TWI448720B - Antireflection material and electronic image display apparatus having the antireflection material - Google Patents

Description

Anti-reflection material and electronic image display device having the same

The present invention relates to an anti-reflection material and an electronic image display device including the same, which can fix a reflectance in a wavelength range of light sensitivity (wavelength of 500 to 650 nm) (hereinafter, referred to as reflectance) In order to reduce the color unevenness caused by the variation in the film thickness of the coating layer.

In recent years, electronic displays have been widely used in televisions and monitors. In particular, the display has been further reduced in size and size, and plasma display (PD), liquid crystal display (LCD), and organic EL display (OELD) have attracted attention. In order to improve visibility, anti-reflection treatment is applied to these large displays, and in order to solve the problem of color reproducibility, it is necessary to use an anti-reflection material with less coloration.

For example, a medical display capable of displaying a diagnostic image having no unnecessary image and color and high image quality has been proposed (for example, refer to Patent Document 1). The antireflection film used in the medical display has a transparent support, a protective layer disposed thereon, and an antireflection layer disposed on the protective layer. The antireflection layer is formed of three layers, starting from the side of the transparent support. The medium refractive index layer, the high flexible layer and the low flexible layer are in this order. The color degree (a* value, b* value) of the specular reflected light under the CIE standard light source D65 is set within a specific range.

Furthermore, the applicant of the present application proposes an antireflection material in which a protective layer is provided on a transparent resin film, and an antireflection layer is provided on the protective layer (for example, refer to Patent Document 2). When the antireflection material is used, the maximum value of the difference between the reflectance amplitudes of the light wavelengths of 500 to 650 nm is set to 1% or less, and the apparent reflectance of the CIE standard light source D65 is set to 2% or less, and the CIE standard light source D65 is ab. The chromaticity Cab*={(a*) ² +(b*) ² }1/2 is set to 10 or less.

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-295055 (pages 2, 5, and 18)

[Patent Document 2] JP-A-2006-116754 (Pages 2, 3, and 12)

However, in the antireflection film disclosed in Patent Document 1, the antireflection layer (antireflection layer) has a three-layer structure and is excellent in anti-reflection characteristics, but the reflectance changes greatly in the wavelength range of the sensitivity, and is not fixed (smooth). In other words, the antireflection layer is liable to change in film thickness, and this film thickness variation causes color unevenness, and the effect of reducing coloration cannot be sufficiently exhibited.

Further, in the antireflection material described in Patent Document 2, when the antireflection layer is composed of a high refractive index layer and a low refractive index layer, the film thickness ratio is 1.0 to 1.1 (Examples 4 and 7 of Patent Document 2) ). Therefore, when the antireflection material of Patent Document 2 is used, the spectral fluctuation of the reflectance corresponding to the wavelength of the light in the wavelength range of the sensitivity becomes large, and it is difficult to fix the reflectance. Due to such a difference, color unevenness of the antireflection material cannot be suppressed.

Accordingly, it is an object of the present invention to provide an antireflection material and an electronic image display apparatus including the same, which can fix a reflectance in a wavelength range of visibility and suppress a variation in film thickness of a coating layer. The color is uneven.

In the present invention, the antireflection material of the first aspect of the invention is characterized in that at least a protective layer, a first optical interference layer, and a second optical interference layer are laminated on the transparent resin film. The refractive index of the first optical interference layer is higher than the refractive index of the protective layer, the difference between the refractive indices of the two optical interference layers is 0.01 to 0.05, and the refractive index of the second optical interference layer is lower than the refractive index of the first optical interference layer. The ratio of the film thickness of the first optical interference layer to the film thickness of the second optical interference layer is 1.6 to 1.8.

According to the first aspect of the invention, the antireflection material according to the second aspect of the invention is characterized in that the maximum value of the difference in reflectance amplitude in the region of the light wavelength of 500 to 650 nm is 1% or less, and based on JIS Z8729, the CIE standard light source D65 is based on JIS Z8729. Ab chromaticity Cab*={(a*) ² +(b*) ² }1/2 is 5 or less.

According to the first or second aspect of the invention, the antireflection material according to the third aspect of the invention is characterized in that the luminosity reflectance Y based on JIS Z8701 is 1.5% or less under the CIE standard light source D65 of JIS Z8720.

The electronic image display device according to the fourth aspect of the invention is characterized in that the antireflection material according to any one of claims 1 to 3 is provided in front of the display.

According to the present invention, the following effects can be exhibited.

According to the antireflection material of the first aspect of the invention, the refractive index of the first optical interference layer is higher than the refractive index of the protective layer, and the difference in refractive index between the two is 0.01 to 0.05, and the refractive index of the second optical interference layer is set lower than The refractive index of the first optical interference layer, the ratio of the film thickness of the first optical interference layer to the film thickness of the second optical interference layer is set to 1.6 to 1.8. Therefore, the reflectance (reflection spectrum) of the antireflection material in the wavelength range of visibility can be made close to a fixed (flattening), and the fluctuation of the reflection spectrum corresponding to the wavelength of the light can be suppressed. Therefore, the reflectance in the illuminance wavelength range can be fixed, and the color unevenness caused by the variation in the film thickness of the coating layer can be suppressed.

According to the antireflection material of the second aspect of the invention, the maximum value of the difference in reflectance amplitude between the wavelengths of 500 to 650 nm is 1% or less, and based on the CIS standard light source D65 of JIS Z8720, the ab color of the JIS Z8729 is Cab*= {(a*) ² + (b ^* ) ² } 1/2 is 5 or less. Therefore, in addition to the effects of the first invention, it is possible to effectively suppress the interference unevenness caused by the difference in refractive index between the transparent resin film and the protective layer, and to suppress the reflection reduction by the first optical interference layer and the second optical interference layer. The color of the structure of the layer.

According to the antireflection material of the third invention, the apparent reflectance Y based on JIS Z8701 is 1.5% or less based on JIS Z8720's CIE standard light source D65. Therefore, in addition to the effects of the first or second invention, since the reflectance of the sensibility is low, an antireflection material having better visibility can be provided.

An electronic image display device according to a fourth aspect of the invention is the one in which the antireflection material is provided on the front surface of the display. Therefore, the effect of the antireflection material of any of the first to third inventions can be exhibited in the electronic image display device.

Hereinafter, the best mode for carrying out the invention will be described in detail.

[anti-reflective material]

As shown in FIG. 1, the antireflection material 10 of the present embodiment is formed by laminating at least a protective layer 12, a first optical interference layer 13a as an antireflection layer 13, and an antireflection layer 13 on the transparent resin film 11. The second optical interference layer 13b. The refractive index of the first optical interference layer 13a is higher than the refractive index of the protective layer 12, and the difference in refractive index between the two is 0.01 to 0.05, and the refractive index of the second optical interference layer 13b is lower than that of the first optical interference layer 13a. The ratio of the film thickness of the first optical interference layer 13a to the film thickness of the second optical interference layer 13b is 1.6 to 1.8.

The refractive index of the first optical interference layer 13a is higher than the refractive index of the protective layer 12, the difference in refractive index between the two is set to 0.01 to 0.05, and the refractive index of the second optical interference layer 13b is made lower than that of the first optical interference layer. The refractive index of 13a is set to 1.6 to 1.8 by the ratio of the film thickness of the first optical interference layer 13a to the film thickness of the second optical interference layer 13b. According to the related structure, the fluctuation of the reflectance can be suppressed, the reflectance can be flattened, and the unevenness in coloring can be suppressed. Therefore, it is possible to effectively suppress color unevenness caused by variations in film thickness.

