JP5163231B2 - Anti-reflective material and electronic image display device including the same - Google Patents

Anti-reflective material and electronic image display device including the same Download PDF

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JP5163231B2
JP5163231B2 JP2008091537A JP2008091537A JP5163231B2 JP 5163231 B2 JP5163231 B2 JP 5163231B2 JP 2008091537 A JP2008091537 A JP 2008091537A JP 2008091537 A JP2008091537 A JP 2008091537A JP 5163231 B2 JP5163231 B2 JP 5163231B2
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refractive index
optical interference
reflectance
hard coat
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JP2009244623A (en
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孝之 野島
裕史 矢野
昌紀 山本
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日油株式会社
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  In the present invention, the reflectance in the visibility wavelength range (light wavelength of 500 to 650 nm) is made constant (hereinafter referred to as flattening of the reflectance) to suppress uneven coloring due to film thickness variation of the coating layer. The present invention relates to an anti-reflective material capable of producing an image and an electronic image display device including the same.

  In recent years, electronic displays are widely used for televisions and monitors. In particular, displays are becoming thinner and larger, and plasma displays (PD), liquid crystal displays (LCD), organic EL displays (OELD), and the like are attracting attention. In order to improve visibility, these large displays are required to be subjected to antireflection treatment and at the same time to have a low-reflection material with less coloring due to the problem of color reproducibility.

  For example, a medical display capable of displaying a high-quality image without reflection and coloring as a diagnostic image has been proposed (see, for example, Patent Document 1). The antireflection film used in this medical display has a transparent support, a hard coat layer provided thereon, and an antireflection layer provided on the hard coat layer, and the antireflection layer is transparently supported. It is formed of three layers of a medium refractive index layer, a high flexibility layer, and a low flexibility layer from the body side. And the color (a * value, b * value) of the regular reflection light with respect to the CIE standard illuminant D65 is set in a specific range.

Furthermore, the applicant of the present application has proposed a reduced reflection material in which a hard coat layer is provided on a transparent resin film and a reduced reflection layer is provided on the hard coat layer (see, for example, Patent Document 2). In this reduced reflection material, the maximum difference in the amplitude of the reflectance at a light wavelength of 500 to 650 nm is 1% or less, the luminous reflectance for the CIE standard illuminant D65 is 2% or less, and the ab chroma Cab * for the CIE standard illuminant D65. = {(A *) 2 + (b *) 2 } 1/2 is set to 10 or less.
JP 2004-295055 A (2nd page, 5th page and 18th page) JP 2006-116754 A (page 2, page 3 and page 12)

  However, in the antireflection film disclosed in Patent Document 1, although the antireflection layer (decrease reflection layer) has a three-layer structure and is excellent in the antireflection property, the reflectivity varies greatly in the visibility wavelength range and is constant. Not flat. That is, the film thickness variation is likely to occur in the antireflection layer, coloring unevenness is seen due to the film thickness variation, and the coloring reduction effect cannot be sufficiently exhibited.

  Moreover, in the reduced reflection material of patent document 2, when a reduced reflection layer is comprised with a high refractive index layer and a low refractive index layer, those film thickness ratios are 1.0-1.1 ( Example 4 and Example 7 of Patent Document 2). For this reason, in the reduced reflection material of Patent Document 2, the fluctuation in the reflectance spectrum with respect to the wavelength of light in the visibility wavelength range becomes large, and it is difficult to make the reflectance constant. Due to such a difference, there is a problem that uneven coloring of the anti-reflection material cannot be suppressed.

  Accordingly, an object of the present invention is to provide a reduced reflection material capable of making the reflectance constant in the visibility wavelength range and suppressing uneven coloring due to film thickness variation of the coating layer, and an electronic image display including the same. To provide an apparatus.

  In the present invention, the antireflection material of the first invention is obtained by laminating at least a hard coat layer, a first optical interference layer, and a second optical interference layer in this order on a transparent resin film. The refractive index of the first optical interference layer is higher than the refractive index of the hard coat layer, the refractive index difference is 0.01 to 0.05, and the refractive index of the second optical interference layer is the first optical interference. It is lower than the refractive index of the layer, and the ratio of the thickness of the first optical interference layer / the thickness of the second optical interference layer is 1.6 to 1.8.

The anti-reflection material of the second invention is the CIE standard illuminant D65 according to the first invention, wherein the maximum value of the difference in the amplitude of the reflectance in the light wavelength region of 500 to 650 nm is 1% or less, and based on JIS Z8720. Ab chroma Cab * = {(a *) 2 + (b *) 2 } 1/2 based on JIS Z8729 is 5 or less.

  In the first or second invention, the reduced reflection material according to the third invention is characterized in that the visibility reflectance Y based on JIS Z8701 against the CIE standard illuminant D65 based on JIS Z8720 is 1.5% or less. .

