferably metal oxide fine particles having an average particle diameter of about 1 to 100 nm to adjust the refractive index. In addition, it is also possible to control the refractive index to 1.58 using only resin.

The hard coat layer 23 is preferably a synthetic resin, particularly preferably an ultraviolet-curable synthetic resin, particularly preferably a multifunctional acrylic resin. The thickness of the hard coat layer 23 is preferably 2 to 20 μm.

In the third aspect, the hard coat layer 23 has a refractive index in the range of 1.48 to 1.55. In this case, when the refractive index of the easy-adhesion layer 22 is denoted as na _and the transparent base film 21 is When the refractive index is denoted as n _b and the refractive index of the hard coat layer 23 is denoted as n _HC , if

(n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03

In particular, (n _b +n _HC )/2-0.01≤n _a ≤(n _b +n _HC )/2+0.01,

And the film thickness T of the easy-adhesive layer 22 satisfies:

(550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm

in particular

(550/4)×(1/n _a )-5nm≤T≤(550/4)×(1/n _a )+5nm,

When it is in the range of , obviously excellent antireflection performance can be obtained, so it is preferable.

The high-refractive index layer 24 preferably comprises at least one selected from the group consisting of conductive high-refractive-index particles made of SnO ₂ and ITO, and high-refractive-index particles selected from TiO ₂ , ZrO ₂ and CeO _{2 .} A binder component comprising high refractive index fine particles and a hexafunctional acrylic compound represented by the following general formula (VI) as main components.

[chemical 9]

(In the above general formula (VI), A ⁴¹ to A ⁴⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluorinated acryloyl group, or a trifluoromethacryloyl group.)

The average primary particle diameter of the high-refractive index particles in the high-refractive index layer is preferably 10 to 150 nm, and particularly preferably the average primary particle diameter of the high-refractive index particles is 30 to 40 nm, and the particle size distribution range is wide around the primary particle diameter. , in the total particles, the primary particle diameter is 30nm or less than the cumulative number of particles is 20% or more, such as 20 to 30%, the primary particle diameter is 45nm or more than the cumulative number of particles is 20% or more, for example, 20 to 60% of fine particles is preferable because high-density filling of high-refractive-index fine particles is possible and a high-refractive-index layer with high refractive index can be formed.

In addition, from the viewpoint of increasing the refractive index and maintaining the antistatic properties of the high refractive index layer, as the high refractive index particles, it is preferable to use conductive high refractive index particles and ultra-high refractive index particles in combination, and in particular, conductive high refractive index particles are preferably used. Index fine particles: ultra-high refractive index fine particles = 80:20 to 50:50 (volume ratio), particularly preferably 27:18 (volume ratio). If there are more conductive high-refractive-index fine particles than this range, the refractive index of the high-refractive index layer will decrease, and if there are too many ultra-high-refractive-index fine particles, the antistatic effect cannot be obtained.

In addition, the following (i) or (ii) is also preferable as the high-refractive-index fine particles of the high-refractive-index layer 24 .

(i) particles made of anatase-type titanium dioxide particles covered with ITO particles, and the average primary particle size of the titanium dioxide particles is 5 to 80 nm, and the thickness of the coating layer formed by the ITO particles is 5 nm or more, such as 5 to 20 nm .

(ii) ITO particles are coated on rutile titanium dioxide particles, and the aspect ratio of the titanium dioxide particles is 3-10, and the thickness of the coating layer formed by the ITO particles is 5nm or more, for example, 5-20nm.

The high-refractive-index particles of (i) or (ii) above, especially the high-refractive-index particles of (ii), have a high aspect ratio and can effectively form a conductive network. It is preferable to use the high-refractive-index fine particles of (i) above and the high-refractive-index fine particles of (ii) above in combination.

The hexafunctional (meth)acrylic compound represented by the general formula (VI) as the binder component of the high refractive index layer 24 specifically includes dipentaerythritol hexaacrylate and its ethylene oxide addition These compounds may be used alone or in combination of two or more.

With regard to the ratio of the high-refractive-index particles in the high-refractive-index layer 24 to the above-mentioned binder component, if there are too many high-refractive-index particles and insufficient binder components, the film strength of the high-refractive-index layer will decrease. Conversely, if the high-refractive-index particles If the amount is too small, the refractive index cannot be sufficiently increased. Therefore, the proportion of the high refractive index particles is preferably 10 to 60% by volume, particularly preferably 20 to 50% by volume, based on the total amount of the high refractive index particles and the binder.

The thickness of such a high refractive index layer 24 is preferably about 80 to 100 nm. In addition, the refractive index of the high refractive index layer 24 is preferably 1.65 or more, particularly preferably 1.66 to 1.85, and in this case, by setting the refractive index of the low refractive index layer 25 to 1.39 to 1.47, it is possible to make the surface An antireflection film excellent in antireflection performance with a minimum reflectance of 1% or less. In particular, when the refractive index of the low refractive index layer 25 is 1.45 or less, the antireflection property can be further improved, and an antireflection film having a surface reflectance with a minimum reflectance of 0.5% or less can be formed.

In the third aspect, the low-refractive-index layer 25 is formed by irradiating ultraviolet rays to a coating film containing hollow diatoms in an atmosphere having an oxygen concentration of 0 to 10,000 ppm to cure it. A binder component and a photopolymerization initiator consisting of silicon oxide and a polyfunctional (meth)acrylic compound.

Hollow silica is hollow shell-shaped silica fine particles, and its average particle diameter is 10 to 200 nm, preferably 10 to 150 nm. If the average particle size of the hollow silica is less than 10 nm, it is difficult to lower the refractive index of the hollow silica, and if it is larger than 200 nm, diffuse reflection of light occurs, and the surface roughness of the formed low refractive index layer increases, etc. The problem.

Hollow silica, which has low refractive index air in its hollow interior (refractive index = 1.0), therefore, has a significantly lower refractive index than ordinary silica (refractive index = 1.46). The refractive index of hollow silica is determined by the volume ratio of the hollow portion thereof, and is generally preferably about 1.20 to 1.40.

In addition, the refractive index of hollow silica: n (hollow silica) is from the refractive index of silica constituting the shell part of hollow fine particles: n (silica), the refractive index of the air inside: n (air ), calculated by the following formula.

n (hollow silica) = n (silica) × volume percentage of silica

As mentioned above, n(silica) is about 1.47, and n(air) is very low at 1.0, so the refractive index of such hollow silica is very low.

In addition, the refractive index of the low-refractive-index layer of the 3rd aspect using such hollow silica: n (low-refractive-index layer) is obtained from the refractive index of hollow silica: n (hollow silica) and the binder The refractive index of the component: n (binder), calculated according to the following formula.

n (low refractive index layer) =

n(hollow silica)×volume ratio of hollow silica in the low refractive index layer+n(binder)×volume ratio of binder in the low refractive index layer.

Among them, in addition to the special fluorine-containing acrylic binder, the refractive index of the binder is usually about 1.50 to 1.55. Therefore, increasing the volume percentage of hollow silica in the low refractive index layer will reduce the refractive index of the low refractive index layer. It is important to reduce the rate.

In the 3rd aspect, the content of the hollow silicon dioxide in the low refractive index layer is more, then the low refractive index layer of low refractive index can be formed more, can obtain the antireflection film that antireflection performance is excellent, and as combined When the content of the agent component is relatively reduced, the film strength of the low-refractive index layer decreases, and the abrasion resistance and durability decrease. However, the reduction in membrane strength caused by the increase in the amount of hollow silica mixed can be compensated by surface treatment of hollow silica, and the membrane strength can also be supplemented by selecting the type of binder component to be mixed.

In the third aspect, the content of hollow silica in the low refractive index layer is preferably 20 to 55% by weight, particularly preferably 30 to 50% by weight, by surface treatment of hollow silica and selection of binder components, In order to realize the low refractive index of the low refractive index layer, the refractive index is about 1.39 to 1.45, and at the same time, the abrasion resistance is ensured.

Next, the polyfunctional (meth)acrylic compound of the binder component of the low-refractive-index layer of 3rd aspect is demonstrated.

The polyfunctional (meth)acrylic compound is preferably a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or a 4-functional (meth)acrylic compound represented by the following general formula (II) The quasi-compound is a main component, and is preferably contained in an amount of 50% by weight or more, particularly preferably 90% by weight or more, of the entire binder component.

[chemical 10]

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

n, m, o, p, q, r each independently represent an integer of 0 to 2,

R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

[chemical 11]

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

s, t, u, and v each independently represent an integer of 0 to 2,

R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

Examples of the hexafunctional (meth)acrylic compound represented by the general formula (I) include dipentaerythritol hexaacrylate, ethylene oxide adducts of dipentaerythritol hexaacrylate, or ethylene oxide adducts. A compound in which H is substituted by F, these compounds may be used alone or in combination of two or more.

In addition, examples of the tetrafunctional (meth)acrylic compound represented by the above general formula (II) include pentaerythritol tetraacrylate, ethylene oxide adducts (1 to 8) of pentaerythritol tetraacrylate, or A compound in which H of ethylene oxide is replaced by F, these compounds may be used alone or in combination of two or more.

As the binder component, one or more hexafunctional (meth)acrylic compounds represented by the above general formula (I) and one or more tetrafunctional (meth)acrylic compounds represented by the above general formula (II) can be used in combination. (meth)acrylic compounds.

The polyfunctional (meth)acrylic compound represented by the above general formula (I), (II), especially the hexafunctional (meth)acrylic compound represented by the above general formula (I) has high hardness and abrasion resistance It is excellent and can effectively form a low-refractive-index layer with high abrasion resistance.

In addition, in the third aspect, as the binder component, it is preferable to use a hexafunctional (meth)acrylic compound represented by the above general formula (I) and/or a tetrafunctional (meth)acrylic compound represented by the above general formula (II) base) acrylic compound, used in combination with a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) or a specific fluorine-containing multifunctional (meth)acrylic compound, by using these binding agents Component that imparts abrasion resistance and stain resistance to the low refractive index layer. In addition, these binder components have a lower refractive index than the hexafunctional (meth)acrylic compound represented by the above general formula (I) or the tetrafunctional (meth)acrylic compound represented by the above general formula (II), Therefore, even if the mixing amount of the hollow silica is reduced, a low-refractive-index layer having a low refractive index can be formed.

A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III)

(In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.)

Examples of the fluorine-containing bifunctional (meth)acrylic compound represented by the above general formula (III) include 2,2,3,3,4,4-hexafluoropentanediol diacrylate, etc., these The compounds may be used alone or in combination of two or more.

In addition, the above-mentioned specific polyfunctional (meth)acrylic compound, that is, a (meth)acrylic compound having 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or less, having 3 to 6 functional groups, and (meth)acrylic compounds having 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1,000 to 5,000 may be used alone or in combination of two or more .

It is also possible to use one or more of the above-mentioned fluorine-containing bifunctional (meth)acrylic compounds in combination with one or more fluorine-containing multifunctional (meth)acrylic compounds.

Using the fluorine-containing bifunctional (meth)acrylic compound can lower the refractive index of the low refractive index layer and improve the antifouling property, but if the compounding amount is too large, the abrasion resistance will decrease. Therefore, it is preferable to mix 5% by weight or more of the fluorine-containing bifunctional (meth)acrylic compound in the total binder components, particularly preferably 5 to 10% by weight.

In addition, although the low refractive index of the low refractive index layer can be achieved by using the above-mentioned fluorine-containing polyfunctional (meth)acrylic compound, and the antifouling property can be improved, but if the compounding amount is too large, the wear resistance reduce. Therefore, it is preferable to mix the polyfunctional (meth)acrylic compound in an amount of 5% by weight or more, particularly preferably 5 to 10% by weight, of the total binder components.

In addition, in the case of using a fluorine-containing bifunctional (meth)acrylic compound in combination with a fluorine-containing polyfunctional (meth)acrylic compound, it is preferable that, among the total binder components, the fluorine-containing bifunctional (meth)acrylic The compound and the fluorine-containing polyfunctional (meth)acrylic compound are mixed in a total of 5% by weight or more, particularly preferably 5 to 10% by weight.

The hollow silica used in the third aspect has a particle diameter larger than that of conventional silica particles (with a particle diameter of about 5 to 20 nm) mixed in an existing low-refractive index layer. Therefore, even in In the case of using the same binder component, the film strength of the formed low-refractive index layer tends to be weaker than in the case of mixing silica particles, and by applying appropriate surface treatment to the hollow silica , can improve the binding force with the binder component, improve the film strength of the formed low refractive index layer, and improve the wear resistance.

As the surface treatment of the hollow silica, it is preferable to use a terminal (meth)acrylic silane coupling agent represented by the following general formula (IV) to perform terminal (meth)acrylic modification on the surface of the hollow silica. sex.

[chemical 12]

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group,

^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms,

R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

Such terminal (meth)acrylic silane coupling agents include, for example, CH ₂ =CH-COO-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ , CH ₂ =C(CH ₃ )-COO -(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

In order to perform terminal (meth)acrylic modification on the surface of hollow silica by using such a terminal (meth)acrylic silane coupling agent, it is preferable to couple the hollow silica with a terminal (meth)acrylic silane The mixed solution of the agent is hydrothermally reacted at 100 to 150° C., or the mixed solution is irradiated with microwaves to cause a reaction. That is, when only the terminal (meth)acrylic silane coupling agent and hollow silica are mixed, the surface cannot be chemically modified with the terminal (meth)acrylic silane coupling agent, and the desired surface modification effect cannot be obtained. In the case of utilizing the hydrothermal reaction, if the reaction temperature is low, sufficient terminal (meth)acrylic acid modification cannot be performed. However, if the reaction temperature is too high, the reactivity will decrease instead, so the hydrothermal reaction temperature is preferably 100 to 150°C. In addition, although the hydrothermal reaction time varies depending on the reaction temperature, it is usually about 0.1 to 10 hours. On the other hand, in the case of using microwaves, if the set temperature is too low, sufficient terminal (meth)acrylic acid modification cannot be performed. Therefore, for the same reason as above, the set temperature is preferably 90 to 150 ℃. The microwave is suitable for microwaves with a frequency of 2.5 GHz. If microwave irradiation is used, the terminal (meth)acrylic acid modification can usually be carried out in a short time of about 10 to 60 minutes. In addition, as the mixed solution used in this reaction, hollow silica of 3.8% by weight, 96% by weight of alcohol solvent (a mixed solvent of 1:4 (weight ratio) of isopropanol and isobutanol), A reaction solution made of 3% by weight of acetic acid, 1% by weight of water, and 0.04% by weight of a silane coupling agent.

By chemically modifying the surface of hollow silica with such a terminal (meth)acrylic silane coupling agent, the hollow silica and the binder component can be firmly bonded, even when the amount of hollow silica mixed is large. Even in the case of , a low-refractive-index layer excellent in wear resistance can be formed, and the low-refractive index of the low-refractive-index layer can be achieved by increasing the blending amount of hollow silica.

In addition, the surface of the hollow silica can also be modified with a terminal fluorinated alkyl silane coupling agent represented by the following general formula (V). In this case, the terminal group The terminal group fluorinated alkyl modification carried out by the fluorinated alkyl silane coupling agent is preferably under the same conditions as when the above-mentioned terminal group (meth)acrylic acid silane coupling agent is used to carry out the terminal group (meth)acrylic acid modification , by hydrothermal method or microwave irradiation method.

[chemical 13]

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.)

In addition, examples of the terminal group fluorinated alkylsilane coupling agent include C ₈ F ₁₇ -(CH ₂ ) ₂ -Si-(OCH ₃ ) ₃ , C ₆ F ₁₃ -(CH ₂ ) ₂ -Si -(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

By chemically modifying the surface of the hollow silica using such a terminal group fluorinated alkylsilane coupling agent, the antifouling property of the formed low refractive index layer can be improved.

The low-refractive-index layer of the third aspect is formed by irradiating the above-mentioned binder component with ultraviolet light to cure it in the presence of a photopolymerization initiator. One or more of Ilugac 184, 819, 651, 1173, 907 and the like are preferably mixed in an amount of 3 to 10 phr based on the binder component. When the compounding quantity of a photoinitiator is less than this range, sufficient crosslinking hardening cannot be performed, and when it exceeds this range, the film strength of a low-refractive-index layer will fall.