Further, the maximum value of the difference in reflectance amplitude between the anti-reflection material 10 in the region of the luminosity wavelength range (light ray wavelength of 500 to 650 nm) is preferably 1% or less, more preferably 0.5% or less. When the maximum value is more than 1%, the interference unevenness caused by the difference in refractive index between the transparent resin film 11 and the protective layer 12 is remarkable, and it is difficult to suppress uneven coloring, which is not preferable. In addition, the lower limit of the relevant maximum value is about 0.1%. Further, based on JIS Z8720's CIE standard light source D65, ab chromaticity Cab*={(a*) ² +(b*) ² } 1/2 based on JIS Z8729 is preferably 5 or less, more preferably 4 the following. If the value exceeds 5, it is difficult to suppress uneven coloring, which is not preferable. In addition, the lower limit of the value is about 0.1.

Further, in the CIE standard light source D65 based on JIS Z8720, the opacity reflectance Y of the antireflection material 10 based on JIS Z8701 is preferably 1.5% or less, more preferably 1.0% or less. When the visual reflectance Y exceeds 1.5%, the reflection becomes large, and the image visibility of the electronic image display device is lowered, which is not preferable. Further, the lower limit of the visual sensitivity reflectance Y is about 0.1%.

As shown in FIG. 2, the anti-reflection material 10 may have a structure in which an adhesive layer 14 is provided between the transparent resin film 11 and the protective layer 12.

(Transparent Resin Film 11)

First, the transparent resin film 11 will be described. The transparent resin film 11 preferably has a refractive index (n) in the range of 1.45 to 1.70. Examples of the transparent resin substrate forming the transparent resin film 11 having a slightly lower refractive index (1.45 to 1.55) include cellulose acetate (cellulose acetate) such as cellulose triacetate (TAC, n=1.48), and acrylic resin (for example). AC, n = 1.50), etc. Further, examples of the transparent resin substrate having a slightly higher refractive index (1.55 to 1.70) include a polyester resin such as polyethylene terephthalate (PET, n = 1.65), and polycarbonate (PC, n = 1.59), polyarylate (PAR, n = 1.60) and polyether oxime (PES, n = 1.65). Among them, the transparent resin film 11 having a slightly lower refractive index is preferably a TAC film, and the transparent resin film 11 having a slightly higher refractive index is preferably a PET film, from the viewpoints of ease of formation and ease of availability.

Further, the film thickness of the transparent resin film 11 is preferably from 25 to 400 μm, more preferably from 40 to 200 μm. When the film thickness is less than 25 μm or exceeds 400 μm, the use property is lowered when the antireflection material 10 is manufactured and used, which is not preferable. The transparent resin film 11 may contain various additives. Examples of the related additives include an ultraviolet absorber, an antistatic agent, a stabilizer, a plasticizer, a lubricant, a flame retardant, and the like.

(protection layer 12)

Next, the protective layer 12 will be described. The refractive index of the protective layer 12 is preferably in the range of 1.45 to 1.70. If the refractive index of the protective layer 12 is less than 1.45 or exceeds 1.70, the unevenness of the interference caused by the difference in refractive index between the transparent resin film 11 and the protective layer 12 is remarkably exhibited, which is not preferable. Further, the film thickness of the protective layer 12 is preferably from 1 to 10 μm. If the film thickness of the protective layer 12 is less than 1 μm, sufficient surface strength cannot be obtained, which is not preferable. On the other hand, when the film thickness exceeds 10 μm, problems such as a decrease in the flexibility of the protective layer 12 occur, which is not preferable.

The refractive index and film thickness of the protective layer 12 are not particularly limited as long as they are within the above range. The material for forming the protective layer 12 is, for example, a cured product such as a monofunctional (meth)acrylate, a polyfunctional (meth)acrylate, or a reactive anthracene compound such as tetraethoxysilane. Here, the (meth) acrylate includes both acrylate and methacrylate. Hereinafter, even if the compound changes, the same is included. Among them, a polymer cured product containing a composition of an ultraviolet curable multifunctional acrylate is particularly preferable from the viewpoint of both productivity and hardness.

The composition containing the ultraviolet curable multifunctional acrylate is not particularly limited. For example, dipentaerythritol hexaacrylate, tetramethylol methane tetraacrylate, tetramethylol methane triacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, 1, Acrylic derivatives of polyfunctional alcohols such as 6-bis(3-propenyloxy-2-hydroxypropoxy)hexane, polyethylene glycol diacrylate, urethane acrylate, and commercially available ultraviolet curing Sexual protection materials, etc.

The composition containing the ultraviolet curable multifunctional acrylate usually contains other components, and the other components are not particularly limited. Examples of the other component include inorganic or organic particulate fillers, inorganic or organic particulate pigments, and other inorganic or organic fine particles, polymers, polymerization initiators, polymerization inhibitors, oxidation inhibitors, dispersants, and surfactants. Additives such as light stabilizers and leveling agents. Further, in the wet coating method, if a drying treatment is performed after film formation, an arbitrary amount of a solvent can be added.

The method for forming the protective layer 12 is not particularly limited, and when an organic material is used, it can be formed by a usual wet coating method such as a roll coating method or a squeeze coating method. The layer formed may be subjected to a hardening reaction by heating or irradiation with an active energy ray such as an ultraviolet ray or an electron beam as needed.

The anti-reflection material 10 can adjust the refractive index and the film thickness of the first optical interference layer 13a and the second optical interference layer 13b to adjust the reflectance, and it is preferable to further increase the wavelength of 500 to 650 nm. The maximum value of the difference in reflectance amplitude is set to 1% or less. Thereby, the interference unevenness caused by the difference in refractive index between the transparent resin film 11 and the protective layer 12 can be reduced, and the effect of the present invention can be further exerted, that is, the color unevenness caused by the variation in the film thickness of the coating layer can be suppressed. . For this reason, it is preferable to further satisfy the following requirements. Here, the case of the TAC film and the PET film as the representative transparent resin film 11 will be described. When a TAC film is used, it is important that the refractive index of the protective layer 12 is within ±0.03 of the (refractive index of the TAC film). More preferably, the refractive index of the protective layer 12 is within the range of ± 0.02 of the refractive index of the TAC film. If the refractive index of the protective layer 12 exceeds (the refractive index of the transparent resin film 11) ± 0.03, the interference unevenness is remarkable, which is not preferable.

When the protective layer 12 is formed on the TAC film by a wet coating method, if it is used alone or in combination with any solvent, the solvent of the surface of the TAC film, such as methyl ethyl ketone, methyl acetate, ethyl acetate, etc., may be eroded. The interface between the TAC film and the protective layer 12 is disordered, and the interference effect of the interface between the TAC film and the protective layer 12 is suppressed. Therefore, in addition to the above effect of the refractive index difference, interference unevenness can be more effectively suppressed.

(adhesive layer 14)

When a PET film is used, it is preferred to laminate the adhesive layer 14 and the protective layer 12 in this order from the side of the transparent resin film 11 on the PET film, thereby reducing interference unevenness. It is preferred that the refractive indices of the PET film, the adhesive layer 14 and the protective layer 12 satisfy the following relationship: refractive index of the PET film > refractive index of the adhesive layer 14 > refractive index of the protective layer 12. At this time, it is preferred to adjust the refractive index and film thickness of the adhesive layer 14 in accordance with the refractive index of the protective layer 12 to be used. When the refractive index of the protective layer 12 is 1.45 to 1.60, the refractive index of the adhesive layer 14 is adjusted within a range of {(refractive index of the PET film) × (refractive index of the protective layer 12) 1/2 ± 0.03, and the film thickness is Adjust within the range of 70 to 130 nm. The refractive index of the adhesive layer 14 is preferably in the above range, and more preferably in the range of {(refractive index of the PET film) × (refractive index of the protective layer 12) 1/2 ± 0.02. When the refractive index of the adhesive layer 14 is {(the refractive index of the PET film) × (the refractive index of the protective layer 12) 1/2, it is most preferable to reduce the interference unevenness.