  According to a fourth aspect of the present invention, there is provided an electronic image display apparatus comprising the antireflection material according to any one of the first to third aspects on a front surface of a display.

According to the present invention, the following effects can be exhibited.
In the antireflection material of the first invention, the refractive index of the first optical interference layer is higher than the refractive index of the hard coat layer, the refractive index difference is 0.01 to 0.05, and the second optical interference layer The refractive index is set lower than the refractive index of the first optical interference layer, and the ratio of the thickness of the first optical interference layer / the thickness of the second optical interference layer is set to 1.6 to 1.8. For this reason, the reflectance (reflection spectrum) in the visibility wavelength range of the anti-reflective material can be made close to (flattened), and fluctuations in the reflection spectrum with respect to the wavelength of light can be suppressed. Therefore, the reflectance can be made constant in the visibility wavelength range, and coloring unevenness due to the film thickness variation of the coating layer can be suppressed.

In the antireflection material of the second invention, the maximum value of the difference in reflectance amplitude in the light wavelength region of 500 to 650 nm is 1% or less, and ab based on JIS Z8729 against CIE standard illuminant D65 based on JIS Z8720 Chroma Cab * = {(a *) 2 + (b *) 2 } 1/2 is 5 or less. For this reason, in addition to the effects of the first invention, it is possible to effectively suppress interference unevenness due to the difference in refractive index between the transparent resin film and the hard coat layer, and the first optical interference layer and the second optical interference layer. Coloring derived from the structure of the reduced antireflection layer can be suppressed.

  In the reduced reflection material according to the third aspect of the invention, the visibility reflectance Y based on JIS Z8701 against the CIE standard illuminant D65 based on JIS Z8720 is 1.5% or less. For this reason, in addition to the effect of 1st or 2nd invention, since the visibility reflectance is low, the reduced reflection material which was more excellent in visibility can be provided.

  According to a fourth aspect of the present invention, there is provided an electronic image display device comprising the antireflection material on a front surface of a display. Therefore, in the electronic image display device, the effect of the antireflection material of any one of the first to third inventions can be exhibited.

Hereinafter, embodiments that are considered to be the best modes of the present invention will be described in detail.
[Anti-reflective material]
As shown in FIG. 1, the reduced reflection material 10 of the present embodiment includes at least a hard coat layer 12 on a transparent resin film 11, a first optical interference layer 13 a as a reduced reflection layer 13, and a reduced reflection layer 13 as well. The second optical interference layer 13b is laminated in this order. And the refractive index of the 1st optical interference layer 13a is higher than the refractive index of the hard-coat layer 12, the refractive index difference is 0.01-0.05, and the refractive index of the 2nd optical interference layer 13b is 1st. The ratio of the film thickness of the first optical interference layer 13a / the film thickness of the second optical interference layer 13b is 1.6 to 1.8 lower than the refractive index of the optical interference layer 13a.

  The refractive index of the first optical interference layer 13a is higher than the refractive index of the hard coat layer 12, the refractive index difference is set to 0.01 to 0.05, and the refractive index of the second optical interference layer 13b is set to the first optical. The ratio of the thickness of the first optical interference layer 13a / the thickness of the second optical interference layer 13b is set to 1.6 to 1.8, which is lower than the refractive index of the interference layer 13a. With such a configuration, it is possible to suppress the variation in reflectance, achieve flattening of the reflectance, and suppress uneven coloring. For this reason, the uneven coloring based on the variation in the film thickness can be effectively suppressed.

Further, in the reduced reflection material 10, the maximum value of the difference in the amplitude of the reflectance in the region of the visibility wavelength range (light wavelength 500 to 650 nm) is preferably 1% or less, and 0.5% or less. Is more preferable. When this maximum value is larger than 1%, the uneven interference caused by the difference in refractive index between the transparent resin film 11 and the hard coat layer 12 becomes conspicuous, and it becomes difficult to suppress the uneven coloring, which is not preferable. The lower limit of the maximum value is about 0.1%. In addition, ab chroma Cab * = {(a *) 2 + (b *) 2 } 1/2 based on JIS Z8729 against CIE standard illuminant (light source) D65 based on JIS Z8720 is preferably 5 or less, and 4 or less It is more preferable that When this value exceeds 5, it becomes difficult to suppress uneven coloring, which is not preferable. Note that the lower limit of this value is about 0.1.

  In addition, the anti-reflective material 10 preferably has a visibility reflectance Y based on JIS Z8701 of CIE standard illuminant D65 based on JIS Z8720 of 1.5% or less, and more preferably 1.0% or less. When the visibility reflectance Y exceeds 1.5%, the reflection becomes so large that the visibility of the image of the electronic image display device is lowered, which is not preferable. Note that the lower limit of the visibility reflectance Y is about 0.1%.