The low-refractive-index layer of the third aspect is a composition obtained by mixing hollow silica, a polyfunctional (meth)acrylic compound as a binder component, and a photopolymerization initiator in a predetermined ratio and applying it to a high refractive index layer. index layer or conductive high-refractive-index hard coat layer, which is formed by irradiating ultraviolet rays in an atmosphere with an oxygen concentration of 0 to 10,000 ppm to cure it. Damage is greatly reduced, so it is controlled to 1000 ppm or less, preferably 200 ppm or less.

The thickness of such a low refractive index layer is preferably 85 to 110 nm.

In the third aspect, in order to form the hard coat layer 23, the high refractive index layer 24, and the low refractive index layer 25 on the base film 21 formed with the easy-adhesive layer 22, or to form a conductive high refractive index layer and a low The refractive index layer is preferably coated with an uncured resin composition (resin composition mixed with the above-mentioned fine particles if necessary), and then irradiated with ultraviolet rays. In this case, it may be cured after each application of one layer, or after application of three or two layers.

Specific methods of coating include a method in which a coating solution obtained by dissolving a binder component in a solvent such as toluene is coated with a gravure coater, dried, and then cured by ultraviolet rays. According to this wet coating method, there is an advantage that a film can be formed uniformly at high speed and at low cost. Curing by irradiating ultraviolet rays after coating has the effect of improving adhesion and film hardness, and can continuously produce anti-reflection films without heating.

Such an antireflection film according to the third aspect can ensure good light transmittance when used for front filters of PDPs of OA devices or liquid crystal panels, or window materials of vehicles or special buildings.

The third aspect will be described in more detail below by enumerating Examples, Comparative Examples and Experimental Examples.

Example 5

A hard coat layer ("Z7503" manufactured by JSR) is applied on a PET film with a thickness of 50 μm and an easy-adhesive layer of about 80 nm in film thickness is formed, and then dried and cured to form a 5 μm-thick, pencil hardness 3H or more on the surface. above the hard coat. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm.

The refractive index n _a of the easy-adhesive layer used is 1.58, the refractive index n _b of the PET film is 1.65, and the injection layer n _HC of the formed hard coat layer is 1.495, (n _b +n _HC )/2=1.57 , is approximately equal to n _a . In addition, the film thickness of the easily-adhesive layer was 80 nm, which was approximately equal to (550/4)×(1/n _a )=87 nm.

Next, a film-forming composition for a high refractive index layer ("Ei-3" manufactured by Dainippon Paint Co., Ltd.) containing ITO microparticles, a polyfunctional acrylic compound, and a photopolymerization initiator is applied, dried, and cured to form a film with a thickness of about 90nm, high refractive index layer with a refractive index of 1.67 to 1.68. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm.

Next, the low-refractive-index layer film-forming composition was coated on the high-refractive-index layer, dried and cured to form a low-refractive-index layer with a thickness of about 95 nm. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 800 mJ/cm ² , and the oxygen concentration during curing was 150 ppm.

In addition, 5 phr of photopolymerization initiator "Irugakuya-184" was added to dipentaerythritol hexaacrylate as a binder component, and hollow silica (average particle diameter: 60 nm, refractive index n = about 1.30) was added to make photopolymerization The total amount of initiator and binder: hollow silica = 62.5: 37.5 (% by weight), which was used as a low-refractive index layer film-forming composition.

For the anti-reflection film prepared by the above method, the wear resistance, minimum reflectance, and chemical corrosion resistance were tested by the following methods, and the results are shown in Table 11.

<Wear resistance>

The surface of the antireflection film (reflection color: purple) was reciprocally rubbed with a plastic eraser at a load pressure of about 4.9×10 ⁴ N/m ² . If the film of the low-refractive index layer is destroyed, the reflected color will gradually change from purple → red → yellow, so the number of reciprocations until the color changes first is the number of rubber rubbing resistance, and the number of rubber rubbing resistance is 100 times or 100 times. When the number of times was more than 100 times, the wear resistance was good (◯), and when it was less than 100 times, it was poor (×).

<Minimum Reflectance>

A black tape was pasted on the inner surface side (the side opposite to the film-forming surface), and the reflection spectrum was measured at 5° regular reflection, and the lowest reflectance at this time was recorded as the minimum reflectance.

<Chemical resistance>

Put tulle on the film-forming surface of the antireflection film, drop a few drops of 3% by weight NaOH aqueous solution, cover the disposable paper cup from above in order to prevent the evaporation of water in the NaOH aqueous solution, and leave it at 25° C. for 30 minutes. Then, the tulle was taken away, washed with pure water, and whether the reflection color of the anti-reflection film changed was visually judged. If there was no change in the reflection color, it was indicated as excellent chemical corrosion resistance (○), and if the reflection color changed, it was indicated as Chemical resistance is poor (×).

In addition, the refractive index of the low refractive index layer was measured by the following method, and the results are shown in Table 11.

<Measurement of Refractive Index>

On a PET film ("Toray Lumira-", film thickness 50 μm) without an easy-adhesive layer, the composition for forming a low-refractive index layer was coated with a thickness of about 1/4λ relative to the light wavelength of 550 nm, Let it solidify. The curing conditions were as follows: the cumulative irradiation amount of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm. Then, a black vinyl tape was stuck on the uncoated surface, the reflectance was measured, and the refractive index was calculated from the minimum reflectance of the reflectance spectrum.

Comparative example 4

In Example 5, except that the substrate film without the easy-adhesion layer was used, an antireflection film was produced in the same manner as in Example 5, and the abrasion resistance, minimum reflectance, and chemical corrosion resistance were checked in the same manner, and simultaneously measured The results of the refractive index of the low refractive index layer are shown in Table 11.

[Table 11] Whether there is an easy-adhesive layer wear resistance Minimum reflectance (%) chemical resistance Refractive index Example 5 have ○ 0.19 ○ 1.43 Comparative example 4 none ○ 0.48 ○ 1.43

Experimental example 5

In order to study the influence of the filling rate of the high-refractive-index particles of the high-refractive-index layer on the refractive index of the high-refractive-index layer, the materials combined as shown in Table 12 are used as the high-refractive-index particles of the high-refractive-index layer, or, as a binder As the components, a compound in which A ⁴¹ to A ⁴⁶ in the above general formula (VI) are all acrylic groups is used, and the high refractive index particle formulation shown in Table 12 is used to prepare a high refractive index layer film-forming composition.

In addition, the high-refractive-index particles used in this experimental example are as follows, and in the composition for forming a high-refractive-index layer, they are all based on the ratio of conductive high-refractive-index particles: ultra-high-refractive-index particles=27:18 (volume fraction) for mixing.

[Conductive high refractive index particles]

A-1: ITO dispersion liquid manufactured by Dainippon Paint Co., Ltd.

(Average particle size of ITO: 60nm)

A-2: ITO dispersion liquid manufactured by Dainippon Paint Co., Ltd.

(Average particle size of ITO: 35nm)

A-3: ITO "ELCOMP Premium A" manufactured by Catalyst Chemicals Co., Ltd.

(Average particle size of ITO: 50nm)

A-4: ITO "ELCOMP Premium B" manufactured by Catalyst Chemicals Co., Ltd.

(Average particle size of ITO: 65nm)

A-5: ITO dispersion liquid manufactured by Catalyst Chemicals Co., Ltd.

(Average particle size of ITO: 40nm)

[Ultra High Refractive Index Particles]

B-1: TiO ₂ dispersion liquid manufactured by Dainippon Paint Co., Ltd.

(Average particle size of _TiO2 : 100nm)

B-2: TiO ₂ (anatase type) "ELCOMP Special Grade D" manufactured by Dainippon Paint Co., Ltd.

(Average particle size of _TiO2 : 40nm)

B-3: TiO ₂ (rutile type) manufactured by China Paint Company

(Average particle size of _TiO2 : 40nm)

B-4: TiO ₂ (anatase type) manufactured by China National Paint Co., Ltd.

(Average particle size of _TiO2 : 8nm)

B-5: TiO ₂ (anatase type) manufactured by China National Paint Co., Ltd.

(Average particle size of _TiO2 : 20nm)

Table 12 shows the results of investigating the particle size distribution of the primary particle size in the composition for this high refractive index layer film-forming composition with a transmission electron microscope.

This high refractive index layer film-forming composition was coated on a PET film ("Toray Lumira", film thickness 50 μm) without an easy-adhesive layer at a thickness of about 1/4λ relative to the light wavelength of 550 nm. , solidified. The curing conditions were as follows: the cumulative irradiation dose of ultraviolet rays was 300 mJ/cm ² , and the oxygen concentration at the time of curing was 150 ppm. Then, a black vinyl tape was stuck on the uncoated surface of the film, the reflectance was measured, and the refractive index was calculated from the minimum reflectance of the reflection spectrum. The results are shown in Table 12.

[Table 12] No. Mixing amount (volume %) of high-refractive-index fine particles in the high-refractive-index layer film-forming composition Particle size distribution of high refractive index particles (volume%) Refractive index evaluate Conductive High Refractive Index Particles Ultra High Refractive Index Particles total Primary particle size of 30nm or less Primary particle size of 45nm or more A-1 A-2 A-3 A-4 A-5 B-1 B-2 B-3 B-4 B-5 1 15 15 20 50 <10 >90 1.71 △ 2 30 20 50 0 100 1.71 △ 3 15 15 20 50 <15 >70 1.72 △ 4 30 10 10 50 25 70 1.73 ○ 5 30 5 10 5 50 25 60 1.73 ○ 6 30 10 10 50 30 50 1.73 ○

It can be seen from Table 12 that by properly using high-refractive-index particles with a primary particle size of 30 nm or less and high-refractive-index particles with a primary particle size of 40 nm or more, the filling amount of high-refractive-index particles can be increased to form a high-refractive-index particle with a significantly improved refractive index. rate layer.

Experimental example 6

Experimental examples are given below to show that the above-mentioned rules for specifying the film thickness and refractive index of the easily-adhesive layer

(n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03

as well as

The basis of (550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm.

If the antireflection film does not have a hard coat layer, the abrasion resistance and pencil height will be lowered, and the film will be easily damaged, so a hard coat layer is usually formed. As its structure, PET film/hard coat layer/high refractive index layer/low refractive index layer are the most common.

The hard coat layer is formed by further mixing acrylic-modified silica particles in a conventional multifunctional acrylic monomer-to-oligomer mixture in order to increase hardness. The acrylic monomer or oligomer of the hard coat layer is usually The refractive index of the hard coating is about 1.49 to 1.55, and the refractive index of silica particles is about 1.47. Therefore, the refractive index of the hard coating is about 1.49 to 1.55. On the other hand, the refractive index of the PET film is about 1.65, which is very different from the refractive index of the hard coat layer.

If a hard coat layer is formed on a base film having a very large difference in refractive index in this way, a characteristic spectrum will be produced, and the minimum reflectance will be increased when an antireflection film is produced.

In order to solve this problem, a method of lowering the minimum reflectance includes a method of controlling the film thickness and the refractive index of the easily-adhesive layer.

First, an antireflection layer having the following composition of hard coat layer/high refractive index layer/low refractive index layer was formed.

[Table 13] Refractive index Optical film thickness (λ) (at 550nm) Film thickness (nm) composition hard coat 1.50 8 2930 _SiO2 microparticles/multifunctional acrylic high refractive index layer 1.68 0.25 81 ITO particles/multifunctional acrylic low refractive index layer 1.43 0.25 96 Hollow Silica/Multifunctional Acrylic

The following experimental results show to what extent the minimum reflectance of the antireflection layer is changed by the film thickness and refractive index of the easy-adhesion layer when the antireflection layer is coated.

Hereinafter, an experimental example suitable for the third aspect will be referred to as "experimental example a", and an experimental example corresponding to the comparative example will be referred to as "experimental example b".

In addition, since the refractive index n _b of the base film is 1.65 and the refractive index n _HC of the hard coat layer is 1.50, (n _b +n _HC )/2≈1.58.

The reflectance spectrum of each experimental example is shown in FIGS. 25 to 36 , and Table 14 shows the minimum reflectance.

[Table 14] Experimental example Refractive index of the easy-adhesive layer The difference between the refractive index of the adhesive layer and (n _b +n _HC )/2 Film thickness of easy-adhesive layer (nm) The difference between the film thickness of the easy-adhesive layer and (550/4)×(1/n _a ) Minimum reflectance (%) Overview b-1 - - - - 0.48 x b-2 1.55 -3 20 -69 0.38 x b-3 1.54 -0.04 89 ±0 0.21 x a-1 1.56 -0.02 88 ±0 0.19 ○ a-2 1.58 ±0 87 ±0 0.19 ○ a-3 1.60 +0.02 86 ±0 0.19 ○ b-4 1.62 +0.04 85 ±0 0.3 x b-5 1.64 +0.06 84 ±0 0.4 x b-6 1.58 0 57 -30 0.21 x b-7 1.58 0 67 -20 0.2 x a-4 1.58 0 77 -10 0.19 ○ a-5 1.58 0 87 ±0 0.19 ○ a-6 1.58 0 97 +10 0.19 ○ b-8 1.58 0 107 +20 0.21 x b-9 1.58 0 117 +30 0.23 x

The reflectance of Experimental Example b-1 without an easy-adhesive layer on the PET film and Experimental Example b-2 with a conventional easy-adhesive layer (refractive index 1.55, film thickness 20nm) is all high, being 0.35 to 0.45 %.

In Experimental Examples b-3~b~5 and Experimental Examples a-1~a-3, the optical film thickness of the easy-adhesive layer is accurately controlled at 1/4λ (0.25λ) relative to the light of 550nm, and the thickness of the easy-adhesive layer is changed. the refractive index. The fact that the optical film thickness is 0.25λ means that the film thickness of the easily bonding layer satisfies exactly (550/4)×(1/n _a ).

Change the index of refraction for easy bonding to 1.54, 1.56, 1.58, 1.60, 1.62. It can be seen from the reflectance spectrum of each experimental example and the minimum reflectance at this time that if the refractive index of the easy-adhesion layer is close to (n _b +n _HC )/2, the minimum reflectance decreases, especially (n _b + n _HC )/2±0.02, a very high anti-reflection effect can be observed. However, when the refractive index of the easily-adhesive layer is away from (n _b +n _HC )/2, a tendency for the minimum reflectance to rise is observed.

Experimental example b-3...n=1.54d=(550/4)×(1/n _a )

Experimental example a-1...n=1.56d=(550/4)×(1/n _a )

Experimental example a-2...n=1.58d=(550/4)×(1/n _a )

Experimental example a-3...n=1.60d=(550/4)×(1/n _a )

Experimental example b-4...n=1.62d=(550/4)×(1/n _a )

Experimental example b-5...n=1.64d=(550/4)×(1/n _a )

Experimental Examples b-6 to b-9 and Examples a-5 and a-6 show the influence of the film thickness of the easy-adhesive layer, that is, the film thickness of the easily-adhesive layer is separated from (550/4)×(1/ n _a ) situation.

Response spectra of various experimental examples in which the film thickness of the easily-adhesive layer was changed by setting the refractive index of the easily-adhesive layer to (n _b +n _HC )/2, that is, exactly 1.58, and the It can be seen from the minimum reflectivity that when the refractive index of the easy-adhesive layer is

(n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03

range, and the film thickness is

In the range of (550/4)×(1/n _a )−10 nm≦T≦(550/4)×(1/n _a )+10 nm, the minimum reflectance decreases.

Experimental example b-6...n=1.58d=(550/4)×(1/n _a )-30[nm](57nm)

Experimental example b-7...n=1.58d=(550/4)×(1/n _a )-20[nm](67nm)

Experimental example a-4...n=1.58d=(550/4)×(1/n _a )-10[nm](77nm)

Experimental example a-5...n=1.58d=(550/4)×(1/n _a ) [nm](87nm)

Experimental example b-7...n=1.58d=(550/4)×(1/n _a )+10[nm](97nm)

Experimental example b-8...n=1.58d=(550/4)×(1/n _a )+20[nm](107nm)

Experimental example b-9...n=1.58d=(550/4)×(1/n _a )+30[nm](117nm)

From these results, it can be seen that when a conventional hard coat layer (n=1.50) is used, very good antireflection properties can be obtained in the range of the easy-adhesion layer having a refractive index of about 1.58 and a film thickness of 77 to 97 nm. Therefore, it was confirmed that, by setting in this way, it is possible to simultaneously eliminate spotty reflection color unevenness due to the difference in refractive index between the hard coat layer and the base film.