Further, when the refractive index of the protective layer 12 is from 1.61 to 1.70, it is preferred that the thickness of the adhesive layer 14 be 20 nm or less. The film thickness of the adhesive layer 14 is more preferably 10 nm or less. If the film thickness of the adhesive layer 14 exceeds 20 nm, the interference unevenness is remarkable, which is not preferable.

The adhesive layer 14 contains a polymer binder and fine particles. From the viewpoint of imparting good adhesion, the polymer binder is preferably a mixture of a polyester resin and an acrylic resin containing an oxazoline group and a polyalkyl ether chain. The polymer binder is preferably soluble or dispersible in water, and may be used in water which is soluble in a little organic solvent. The content of the polyester resin constituting the polymer binder of the adhesive layer 14 in the adhesive layer 14 is preferably from 5 to 95% by mass, more preferably from 50 to 90% by mass. The polymer binder constituting the adhesive layer 14 and the acrylic resin containing the oxazoline group and the polyalkyl ether chain are preferably contained in the adhesive layer 14 in an amount of 5 to 95% by mass, more preferably 10 to 50% by mass. .

If the polyester resin exceeds 95% by mass, or the acrylic resin containing the oxazoline group and the polyalkyl ether chain is less than 5% by mass, the cohesive force of the adhesive layer 14 is lowered, and the adhesion to the protective layer 12 or the adhesive layer 14 is Adhesion is not sufficient, so it is not ideal. When the acrylic resin containing the oxazoline group and the polyalkyl ether chain exceeds 95% by mass, or the polyester resin is less than 5% by mass, the adhesion to the polyester film is lowered, and the adhesion to the protective layer 12 is insufficient. Or the adhesion of the adhesive layer 14 is insufficient.

As the fine particles constituting the above-mentioned adhesive layer 14, composite inorganic particles of cerium oxide and titanium oxide are preferably used. The composite inorganic particles of cerium oxide and titanium dioxide can be arbitrarily adjusted in refractive index, and the refractive index can be easily adjusted. The difference in refractive index between the polymer binder of the adhesive layer 14 and the fine particles is preferably within 0.02, more preferably within 0.01. When the difference in refractive index exceeds 0.02, the light is largely scattered by the difference in refractive index between the polymer binder and the fine particles, and the turbidity of the adhesive layer 14 becomes high, and the transparency is deteriorated, which is not preferable. .

The average particle diameter of the fine particles is preferably in the range of 40 to 120 nm. When the average particle diameter is more than 120 nm, the fine particles are liable to fall off. On the other hand, when the average particle diameter is less than 40 nm, sufficient lubricity and scratch resistance may not be obtained, which is not preferable. The content of the fine particles in the adhesive layer 14 is preferably from 0.1 to 10% by mass. When the content is less than 0.1% by mass, sufficient lubricity and scratch resistance are not obtained. On the other hand, when the content is more than 10% by mass, the cohesive force of the adhesive layer 14 is lowered, and the adhesiveness is lowered, which is not preferable.

The adhesive layer 14 preferably contains an aliphatic wax, and the content thereof is preferably from 0.5 to 30% by mass, more preferably from 1 to 10% by mass. If the content is less than 0.5% by mass, the surface of the adhesive layer 14 may not have lubricity, which is not preferable. If it is more than 30% by mass, the adhesion to the transparent resin film 11 or the protective layer 12 may be insufficient, which is not preferable. As a specific example of the aliphatic wax, water dispersion such as carnauba wax, canary lilac wax, rice bran wax, wood wax, palm wax, montan wax, ceresin wax, white wax, paraffin wax, polyethylene glycol, or polypropylene glycol is preferred. Sexual or water soluble waxes.

The coating liquid is applied to one surface or both surfaces of the transparent resin film 11 to provide the adhesive layer 14 on the transparent resin film 11. The coating can be carried out at any stage, but it is preferably carried out in the production process of the transparent resin film 11, and the efficiency is good. As the coating method, any well-known coating method can be employed. For example, a gravure coating method, a rolling cleaning method, a spray coating method, a pneumatic blade coating method, a wire bar coating method, a dip coating method, and the like can be given.

(anti-reflection layer 13)

Next, the anti-reflection layer 13 will be described. The related anti-reflection layer 13 is composed of a first optical interference layer 13a and a second optical interference layer 13b. The refractive index of the first optical interference layer 13a is set to be higher than that of the protective layer 12 and the second optical interference layer 13b, and the refractive index difference between the first optical interference layer 13a and the protective layer 12 is set to 0.01 to 0.05. The difference in refractive index is preferably from 0.01 to 0.03. When the refractive index difference is less than 0.01, the reflected light at the interface between the protective layer 12 and the first optical interference layer 13a is too weak, which is not preferable. On the other hand, when the refractive index difference is more than 0.05, the reflected light at the interface between the protective layer 12 and the first optical interference layer 13a is too strong, and the reflectance cannot be flattened, which is not preferable.

Further, the refractive index of the second optical interference layer 13b is set to be lower than the refractive index of the first optical interference layer 13a, and the refractive index thereof is preferably 1.28 to 1.45. When the refractive index is less than 1.28, it is difficult to sufficiently form a hard layer. On the other hand, when the refractive index exceeds 1.45, it is difficult to obtain a sufficient antireflection effect especially when a wet coating method is used.

Then, the ratio of the film thickness of the first optical interference layer 13a to the film thickness of the second optical interference layer 13b is set to be the film thickness of the first optical interference layer 13a/the thickness of the second optical interference layer 13b = 1.6 to 1.8. When the ratio of the film thickness is less than 1.6 and exceeds 1.8, the change in the reflection spectrum due to the variation in the film thickness becomes large, and the reflectance is not flattened, which is not preferable.

The method of forming the anti-reflection layer 13 is not particularly limited, and methods such as a dry coating method and a wet coating method can be employed. Among these methods, a wet coating method is particularly preferable in terms of productivity and production cost. A well-known wet coating method can be employed, and examples thereof include a representative method such as a drum coating method, a spin coating method, and a dip coating method. Among them, from the viewpoint of productivity, a method of continuously forming the anti-reflection layer 13 such as a drum coating method is preferable.

The material constituting the first optical interference layer 13a is not particularly limited, and an inorganic material or an organic material can be used. Examples of the inorganic material include fine particles such as zinc oxide, titanium oxide, cerium oxide, aluminum oxide, cerium oxide, cerium oxide, cerium oxide, zirconium oxide, indium tin oxide, and antimony-containing tin oxide. Particularly preferred are conductive particles such as indium tin oxide and antimony-containing tin oxide, which can lower the surface resistivity and impart an antistatic function. On the other hand, as the organic material, for example, a composition in which a polymerizable monomer is polymerized and cured can be used, and the polymerizable monomer has an anthracene skeleton.

As a material constituting the second optical interference layer 13b, an inorganic substance such as cerium oxide, cesium fluoride, magnesium fluoride or cesium fluoride, a fluorine-containing organic compound or a mixture thereof, or a composition containing a polymer containing a fluorine-containing organic compound can be used. . Further, a fluorine-free monomer (abbreviated as a non-fluorine-based monomer) or a polymer can be used as the binder. Among them, particularly preferred are cerium oxide-based fine particles, particularly hollow cerium oxide-based fine particles or fluorine-containing organic compounds, which have a low refractive index.