As shown in FIG. 2, the antireflection material 10 may have a configuration in which an adhesive layer 14 is provided between the transparent resin film 11 and the hard coat 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. As a transparent resin base material for forming the transparent resin film 11 having a low refractive index (1.45 to 1.55), for example, acetyl cellulose (cellulose acetate) such as triacetyl cellulose (TAC, n = 1.48), An acrylic resin (AC, n = 1.50) etc. are mentioned. Moreover, as a transparent resin base material with a high refractive index (1.55 to 1.70), for example, polyester resin such as polyethylene terephthalate (PET, n = 1.65), polycarbonate (PC, n = 1.59) , Polyarylate (PAR, n = 1.60), polyether sulfone (PES, n = 1.65) and the like. Among these, a TAC film is preferable as the transparent resin film 11 with a lower refractive index, and a PET film is preferable as the transparent resin film 11 with a higher refractive index, from the viewpoint of ease of molding and availability.

Moreover, the film thickness of the transparent resin film 11 becomes like this. Preferably it is 25-400 micrometers, More preferably, it is 40-200 micrometers. When this film thickness is less than 25 μm or more than 400 μm, the handleability of the anti-reflective material 10 at the time of manufacture and use is unfavorable. The transparent resin film 11 may contain various additives. Examples of such additives include ultraviolet absorbers, antistatic agents, stabilizers, plasticizers, lubricants, flame retardants, and the like.
(Hard coat layer 12)
Next, the hard coat layer 12 will be described. The refractive index of the hard coat layer 12 is preferably in the range of 1.45 to 1.70. When the refractive index of the hard coat layer 12 is less than 1.45 or exceeds 1.70, interference unevenness resulting from the difference in refractive index between the transparent resin film 11 and the hard coat layer 12 appears remarkably, which is not preferable. Moreover, it is preferable that the film thickness of the hard-coat layer 12 is 1-10 micrometers. When the film thickness of the hard coat layer 12 is less than 1 μm, it is not preferable because sufficient surface strength cannot be obtained. On the other hand, when the film thickness exceeds 10 μm, problems such as a decrease in flex resistance of the hard coat layer 12 occur, which is not preferable.

  The hard coat layer 12 is not particularly limited as long as the refractive index and the film thickness are within the above ranges. Examples of the material for forming the hard coat layer 12 include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and cured products such as reactive silicon compounds such as tetraethoxysilane. Here, (meth) acrylate means a concept including both acrylate and methacrylate. The same applies to the following compounds. Among these, a polymerized cured product of a composition containing an ultraviolet curable polyfunctional acrylate is particularly preferable from the viewpoint of both productivity and hardness.

  It does not specifically limit as a composition containing a ultraviolet curable polyfunctional acrylate. For example, dipentaerythritol hexaacrylate, tetramethylol methane tetraacrylate, tetramethylol methane triacrylate, trimethylol propane triacrylate, 1,6-hexanediol diacrylate, 1,6-bis (3-acryloyloxy-2-hydroxypropyl) Examples thereof include acrylic derivatives of polyfunctional alcohols such as oxy) hexane, polyethylene glycol diacrylate, polyurethane acrylate, and those commercially available as ultraviolet curable hard coat materials.

  The composition containing an ultraviolet curable polyfunctional acrylate usually contains other components, but the other components are not particularly limited. Examples of other components include inorganic or organic fine particle fillers, inorganic or organic fine particle pigments, and other inorganic or organic fine particles, polymers, polymerization initiators, polymerization inhibitors, antioxidants, dispersants, Examples thereof include additives such as surfactants, light stabilizers and leveling agents. Further, any amount of solvent can be added as long as it is dried after film formation in the wet coating method.

  The method for forming the hard coat layer 12 is not particularly limited. When an organic material is used, the hard coat layer 12 can be formed by a general wet coat method such as a roll coat method or a die coat method. The formed layer can be subjected to a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams, as necessary.

  The anti-reflective member 10 can achieve flattening of the reflectance by adjusting (controlling) the refractive index and film thickness of the first optical interference layer 13a and the second optical interference layer 13b. It is preferable that the maximum value of the difference in reflectance amplitude in the region of ˜650 nm is 1% or less. As a result, the interference unevenness caused by the difference in refractive index between the transparent resin film 11 and the hard coat layer 12 can be reduced, so that the effect of the present invention, that is, the uneven coloring due to the film thickness variation of the coating layer can be further suppressed. Can do. For that purpose, it is further preferable to satisfy the following requirements. Here, the case of the TAC film and PET film which are the typical transparent resin films 11 is demonstrated. When the TAC film is used, it is important that the refractive index of the hard coat layer 12 is in the range of (refractive index of the TAC film) ± 0.03. More preferably, the refractive index of the hard coat layer 12 is in the range of (refractive index of the TAC film) ± 0.02. If the refractive index of the hard coat layer 12 exceeds (refractive index of the transparent resin film 11) ± 0.03, the interference unevenness is clearly recognized, which is not preferable.