IV. Implementation of the fourth aspect

Embodiments of the electromagnetic shielding light transmission type window material and the gas discharge type light emitting panel of the fourth aspect will be described below.

The overall structure of the electromagnetic shielding light transmission type window material and the gas discharge type light emitting panel itself of the fourth aspect can be the same as the existing electromagnetic shielding light transmission type window material and the gas discharge type light emitting panel, for example, can be listed, In the electromagnetic shielding window material as shown in Figure 38a, or the gas discharge type light-emitting panel as shown in Figure 38b, the electromagnetic shielding properties of the antireflection film using the low refractive index layer of the fourth aspect are used as the antireflection film. Light transmission type window material and gas discharge type light emitting panel.

Next, the antireflection film will be described with reference to FIG. 37 .

The structure of this antireflection film 80 is as follows: On a transparent base film 81, a hard coat layer 82, a high refractive index layer 83, and a low refractive index layer 84 are sequentially laminated, and an adhesive layer is formed on the surface opposite to the laminated surface. 85, and paste release film 86. When this antireflection film 80 is used in the electromagnetic shielding light transmission window material shown in FIG. Paste on the outermost surface of electromagnetic shielding light transmission type window material or gas discharge type light emitting panel.

In the fourth aspect, as the base film 81, polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), Acrylic resin, polycarbonate (PC), polystyrene, cellulose triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane , cellophane, etc., preferably PET, PC, PMMA transparent film.

The thickness of the base film 81 is usually in the range of 100 μm to 188 μm.

The hard coat layer 82 is preferably a synthetic resin hard coat layer, particularly preferably an ultraviolet curable synthetic resin, and particularly preferably a combination of a polyfunctional acrylic resin and silica fine particles. The thickness of the hard coat layer 82 is preferably 2 to 20 μm.

The high-refractive index layer 83 is preferably an ultraviolet-curable material containing metal oxide fine particles and a binder component having an aromatic group. Examples of the binder component having an aromatic group include epoxy acrylate, urethane acrylate, Acrylate resin containing bisphenol A, etc. In addition, as the metal oxide fine particles, at least one selected from the group consisting of ITO, TiO ₂ , ZrO ₂ , CeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ and Ho ₂ O ₃ is preferable. or a plurality of high refractive index metal oxide particles, particularly preferably TiO ₂ particles and ITO particles.

Regarding the ratio of the metal oxide fine particles and the binder component in the high refractive index layer 83, if the metal oxide fine particles are too much and the binder component is insufficient, the film strength of the high refractive index layer will decrease. Conversely, if the metal oxide fine particles are too If the amount is small, the refractive index cannot be sufficiently increased. Therefore, the ratio of the metal oxide fine particles is preferably 10 to 60% by volume, particularly preferably 20 to 50% by volume, based on the total amount of the metal oxide fine particles and the binder component.

The thickness of such high refractive index layer 83 is preferably about 80 to 100 nm. In addition, the refractive index of the high refractive index layer 83 is preferably 1.65 or more, particularly preferably 1.66 to 1.85. In this case, by controlling the refractive index of the low refractive index layer 84 to 1.39 to 1.47, the surface can be obtained. An antireflection film excellent in antireflection performance with a minimum reflectance of 1% or less. In particular, when the refractive index of the low-refractive index layer 84 is controlled to 1.45 or less, the anti-reflection performance can be further improved, and an anti-reflection film having a surface reflectance with a minimum reflectance of 0.5% or less can be produced.

The low-refractive-index layer 84 is obtained by irradiating ultraviolet rays to a coating film containing hollow silica and a binder formed of a polyfunctional (meth)acrylic compound in an atmosphere having an oxygen concentration of 0 to 10,000 ppm. components and photopolymerization initiators.

Hollow silica is hollow shell-shaped silica fine particles, and its average particle diameter is 10 to 200 nm, particularly preferably 10 to 150 nm. When the average particle diameter of the hollow silica is less than 10 nm, it is difficult to lower the refractive index of the hollow silica, and if it exceeds 200 nm, there is diffuse reflection of light and the surface roughness of the formed low refractive index layer increases. and so on.

Hollow silica has low-refractive-index air (refractive index=1.0) in its hollow interior, and therefore, its refractive index is significantly lower than that of conventional silica (refractive index=1.46). The refractive index of hollow silica is determined by the volume ratio of the hollow portion thereof, and is generally preferably about 1.20 to 1.40.

In addition, the refractive index of hollow silica: n (hollow silica) is composed of the refractive index of silica constituting the shell of hollow fine particles: n (silica), and the refractive index of the air inside: n (air ), calculated according to the following formula.

n (hollow silica) = n (silica) × volume percentage of silica

As mentioned above, n(silica) is about 1.47, and n(air) is very low at 1.0, so the refractive index of such hollow silica is very low.

Furthermore, the refractive index of the low-refractive-index layer of the fourth aspect using such hollow silica: n (low-refractive-index layer) is composed of the refractive index of hollow silica: n (hollow silica) and a binder The refractive index of the component: n (binder), calculated according to the following formula.

n (low refractive index layer) =

n(hollow silica)×volume ratio of hollow silica in the low refractive index layer+n(binder)×volume ratio of binder in the low refractive index layer.

Among them, in addition to the special fluorine-containing acrylic binder, the refractive index of the binder is usually about 1.50 to 1.55. Therefore, increasing the volume percentage of hollow silica in the low refractive index layer will reduce the refractive index of the low refractive index layer. It is important to reduce the rate.

In the 4th aspect, the more content of hollow silicon dioxide in the low-refractive index layer, the more low-refractive-index layer can be formed, and the anti-reflection film with excellent anti-reflection performance can be obtained. When the content of the agent component is relatively reduced, the film strength of the low-refractive index layer decreases, and the abrasion resistance and durability decrease. However, the reduction in membrane strength caused by the increase in the amount of hollow silica mixed can be compensated by surface treatment of hollow silica, and the membrane strength can also be supplemented by selecting the type of binder component to be mixed.

In the fourth aspect, the content of hollow silica in the low refractive index layer is preferably 20 to 55% by weight, particularly preferably 30 to 50% by weight, by surface treatment of hollow silica and selection of binder components, In order to realize the low refractive index of the low refractive index layer, the refractive index is about 1.39 to 1.45, and at the same time, the abrasion resistance is ensured.

Next, the polyfunctional (meth)acrylic compound of the binder component of the low refractive index layer of the fourth aspect will be described.

The polyfunctional (meth)acrylic compound is preferably a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or a 4-functional (meth)acrylic compound represented by the following general formula (II) The quasi-compound is a main component, and is preferably contained in an amount of 50% by weight or more, particularly preferably 90% by weight or more, of the entire binder component.

[chemical 14]

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

n, m, o, p, q, r each independently represent an integer of 0 to 2,

R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

[chemical 15]

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

s, t, u, and v each independently represent an integer of 0 to 2,

R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

Examples of the hexafunctional (meth)acrylic compound represented by the general formula (I) include dipentaerythritol hexaacrylate, ethylene oxide adducts of dipentaerythritol hexaacrylate, or ethylene oxide adducts. A compound in which H is substituted by F, these compounds may be used alone or in combination of two or more.

In addition, examples of the tetrafunctional (meth)acrylic compound represented by the above general formula (II) include pentaerythritol tetraacrylate, ethylene oxide adducts (1 to 8) of pentaerythritol tetraacrylate, or A compound in which H of ethylene oxide is replaced by F, these compounds may be used alone or in combination of two or more.

As the binder component, one or more hexafunctional (meth)acrylic compounds represented by the above general formula (I) and one or more tetrafunctional (meth)acrylic compounds represented by the above general formula (II) can be used in combination. (meth)acrylic compounds.

The polyfunctional (meth)acrylic compound represented by the above general formula (I), (II), especially the hexafunctional (meth)acrylic compound represented by the above general formula (I) has high hardness and abrasion resistance It is excellent and can effectively form a low-refractive-index layer with high abrasion resistance.

In addition, in the fourth aspect, as the binder component, it is preferable to use a hexafunctional (meth)acrylic compound represented by the above general formula (I) and/or a tetrafunctional (meth)acrylic compound represented by the above general formula (II) base) acrylic compound, used in combination with a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) or a specific fluorine-containing multifunctional (meth)acrylic compound, by using these binding agents Component that imparts abrasion resistance and stain resistance to the low refractive index layer. In addition, these binder components have a lower refractive index than the hexafunctional (meth)acrylic compound represented by the above general formula (I) or the tetrafunctional (meth)acrylic compound represented by the above general formula (II), Therefore, even if the mixing amount of the hollow silica is reduced, a low-refractive-index layer having a low refractive index can be formed.

A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III)

(In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.)

Examples of the fluorine-containing bifunctional (meth)acrylic compound represented by the above general formula (III) include 2,2,3,3,4,4-hexafluoropentanediol diacrylate, etc., these The compounds may be used alone or in combination of two or more.

In addition, the above-mentioned specific polyfunctional (meth)acrylic compound, that is, a (meth)acrylic compound having 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or less, having 3 to 6 functional groups, and (meth)acrylic compounds having 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1,000 to 5,000 may be used alone or in combination of two or more .

It is also possible to use one or more of the above-mentioned fluorine-containing bifunctional (meth)acrylic compounds in combination with one or more fluorine-containing multifunctional (meth)acrylic compounds.

Using the fluorine-containing bifunctional (meth)acrylic compound can lower the refractive index of the low refractive index layer and improve the antifouling property, but if the compounding amount is too large, the abrasion resistance will decrease. Therefore, it is preferable to mix 5% by weight or more of the fluorine-containing bifunctional (meth)acrylic compound in the total binder components, particularly preferably 5 to 10% by weight.

In addition, although the low refractive index of the low refractive index layer can be achieved by using the above-mentioned fluorine-containing polyfunctional (meth)acrylic compound, and the antifouling property can be improved, but if the compounding amount is too large, the wear resistance reduce. Therefore, it is preferable to mix the polyfunctional (meth)acrylic compound in an amount of 5% by weight or more, particularly preferably 5 to 10% by weight, of the total binder components.

In addition, in the case of using a fluorine-containing bifunctional (meth)acrylic compound in combination with a fluorine-containing polyfunctional (meth)acrylic compound, it is preferable that, among the total binder components, the fluorine-containing bifunctional (meth)acrylic The compound and the fluorine-containing polyfunctional (meth)acrylic compound are mixed in a total of 5% by weight or more, particularly preferably 5 to 10% by weight.

The hollow silica used in the fourth aspect has a particle diameter larger than that of conventional silica particles (with a particle diameter of about 5 to 20 nm) mixed in an existing low-refractive index layer. Therefore, even in In the case of using the same binder component, the film strength of the formed low-refractive index layer tends to be weaker than in the case of mixing silica particles, and by applying appropriate surface treatment to the hollow silica , can improve the binding force with the binder component, improve the film strength of the formed low refractive index layer, and improve the wear resistance.

As the surface treatment of the hollow silica, it is preferable to use a terminal (meth)acrylic silane coupling agent represented by the following general formula (IV) to perform terminal (meth)acrylic modification on the surface of the hollow silica. sex.

[chemical 16]

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group,

^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms,

R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

Such terminal (meth)acrylic silane coupling agents include, for example, CH ₂ =CH-COO-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ , CH ₂ =C(CH ₃ )-COO -(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

In order to perform terminal (meth)acrylic modification on the surface of hollow silica by using such a terminal (meth)acrylic silane coupling agent, it is preferable to couple the hollow silica with a terminal (meth)acrylic silane The mixed solution of the agent is hydrothermally reacted at 100 to 150° C., or the mixed solution is irradiated with microwaves to cause a reaction. That is, when only the terminal (meth)acrylic silane coupling agent and hollow silica are mixed, the surface cannot be chemically modified with the terminal (meth)acrylic silane coupling agent, and the desired surface modification effect cannot be obtained. In the case of utilizing the hydrothermal reaction, if the reaction temperature is low, sufficient terminal (meth)acrylic acid modification cannot be performed. However, if the reaction temperature is too high, the reactivity will decrease instead, so the hydrothermal reaction temperature is preferably 100 to 150°C. In addition, although the hydrothermal reaction time varies depending on the reaction temperature, it is usually about 0.1 to 10 hours. On the other hand, in the case of using microwaves, if the set temperature is too low, sufficient terminal (meth)acrylic acid modification cannot be performed. Therefore, for the same reason as above, the set temperature is preferably 90 to 150 ℃. The microwave is suitable to use a microwave with a frequency of 2.5 GHz. If the microwave is irradiated, the terminal group (meth)acrylic acid modification can be carried out in a short time of about 10 to 60 minutes. In addition, as a mixed solution used in this reaction, for example, hollow silica of 3.8% by weight, alcohol solvent of 96% by weight (a mixed solvent of 1:4 (weight ratio) of isopropanol and isobutanol), A reaction solution made of 3% by weight of acetic acid, 1% by weight of water, and 0.04% by weight of a silane coupling agent.

By chemically modifying the surface of hollow silica with such a terminal (meth)acrylic silane coupling agent, the hollow silica and the binder component can be firmly bonded, even when the amount of hollow silica mixed is large. Even in the case of , a low-refractive-index layer excellent in wear resistance can be formed, and the low-refractive index of the low-refractive-index layer can be achieved by increasing the blending amount of hollow silica.

In addition, the surface of the hollow silica can also be modified with a terminal fluorinated alkyl silane coupling agent represented by the following general formula (V). In this case, the terminal group The terminal group fluorinated alkyl modification carried out by the fluorinated alkyl silane coupling agent is preferably under the same conditions as when the above-mentioned terminal group (meth)acrylic acid silane coupling agent is used to carry out the terminal group (meth)acrylic acid modification , by hydrothermal method or microwave irradiation method.

[chemical 17]

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.)

In addition, examples of the terminal group fluorinated alkylsilane coupling agent include C ₈ F ₁₇ -(CH ₂ ) ₂ -Si-(OCH ₃ ) ₃ , C ₆ F ₁₃ -(CH ₂ ) ₂ -Si -(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

By chemically modifying the surface of the hollow silica using such a terminal group fluorinated alkylsilane coupling agent, the antifouling property of the formed low refractive index layer can be improved.

The low-refractive-index layer of the fourth aspect is formed by irradiating the above-mentioned binder component with ultraviolet light to cure it in the presence of a photopolymerization initiator. One or more of Ilugac 184, 819, 651, 1173, 907 and the like are preferably mixed in an amount of 3 to 10 phr based on the binder component. When the compounding quantity of a photoinitiator is less than this range, sufficient crosslinking hardening cannot be performed, and when it exceeds this range, the film strength of a low-refractive-index layer will fall.

The low refractive index layer of the fourth aspect is a composition obtained by mixing hollow silica, a multifunctional (meth)acrylic compound as a binder component, and a photopolymerization initiator in a predetermined ratio and applied to a high refractive index layer. index layer or conductive high-refractive-index hard coat layer, which is formed by irradiating ultraviolet rays in an atmosphere with an oxygen concentration of 0 to 10,000 ppm to cure it. Damage is greatly reduced, so it is controlled to 1000 ppm or less, preferably 200 ppm or less.

The thickness of such a low refractive index layer is preferably 85 to 110 nm, particularly preferably about 100 nm.

In the fourth aspect, in order to form the hard coat layer 82, the high refractive index layer 83, and the low refractive index layer 84 on the base film 81, it is preferable to coat an uncured resin composition (resin composition in which the above-mentioned fine particles are mixed as needed). object), followed by ultraviolet radiation. In this case, it may be cured after each application of one layer, or after application of three or two layers.

Specific methods of coating include a method in which a coating solution obtained by dissolving a binder component in a solvent such as toluene is coated with a gravure coater, dried, and then cured by ultraviolet rays. According to this wet coating method, there is an advantage that a film can be formed uniformly at high speed and at low cost. Curing by irradiating ultraviolet light after the coating has the effect of improving the adhesiveness and the hardness of the film, and the antireflection film can be continuously produced without heating.

A transparent adhesive such as acrylic is preferable as the adhesive for the adhesive layer 85 formed on the inner surface side of the base film 81, and the thickness of the adhesive layer 85 is usually about 1 to 100 μm, particularly preferably about 25 μm.