Examples of the hollow cerium oxide-based fine particles include those having voids inside the outer casing and porous cerium oxide fine particles. The average particle diameter of the fine particles is preferably not excessively larger than the thickness of the second optical interference layer 13b, and particularly preferably 0.1 μm or less. When the average particle diameter becomes large, scattering occurs and the turbidity increases, which is unsuitable as the antireflection material 10. Further, the surface of the fine particles may be modified by various coupling agents or the like as needed. Examples of the various coupling agents include an organically substituted anthracene compound, a metal alkoxide such as aluminum, titanium, zirconium or hafnium, an organic acid salt or the like. In particular, the surface can be modified by a reactive group such as a (meth) acrylonitrile group to form a high-hardness film.

The fluorine-containing organic compound is not particularly limited, and examples thereof include fluorine-containing monofunctional (meth)acrylate, fluorine-containing polyfunctional (meth)acrylate, fluorine-containing itaconate, and fluorine-containing maleate. A monomer such as a fluorine-containing cerium compound, a polymer such as these, or the like. Among them, a fluorine-containing (meth) acrylate is preferred from the viewpoint of reactivity, and a fluorine-containing polyfunctional (meth) acrylate is preferable in terms of hardness and refractive index. By curing the fluorine-containing organic compound, the second optical interference layer 13b having a low refractive index and a high hardness can be formed.

The fluorine-containing monofunctional (meth) acrylate may, for example, be 1-(methyl)propenyloxy-1-perfluoroalkylmethane or 1-(meth)acryloxy-2-perfluoro Alkyl ethane and the like. Examples of the perfluoroalkyl group include a linear one having a carbon number of 1 to 8, a branched shape, or a ring shape.

As the fluorine-containing polyfunctional (meth) acrylate, a fluorine-containing bifunctional (meth) acrylate, a fluorine-containing trifunctional (meth) acrylate, and a fluorine-containing tetrafunctional (meth) acrylate are preferable. Examples of the fluorine-containing bifunctional (meth) acrylate include 1,2-bis(methyl)propenyloxy-3-perfluoroalkylbutane, 2-hydroxy-1H, 1H, 2H, 3H. 3H-perfluoroalkyl-2', 2'-bis{(meth)acrylomethoxymethyl}propionate, α,ω-di(meth)acrylomethoxymethyl perfluoroalkane, and the like. The perfluoroalkyl group is a linear, branched or cyclic carbon number of 1 to 11, and a perfluoroalkyl group is preferably a linear one. When used, the fluorine-containing bifunctional (meth) acrylates may be used singly or as a mixture.

Examples of the fluorine-containing trifunctional (meth) acrylate include 2-(meth)acryloxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2', 2'-. Double {(meth)acrylomethoxymethyl}propionate and the like. The perfluoroalkyl group is preferably a linear, branched or cyclic carbon number of 1 to 11.

As an example of the fluorine-containing tetrafunctional (meth) acrylate, α, β, ψ, ω-tetra{(meth) propylene oxime}-αH, αH, βH, γH, γH, χH, are preferable. χH, ψH, ωH, ωH-perfluoroalkane, and the like. The perfluoroalkyl group is preferably a linear one having a carbon number of 1 to 14. When used, the fluorine-containing tetrafunctional (meth) acrylate may be used singly or as a mixture.

Specific examples of the fluorine-containing cerium compound are (1H, 1H, 2H, 2H-perfluoroalkyl)trimethoxynonane and the like. The perfluoroalkyl group is preferably a linear, branched or cyclic carbon number of 1 to 10. The polymer of the fluorine-containing organic compound or the polymer of another fluorine-containing monomer may, for example, be a linear polymerization of a homopolymer or a copolymer of the above fluorine-containing monomer or a copolymer with a non-fluorine-based monomer. A polymer having a carbocyclic or heterocyclic ring, a cyclic polymer, a comb polymer, or the like in the chain or the chain. As the above non-fluorine-based monomer, those previously known can be used. For example, an anthracene compound such as a monofunctional or polyfunctional (meth) acrylate or tetraethoxy decane may, for example, be mentioned.

In addition to the above compounds, other components may be contained in the anti-reflection layer 13 within a range that does not impair the effects of the present invention. The other components are not particularly limited, and examples thereof include inorganic or organic pigments, polymers, polymerization initiators, photopolymerization initiators, polymerization inhibitors, oxidation inhibitors, dispersants, surfactants, light stabilizers, and leveling agents. Such as additives. Further, in the wet coating method, if a drying treatment is performed after film formation, an arbitrary amount of a solvent can be added. After the film is formed by wet coating, the active energy ray such as ultraviolet rays or electron beams may be irradiated or heated as needed to perform a curing reaction to form the antireflection layer 13. The hardening reaction by the active energy ray is preferably carried out under an inert gas atmosphere such as nitrogen or argon.

The anti-reflection material 10 can form an adhesive layer on the surface of the transparent resin film 11 opposite to the protective layer 12 and the anti-reflection layer 13. The material to be used for the adhesive layer is not particularly limited, and examples thereof include an acrylic resin adhesive, a polyoxynoxy adhesive, an ultraviolet curable adhesive, and a thermosetting adhesive. The adhesive layer may be provided with one or more of light blocking, contrast improvement, and color tone correction in a specific wavelength region. For example, when the transmitted light of the anti-reflective material 10 is yellow or the like, it is not preferable, and a coloring matter or the like may be added to perform color tone correction.

[Electronic image display device]

The anti-reflection material 10 of the present embodiment is suitably used for applications requiring an effect of improving color reproducibility, an effect of suppressing uneven light interference, and an anti-reflection effect. In particular, it can be used in front of a display of an electronic image display device. Examples of the electronic image display device include a plasma display, a liquid crystal display, and a cathode ray tube. The anti-reflective material 10 can be used directly on the surface of the display (picture) or on the board disposed on the front of the display via an adhesive layer.

[Summary of the role and effect of the embodiment]

‧ According to the anti-reflection material 10 of the present embodiment, the refractive index of the first optical interference layer 13a is higher than the refractive index of the protective layer 12, and the refractive index difference between the two is 0.01 to 0.05, and the refractive index of the second optical interference layer 13b The ratio of the film thickness of the first optical interference layer 13a to the film thickness of the second optical interference layer 13b is set to be 1.6 to 1.8, which is set to be lower than the refractive index of the first optical interference layer 13a. Therefore, the smoothing of the reflectance of the anti-reflective material 10 in the wavelength range of the sensibility can be achieved. The colors in the flat wavelength range are mixed and look like they are not colored and whitened. Further, if the reflection spectrum is V-shaped, the color of the complementary color of the bottom wavelength of the V word can be seen. Therefore, as the film thickness of the first optical interference layer 13a and the second optical interference layer 13b fluctuates, the reflection spectrum also fluctuates, and the V-shaped bottom wavelength shifts, whereby various colors may be observed and uneven coloration may occur. The phenomenon. Therefore, by using the anti-reflection material 10, the reflectance in the wavelength range of the sensibility can be fixed, and the color unevenness caused by the variation in the film thickness of the coating layer can be suppressed.

‧ In addition, according to the anti-reflection material 10, the maximum value of the difference in reflectance amplitude in the region of the light wavelength of 500 to 650 nm is 1% or less, and based on the CIS standard light source D65 of JIS Z8720, the ab chromaticity Cab* based on JIS Z8729 {(a*) ² + (b*) ² } 1/2 is 5 or less. Therefore, interference unevenness due to the difference in refractive index between the transparent resin film 11 and the protective layer 12 can be effectively suppressed, and the structure of the anti-reflection layer 13 including the first optical interference layer 13a and the second optical interference layer 13b can be suppressed. Coloring.

‧ According to JIS Z8720, the CIE standard light source D65 based on the anti-reflection material 10 has a luminosity reflectance Y of 1.5% or less based on JIS Z8701. Since the reflectance of the sensibility is low, the antireflection material 10 having better visibility can be provided.

‧ The electronic image display device is provided with the above-mentioned anti-reflection material 10 on the front of the display. Therefore, in the electronic image display device, the effect of the above-described antireflection material 10 can be exhibited. Therefore, it is suitable to use the anti-reflection material 10 in a plasma display or a liquid crystal display.

[Examples]

Hereinafter, the above-described embodiments will be specifically described by way of production examples, examples, and comparative examples, but the present invention is not limited to the scope of the examples. Further, the refractive index of the cured product of the coating liquid for the antireflection layer 13 prepared in the production example was measured by the method shown below.

(1) Applying anti-reflection to each of the acrylic resin sheets having a refractive index of 1.49 (product name: "DELAGLAS A", manufactured by Asahi Kasei Chemicals Co., Ltd.) by a dip coating machine [manufactured by Sugiyama Pharmaceutical Co., Ltd.] The layer 13 was coated with a liquid, and the layer thickness was adjusted so that the dried optical film thickness was about 550 nm.

(2) After the solvent was dried, an ultraviolet ray irradiation device (manufactured by Iwasaki Electric Co., Ltd.) was used, and a 120 W high-pressure mercury lamp was used in a nitrogen atmosphere to irradiate ultraviolet rays of 400 mJ to cure the anti-reflection layer 13 with a coating liquid.

(3) The back surface of the acrylic resin plate was rubbed with a sandpaper to make it rough, and all of the black paint was applied, and it was measured by a spectrophotometer ["U-Best V560", manufactured by JASCO Corporation] at 5 ° in the region of 400 to 650 nm. -5° positive reflectance, reading the minimum or maximum value of its reflectivity.

(4) Calculate the refractive index based on the extreme value of the reflectance and using the following formula.

The physical properties of the obtained antireflection material 10 were evaluated in the following manner.

1) Spectral reflectance: The back surface of the anti-reflective material 10 (the back surface of the transparent resin film 11) is rubbed with a sandpaper to make it rough, and all of the black paint is applied, and a spectrophotometer is used ["U-Best V560", Japan Spectroscopic Co., Ltd. The system measures the 5° and -5° specular reflection spectra in the region of the 380-780 nm wavelength of light. Thereby, the reflection spectrum of the anti-reflection layer 13 can be measured.

2) Vision reflectance Y: The object color of the XYZ color system specified in JIS Z8701 is calculated by using the spectral reflectance of the 380-780 nm region of the measured light wavelength and the relative spectral distribution of the CIE standard light source D65 based on JIS Z8720. The tristimulus value Y (%).

3) Maximum value of difference in reflectance amplitude in a region of a light wavelength of 500 to 650 nm: reading a difference in reflectance (%) amplitude of a region of a light beam having a wavelength of 500 to 650 nm based on a reflection spectrum obtained by measuring the spectral reflectance. Maximum value.

4) ab chromaticity Cab*: Calculate the color space CIE1976L*a prescribed by JIS Z8729 using the spectral reflectance of the wavelength range of 380 to 780 nm measured by the above 1) and the relative spectral distribution of the CIE standard light source D65 based on JIS Z8720. The *b* color system calculates ab chromaticity Cab*={(a*) ² +(b*) ² }1/2 based on the calculated a* value and b* value.

5) Coloring suppressing effect: An acrylic resin-based pressure-sensitive adhesive sheet was used on one surface of a glass plate having a size of 10 cm in length and 10 cm in width, and an anti-reflection film was attached thereto, and a black film was stuck on the other surface to prepare a sample. The sample was observed under a fluorescent lamp of a non-three-wavelength fluorescent lamp (for example, Palook (FL20SSD/18) manufactured by Matsushita Electric Industrial Co., Ltd.), and the uneven coloring caused by the variation in the thickness of the coating layer was evaluated. The sample was observed under a three-wavelength fluorescent lamp (for example, Palook (FL20SS EX-N/18) manufactured by Matsushita Electric Industrial Co., Ltd.) to evaluate the unevenness of the interference. As a basis for the evaluation, the case where the unevenness of the unevenness was not observed and the unevenness of the coloring was not observed was ◎, and the unevenness of the interference was observed, but the unevenness of the coloration was found to be ○, and the uneven coloration was found regardless of the presence or absence of the interference unevenness. The case is ×, and evaluation is performed.

[Manufacturing Example 1, Preparation of Coating Liquid Forming Adhesive Layer 14 (hereinafter referred to as Adhesive Layer Coating Liquid)]

(1) Synthesis of polyester 1

47 parts by mass of dimethyl terephthalate, 9 parts by mass of dimethyl isophthalate, 5 parts by mass of dimethyl isophthalate 5-sulfonate, 36 parts by mass of ethylene glycol, diethylene glycol 3 parts by mass was charged into the reactor, and 0.05 parts by mass of tetrabutoxytitanium was added, and the temperature was adjusted to 230 ° C under a nitrogen atmosphere and heated, and the produced methanol was distilled off to carry out a transesterification reaction. Then, the temperature of the reaction system was gradually increased to 255 ° C, and the internal pressure was reduced to 133 Pa (1 mmHg) to carry out a polycondensation reaction to obtain a polyester 1 (Tg = 71 ° C, mass average molecular weight: 16,000).

(2) Synthesis of acrylic resin aqueous dispersion

302 parts by mass of ion-exchanged water was placed in a four-necked flask, and the temperature was raised to 60 ° C in a nitrogen stream, and then 0.5 parts by mass of ammonium persulfate and 0.2 parts by mass of sodium hydrogen nitrite were added as a polymerization initiator, and then dropped for 3 hours. 23.3 parts by mass of methyl methacrylate, 22.6 parts by mass of 2-isopropenyl-2-oxazoline, 40.7 parts by mass of polyethylene oxide (n=10) methacrylate, and 13.3 parts by mass of acrylamide as a single Body, while adjusting the liquid temperature to 60 ~ 70 ° C. After completion of the dropwise addition, the mixture was kept at this temperature for 2 hours, stirred, and the reaction was continued, followed by cooling to obtain an aqueous dispersion of an acrylic resin having a solid content of 25% by mass (Tg = 50 ° C).

(3) Synthesis of composite inorganic particles of cerium oxide and titanium dioxide

140 parts by mass of methanol, 260 parts by mass of isopropyl alcohol, and 100 parts by mass of ammonia water (25 mass%) were placed in a reaction vessel made of glass with a stirring blade and an internal volume of 4 liters to prepare a reaction liquid, and the temperature of the reaction liquid was maintained. At 40 ° C and stirring. Next, 434 parts by mass of tetramethoxy fluorene [Si(OMe) 4, COLCOAT Co., Ltd., trade name; methyl phthalate 39] was placed in a 3-liter Erlenmeyer flask, and 195 parts by mass of methanol was added thereto while stirring. A mass% of 0.1% by mass of hydrochloric acid [35% by mass of hydrochloric acid and Wako Pure Chemical Industries, Ltd. diluted to 1/1000] was 28 parts by mass, and stirred for about 10 minutes.