Also, as the release film 86 , a film formed of the same material as the base film and having a thickness of preferably about 20 to 175 μm, particularly preferably about 35 μm, subjected to a surface release treatment can be used.

The electromagnetic-shielding light-transmitting window material and the gas discharge type light-emitting panel of the fourth aspect are used, for example, in the electromagnetic-shielding light-transmitting window material shown in FIG. 38a or the gas discharge type light-emitting panel shown in FIG. 38b. The anti-reflection film can be manufactured using the anti-reflection film shown in FIG. Then, it can be manufactured by directly stacking the above-mentioned high-refractive-index layer and low-refractive-index layer on the transparent substrate and forming a film. Also, when an antireflection film is attached to a transparent substrate such as a glass substrate on the outermost surface, the antireflection film may be one in which the hard coat layer is omitted in FIG. 37 .

In the electromagnetic shielding light-transmitting window material and the gas discharge type light-emitting panel of the fourth aspect, for example, in the antireflection layer formed by the laminated film of the above-mentioned antireflection film, high refractive index layer and low refractive index layer, by By making the following adjustments, it is possible to realize a high-visibility electromagnetic shielding light-transmitting window material and a gas discharge type light-emitting panel with excellent antireflection and antifouling properties.

(1) An easy-adhesion layer is provided between the transparent base film and the hard coat layer. The easy-adhesive layer is used to improve the adhesion between the hard coat layer and the substrate film, and is usually used to mix SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , etc. in thermosetting resins such as copolyester resins and polyurethane resins. Metal oxide fine particles, preferably metal oxide fine particles having an average particle diameter of about 1 to 100 nm, are used to adjust the refractive index. In addition, when the cost increases due to the mixing of metal oxide fine particles, the refractive index can be adjusted by mixing 0 to 50% by weight of a polymer containing a large number of phenyl groups, bromine atoms, and sulfur atoms in the structure.

At this time, if the refractive index of the hard coat layer is in the range of 1.48 to 1.55, when the refractive index of the easy-adhesion layer is expressed as _na , the refractive index of the transparent base film is expressed as _nb , and the refractive index of the hard coat layer is When the refractive index is recorded as n _HC ,

(n _b +n _HC )/2-0.02≤n _a ≤(n _b +n _HC )/2+0.02

In particular, (n _b +n _HC )/2-0.01≤n _a ≤(n _b +n _HC )/2+0.01, and the film thickness T of the easy-adhesive layer 2 satisfies:

(550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm

in particular

In the range of (550/4)×(1/n _a )-5nm≤T≤(550/4)×(1/n _a )+5nm, it is preferable because obviously excellent antireflection performance can be obtained.

This has the effect that the refractive index of the substrate film is substantially equal to that of the hard coat layer with respect to a light wavelength of 550 nm, and has the effect of eliminating reflection between the hard coat layer/substrate film. In the fourth aspect, the easy-adhesion layer is preferably formed on the transparent base film when the transparent base film is formed.

(2) As the high-refractive-index microparticles of the high-refractive-index layer, it is preferable to use conductive high-refractive-index microparticles selected from _SnO2 and ITO, and ultra-high-refractive-index microparticles composed of _TiO2 , _ZrO2 , and _CeO2 . At least one kind of high-refractive-index particles in the composed particle group is composed of high-refractive-index particles with different particle sizes, so that the average primary particle size of the high-refractive index particles is 30-40 nm, and the average primary particle size is the center, The particle size distribution range is wide, and among the total particles, the cumulative number of particles with a primary particle size of 30 nm or less is 20% or more, for example, 20% to 50%, and the primary particle size is 45 nm or more The cumulative number of fine particles is 20% or more, for example, 20% to 50%.

That is, in the high-refractive-index layer, it is important to contain as many high-refractive-index particles as possible, so that the filling of high-refractive-index particles in the high-refractive-index layer can be improved by using high-refractive-index particles with different particle sizes in combination. amount, forming a high-refractive-index layer with a very high refractive index at a high packing density.

In addition, as the high-refractive-index fine particles, it is preferable to use conductive high-refractive-index fine particles and ultra-high-refractive-index fine particles in combination, particularly preferably conductive high-refractive-index fine particles : ultra-high refractive index fine particles = 50-70:50-30 (volume ratio), particularly preferably 27:18 (volume ratio). If the conductive high-refractive-index fine particles are more than this range, the refractive index of the high-refractive index layer will decrease, and if there are too many ultra-high-refractive-index fine particles, the antistatic effect cannot be obtained.

(3) By using the above-mentioned fluorine-containing binder component as the binder component of the low-refractive index layer, the antifouling property is improved.

(4) By adjusting the film thickness of the high-refractive index layer and the film thickness of the low-refractive index layer, average reflectance in the visible light range and low reflectance at wavelengths requiring low reflectance are realized. For example, when the red color of the luminescent color is weak, by increasing the film thickness of the high refractive index layer or increasing the film thickness of the low refractive index layer, the wavelength of the minimum reflectance (valley wavelength) is shifted to the long-wave direction, and by making the valley wavelength Reach the wavelength of red light to increase the transmittance of red. On the contrary, when the blue is weak, reduce the film thickness of the high refractive index layer or reduce the film thickness of the low refractive index layer to make the valley wavelength to the short wave direction By shifting the valley wavelength to the wavelength of blue light, increasing the blue transmittance, etc., using this method, an anti-reflection layer with reflection characteristics suitable for the purpose is formed.

V. Form of the fifth aspect

Next, embodiments of the flat display panel and window material of the fifth aspect will be described.

The flat panel display panel and window material of the fifth aspect may have an anti-reflection film attached to its surface, for example, as shown in FIG. 39 .

The structure of the antireflection film 90 is as follows: on the antireflection film 91, a hard coat layer 92, a high refractive index layer 93 and a low refractive index layer 94 are sequentially laminated, an adhesive layer 95 is formed on the surface opposite to the laminated surface, and the adhesive layer 95 is pasted. Release film 96. When this antireflection film 90 is used on the surface of the flat panel display panel or transparent substrates such as glass substrates of window materials, the release film 96 of the antireflection film 90 can be peeled off and pasted on the surface of the flat panel display panel or the window through the adhesive layer 95. materials on transparent substrates such as glass substrates.

In this antireflection film 90, as the base film 91, polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA) can be mentioned. , acrylic resin, polycarbonate (PC), polystyrene, cellulose triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, Polyurethane, cellophane, etc., preferably PET, PC, PMMA transparent film.

The thickness of the base film 91 is usually in the range of 100 μm to 188 μm.

As the hard coat layer 92, a synthetic resin hard coat layer is preferable, an ultraviolet curable resin is particularly preferable, and a combination of polyfunctional acrylate and silica fine particles is particularly preferable. The thickness of the hard coat layer 92 is preferably 2 to 20 μm.

The high-refractive index layer 93 is preferably an ultraviolet-curable material containing metal oxide fine particles and a binder component having an aromatic group. Examples of the binder component having an aromatic group include epoxy acrylate, urethane acrylate, Acrylic resin containing bisphenol A, etc. In addition, as the metal oxide fine particles, one selected from the group consisting of ITO, TiO ₂ , ZrO ₂ , CeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ and Ho ₂ O ₃ or A variety of high refractive index metal oxide particles, particularly TiO ₂ particles and ITO particles are preferred.

With regard to the ratio of metal oxide particles and binder components in the high refractive index layer 93, if there are too many metal oxide particles and insufficient binder components, the film strength of the high refractive index layer will decrease. Conversely, if the metal oxide particles are too small , the refractive index cannot be sufficiently increased. Therefore, the ratio of the metal oxide fine particles is preferably 10 to 60% by volume, particularly preferably 20 to 50% by volume, based on the total amount of the metal oxide fine particles and the binder component.

The thickness of such high refractive index layer 93 is preferably about 80 to 100 nm. In addition, the refractive index of the high refractive index layer 93 is preferably 1.65 or more, particularly preferably 1.66 to 1.85. In this case, by controlling the refractive index of the low refractive index layer 94 to 1.39 to 1.47, the surface can be obtained. An antireflection film excellent in antireflection performance with a minimum reflectance of 1% or less. In particular, when the refractive index of the low-refractive index layer 94 is controlled to 1.45 or less, the anti-reflection performance can be further improved, and an anti-reflection film having a surface reflectance with a minimum reflectance of 0.5% or less can be produced.

In the fifth aspect, the low-refractive index layer 94 is obtained by irradiating ultraviolet rays to a coating film containing hollow silica, polyfunctional (methyl) A binder component and a photopolymerization initiator formed of an acrylic compound.

Hollow silica is hollow shell-shaped silica fine particles, and its average particle diameter is 10 to 200 nm, particularly preferably 10 to 150 nm. When the average particle diameter of the hollow silica is less than 10 nm, it is difficult to lower the refractive index of the hollow silica, and if it exceeds 200 nm, there is diffuse reflection of light and the surface roughness of the formed low refractive index layer increases. and so on.

Hollow silica has air with a low refractive index (refractive index = 1.0) inside the hollow, and thus, its refractive index is significantly lower than that of conventional silica (refractive index = 1.46). The refractive index of hollow silica is determined by the volume ratio of the hollow portion thereof, and is generally preferably about 1.20 to 1.40.

In addition, the refractive index of hollow silica: n (hollow silica) is composed of the refractive index of silica constituting the shell of hollow fine particles: n (silica), and the refractive index of the air inside: n (air ), calculated according to the following formula.

n (hollow silica) = n (silica) × volume percentage of silica

As mentioned above, n(silica) is about 1.47, and n(air) is very low at 1.0, so the refractive index of such hollow silica is very low.

In addition, the refractive index of the low-refractive-index layer of the present invention using such hollow silica: n (low-refractive-index layer) is determined by the refractive index of hollow silica: n (hollow silica) and the binder component. Refractive index: n (binder), calculated according to the following formula.

n (low refractive index layer) =

n(hollow silica)×volume ratio of hollow silica in the low refractive index layer+n(binder)×volume ratio of binder in the low refractive index layer.

Among them, in addition to the special fluorine-containing acrylic binder, the refractive index of the binder is usually about 1.50 to 1.55. Therefore, increasing the volume percentage of hollow silica in the low refractive index layer will reduce the refractive index of the low refractive index layer. It is important to reduce the rate.

In the fifth aspect, the more content of hollow silicon dioxide in the low refractive index layer, the more the low refractive index layer can be formed, and the antireflection film with excellent antireflection performance can be obtained. When the content of the agent component is relatively reduced, the film strength of the low-refractive index layer decreases, and the abrasion resistance and durability decrease. However, the reduction in membrane strength caused by the increase in the amount of hollow silica mixed can be compensated by surface treatment of hollow silica, and the membrane strength can also be supplemented by selecting the type of binder component to be mixed.

In the fifth aspect, the content of hollow silica in the low refractive index layer is preferably 20 to 55% by weight, particularly preferably 30 to 50% by weight, by surface treatment of hollow silica and selection of binder components, In order to realize the low refractive index of the low refractive index layer, the refractive index is about 1.39 to 1.45, and at the same time, the abrasion resistance is ensured.

Next, the polyfunctional (meth)acrylic compound that is the binder component of the low refractive index layer of the fifth aspect will be described.

The polyfunctional (meth)acrylic compound is preferably a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or a 4-functional (meth)acrylic compound represented by the following general formula (II) The quasi-compound is a main component, and is preferably contained in an amount of 50% by weight or more, particularly preferably 90% by weight or more, of the entire binder component.

[chemical 18]

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

n, m, o, p, q, r each independently represent an integer of 0 to 2,

R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

[chemical 19]

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

s, t, u, and v each independently represent an integer of 0 to 2,

R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

Examples of the hexafunctional (meth)acrylic compound represented by the general formula (I) include dipentaerythritol hexaacrylate, ethylene oxide adducts of dipentaerythritol hexaacrylate, or ethylene oxide adducts. A compound in which H is substituted by F, these compounds may be used alone or in combination of two or more.

In addition, examples of the tetrafunctional (meth)acrylic compound represented by the above general formula (II) include pentaerythritol tetraacrylate, ethylene oxide adducts (1 to 8) of pentaerythritol tetraacrylate, or Compounds in which H of ethylene oxide is replaced by F, etc. These compounds may be used alone or in combination of two or more.

As the binder component, one or more hexafunctional (meth)acrylic compounds represented by the above general formula (I) and one or more tetrafunctional (meth)acrylic compounds represented by the above general formula (II) can be used in combination. (meth)acrylic compounds.

The polyfunctional (meth)acrylic compound represented by the above general formula (I), (II), especially the hexafunctional (meth)acrylic compound represented by the above general formula (I) has high hardness and abrasion resistance It is excellent and can effectively form a low-refractive-index layer with high abrasion resistance.

In addition, in the fifth aspect, as the binder component, it is preferable to use a hexafunctional (meth)acrylic compound represented by the above general formula (I) and/or a tetrafunctional (meth)acrylic compound represented by the above general formula (II) base) acrylic compound, used in combination with a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) or a specific fluorine-containing multifunctional (meth)acrylic compound, by using these binding agents Component that imparts abrasion resistance and stain resistance to the low refractive index layer. In addition, these binder components have a lower refractive index than the hexafunctional (meth)acrylic compound represented by the above general formula (I) or the tetrafunctional (meth)acrylic compound represented by the above general formula (II), Therefore, even if the mixing amount of the hollow silica is reduced, a low-refractive-index layer having a low refractive index can be formed.

A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III)

(In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.)

Examples of the fluorine-containing bifunctional (meth)acrylic compound represented by the above general formula (III) include 2,2,3,3,4,4-hexafluoropentanediol diacrylate, etc., these The compounds may be used alone or in combination of two or more.

In addition, the above-mentioned specific polyfunctional (meth)acrylic compound, that is, a (meth)acrylic compound having 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or less, having 3 to 6 functional groups, and (meth)acrylic compounds having 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1,000 to 5,000 may be used alone or in combination of two or more .

It is also possible to use one or more of the above-mentioned fluorine-containing bifunctional (meth)acrylic compounds in combination with one or more fluorine-containing multifunctional (meth)acrylic compounds.

Using the fluorine-containing bifunctional (meth)acrylic compound can lower the refractive index of the low refractive index layer and improve the antifouling property, but if the compounding amount is too large, the abrasion resistance will decrease. Therefore, it is preferable to mix 5% by weight or more of the fluorine-containing bifunctional (meth)acrylic compound in the total binder components, particularly preferably 5 to 10% by weight.

In addition, although the low refractive index of the low refractive index layer can be achieved by using the above-mentioned fluorine-containing polyfunctional (meth)acrylic compound, and the antifouling property can be improved, but if the compounding amount is too large, the wear resistance reduce. Therefore, it is preferable to mix the polyfunctional (meth)acrylic compound in an amount of 5% by weight or more, particularly preferably 5 to 10% by weight, of the total binder components.

In addition, in the case of using a fluorine-containing bifunctional (meth)acrylic compound in combination with a fluorine-containing polyfunctional (meth)acrylic compound, it is preferable that, among the total binder components, the fluorine-containing bifunctional (meth)acrylic The compound and the fluorine-containing polyfunctional (meth)acrylic compound are mixed in a total of 5% by weight or more, particularly preferably 5 to 10% by weight.

The hollow silica used in the fifth aspect has a particle diameter larger than that of conventional silica particles (with a particle diameter of about 5 to 20 nm) mixed in an existing low-refractive index layer. Therefore, even in In the case of using the same binder component, the film strength of the formed low-refractive index layer tends to be weaker than in the case of mixing silica particles, and by applying appropriate surface treatment to the hollow silica , can improve the binding force with the binder component, improve the film strength of the formed low refractive index layer, and improve the wear resistance.

As the surface treatment of the hollow silica, it is preferable to use a terminal (meth)acrylic silane coupling agent represented by the following general formula (IV) to perform terminal (meth)acrylic modification on the surface of the hollow silica. sex.