Then, a diluent diluted with 300 parts by mass of titanium isopropoxide [Ti(Oi-Pr) 4 , Japan Soda Co., Ltd., trade name; A-1 (TPT)] was added with 634 parts by mass of isopropyl alcohol. A clear, homogeneous solution (copolymer of tetraalkoxyquinone and tetraalkoxy titanium) is obtained. 1699 parts by mass of the above homogeneous solution and 480 parts by mass of aqueous ammonia (25% by mass) were simultaneously dropped into the above reaction liquid over 2 hours, so that the drip acceleration at the beginning was slow, and then the speed was slowly increased until the completion of the dropwise addition. After completion of the dropwise addition, the obtained cohydrolyzed product was filtered, and the organic solvent was dried at 50 ° C, and then dispersed in water to obtain a composite inorganic particle having a concentration of 10% by mass and a refractive index of 1.56 of cerium oxide and titanium oxide (average Particle size: 100 nm).

(4) Preparation of adhesive layer coating solution

167 parts by mass of a polyester, 20 parts by mass of an aqueous acrylic resin dispersion, 3 parts by mass of cerium oxide and titanium dioxide composite inorganic particles, and 5 parts by mass of carnauba wax (product name Serozol 524, manufactured by Nakagisa Oil & Fat Co., Ltd.) as an additive and 5 parts by mass of polyoxyethylene (n=7) lauryl ether (manufactured by Sanyo Chemical Industries, Ltd., trade name Naroacty N-70) was mixed as a wetting agent to obtain an adhesive layer coating liquid.

[Manufacturing Example 2, Preparation of Coating Liquid (N-1)]

70 parts by mass of dipentaerythritol hexaacrylate and 30 parts by mass of 1,6-bis(3-propenyloxy-2-hydroxypropoxy)hexane, photopolymerization initiator [product name "IRGACURE 184", Japan Ciba 4 parts by mass and 100 parts by mass of isopropyl alcohol were mixed to prepare a coating liquid (N-1). The polymer cured product of the coating liquid (N-1) (cured by ultraviolet rays of 400 mJ/cm 2 in a nitrogen atmosphere) had a refractive index of 1.52.

[Manufacturing Example 3, Preparation of Coating Liquid (N-2)]

50 parts by mass of dipentaerythritol hexaacrylate, cerium oxide organosol [trade name: "IPA-ST", manufactured by Nissan Chemical Industries Co., Ltd.), 166 parts by mass, methyl ethyl ketone 20 parts by mass, and photopolymerization initiator [Product name: "IRGACURE 184", manufactured by Nippon Ciba Co., Ltd.] 4 parts by mass was mixed to prepare a coating liquid (N-2). The polymer cured product of the coating liquid (N-2) (cured by ultraviolet rays of 400 mJ/cm 2 in a nitrogen atmosphere) had a refractive index of 1.49.

[Manufacturing Example 4, Preparation of Coating Liquid (N-3)]

233 parts by mass of a 30% by mass methyl ethyl ketone dispersion (trade name: "SNS-10M", manufactured by Ishihara Sangyo Co., Ltd.), 30 parts by mass of dipentaerythritol hexaacrylate, and light. 5 parts by mass of a polymerization initiator [trade name: "IRGACURE 184", manufactured by Nippon Ciba Co., Ltd.] was mixed to prepare a coating liquid (N-3). The polymer cured product of the coating liquid (N-3) (cured by ultraviolet rays of 400 mJ/cm 2 in a nitrogen atmosphere) had a refractive index of 1.64.

[Manufacturing Example 5, Preparation of Coating Liquid (N-4)]

30 mass% methyl ethyl ketone dispersion doped with tin oxide (product name: "SNS-10M", manufactured by Ishihara Sangyo Co., Ltd.) 100 parts by mass, tetramethylol methane triacrylate 70 mass 5 parts by mass of a photopolymerization initiator [product name: "KAYACURE BMS", manufactured by Nippon Kayaku Co., Ltd.) and 830 parts by mass of butanol were mixed to prepare a coating liquid (N-4). The polymer cured product of the coating liquid (N-4) (cured by ultraviolet rays of 400 mJ/cm 2 under a nitrogen atmosphere) had a refractive index of 1.54.

[Manufacturing Example 6, Preparation of Coating Liquid (N-5)]

283 parts by mass of zirconia [product name: "Nano Use ZR-30AL", manufactured by Nissan Chemical Co., Ltd.), 15 parts by mass of tetramethylol methane triacrylate, and photopolymerization initiator [product name: "KAYACURE BMS" 5 parts by mass of Nippon Chemical Co., Ltd. and 702 parts by mass of butanol were mixed to prepare a coating liquid (N-5). The polymer cured product of the coating liquid (N-5) (cured by ultraviolet rays of 400 mJ/cm 2 in a nitrogen atmosphere) had a refractive index of 1.68.

[Manufacturing Example 7, Preparation of Coating Liquid (N-6)]

40 parts by mass of dipentaerythritol hexaacrylate, 300 parts by mass of hollow cerium oxide sol [trade name: "NY-1016SIV", solid content concentration: 20% by mass, average particle diameter: 60 nm, manufactured by Catalyst Chemical Co., Ltd.) 5 parts by mass of a photopolymerization initiator [product name: "KAYACURE BMS", manufactured by Nippon Kayaku Co., Ltd.) was mixed to prepare a coating liquid (N-6). The polymer cured product of the coating liquid (N-6) (cured by ultraviolet rays of 400 mJ/cm 2 in a nitrogen atmosphere) had a refractive index of 1.35.

[Manufacturing Example 8, Preparation of Coating Liquid [N-7]]

For the mass of 1,10-dipropenyloxy-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane Part, hollow cerium oxide sol [trade name: "NY-1016SIV", solid content concentration: 20% by mass, average particle diameter: 60 nm, manufactured by Catalyst Chemical Co., Ltd.), 300 parts by mass, photopolymerization initiator [product name: 5 parts by mass of "KAYACURE BMS" and manufactured by Nippon Kayaku Co., Ltd. were mixed to prepare a coating liquid (N-7). The polymer cured product of the coating liquid (N-7) (cured by ultraviolet rays of 400 mJ/cm 2 under a nitrogen atmosphere) had a refractive index of 1.32.

(Example 1)

The surface of the polyethylene terephthalate (PET) film having a thickness of 100 μm (trade name: "A4100", manufactured by Toyobo Co., Ltd.) is not formed on the surface of the easy-adhesion layer, and is coated by gravure coating. The adhesive layer coating liquid of Example 1 was prepared, and the layer thickness was adjusted so that the thickness of the adhesive layer 14 was 40 nm.

The coating liquid (N-1) was applied thereon by a bar coater, and the layer thickness was adjusted to have a film thickness of 3 μm. After drying, it was cured by ultraviolet rays of 400 mJ/cm 2 in the air to obtain a protective layer. Next, the first optical interference layer 13a was formed on the protective layer 12, that is, the coating liquid (N-4) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 170 nm. After drying, the atmosphere was exposed to nitrogen. It is hardened by ultraviolet rays of 400 mJ/cm2.

Further, the second optical interference layer 13b was formed thereon, that is, the coating liquid (N-6) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 100 nm. After drying, the coating liquid was used in a nitrogen atmosphere at 400 mJ/ The ultraviolet light of cm2 is hardened to produce an antireflection material 10. As shown in FIG. 1, the obtained anti-reflection material 10 is provided with a protective layer 12 on the transparent resin film 11, and a first optical interference layer 13a and a second optical layer as the anti-reflection layer 13 are provided on the surface of the protective layer 12. Interference layer 13b.

The results of evaluation of the difference between the sensitivity reflectance of the obtained antireflection material 10 and the reflectance amplitude of the region of the light ray wavelength of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppression effect are shown in Table 1, respectively. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(a). In Fig. 3(a), the maximum value of the difference in reflectance amplitude is represented by X. Further, in Fig. 3(a), the line connecting the wave center of the reflectance spectrum is indicated by a broken line, and the degree of smoothing is determined based on the broken line. As a result, as shown in FIG. 3(a), it is understood that the spectral center line of the first embodiment is larger than the comparative example 1 [shown in FIG. 3(b)] in the luminosity wavelength range (light ray wavelength of 500 to 650 nm). Very gentle.

(Example 2)

The surface of the polyethylene terephthalate (PET) film having a thickness of 100 μm (trade name: "A4100", manufactured by Toyobo Co., Ltd.) is not formed on the surface of the easy-adhesion layer, and is coated by gravure coating. The adhesive layer coating liquid of Example 1 was prepared, and the layer thickness was adjusted so that the film thickness was 85 nm.

The coating liquid (N-1) was applied thereon by a bar coater, and the layer thickness was adjusted to have a film thickness of 3 μm. After drying, it was cured by ultraviolet rays of 400 mJ/cm 2 in the atmosphere to obtain a protective layer 12. Next, the first optical interference layer 13a was formed on the protective layer 12, that is, the coating liquid (N-4) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 170 nm. After drying, the atmosphere was exposed to nitrogen. It is hardened by ultraviolet rays of 400 mJ/cm2. Further, the second optical interference layer 13b was formed thereon, that is, the coating liquid (N-7) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 100 nm. After drying, the coating liquid was used in a nitrogen atmosphere at 400 mJ/ The ultraviolet light of cm2 is hardened to produce an antireflection material 10. As shown in FIG. 2, the obtained anti-reflection material 10 is provided with a protective layer 12 on the transparent resin film 11 via the adhesive layer 14, and a first optical interference as the anti-reflection layer 13 is provided on the surface of the protective layer 12. Layer 13a and second optical interference layer 13b.

The results of evaluation of the difference between the sensitivity reflectance of the obtained antireflection material 10 and the reflectance amplitude of the region of the light ray wavelength of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppression effect are shown in Table 1, respectively. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(c). In Fig. 3(c), the maximum value of the difference in reflectance amplitude is represented by X. As shown in FIG. 3(c), it is understood that the spectral center line of the second embodiment is very gentle compared to the comparative example 2 [shown in FIG. 3(d)] in the luminosity wavelength range.

(Example 3)

The coating liquid (N-2) was applied by a bar coater on a cellulose triacetate (TAC) film having a thickness of 80 μm (trade name: "KC8UY", manufactured by Konica Minolta Opto Co., Ltd.), and adjusted. The layer thickness was such that the film thickness was 3 μm, and it was cured by ultraviolet rays of 400 mJ/cm 2 to obtain a protective layer 12. Next, the first optical interference layer 13a was formed on the protective layer 12, that is, the coating liquid (N-4) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 160 nm, and dried under a nitrogen atmosphere. It is hardened by ultraviolet rays of 400 mJ/cm2. Further, the second optical interference layer 13b was formed thereon, that is, the coating liquid (N-6) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 95 nm. After drying, the coating liquid was used in a nitrogen atmosphere at 400 mJ/ The ultraviolet light of cm2 is hardened to produce an antireflection material 10. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(e). As shown in FIG. 3(e), it can be seen that in the luminosity wavelength range, compared with Comparative Example 3 [shown in FIG. 3(f)] or Comparative Example 4 [shown in FIG. 3(h)], Example 3 The spectral centerline is more gradual.

(Example 4)

The antireflection material 10 was produced in the same manner as in Example 3 except that the coating liquid (N-7) was used as the second optical interference layer 13b. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(g). As shown in Fig. 3(g), it is understood that the spectral center line of the fourth embodiment is more gradual than the comparative example 4 [shown in Fig. 3(h)) in the luminosity wavelength range (light ray wavelength of 500 to 650 nm).

(Example 5)

The surface of the polyethylene terephthalate (PET) film having a thickness of 100 μm (trade name: "A4100", manufactured by Toyobo Co., Ltd.) is not formed on the surface of the easy-adhesion layer, and is coated by gravure coating. The cloth was adhered to the coating liquid, and the layer thickness was adjusted to have a film thickness of 10 nm.

The coating liquid (N-3) was applied thereon by a bar coater, and the layer thickness was adjusted to have a film thickness of 3 μm. After drying, it was cured by ultraviolet rays of 400 mJ/cm 2 in the atmosphere to obtain a protective layer 12. Next, the first optical interference layer 13a was formed on the protective layer 12, that is, the coating liquid (N-5) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 155 nm. After drying, the atmosphere was exposed to nitrogen. It is hardened by ultraviolet rays of 400 mJ/cm2. Further, the second optical interference layer 13b was formed thereon, that is, the coating liquid (N-7) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 96 nm. After drying, the coating liquid was used in a nitrogen atmosphere at 400 mJ/ The ultraviolet light of cm2 is hardened to produce an antireflection material 10. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(i). As shown in Fig. 3(i), it can be seen that the spectral center line of Example 5 is well realized in the luminosity wavelength range (light wavelength of 500 to 650 nm) as compared with Comparative Example 5 [shown in Fig. 3(j)]. Smoothed down.

(Comparative Example 1)

In a polyethylene terephthalate (PET) film having a thickness of 100 μm (trade name: "A4100", manufactured by Toyobo Co., Ltd.), the surface of the easy-adhesion layer is not formed, and it is coated by a wire bar coater. The coating liquid (N-2) was adjusted to have a thickness of 3 μm, dried, and then cured by ultraviolet rays of 400 mJ/cm 2 in the atmosphere to obtain a protective layer 12. Next, the first optical interference layer 13a is formed on the protective layer 12, that is, the coating liquid (N-4) is applied by a spin coater, and the layer thickness is adjusted to have a film thickness of 100 nm. After drying, the atmosphere is exposed to nitrogen. It is hardened by ultraviolet rays of 400 mJ/cm2.

Further, the second optical interference layer 13b was formed thereon, that is, the coating liquid (N-6) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 100 nm. After drying, the coating liquid was used in a nitrogen atmosphere at 400 mJ/ The ultraviolet light of cm2 is hardened to produce an antireflection material 10. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(b).

(Comparative Example 2)

The antireflection material 10 was produced in the same manner as in Example 2 except that the coating liquid (N-2) was used as the coating liquid of the first optical interference layer 13a. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(d).

(Comparative Example 3)

The antireflection material 10 was produced in the same manner as in Example 3 except that the film thickness of the layer was adjusted at the time of coating, and the film thickness of the first optical interference layer 13a was changed to 100 nm. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(f).

(Comparative Example 4)

The antireflection material 10 was produced in the same manner as in Example 3 except that the film thickness of the layer was adjusted at the time of coating, and the film thickness of the first optical interference layer 13a was 260 nm. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(h).