[chemical 20]

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group,

^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms,

R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

Such terminal (meth)acrylic silane coupling agents include, for example, CH ₂ =CH-COO-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ , CH ₂ =C(CH ₃ )-COO -(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

In order to perform terminal (meth)acrylic modification on the surface of hollow silica by using such a terminal (meth)acrylic silane coupling agent, it is preferable to couple the hollow silica with a terminal (meth)acrylic silane The mixed solution of the agent is hydrothermally reacted at 100 to 150° C., or the mixed solution is irradiated with microwaves to cause a reaction. That is, when only the terminal (meth)acrylic silane coupling agent and hollow silica are mixed, the surface cannot be chemically modified with the terminal (meth)acrylic silane coupling agent, and the desired surface modification effect cannot be obtained. In the case of utilizing the hydrothermal reaction, if the reaction temperature is low, sufficient terminal (meth)acrylic acid modification cannot be performed. However, if the reaction temperature is too high, the reactivity will decrease instead, so the hydrothermal reaction temperature is preferably 100 to 150°C. In addition, although the hydrothermal reaction time varies depending on the reaction temperature, it is usually about 0.1 to 10 hours. On the other hand, in the case of using microwaves, if the set temperature is too low, sufficient terminal (meth)acrylic acid modification cannot be performed. Therefore, for the same reason as above, the set temperature is preferably 90 to 150 ℃. The microwave is suitable to use a microwave with a frequency of 2.5 GHz. If the microwave is irradiated, the terminal group (meth)acrylic acid modification can be carried out in a short time of about 10 to 60 minutes. In addition, as the mixed solution used in this reaction, hollow silica of 3.8% by weight, 96% by weight of alcohol solvent (a mixed solvent of 1:4 (weight ratio) of isopropanol and isobutanol), A reaction solution made of 3% by weight of acetic acid, 1% by weight of water, and 0.04% by weight of a silane coupling agent.

By chemically modifying the surface of hollow silica with such a terminal (meth)acrylic silane coupling agent, the hollow silica and the binder component can be firmly bonded, even when the amount of hollow silica mixed is large. Even in the case of , a low-refractive-index layer excellent in wear resistance can be formed, and the low-refractive index of the low-refractive-index layer can be achieved by increasing the blending amount of hollow silica.

In addition, the surface of the hollow silica can also be modified with a terminal fluorinated alkyl silane coupling agent represented by the following general formula (V). In this case, the terminal group The terminal group fluorinated alkyl modification carried out by the fluorinated alkyl silane coupling agent is preferably under the same conditions as when the above-mentioned terminal group (meth)acrylic acid silane coupling agent is used to carry out the terminal group (meth)acrylic acid modification , by hydrothermal method or microwave irradiation method.

[chem 21]

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.)

In addition, examples of the terminal group fluorinated alkylsilane coupling agent include C ₈ F ₁₇ -(CH ₂ ) ₂ -Si-(OCH ₃ ) ₃ , C ₆ F ₁₃ -(CH ₂ ) ₂ -Si -(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

By chemically modifying the surface of the hollow silica using such a terminal group fluorinated alkylsilane coupling agent, the antifouling property of the formed low refractive index layer can be improved.

The low-refractive-index layer of the fifth aspect is formed by irradiating the above-mentioned binder component with ultraviolet rays to cure it in the presence of a photopolymerization initiator. One or more of Ilugac 184, 819, 651, 1173, 907 and the like are preferably mixed in an amount of 3 to 10 phr based on the binder component. When the compounding quantity of a photoinitiator is less than this range, sufficient crosslinking hardening cannot be performed, and when it exceeds this range, the film strength of a low-refractive-index layer will fall.

The low-refractive-index layer of the fifth aspect is a composition obtained by mixing hollow silica, a polyfunctional (meth)acrylic compound as a binder component, and a photopolymerization initiator in a predetermined ratio and applying it to a high refractive index layer. index layer or conductive high-refractive-index hard coat layer, which is formed by irradiating ultraviolet rays in an atmosphere with an oxygen concentration of 0 to 10,000 ppm to cure it. Damage is greatly reduced, so it is controlled to 1000 ppm or less, preferably 200 ppm or less.

The thickness of such a low refractive index layer is preferably 85 to 110 nm, particularly preferably about 100 nm.

In the fifth aspect, in order to form the hard coat layer 92, the high refractive index layer 93, and the low refractive index layer 94 on the base film 91, it is preferable to apply an uncured resin composition (a resin composition in which the above-mentioned fine particles are mixed as needed). object), followed by ultraviolet radiation. In this case, it may be cured after each application of one layer, or after application of three or two layers.

Specific methods of coating include a method in which a coating solution obtained by dissolving a binder component in a solvent such as toluene is coated with a gravure coater, dried, and then cured by ultraviolet rays. According to this wet coating method, there is an advantage that a film can be formed uniformly at high speed and at low cost. Curing by irradiating ultraviolet light after the coating has the effect of improving the adhesiveness and the hardness of the film, and the antireflection film can be continuously produced without heating.

The adhesive used for the adhesive layer 95 formed on the inner surface side of the base film 91 is preferably a transparent adhesive such as acrylic, and the thickness of the adhesive layer 95 is usually about 1 to 100 μm, particularly preferably about 25 μm.

In addition, as the release film 96, a film having a thickness of about 20 to 175 μm, especially about 35 μm, which is made of the same material as the above-mentioned base film and subjected to a surface release treatment can be used.

The flat display panel and window material of the fifth aspect can be manufactured by using such an anti-reflection film 90. In addition, for example, if it is a flat display panel provided with a transparent substrate such as a glass substrate on the outermost surface, it can be made by adding The high-refractive-index layer and the low-refractive-index layer are directly stacked on the substrate and formed into a film. Similarly, the window material can also be produced by directly laminating the above-mentioned high-refractive-index layer and low-refractive-index layer on a transparent substrate such as a glass substrate, and forming a film. In addition, when an antireflection film is attached to a transparent substrate such as a glass substrate, the antireflection film may be one in which the hard coat layer is omitted in FIG. 39 .

In the flat panel display panel and the window material of the fifth aspect, for example, in the above-mentioned antireflection film, the antireflection layer formed by the lamination film of the high refractive index layer and the low refractive index layer, by performing the following adjustment, it is possible to realize more High-visibility flat-panel display panels and window materials with good anti-reflection and anti-fouling properties.

(1) An easy-adhesion layer is provided between the transparent base film and the hard coat layer. The easy-adhesive layer is used to improve the adhesion between the hard coat layer and the substrate film, and is usually used to mix SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , etc. in thermosetting resins such as copolyester resins and polyurethane resins. Metal oxide fine particles, preferably metal oxide fine particles having an average particle diameter of about 1 to 100 nm, are used to adjust the refractive index. In addition, when the cost increases due to the mixing of metal oxide fine particles, the refractive index can be adjusted by mixing 0 to 50% by weight of a polymer containing a large number of phenyl groups, bromine atoms, and sulfur atoms in the structure.

At this time, the refractive index of the hard coat layer is in the range of 1.48 to 1.55. When the refractive index of the easy-adhesion layer is expressed as _na , the refractive index of the transparent base film is expressed as _nb , and the refractive index of the hard coat layer is When the rate is denoted as n _HC ,

(n _b +n _HC )/2-0.02≤n _a ≤(n _b +n _HC )/2+0.02

In particular, (n _b +n _HC )/2-0.01≤n _a ≤(n _b +n _HC )/2+0.01, and the film thickness T of the easy-adhesive layer satisfies:

(550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm

in particular

The range of (550/4)×(1/n _a )-5nm≤T≤(550/4)×(1/n _a )+5nm is preferable since obviously excellent antireflection performance can be obtained.

This has the effect that the refractive index of the substrate film is substantially equal to that of the hard coat layer with respect to a light wavelength of 550 nm, and has the effect of eliminating reflection between the hard coat layer/substrate film. In the fifth aspect, the easy-adhesion layer is preferably formed on the transparent base film when the transparent base film is formed.

(2) As the high-refractive-index microparticles of the high-refractive-index layer, it is preferable to use conductive high-refractive-index microparticles selected from _SnO2 and ITO, and ultra-high-refractive-index microparticles composed of _TiO2 , _ZrO2 , and _CeO2 . At least one high-refractive-index particle in the composed particle group, and use high-refractive-index particles with different particle sizes in combination, so that the average primary particle size of the high-refractive index particle is 30-40 nm, and the average primary particle size is the center , the particle size distribution range is wide, and among the total particles, the cumulative number of particles with a primary particle size of 30 nm or less is 20% or more, such as 20% to 50%, and the primary particle size is 45 nm or more The cumulative number of fine particles is 20% or more, for example, 20% to 50%.

That is, in the high-refractive-index layer, it is important to contain as many high-refractive-index particles as possible, so that the filling of high-refractive-index particles in the high-refractive-index layer can be improved by using high-refractive-index particles with different particle sizes in combination. amount, forming a high-refractive-index layer with a very high refractive index at a high packing density.

In addition, as the high-refractive-index fine particles, it is preferable to use conductive high-refractive-index fine particles and ultra-high-refractive-index fine particles in combination, particularly preferably conductive high-refractive-index fine particles : ultra-high refractive index fine particles = 50-70:50-30 (volume ratio), particularly preferably 27:18 (volume ratio). If the conductive high-refractive-index fine particles are more than this range, the refractive index of the high-refractive index layer will decrease, and if there are too many ultra-high-refractive-index fine particles, the antistatic effect cannot be obtained.

(3) As the binder component of the low-refractive index layer, the antifouling property is improved by using the above-mentioned fluorine-containing binder component.

(4) By adjusting the film thickness of the high-refractive index layer and the film thickness of the low-refractive index layer, average reflectance in the visible light range and low reflectance at wavelengths requiring low reflectance are realized. For example, it is possible to increase the film thickness of the high-refractive index layer while decreasing the film thickness of the low-refractive index layer without changing the wavelength of the minimum reflectance (valley wavelength). The average reflectance is reduced, so that the surface reflection color of the display can be close to the neutral color. In addition, in the window material, by performing the same film thickness adjustment, the visible light reflectance can be reduced on average, and the difference (color difference) between the actual color of the exhibit displayed on the window material and the color seen can be reduced.

Next, the structure of increasing the film thickness of the high refractive index layer without changing the minimum reflection color of the antireflection layer in this way will be described in detail.

The anti-reflection layer is composed of a hard coat layer, a high refractive index layer, and a low refractive index layer layered in sequence, and the film thickness of the hard coat layer is about 2 to 10 μm, and the film thickness of the high refractive index layer is 1/4λ. By making the film thickness of the formed high-refractive index layer thicker than 1/4λ, the reflectance on the short-wavelength side can be reduced, and the transmittance of blue light emission on the short-wavelength side can be increased. .

For example, a hard coat layer, a high refractive index layer, and a low refractive index layer ("Z-7503" manufactured by JSR) are sequentially coated on a TAC ("TAC" manufactured by Fujifilm Co., Ltd.) film. The high refractive index layer (n=1.68) and the low refractive index layer of ITO microparticles ("Ei-3" manufactured by Dainippon Paint Co., Ltd.) are pentaerythritol tetraacrylate ("PE-4A" manufactured by Kyoei Co., Ltd.) containing hollow silica. ") (n=1.43), and the average reflectance when changing the film thickness of the high refractive index layer is shown in Table 15 below.

[Table 15] No. Thickness of high refractive index layer (nm) Thickness of low refractive index layer (nm) Average reflectance (%) Overview 1 81 96 2.55 △ 2 90 92 2.49 ○ 3 98 88 2.43 ○ 4 104 84 2.39 ○ 5 114 80 2.32 ○ 6 131 69 2.58 △

In addition, the reflectances of No. 1 and No. 4 are shown in FIG. 40 , and the reflectances of No. 1, No. 5, and 6 are shown in FIG. 41 .

From these results, it can be seen that if the film thickness of the high-refractive index layer is increased, the reflectance on the short-wavelength side decreases, and the average reflectance decreases, and if the film thickness of the high-refractive index layer increases beyond a certain level, the minimum reflectance , and the average reflectance increase at the same time, so it can be seen that the film thickness of the high refractive index layer is 90 nm to 130 nm is suitable.

Such a flat display panel according to the fifth aspect is suitable for flat display panels such as LCD, organic EL, and CRT, and car navigation systems, touch panels, and the like using these displays. In addition, the window material of the fifth aspect is particularly suitable for display windows of high-end exhibits such as artworks, decorations, and precious metals.

VI. Implementation of the sixth aspect

Embodiments of the solar cell module according to the sixth aspect will be described below.

42a to 42c are schematic cross-sectional views showing the antireflection layer portion on the surface of an embodiment of the solar cell module according to the sixth aspect. The solar cell module of Fig. 42a is pasted with anti-reflection film 101A on the surface of glass substrate 111 as the surface side transparent protection member, and the solar cell module of Fig. 42b is pasted with antireflection film on the surface of glass substrate 111 as the front side transparent protection part 101B, in the solar cell module of FIG. 42c, an antireflection layer 101C is directly formed on the surface of a glass substrate 111 as a surface-side transparent protective member.

In addition, in the sixth aspect, the main structure of the solar cell module itself is not particularly limited, and a conventional solar cell module structure as shown in FIG. 43 can be used.

The antireflection film 101A shown in Fig. 42a is formed by sequentially laminating a hard coat layer 103, a high refractive index layer 104, and a low refractive index layer 105 on a transparent base film 102, and is formed on the opposite side of the laminated surface. An adhesive layer 106 is formed on the surface.

In the antireflection film 101A, examples of the base film 102 include polyester, polyethylene terephthalate (PET), polybutylene terephthalate, polymethyl methacrylate (PMMA), Acrylic resin, polycarbonate (PC), polystyrene, cellulose triacetate (TAC), polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane , cellophane, etc., preferably PET, PC, PMMA transparent film.

The thickness of the base film 102 is usually in the range of 100 μm to 188 μm.

As the hard coat layer 103, a synthetic resin hard coat layer is preferable, an ultraviolet curable resin is particularly preferable, and a combination of polyfunctional acrylate and silica fine particles is particularly preferable. The thickness of the hard coat layer 103 is preferably 2 to 20 μm.

The high-refractive index layer 104 is preferably an ultraviolet-curable material containing metal oxide fine particles and a binder component having an aromatic group. Examples of the binder component having an aromatic group include epoxy acrylate, urethane acrylate, Acrylate resin containing bisphenol A, etc. In addition, as the metal oxide fine particles, at least one selected from the group consisting of ITO, TiO ₂ , ZrO ₂ , CeO ₂ , Al ₂ O ₃ , Y ₂ O ₃ , La ₂ O ₃ and Ho ₂ O ₃ is preferable. or a plurality of high refractive index metal oxide particles, particularly preferably TiO ₂ particles and ITO particles.

With regard to the ratio of the metal oxide fine particles and the binder component in the high refractive index layer 104, if there are too many metal oxide fine particles and not enough binder components, the film strength of the high refractive index layer will decrease. Conversely, if the metal oxide fine particles are too If the amount is small, the refractive index cannot be sufficiently increased. Therefore, the ratio of the metal oxide fine particles is preferably 10 to 60% by volume, particularly preferably 20 to 50% by volume, based on the total amount of the metal oxide fine particles and the binder component.

The thickness of such a high refractive index layer 104 is preferably about 80 to 100 nm. In addition, the refractive index of the high refractive index layer 104 is preferably 1.65 or more, particularly preferably 1.66 to 1.85. In this case, by controlling the refractive index of the low refractive index layer 105 to 1.39 to 1.47, the surface can be obtained. An antireflection film excellent in antireflection performance with a minimum reflectance of 1% or less. In particular, when the refractive index of the low-refractive index layer 105 is controlled to 1.45 or less, the anti-reflection performance can be further improved, and an anti-reflection film having a surface reflectance with a minimum reflectance of 0.5% or less can be formed.

In the sixth aspect, the low-refractive index layer 105 is obtained by irradiating ultraviolet rays to a coating film containing hollow silica, polyfunctional group A binder component and a photopolymerization initiator formed of a (meth)acrylic compound.

Hollow silica is hollow shell-shaped silica fine particles, and its average particle diameter is preferably 10 to 200 nm, particularly preferably 10 to 150 nm. When the average particle diameter of the hollow silica is less than 10 nm, it is difficult to lower the refractive index of the hollow silica, and if it exceeds 200 nm, there is diffuse reflection of light and the surface roughness of the formed low refractive index layer increases. and so on.

Hollow silica has air with a low refractive index (refractive index = 1.0) inside the hollow, and thus, its refractive index is significantly lower than that of conventional silica (refractive index = 1.46). The refractive index of hollow silica is determined by the volume ratio of the hollow portion thereof, and is generally preferably about 1.20 to 1.40.

In addition, the refractive index of hollow silica: n (hollow silica) is composed of the refractive index of silica constituting the shell of hollow fine particles: n (silica), and the refractive index of the air inside: n (air ), calculated according to the following formula.

n (hollow silica) = n (silica) × volume percentage of silica

As mentioned above, n(silica) is about 1.47, and n(air) is very low at 1.0, so the refractive index of such hollow silica is very low.

Furthermore, the refractive index of the low-refractive-index layer of the sixth aspect using such hollow silica: n (low-refractive-index layer) is composed of the refractive index of hollow silica: n (hollow silica) and a binder The refractive index of the component: n (binder), calculated according to the following formula.

n (low refractive index layer) =

n(hollow silica)×volume ratio of hollow silica in the low refractive index layer+n(binder)×volume ratio of binder in the low refractive index layer.

Among them, in addition to the special fluorine-containing acrylic binder, the refractive index of the binder is usually about 1.50 to 1.55. Therefore, increasing the volume percentage of hollow silica in the low refractive index layer will reduce the refractive index of the low refractive index layer. It is important to reduce the rate.

In the 6th aspect, the more content of hollow silicon dioxide in the low refractive index layer, the more the low refractive index layer can be formed, and the antireflection film with excellent antireflection performance can be obtained. When the content of the agent component is relatively reduced, the film strength of the low-refractive index layer decreases, and the abrasion resistance and durability decrease. However, the reduction in membrane strength caused by the increase in the amount of hollow silica mixed can be compensated by surface treatment of hollow silica, and the membrane strength can also be supplemented by selecting the type of binder component to be mixed.

In the sixth aspect, the hollow silica content in the low-refractive index layer is preferably 20 to 55% by weight, particularly preferably 30 to 50% by weight, through surface treatment of the hollow silica and selection of binder components, In order to realize the low refractive index of the low refractive index layer, the refractive index is about 1.39 to 1.45, and at the same time, the abrasion resistance is ensured.

Next, the polyfunctional (meth)acrylic compound which is the binder component of the low refractive index layer of the sixth aspect will be described.

The polyfunctional (meth)acrylic compound is preferably a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or a 4-functional (meth)acrylic compound represented by the following general formula (II) The quasi-compound is a main component, and is preferably contained in an amount of 50% by weight or more, particularly preferably 90% by weight or more, of the entire binder component.

[chem 22]

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

n, m, o, p, q, r each independently represent an integer of 0 to 2,

R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

[chem 23]

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group,

s, t, u, and v each independently represent an integer of 0 to 2,

R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. )

Examples of the hexafunctional (meth)acrylic compound represented by the general formula (I) include dipentaerythritol hexaacrylate, ethylene oxide adducts of dipentaerythritol hexaacrylate, or ethylene oxide adducts. A compound in which H is substituted by F, these compounds may be used alone or in combination of two or more.

In addition, examples of the tetrafunctional (meth)acrylic compound represented by the above general formula (II) include pentaerythritol tetraacrylate, ethylene oxide adducts (1 to 8) of pentaerythritol tetraacrylate, or Compounds in which H of ethylene oxide is replaced by F, etc. These compounds may be used alone or in combination of two or more.

As the binder component, one or more hexafunctional (meth)acrylic compounds represented by the above general formula (I) and one or more tetrafunctional (meth)acrylic compounds represented by the above general formula (II) can be used in combination. (meth)acrylic compounds.

The polyfunctional (meth)acrylic compound represented by the above general formula (I), (II), especially the hexafunctional (meth)acrylic compound represented by the above general formula (I) has high hardness and abrasion resistance It is excellent and can effectively form a low-refractive-index layer with high abrasion resistance.

In addition, in the sixth aspect, as the binder component, it is preferable to use a hexafunctional (meth)acrylic compound represented by the above general formula (I) and/or a tetrafunctional (meth)acrylic compound represented by the above general formula (II) base) acrylic compound, used in combination with a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) or a specific fluorine-containing multifunctional (meth)acrylic compound, by using these binding agents Component that imparts abrasion resistance and stain resistance to the low refractive index layer. In addition, these binder components have a lower refractive index than the hexafunctional (meth)acrylic compound represented by the above general formula (I) or the tetrafunctional (meth)acrylic compound represented by the above general formula (II), Therefore, even if the mixing amount of the hollow silica is reduced, a low-refractive-index layer having a low refractive index can be formed.

A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III)

(In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.)

Examples of the fluorine-containing bifunctional (meth)acrylic compound represented by the above general formula (III) include 2,2,3,3,4,4-hexafluoropentanediol diacrylate, etc., these The compounds may be used alone or in combination of two or more.

In addition, the above-mentioned specific polyfunctional (meth)acrylic compound, that is, a (meth)acrylic compound having 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or less, having 3 to 6 functional groups, and (meth)acrylic compounds having 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1,000 to 5,000 may be used alone or in combination of two or more .

It is also possible to use one or more of the above-mentioned fluorine-containing bifunctional (meth)acrylic compounds in combination with one or more fluorine-containing multifunctional (meth)acrylic compounds.

Using the fluorine-containing bifunctional (meth)acrylic compound can lower the refractive index of the low refractive index layer and improve the antifouling property, but if the compounding amount is too large, the abrasion resistance will decrease. Therefore, it is preferable to mix 5% by weight or more of the fluorine-containing bifunctional (meth)acrylic compound in the total binder components, particularly preferably 5 to 10% by weight.

In addition, although the low refractive index of the low refractive index layer can be achieved by using the above-mentioned fluorine-containing polyfunctional (meth)acrylic compound, and the antifouling property can be improved, but if the compounding amount is too large, the wear resistance reduce. Therefore, it is preferable to mix the polyfunctional (meth)acrylic compound in an amount of 5% by weight or more, particularly preferably 5 to 10% by weight, of the total binder components.

In addition, in the case of using a fluorine-containing bifunctional (meth)acrylic compound in combination with a fluorine-containing polyfunctional (meth)acrylic compound, it is preferable that, among the total binder components, the fluorine-containing bifunctional (meth)acrylic The compound and the fluorine-containing polyfunctional (meth)acrylic compound are mixed in a total of 5% by weight or more, particularly preferably 5 to 10% by weight.

The hollow silica used in the sixth aspect has a particle diameter larger than that of conventional silica particles (with a particle diameter of about 5 to 20 nm) mixed in an existing low-refractive index layer. Therefore, even in In the case of using the same binder component, the film strength of the formed low-refractive index layer tends to be weaker than in the case of mixing silica particles, and by applying appropriate surface treatment to the hollow silica , can improve the binding force with the binder component, improve the film strength of the formed low refractive index layer, and improve the wear resistance.

As the surface treatment of the hollow silica, it is preferable to use a terminal (meth)acrylic silane coupling agent represented by the following general formula (IV) to perform terminal (meth)acrylic modification on the surface of the hollow silica. sex.

[chem 24]

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group,

^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms,

R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

Such terminal (meth)acrylic silane coupling agents include, for example, CH ₂ =CH-COO-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ , CH ₂ =C(CH ₃ )-COO -(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

In order to perform terminal (meth)acrylic modification on the surface of hollow silica by using such a terminal (meth)acrylic silane coupling agent, it is preferable to couple the hollow silica with a terminal (meth)acrylic silane The mixed solution of the agent is hydrothermally reacted at 100 to 150° C., or the mixed solution is irradiated with microwaves to cause a reaction. That is, when only the terminal (meth)acrylic silane coupling agent and hollow silica are mixed, the surface cannot be chemically modified with the terminal (meth)acrylic silane coupling agent, and the desired surface modification effect cannot be obtained. In the case of utilizing the hydrothermal reaction, if the reaction temperature is low, sufficient terminal (meth)acrylic acid modification cannot be performed. However, if the reaction temperature is too high, the reactivity will decrease instead, so the hydrothermal reaction temperature is preferably 100 to 150°C. In addition, although the hydrothermal reaction time varies depending on the reaction temperature, it is usually about 0.1 to 10 hours. On the other hand, in the case of using microwaves, if the set temperature is too low, sufficient terminal (meth)acrylic acid modification cannot be performed. Therefore, for the same reason as above, the set temperature is preferably 90 to 150 ℃. The microwave is suitable to use a microwave with a frequency of 2.5 GHz. If the microwave is irradiated, the terminal group (meth)acrylic acid modification can be carried out in a short time of about 10 to 60 minutes. In addition, as the mixed solution used in this reaction, hollow silica of 3.8% by weight, 96% by weight of alcohol solvent (a mixed solvent of 1:4 (weight ratio) of isopropanol and isobutanol), A reaction solution made of 3% by weight of acetic acid, 1% by weight of water, and 0.04% by weight of a silane coupling agent.

By chemically modifying the surface of hollow silica with such a terminal (meth)acrylic silane coupling agent, the hollow silica and the binder component can be firmly bonded, even when the amount of hollow silica mixed is large. Even in the case of , a low-refractive-index layer excellent in wear resistance can be formed, and the low-refractive index of the low-refractive-index layer can be achieved by increasing the blending amount of hollow silica.

In addition, the surface of the hollow silica can also be modified with a terminal fluorinated alkyl silane coupling agent represented by the following general formula (V). In this case, the terminal group The terminal group fluorinated alkyl modification carried out by the fluorinated alkyl silane coupling agent is preferably under the same conditions as when the above-mentioned terminal group (meth)acrylic acid silane coupling agent is used to carry out the terminal group (meth)acrylic acid modification , by hydrothermal method or microwave irradiation method.

[chem 25]

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.)

In addition, examples of the terminal group fluorinated alkylsilane coupling agent include C ₈ F ₁₇ -(CH ₂ ) ₂ -Si-(OCH ₃ ) ₃ , C ₆ F ₁₃ -(CH ₂ ) ₂ -Si -(OCH ₃ ) ₃ etc. These compounds may be used alone or in combination of two or more.

By chemically modifying the surface of the hollow silica using such a terminal group fluorinated alkylsilane coupling agent, the antifouling property of the formed low refractive index layer can be improved.

The low-refractive-index layer of the sixth aspect is formed by irradiating the above-mentioned binder component with ultraviolet light to cure it in the presence of a photopolymerization initiator. One or more of Ilugac 184, 819, 651, 1173, 907 and the like are preferably mixed in an amount of 3 to 10 phr based on the binder component. When the compounding quantity of a photoinitiator is less than this range, sufficient crosslinking hardening cannot be performed, and when it exceeds this range, the film strength of a low-refractive-index layer will fall.

The low-refractive-index layer of the sixth aspect is a composition obtained by mixing hollow silica, a multifunctional (meth)acrylic compound as a binder component, and a photopolymerization initiator in a predetermined ratio and applying it to a high refractive index layer. index layer or conductive high-refractive-index hard coat layer, which is formed by irradiating ultraviolet rays in an atmosphere with an oxygen concentration of 0 to 10,000 ppm to cure it. Damage is greatly reduced, so it is controlled to 1000 ppm or less, preferably 200 ppm or less.

The thickness of such a low refractive index layer is preferably 85 to 110 nm, particularly preferably about 100 nm.

In the sixth aspect, in order to form the hard coat layer 103, the high refractive index layer 104, and the low refractive index layer 105 on the base film 102, it is preferable to apply an uncured resin composition (resin composition in which the above-mentioned fine particles are mixed as needed) object), followed by ultraviolet radiation. In this case, it may be cured after each application of one layer, or after application of three or two layers.

Specific methods of coating include a method in which a coating solution obtained by dissolving a binder component in a solvent such as toluene is coated with a gravure coater, dried, and then cured by ultraviolet rays. According to this wet coating method, there is an advantage that a film can be formed uniformly at high speed and at low cost. Curing by irradiating ultraviolet rays after coating has the effect of improving adhesion and film hardness, and can continuously produce anti-reflection films without heating.

A transparent adhesive such as acrylic is preferable as the adhesive for the adhesive layer 106 formed on the inner surface side of the base film 102, and the thickness of the adhesive layer 106 is usually about 1 to 100 μm, particularly preferably about 25 μm.

In the solar cell module of FIG. 42a, such an antireflection film 101A is pasted on a glass substrate 111 as a transparent protective member on the front side, and when the antireflection film is pasted on a transparent substrate such as a glass substrate, a hard coat layer is not necessary. It can be omitted.

In the solar cell module of FIG. 42 b, the antireflection film 101B without the hard coat layer is pasted on the glass substrate 111 as a transparent protective member on the front side, and the hard coat layer is not provided on the antireflection film 101B, and the transparent base film 102 Except that the high-refractive-index layer 104 and the low-refractive-index layer 105 are directly formed on it, the structure is the same as that of the above-mentioned solar cell module shown in FIG. 42a.

In addition, as shown in FIG. 42c, in the solar cell module of the sixth aspect, the high-refractive-index layer 104 and the low-refractive-index layer 105 can be directly stacked and formed on the glass substrate 111 as the surface-side transparent protective member, and the The anti-reflection layer 101C is directly formed on the substrate 111 .

In such a solar cell module according to the sixth aspect, for example, in the antireflection layer formed of the above-mentioned antireflection film, the laminated film of the high refractive index layer and the low refractive index layer, by performing the following adjustments, better performance can be realized. A solar cell module with high power generation efficiency and excellent antireflection and antifouling properties.

(1) An easy-adhesion layer is provided between the transparent base film and the hard coat layer. The easy-adhesive layer is used to improve the adhesion between the hard coat layer and the substrate film, and is usually used to mix SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , etc. in thermosetting resins such as copolyester resins and polyurethane resins. Metal oxide fine particles, preferably metal oxide fine particles having an average particle diameter of about 1 to 100 nm, are used to adjust the refractive index. In addition, when the cost increases due to the mixing of metal oxide fine particles, the refractive index can be adjusted by mixing 0 to 50% by weight of a polymer containing a large number of phenyl groups, bromine atoms, and sulfur atoms in the structure.

At this time, the refractive index of the hard coat layer is in the range of 1.48 to 1.55. When the refractive index of the easy-adhesion layer is expressed as _na , the refractive index of the transparent base film is expressed as _nb , and the refractive index of the hard coat layer is When the rate is denoted as n _HC ,

(n _b +n _HC )/2-0.02≤n _a ≤(n _b +n _HC )/2+0.02

In particular, (n _b +n _HC )/2-0.01≤n _a ≤(n _b +n _HC )/2+0.01,

And the film thickness T of the easy-adhesive layer satisfies:

(550/4)×(1/n _a )-10nm≤T≤(550/4)×(1/n _a )+10nm

in particular

In the range of (550/4)×(1/n _a )-5nm≤T≤(550/4)×(1/n _a )+5nm, it is preferable because obviously excellent antireflection performance can be obtained.

This has the effect that the refractive index of the substrate film is substantially equal to that of the hard coat layer with respect to a light wavelength of 550 nm, and has the effect of eliminating reflection between the hard coat layer/substrate film. In the sixth aspect, the easy-adhesion layer is preferably formed on the transparent base film when the transparent base film is formed.

(2) As the high-refractive-index microparticles of the high-refractive-index layer, it is preferable to use conductive high-refractive-index microparticles selected from _SnO2 and ITO, and ultra-high-refractive-index microparticles composed of _TiO2 , _ZrO2 , and _CeO2 . At least one high-refractive-index particle in the composed particle group, and combine high-refractive-index particles with different particle sizes, so that the average primary particle size of the high-refractive index particles is 30-40 nm, and centering on the average primary particle size, The particle size distribution range is wide, and among the total particles, the cumulative number of particles with a primary particle size of 30 nm or less is 20% or more, for example, 20% to 30%, and the primary particle size is 45 nm or more The cumulative number of fine particles is 20% or more, for example, 20% to 60%.

That is, in the high-refractive-index layer, it is important to contain as many high-refractive-index particles as possible, so that the filling of high-refractive-index particles in the high-refractive-index layer can be improved by using high-refractive-index particles with different particle sizes in combination. amount, forming a high-refractive-index layer with a very high refractive index at a high packing density.