(Comparative Example 5)

The coating liquid (N-1) was applied by a bar coater on a cellulose triacetate (TAC) film having a thickness of 80 μm (trade name: "KC8UY", manufactured by Konica Minolta Opto Co., Ltd.), and adjusted. The layer thickness was such that the film thickness was 3 μm, and it was cured by ultraviolet rays of 400 mJ/cm 2 to obtain a protective layer 12. Next, the first optical interference layer 13a was formed on the protective layer 12, that is, the coating liquid (N-3) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 100 nm. After drying, the atmosphere was exposed to nitrogen. It is hardened by ultraviolet rays of 400 mJ/cm2. Further, the second optical interference layer 13b was formed thereon, that is, the coating liquid (N-6) was applied by a spin coater, and the layer thickness was adjusted to have a film thickness of 100 nm. After drying, the coating liquid was used in a nitrogen atmosphere at 400 mJ/ The ultraviolet light of cm2 is hardened to produce an antireflection material 10. Table 1 shows the evaluation results of the difference between the visual reflectance of the obtained antireflection material 10 and the maximum value of the reflectance amplitude of the region in the wavelength range of 500 to 650 nm, the ab chromaticity Cab*, and the coloring suppressing effect. The spectrum of the spectral reflectance of the anti-reflective material 10 is shown in Fig. 3(j).

The results shown in Table 1 indicate that the anti-reflection material 10 produced in Example 1 has a viewing wavelength by controlling the refractive index and film thickness of the protective layer 12, the first optical interference layer 13a, and the second optical interference layer 13b. The reflectance in the range is fixed, and the color unevenness caused by the variation in the film thickness of the coating layer is not remarkable. Further, in Examples 2 and 5, the adhesive layer 14 and the protective layer 12 having a proper refractive index and film thickness were provided, and in Examples 3 and 4, the refractive index (refractive index of the TAC film) ± 0.02 was used. Protective layer 12 within. Therefore, the maximum value of the difference in the reflectance amplitude of the light wavelength of 500 to 650 nm is 0.5% or less, and in addition to the smoothing of the reflectance, the interference unevenness can be reduced, and the coloring caused by the film thickness variation of the coating layer can be more effectively reduced. Uneven. Further, the ab chromaticity Cab* of any of the antireflection materials under the CIE standard light source D65 is 5 or less, and the visual reflectance Y is 1.5% or less, and has both excellent appearance and low reflectance.

On the other hand, in Comparative Example 2, the refractive index of the first optical interference layer 13a was lower than that of the protective layer 12, and in the comparative example 1 and the comparative examples 3 to 5, the film thickness of the first optical interference layer 13a / the second optical interference layer The ratio of the film thickness of 13b is outside the range of 1.6 to 1.8, so the spectrum is not smooth in the wavelength range of the visual sensitivity, and the Ab* value of the ab color is also more than 5. Further, in Comparative Example 1, the adhesive layer 14 was absent, so that the maximum value of the difference in reflectance amplitude of the light wavelength of 500 to 650 nm exceeded 1.0%, the interference unevenness of the protective layer 12 was large, and the oil-repellent appearance appeared on the surface of the anti-reflection layer 13. . Further, in any of the comparative examples, the color unevenness caused by the variation in the film thickness of the coating layer was remarkable.

Further, the above embodiment can be modified and implemented as follows.

‧ A monomer having a carboxyl group, an amine group or the like is added to the composition forming the protective layer 12 to improve the adhesion between the protective layer 12 and the transparent resin film 11.

‧ The protective layer-forming composition may contain a near-infrared ray absorbing agent, an ultraviolet ray absorbing agent, or the like, and the protective layer 12 may exhibit a near-infrared absorbing effect or an ultraviolet absorbing effect, or the transparent resin film 11 may contain a near-infrared absorbing agent or ultraviolet ray. An absorbent or the like is used to exert a near-infrared absorption effect or an ultraviolet absorption effect.

Furthermore, the technical idea obtained by the above embodiment is as follows.

The antireflection material according to any one of claims 1 to 3, wherein the transparent resin film is formed of a polyester resin or cellulose acetate. According to this configuration, in addition to the effects of the invention of any one of claims 1 to 3, the molding is easy and easy to obtain, and the transparent resin film can be set to have a high or low refractive index.

The antireflection material according to any one of claims 1 to 3, wherein an adhesive layer is formed between the transparent resin film and the protective layer. According to the structure of any one of the first to third aspects of the patent application, the adhesion between the transparent resin film and the protective layer can be improved, and the interference of the anti-reflection material can be reduced. All.

The antireflection material according to any one of claims 1 to 3, wherein the protective layer is a polymer cured product of a monomer containing an ultraviolet curable multifunctional acrylate. According to this configuration, in addition to the effects of the invention of any one of claims 1 to 3, the hardness of the protective layer can be improved, and the productivity of the antireflection material can be improved.

The antireflection material according to any one of claims 1 to 3, wherein the second optical interference layer has a refractive index of 1.28 to 1.45. According to this configuration, in addition to the effects of the invention of any one of claims 1 to 3, the second optical interference layer can be made into a sufficiently hard layer, and a sufficient anti-reflection effect can be obtained.

10. . . Anti-reflective material

11. . . Transparent resin film

12. . . The protective layer

13. . . Antireflection layer

13a. . . First optical interference layer

13b. . . Second optical interference layer

Fig. 1 is a schematic cross-sectional view showing the structure of an antireflection material of an embodiment.

Fig. 2 is a schematic cross-sectional view showing another form of the antireflection material.

Fig. 3(a) is a spectrum diagram showing the relationship between the wavelength of light of the first embodiment and the reflectance, and Fig. 3(b) is a spectrum diagram showing the relationship between the wavelength of the light of the comparative example 1 and the reflectance, Fig. 3 (Fig. 3) c) is a spectrum diagram showing the relationship between the wavelength of light of the second embodiment and the reflectance, and Fig. 3(d) is a spectrum diagram showing the relationship between the wavelength of the light of Comparative Example 2 and the reflectance, and Fig. 3(e) shows Fig. 3 is a spectrum diagram showing the relationship between the wavelength of light and the reflectance in the third embodiment, Fig. 3(f) is a spectrum diagram showing the relationship between the wavelength of the light of Comparative Example 3 and the reflectance, and Fig. 3(g) is a diagram showing the relationship of the fourth embodiment. A spectrum of the relationship between the wavelength of the light and the reflectance, Fig. 3(h) is a spectrum showing the relationship between the wavelength of the light of Comparative Example 4 and the reflectance, and Fig. 3(i) is a diagram showing the wavelength and reflection of the light of Example 5. The spectrum of the relationship of the rate, Fig. 3 (j) shows the spectrum of the relationship between the wavelength of the light of Comparative Example 5 and the reflectance.

10. . . Anti-reflective material

11. . . Transparent resin film

12. . . The protective layer

13. . . Antireflection layer

13a. . . First optical interference layer

13b. . . Second optical interference layer

Claims (4)

An antireflection material having at least a protective layer, a first optical interference layer, and a second optical interference layer laminated on a transparent resin film, wherein a refractive index of the first optical interference layer is higher than a refractive index of the protective layer The difference between the refractive indices of the two is 0.01 to 0.05, and the refractive index of the second optical interference layer is lower than the refractive index of the first optical interference layer, and the film thickness of the first optical interference layer and the film thickness of the second optical interference layer are The ratio is 1.6 to 1.8. The anti-reflection material according to claim 1, wherein a maximum value of a difference in reflectance amplitude of a region of a light wavelength of 500 to 650 nm is 1% or less, and based on a CIS standard light source D65 of JIS Z8720, based on JIS Z8729 The ab chromaticity Cab*={(a*) ² +(b*) ² } ^1/2 is 5 or less. The antireflection material according to the first or second aspect of the invention, wherein the sensibility reflectance Y based on JIS Z8701 is 1.5% or less under the CIS standard light source D65 of JIS Z8720. An electronic image display device comprising the antireflection material according to any one of claims 1 to 3 in front of the display.