In addition, as the high-refractive-index fine particles, it is preferable to use conductive high-refractive-index fine particles and ultra-high-refractive-index fine particles in combination, particularly preferably conductive high-refractive-index fine particles : ultra-high refractive index fine particles = 50-70:50-30 (volume ratio), particularly preferably 27:18 (volume ratio). If the conductive high-refractive-index fine particles are more than this range, the refractive index of the high-refractive index layer will decrease, and if there are too many ultra-high-refractive-index fine particles, the antistatic effect cannot be obtained.

(3) By using the above-mentioned fluorine-containing binder component as the binder of the low-refractive index layer, the antifouling property is improved.

(4) By adjusting the film thickness of the high-refractive index layer and the low-refractive index layer, for example, by reducing the film thickness of the high-refractive index layer or reducing the film thickness of the low-refractive index layer, the minimum reflectance of the antireflection layer The wavelength (valley wavelength) shifts to the short wave direction, reduces the reflectivity of the high ultraviolet range of solar energy, and improves the energy conversion efficiency.

Next, a method for shifting the minimum reflectance of the antireflection layer to the short-wavelength direction by adjusting the film thickness of the high-refractive index layer and/or the low-refractive index layer in this manner will be described.

In the antireflection layer, the transmittance of wavelengths with low reflectance must increase. Therefore, if the reflectance of the wavelength of light at which the pigment of the color-sensitive solar cell most easily absorbs decreases, the transmittance of the wavelength increases. In addition, since the energy of light on the short-wavelength side is large, the pigment can absorb light with higher energy by reducing the reflectance of this wavelength.

A general anti-reflection film is designed so that the wavelength at which the minimum reflectance is achieved is in the range of 550 to 600 nm. This is because the wavelength with the highest human visual sensitivity is 550nm, so the reflectance at this wavelength must be minimized.

However, color-sensitive solar cells absorb different wavelengths depending on the pigment, so it is necessary to design them in accordance with the pigment.

For example, a hard coat layer, a high refractive index layer, and a low refractive index layer ("Z-7503" manufactured by JSR) are sequentially coated on a TAC ("TAC" manufactured by Fujifilm Co., Ltd.) film. The high refractive index layer (n=1.68) and the low refractive index layer of ITO microparticles ("Ei-3" manufactured by Dainippon Paint Co., Ltd.) are pentaerythritol tetraacrylate ("PE-4A" manufactured by Kyoei Co., Ltd.) containing hollow silica. ") (n=1.43), the reflectance when changing the film thickness of the high refractive index layer and the low refractive index layer is shown in Figure 44, and the reflectance at a wavelength of 400nm is shown in Table 16 below.

[Table 16] No. Thickness of high refractive index layer (nm) Thickness of low refractive index layer (nm) 400nm reflectance (%) 1 81 96 >4 2 81 73 <2 3 33 96 <2

From these results, it can be seen that by reducing the film thickness of the low-refractive index layer and the high-refractive index layer, the wavelength at which the minimum reflectance is achieved can be changed, and the reflectance on the short-wavelength side can be reduced (the transmittance can be increased).

Claims (89)

1. An antireflection film, which is formed by successively laminating a hard coat layer, a high-refractive index layer and a low-refractive index layer on a transparent base film, is characterized in that, The low refractive index layer is formed by irradiating ultraviolet rays to the coating film to cure it in an atmosphere with an oxygen concentration of 0 to 10000 ppm, wherein the coating film includes: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 2. A kind of antireflection film, this antireflection film is formed by sequentially laminating conductive high refractive index hard coating layer and low refractive index layer on transparent substrate film, it is characterized in that, The low refractive index layer is formed by irradiating ultraviolet rays to the coating film to cure it in an atmosphere with an oxygen concentration of 0 to 10000 ppm, wherein the coating film includes: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 3. The antireflection film according to claim 1, characterized in that, the multifunctional (meth)acrylic compound is represented by the following general formula (I) with 6 functional group (meth)acrylic compounds and/or the following The 4-functional group (meth)acrylic compound represented by the general formula (II) is the main component: (In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ), (In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 4. The antireflection film according to claim 3, characterized in that, the polyfunctional (meth)acrylic compound further comprises a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) , and in the total multifunctional (meth)acrylic compound, the proportion of the fluorine-containing bifunctional (meth)acrylic compound is 5% by weight or more, A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III) (In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.). 5. The antireflection film according to claim 3, wherein the polyfunctional (meth)acrylic compound further comprises a compound selected from the group consisting of 6 or more fluorine atoms in 1 molecule and a molecular weight of 1000 or its Of the following (meth)acrylic compounds with 3 to 6 functional groups, and (meth)acrylic compounds with 6 to 15 functional groups with a molecular weight of 1000 to 5000 having 10 or more fluorine atoms per molecular weight One or more fluorine-containing multifunctional (meth)acrylic compounds, and in the total multifunctional (meth)acrylic compounds, the proportion of the fluorine-containing multifunctional (meth)acrylic compounds is 5 weight % or more. 6. The antireflection film according to claim 1, characterized in that, the above-mentioned hollow silica is a terminal group (meth)acrylic acid silane coupling agent represented by the following general formula (IV), and the surface is treated Terminal (meth)acrylic acid modified (meth)acrylic acid modified hollow silica,

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 7. The antireflection film according to claim 6, wherein the hollow silica is formed by a hydrothermal reaction with the terminal (meth)acrylic silane coupling agent at 100 to 150° C. Reaction under microwave irradiation, (meth)acrylic acid-modified hollow silica with terminal (meth)acrylic acid modification on the surface. 8. The antireflection film according to claim 1, wherein the above-mentioned hollow silica is a terminal fluorinated alkylsilane coupling agent represented by the following general formula (V), and the surface is terminated. Fluorinated alkyl-modified hollow silica, (In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 9. The anti-reflection film according to claim 8, wherein the hollow silica is formed by hydrothermal reaction at 100-150°C with the terminal-group fluorinated alkylsilane coupling agent, or by microwave Under the reaction under irradiation, the fluorinated alkyl-modified hollow silica whose surface has been modified by terminal fluorinated alkyl groups. 10. An anti-reflection film, which is formed by sequentially laminating a hard coat layer, a transparent conductive layer, a light-absorbing layer and a low-refractive index layer on a transparent substrate film, characterized in that, The low refractive index layer is formed by irradiating ultraviolet rays to the coating film to cure it in an atmosphere with an oxygen concentration of 0 to 10000 ppm, wherein the coating film includes: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, photopolymerization initiator, In addition, the antireflection film has a minimum reflectance of 0.5% or less, a transmittance of 70% or more at a wavelength of 550 nm, and a reflectance of 2% or less at a wavelength of 400 nm. 11. An antireflection film, which is formed by sequentially laminating a hard coat layer, a conductive light-absorbing layer, and a low-refractive index layer on a transparent base film, characterized in that, The low refractive index layer is formed by irradiating ultraviolet rays to the coating film to cure it in an atmosphere with an oxygen concentration of 0 to 10000 ppm, wherein the coating film includes: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, photopolymerization initiator, In addition, the antireflection film has a minimum reflectance of 0.5% or less, a transmittance of 70% or more at a wavelength of 550 nm, and a reflectance of 2% or less at a wavelength of 400 nm. 12. anti-reflection film according to claim 10, is characterized in that, is provided with easy adhesive layer on this transparent substrate film, is provided with hard coating on this easy adhesive layer, The hard coating has a refractive index of 1.48 to 1.55, If the refractive index of the easy-adhesive layer is denoted as _na , the refractive index of the transparent substrate film is denoted as _nb , and the refractive index of the hard coat layer is denoted as _nHC , then (n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03 The film thickness T of the easy-adhesive layer satisfies: (550/4)×(1/n _a )−10 nm≦T≦(550/4)×(1/n _a )+10 nm. 13. The anti-reflection film according to claim 12, wherein the easy-adhesive layer is formed on the transparent base film when forming the transparent base film. 14. The antireflection film according to claim 10, characterized in that, the polyfunctional (meth)acrylic compound is represented by the following general formula (I) with 6 functional group (meth)acrylic compounds and/or the following The 4-functional group (meth)acrylic compound represented by the general formula (II) is the main component: (In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ), (In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 15. The antireflection film according to claim 10, characterized in that, the above-mentioned hollow silica is 100 to 150 Å of the terminal (meth)acrylic silane coupling agent represented by the following general formula (IV). The hydrothermal reaction at ℃, or the reaction under microwave irradiation, the (meth)acrylic modified hollow silica whose surface has been modified with terminal (meth)acrylic acid,

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 16. The antireflection film according to claim 10, wherein the hollow silica is heated at 100 to 150° C. Under the hydrothermal reaction, or the reaction under microwave irradiation, the fluorinated alkyl-modified hollow silica with terminal fluorinated alkyl modified on the surface,

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 17. The antireflection film according to claim 10, wherein the above-mentioned transparent conductive layer is cured with a (meth)acrylic binder resin selected from ATO, ZnO, Sb ₂ O ₅ , SnO ₂ , ITO and In ₂ O ₃ at least one particle, and its film thickness is 80-200nm. 18. The antireflection film according to claim 10, wherein the above-mentioned light-absorbing layer comprises carbon black particles and titanium nitride particles, and if the complex refractive index of the light-absorbing layer is denoted as n+ik, then n=1.45～1.75, k = 0.1 to 0.35. 19. The antireflection film according to claim 11, wherein the above-mentioned conductive light-absorbing layer comprises carbon black particles, and if the complex refractive index of the conductive light-absorbing layer is denoted as n+ik, then n=1.45～1.75, k = 0.1 to 0.35. 20. The anti-reflection film according to claim 10, wherein the transparent substrate film is a PET film, and the above-mentioned hard coat side of the PET film is formed with a film having a refractive index of 1.55 to 1.61 and a film thickness of 75. ~95nm easy-adhesion layer. 21. An antireflection film, which is formed by sequentially laminating an easy-adhesive layer, a hard coat layer, a high refractive index layer and a low refractive index layer on a transparent base film, characterized in that, The low refractive index layer is formed by irradiating ultraviolet rays to the coating film to cure it in an atmosphere with an oxygen concentration of 0 to 10000 ppm, wherein the coating film includes: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 22. An antireflection film, which is formed by sequentially laminating an easy-adhesive layer, a high-refractive-index hard coat layer, and a low-refractive-index layer on a transparent substrate film, characterized in that, The low refractive index layer is formed by irradiating ultraviolet rays to the coating film to cure it in an atmosphere with an oxygen concentration of 0 to 10000 ppm, wherein the coating film includes: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 23. The anti-reflection film according to claim 21, characterized in that, the hard coating has a refractive index of 1.48-1.55, If the refractive index of the easy-adhesive layer is denoted as _na , the refractive index of the transparent substrate film is denoted as _nb , and the refractive index of the hard coat layer is denoted as _nHC , then (n _b +n _HC )/2-0.03≤n _a ≤(n _b +n _HC )/2+0.03 The film thickness T of the easy-adhesive layer satisfies: (550/4)×(1/n _a )−10 nm≦T≦(550/4)×(1/n _a )+10 nm. 24. The anti-reflection film according to claim 21, wherein the easy-adhesive layer is formed on the transparent base film when forming the transparent base film. 25. The anti-reflection film according to claim 21, characterized in that, the refractive index of the above-mentioned high refractive index layer is 1.68 or more, and the high refractive index layer comprises a highly conductive material selected from SnO ₂ and ITO. Refractive index particles, and at least one high refractive index particle in the particle group composed of TiO ₂ , ZrO ₂ and CeO ₂ composed of ultra-high refractive index particles, and six functional groups represented by the following general formula (VI) ( meth)acrylic compound as the binder component of the main component,

(In the above general formula (VI), A ⁴¹ to A ⁴⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluorinated acryloyl group, or a trifluoromethacryloyl group.). 26. The antireflection film according to claim 25, wherein the average primary particle diameter of the high refractive index particles is 10 to 150 nm. 27. The antireflection film according to claim 25, wherein the average primary particle diameter of the above-mentioned high refractive index particles is 30 to 40 nm, and among the total particles, the primary particle diameter is 30 nm or less. The cumulative number of particles having a cumulative number of 20% or more and a primary particle diameter of 45 nm or more is 20% or more. 28. The antireflection film according to claim 25, characterized in that, the above-mentioned high-refractive-index particles are high-refractive-index particles made by covering ITO particles on the anatase titanium dioxide particles, and the average primary particle diameter of the titanium dioxide particles is The thickness of the covering layer formed by ITO particles is 5-80nm, and the thickness is 5nm or more. 29. The anti-reflection film according to claim 25, characterized in that, the above-mentioned high-refractive-index particles are high-refractive-index particles made by covering ITO particles on rutile-type titanium dioxide particles, and the aspect ratio of the titanium dioxide particles is 2 to 10. 1. The thickness of the covering layer formed by ITO particles is 5nm or more. 30. The antireflection film according to claim 21, characterized in that, the polyfunctional (meth)acrylic compound is represented by the following general formula (I) with 6 functional group (meth)acrylic compounds and/or the following The 4-functional group (meth)acrylic compound represented by the general formula (II) is the main component:

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ),

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 31. The antireflection film according to claim 30, characterized in that, the polyfunctional (meth)acrylic compound further comprises a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) , and in the total multifunctional (meth)acrylic compound, the proportion of the fluorine-containing bifunctional (meth)acrylic compound is 5% by weight or more. A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III) (In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.). 32. The antireflection film according to claim 30, wherein the polyfunctional (meth)acrylic compound further comprises a compound selected from the group consisting of 6 or more fluorine atoms in 1 molecule and a molecular weight of 1000 or its Of the following (meth)acrylic compounds with 3 to 6 functional groups, and (meth)acrylic compounds with 6 to 15 functional groups with a molecular weight of 1000 to 5000 having 10 or more fluorine atoms per molecular weight One or more fluorine-containing multifunctional (meth)acrylic compounds, and in the total multifunctional (meth)acrylic compounds, the proportion of the fluorine-containing multifunctional (meth)acrylic compounds is 5 weight % or more. 33. The antireflection film according to claim 21, characterized in that, the above-mentioned hollow silica is a terminal group (meth)acrylic silane coupling agent represented by the following general formula (IV), and the surface is treated Terminal (meth)acrylic acid modified (meth)acrylic acid modified hollow silica, (In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 34. The antireflection film according to claim 33, wherein the hollow silica is formed by hydrothermal reaction with the terminal (meth)acrylic silane coupling agent at 100 to 150° C. Reaction under microwave irradiation, (meth)acrylic acid-modified hollow silica with (meth)acrylic acid-modified surface. 35. The antireflection film according to claim 21, wherein the hollow silica is a terminal fluorinated alkylsilane coupling agent represented by the following general formula (V), and the surface is terminated. Fluorinated alkyl-modified hollow silica, (In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 36. The anti-reflection film according to claim 35, wherein the hollow silica is formed by hydrothermal reaction at 100-150°C with the terminal-group fluorinated alkylsilane coupling agent, or by microwave Under the reaction under irradiation, the fluorinated alkyl-modified hollow silica whose surface has been modified by terminal fluorinated alkyl groups. 37. An electromagnetic shielding light-transmitting window material, which is formed by laminating and integrating at least an electromagnetic shielding layer, a transparent substrate, and an outermost antireflection layer, wherein: The anti-reflection layer has a high-refractive-index layer and a low-refractive-index layer disposed on the high-refractive-index layer, The low refractive index layer is formed by photocuring a coating film comprising: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 38. The electromagnetic-shielding light-transmitting window material according to claim 37, wherein the polyfunctional (meth)acrylic compound is represented by the following general formula (I) with six functional groups (meth)acrylic compound and/or the 4-functional group (meth)acrylic compound represented by the following general formula (II) as the main component:

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ),

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 39. The electromagnetic-shielding light-transmitting window material according to claim 38, wherein the polyfunctional (meth)acrylic compound further comprises a fluorine-containing bifunctional group represented by the following general formula (III). base) acrylic compound, and in the total polyfunctional (meth)acrylic compound, the proportion of the fluorine-containing bifunctional (meth)acrylic compound is 5% by weight or more, A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III) (In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.). 40. The electromagnetic-shielding light-transmitting window material according to claim 38, wherein the polyfunctional (meth)acrylic compound further comprises 6 or more fluorine atoms in one molecule and (meth)acrylic compounds with 3 to 6 functional groups having a molecular weight of 1,000 or less, and (meth)acrylic compounds having 10 or more fluorine atoms per molecular weight and a molecular weight of 1,000 to 5,000 with 6 to 15 functional groups (methyl) One or more fluorine-containing multifunctional (meth)acrylic compounds among the acrylic compounds, and among the total multifunctional (meth)acrylic compounds, the fluorine-containing multifunctional (meth)acrylic compounds The ratio is 5% by weight or more. 41. The electromagnetic-shielding light-transmitting window material according to claim 37, wherein the above-mentioned hollow silica is coupled with a terminal (meth)acrylic silane represented by the following general formula (IV). The hydrothermal reaction at 100-150°C of the agent, or the reaction under microwave irradiation, the (meth)acrylic acid-modified hollow silica whose surface has been (meth)acrylic modified,

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 42. The electromagnetic-shielding light-transmitting window material according to claim 37, wherein the above-mentioned hollow silica is made of a terminal group fluorinated alkylsilane coupling agent represented by the following general formula (V). The hydrothermal reaction at 100-150°C, or the reaction under microwave irradiation, the fluorinated alkyl-modified hollow silica with terminal fluorinated alkyl modified on the surface,

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 43. The electromagnetic-shielding light-transmitting window material according to claim 37, wherein the high-refractive-index layer contains high-refractive-index particles and a binder component having an aryl group. 44. The electromagnetic-shielding light-transmitting window material according to claim 37, wherein the anti-reflection layer is directly formed on the transparent substrate. 45. The electromagnetic-shielding light-transmitting window material according to claim 37, characterized in that, the above-mentioned anti-reflection layer is an anti-reflection film pasted on the outermost surface, and the anti-reflection film is passed through the transparent substrate film It is formed by sequentially laminating a hard coat layer, a high refractive index layer and a low refractive index layer. 46. The electromagnetic-shielding light-transmitting window material according to claim 37, characterized in that it is arranged on the front surface of the light-emitting panel with weaker red in the light-emitting color, and by adding the above-mentioned high-refractive index layer or low-refractive The wavelength of the minimum reflectance of the electromagnetic shielding light-transmitting window material is shifted to the long-wave direction, and the red transmittance is increased by making the wavelength of the minimum reflectance reach the wavelength of red light. 47. The electromagnetic-shielding light-transmitting window material according to claim 37, characterized in that it is arranged on the front surface of the light-emitting panel with weaker blue in the light-emitting color, and by reducing the above-mentioned high refractive index layer or The film thickness of the low refractive index layer shifts the wavelength of the minimum reflectance of the electromagnetic shielding light-transmitting window material to the short-wave direction, and increases the blue transmittance by making the wavelength of the minimum reflectance reach the wavelength of blue light . 48. A gas discharge type light-emitting panel, which is formed by laminating and integrating a light-emitting panel body, an electromagnetic shielding layer disposed on the front surface of the light-emitting panel body, and an outermost anti-reflection layer, characterized in is that The anti-reflection layer has a high-refractive-index layer and a low-refractive-index layer disposed on the high-refractive-index layer, The low-refractive index layer is formed by photocuring the coating film, and the coating film comprises: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 49. The gas discharge type luminous panel according to claim 48, characterized in that, the polyfunctional (meth)acrylic compound is a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or Or the 4-functional group (meth)acrylic compound represented by the following general formula (II) is the main component:

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ),

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 50. The gas discharge light-emitting panel according to claim 49, characterized in that the polyfunctional (meth)acrylic compound further comprises a fluorine-containing bifunctional (meth)acrylic acid represented by the following general formula (III) compounds, and in the total polyfunctional (meth)acrylic compounds, the proportion of the fluorine-containing bifunctional (meth)acrylic compound is 5% by weight or more, A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III) (In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.). 51. The gas discharge light-emitting panel according to claim 49, wherein the polyfunctional (meth)acrylic compound further comprises a compound selected from the group consisting of six or more fluorine atoms in one molecule and a molecular weight of 1000. (Meth)acrylic compounds with 3 to 6 functional groups or less, and (meth)acrylic compounds with 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1,000 to 5,000 One or more fluorine-containing multifunctional (meth)acrylic compounds, and in the total multifunctional (meth)acrylic compounds, the proportion of the fluorine-containing multifunctional (meth)acrylic compounds is 5% by weight or more. 52. The gas discharge light-emitting panel according to claim 48, characterized in that the above-mentioned hollow silicon dioxide is 100% of the terminal (meth)acrylic acid silane coupling agent represented by the following general formula (IV). Hydrothermal reaction at ~150°C, or reaction under microwave irradiation, (meth)acrylic acid-modified hollow silica whose surface has been modified with (meth)acrylic acid, (In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 53. The gas discharge type light-emitting panel according to claim 48, characterized in that the above-mentioned hollow silica is 100 to Hydrothermal reaction at 150°C, or reaction under microwave irradiation, fluorinated alkyl-modified hollow silica whose surface has been modified with terminal fluorinated alkyl group, (In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 54. The gas discharge type light-emitting panel according to claim 48, wherein the high-refractive-index layer contains high-refractive-index fine particles and a binder component having an aryl group. 55. The gas discharge light-emitting panel according to claim 48, wherein a transparent substrate is provided on the front side of the light-emitting panel body, and the anti-reflection layer is directly formed on the transparent substrate. 56. The gas discharge light-emitting panel according to claim 48, wherein the above-mentioned anti-reflection layer is an anti-reflection film pasted on the outermost surface, and the anti-reflection film is sequentially stacked on a transparent substrate film Hard coating layer, high refractive index layer and low refractive index layer are formed. 57. The gas discharge type light-emitting panel according to claim 48, characterized in that, the light-emitting panel body is a light-emitting panel body with a weaker red color in the luminescent light, and by adding the film of the above-mentioned high-refractive index layer or low-refractive index layer thicker, the wavelength of the minimum reflectance of the anti-reflection layer is shifted to the long-wave direction, and the red transmittance is increased by making the wavelength of the minimum reflectance reach the wavelength of red light. 58. The gas discharge type light-emitting panel according to claim 48, characterized in that, the light-emitting panel body is a light-emitting panel body with weaker blue in the light-emitting color, and by reducing the above-mentioned high-refractive index layer or low-refractive index layer The film thickness of the anti-reflection layer shifts the minimum reflectance wavelength of the anti-reflection layer to the short-wave direction, and increases the blue transmittance by making the minimum reflectance wavelength reach the wavelength of blue light. 59. A flat display panel, which is provided with an anti-reflection layer on the surface, the anti-reflection layer has a high refractive index layer and a low refractive index layer arranged on the high refractive index layer, characterized in that, The low-refractive index layer is formed by photocuring the coating film, and the coating film comprises: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 60. The flat display panel according to claim 59, characterized in that, the polyfunctional (meth)acrylic compound is a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or the following The 4-functional group (meth)acrylic compound represented by the general formula (II) is the main component:

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ), (In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 61. The flat panel display panel according to claim 60, wherein the multifunctional (meth)acrylic compound further comprises a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) , and in the total polyfunctional (meth)acrylic compound, the proportion of the fluorine-containing bifunctional (meth)acrylic compound is 5% by weight or more, A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III) (In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.). 62. The flat panel display panel according to claim 60, wherein the polyfunctional (meth)acrylic compound further comprises a compound selected from the group consisting of 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or its Of the following (meth)acrylic compounds with 3 to 6 functional groups, and (meth)acrylic compounds with 6 to 15 functional groups with a molecular weight of 1000 to 5000 having 10 or more fluorine atoms per molecular weight One or more fluorine-containing multifunctional (meth)acrylic compounds, and in the total multifunctional (meth)acrylic compounds, the proportion of the fluorine-containing multifunctional (meth)acrylic compounds is 5 weight % or more. 63. The flat panel display panel according to claim 59, characterized in that, the above-mentioned hollow silica is 100 to 150% of the terminal (meth)acrylic silane coupling agent represented by the following general formula (IV). ℃ hydrothermal reaction, or reaction under microwave irradiation, (meth)acrylic modified hollow silica with terminal (meth)acrylic acid modification on the surface, (In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 64. The flat panel display panel according to claim 59, characterized in that the hollow silica is heated at 100 to 150° C. Under the hydrothermal reaction, or the reaction under microwave irradiation, the fluorinated alkyl-modified hollow silica with terminal fluorinated alkyl modified on the surface,

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 65. The flat panel display panel according to claim 59, wherein the high-refractive-index layer comprises high-refractive-index particles and a binder component having an aromatic group. 66. The flat panel display panel according to claim 59, characterized in that it has a transparent substrate on one side of the surface, and the anti-reflection layer is directly formed on the transparent substrate. 67. The flat panel display panel according to claim 59, wherein the above-mentioned anti-reflection layer is an anti-reflection film pasted on the outermost surface, and the anti-reflection film is formed by sequentially laminating hard-coated films on a transparent substrate film. layer, high refractive index layer and low refractive index layer. 68. The flat panel display panel according to claim 59, characterized in that, without changing the wavelength of the minimum reflectivity of the anti-reflection layer, the film thickness of the above-mentioned high refractive index layer is increased and the thickness of the above-mentioned low refractive index layer is decreased The film thickness increases the reflectance at the wavelength of the minimum reflectance, and reduces the average reflectance in the visible light range, so that the surface reflection color of the display is close to the neutral color. 69. A window material, which is provided with an anti-reflection layer on the surface, the anti-reflection layer has a high refractive index layer and a low refractive index layer arranged on the high refractive index layer, characterized in that, The low-refractive index layer is formed by photocuring the coating film, and the coating film comprises: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 70. The window material according to claim 69, characterized in that, the polyfunctional (meth)acrylic compound is represented by the following general formula (I) with 6 functional group (meth)acrylic compounds and/or the following The 4-functional group (meth)acrylic compound represented by the general formula (II) is the main component: (In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ),

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 71. The window material according to claim 70, characterized in that, the polyfunctional (meth)acrylic compound further comprises a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III), And in the total polyfunctional (meth)acrylic compound, the proportion of the fluorine-containing bifunctional (meth)acrylic compound is 5% by weight or more, A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III) (In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.). 72. The window material according to claim 70, wherein the polyfunctional (meth)acrylic compound further comprises a compound selected from the group consisting of six or more fluorine atoms in one molecule and a molecular weight of 1000 or less. 1 of (meth)acrylic compounds with 3 to 6 functional groups and (meth)acrylic compounds with 10 or more fluorine atoms in 1 molecular weight and 6 to 15 functional groups with a molecular weight of 1000 to 5000 One or more fluorine-containing multifunctional (meth)acrylic compounds, and in the total multifunctional (meth)acrylic compounds, the proportion of the fluorine-containing multifunctional (meth)acrylic compounds is 5% by weight or above. 73. The window material according to claim 69, characterized in that the hollow silica is heated at 100 to 150° C. with a terminal (meth)acrylic silane coupling agent represented by the following general formula (IV). Under the hydrothermal reaction, or the reaction under microwave irradiation, the (meth)acrylic acid-modified hollow silica with terminal (meth)acrylic acid modification on the surface,

(In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 74. The window material according to claim 69, characterized in that, the above-mentioned hollow silica is formed at 100-150° C. The hydrothermal reaction, or the reaction under microwave irradiation, the fluorinated alkyl-modified hollow silica modified with terminal fluorinated alkyl groups on the surface,

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 75. The window material according to claim 69, wherein the high-refractive-index layer comprises high-refractive-index particles and a binder component having an aryl group. 76. The window material according to claim 69, comprising a transparent substrate and an antireflection layer formed directly on the surface of the transparent substrate. 77. The window material according to claim 69, characterized in that, it comprises a transparent substrate and an anti-reflection film stuck on the surface of the transparent substrate, and the anti-reflection film is formed by sequentially laminating a hard coat layer on a transparent base film. , high refractive index layer and low refractive index layer formed. 78. The flat panel display panel according to claim 69, characterized in that by increasing the film thickness of the above-mentioned high refractive index layer and reducing the above-mentioned low refractive index without changing the wavelength of the minimum reflectance of the above-mentioned anti-reflection layer The film thickness increases the reflectance at the wavelength of the minimum reflectance, and reduces the average reflectance in the visible light range, thereby reducing the color difference between the actual color of the display and the color seen. 79. A solar cell module formed by sealing cells for solar cells between a surface side transparent protective member and an inner surface side protective member, characterized in that, An anti-reflection layer is formed on the surface of the transparent protective member on the surface side, The anti-reflection layer has a high-refractive-index layer and a low-refractive-index layer disposed on the high-refractive-index layer, The low-refractive index layer is formed by photocuring the coating film, and the coating film comprises: Hollow silica particles (hereinafter referred to as "hollow silica"), Multifunctional (meth)acrylic compounds, Photopolymerization initiator. 80. The solar cell module according to claim 79, wherein the polyfunctional (meth)acrylic compound is a 6-functional (meth)acrylic compound represented by the following general formula (I) and/or the following The 4-functional group (meth)acrylic compound represented by the general formula (II) is the main component:

(In the above general formula (I), A ¹ to A ⁶ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, n, m, o, p, q, r each independently represent an integer of 0 to 2, R ¹ to R ⁶ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ),

(In the above general formula (II), A ¹¹ to A ¹⁴ each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, s, t, u, and v each independently represent an integer of 0 to 2, R ¹¹ to R ¹⁴ each independently represent an alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms. ). 81. The solar cell module according to claim 80, characterized in that the multifunctional (meth)acrylic compound further comprises a fluorine-containing bifunctional (meth)acrylic compound represented by the following general formula (III) , and in the total polyfunctional (meth)acrylic compound, the proportion of the fluorine-containing bifunctional (meth)acrylic compound is 5% by weight or more, A ^a -O-(CH ₂ ) _xa -Rf-(CH ₂ ) _xb -OA ^b ......(III) (In the above general formula (III), A ^a and A ^b each independently represent an acryloyl group, a methacryloyl group, an α-fluoroacryloyl group, or a trifluoromethacryloyl group, Rf represents a perfluoroalkylene group, xa and xb each independently represent an integer of 0 to 3.). 82. The solar cell module according to claim 80, wherein the polyfunctional (meth)acrylic compound further comprises a compound selected from the group consisting of 6 or more fluorine atoms in one molecule and a molecular weight of 1000 or its Of the following (meth)acrylic compounds with 3 to 6 functional groups, and (meth)acrylic compounds with 6 to 15 functional groups with a molecular weight of 1000 to 5000 having 10 or more fluorine atoms per molecular weight One or more fluorine-containing multifunctional (meth)acrylic compounds, and in the total multifunctional (meth)acrylic compounds, the proportion of the fluorine-containing multifunctional (meth)acrylic compounds is 5 weight % or more. 83. The solar cell module according to claim 79, characterized in that the hollow silica is 100 to 150 of the terminal (meth)acrylic silane coupling agent represented by the following general formula (IV). The hydrothermal reaction at ℃, or the reaction under microwave irradiation, the (meth)acrylic modified hollow silica whose surface has been modified with terminal (meth)acrylic acid, (In the above general formula (IV), R ²¹ represents a hydrogen atom, a fluorine atom or a methyl group, ^R22 represents an alkylene group with 1 to 8 carbon atoms, or a fluorinated alkylene group with 1 to 8 carbon atoms in which one or more hydrogen atoms are replaced by fluorine atoms, R ²³ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). 84. The solar cell module according to claim 79, wherein the hollow silica is heated at 100 to 150° C. Under the hydrothermal reaction, or the reaction under microwave irradiation, the fluorinated alkyl-modified hollow silica with terminal fluorinated alkyl modified on the surface,

(In the above general formula (V), R ³¹ to R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ya represents an integer of 1 to 8, and yb represents an integer of 1 to 3.) . 85. The solar cell module according to claim 79, wherein the high refractive index layer comprises high refractive index particles and a binder component having an aromatic group. 86. The solar cell module according to claim 79, wherein the anti-reflection layer is formed directly on the surface-side transparent protective member. 87. The solar cell module according to claim 79, wherein the anti-reflection layer is an anti-reflection film pasted on the transparent protective member on the surface side, and the anti-reflection film is sequentially laminated on a transparent base film. It is formed by high refractive index layer and low refractive index layer. 88. The solar cell module according to claim 87, wherein a hard coat layer is provided between the transparent base film and the high refractive index layer. 89. The solar cell module according to claim 79, wherein the wavelength of the minimum reflectance of the anti-reflection layer is shifted to the short-wave direction by reducing the film thickness of the high-refractive index layer or the low-refractive index layer.

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