When the hard coat layer 12 is formed on the TAC film by the wet coating method, a solvent that erodes the surface of the TAC film, for example, methyl ethyl ketone, methyl acetate, ethyl acetate or the like, is used alone or mixed with any solvent. Then, when the interface between the TAC film and the hard coat layer 12 is disturbed, the interference effect between the TAC film and the hard coat layer 12 is suppressed. For this reason, in addition to the effect of the refractive index difference, interference unevenness can be more effectively suppressed.
(Adhesive layer 14)
When using a PET film, it is desirable to reduce interference unevenness by laminating the adhesive layer 14 and the hard coat layer 12 on the PET film from the transparent resin film 11 side. The refractive index of the PET film, the adhesive layer 14 and the hard coat layer 12 preferably satisfies the relationship of the refractive index of the PET film> the refractive index of the adhesive layer 14> the refractive index of the hard coat layer 12. At this time, it is desirable to adjust the refractive index and film thickness of the adhesive layer 14 according to the refractive index of the hard coat layer 12 to be used. When the refractive index of the hard coat layer 12 is 1.45 to 1.60, the refractive index of the adhesive layer 14 is {(refractive index of the PET film)} × (refractive index of the hard coat layer 12)} 1/2 The film thickness is adjusted within a range of ± 0.03 and a thickness of 70 to 130 nm. The refractive index of the adhesive layer 14 is preferably within the above range, and more preferably {(refractive index of the PET film) × (refractive index of the hard coat layer 12)} 1/2 ± 0.02. . When the refractive index of the adhesive layer 14 is {(refractive index of the PET film) × (refractive index of the hard coat layer 12)} 1/2 , the interference unevenness can be reduced most.

  Moreover, when the refractive index of the hard-coat layer 12 is 1.61-1.70, it is preferable that the film thickness of the contact bonding layer 14 shall be 20 nm or less. The film thickness of the adhesive layer 14 is more preferably 10 nm or less. When the film thickness of the adhesive layer 14 exceeds 20 nm, interference unevenness becomes conspicuous, which is not preferable.

  The adhesive layer 14 contains a polymer binder and fine particles. The polymer binder is preferably a polyester resin and a mixture of an acrylic resin having an oxazoline group and a polyalkylene oxide chain from the viewpoint of imparting good adhesiveness. The polymer binder is preferably soluble or dispersible in water, but water-soluble one containing some organic solvent can also be used. The content ratio of the polyester resin constituting the polymer binder of the adhesive layer 14 in the adhesive layer 14 is preferably 5 to 95% by mass, and more preferably 50 to 90% by mass. The content of the acrylic resin having an oxazoline group and a polyalkylene oxide chain constituting the polymer binder of the adhesive layer 14 in the adhesive layer 14 is preferably 5 to 95% by mass, more preferably 10 to 50% by mass. .

  When the polyester resin exceeds 95% by mass, or the acrylic resin having an oxazoline group and a polyalkylene oxide chain is less than 5% by mass, the cohesive force of the adhesive layer 14 is reduced, and the adhesiveness and adhesion to the hard coat layer 12 are reduced. The expression of the adhesive strength of the layer 14 may be insufficient, which is not preferable. When the acrylic resin having an oxazoline group and a polyalkylene oxide 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 hard coat layer 12 is insufficient. Or the expression of the adhesive strength of the adhesive layer 14 may be insufficient.

  As the fine particles constituting the adhesive layer 14, it is preferable to use composite inorganic particles of silica and titania. The composite inorganic particles of silica and titania can arbitrarily adjust the refractive index, and can easily adjust the refractive index. The difference in refractive index between the polymer binder and the fine particles of the adhesive layer 14 is preferably within 0.02 and more preferably within 0.01. If the difference in refractive index exceeds 0.02, light is greatly scattered due to the difference in refractive index at the boundary between the polymer binder and the fine particles, the haze value of the adhesive layer 14 is increased, and the transparency is deteriorated. Absent.

  The average particle diameter of the fine particles is preferably in the range of 40 to 120 nm. If the average particle size is larger than 120 nm, the particles are likely to fall off. On the other hand, if the average particle size is smaller than 40 nm, sufficient lubricity and scratch resistance may not be obtained. The content of the fine particles is preferably 0.1 to 10% by mass with respect to the adhesive layer 14. If the content is less than 0.1% by mass, sufficient lubricity and scratch resistance cannot be obtained. On the other hand, if the content exceeds 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 0.5 to 30% by mass, and more preferably 1 to 10% by mass. When this content is less than 0.5% by mass, the lubricity of the surface of the adhesive layer 14 may not be obtained, which is not preferable. When it is more than 30% by mass, the adhesiveness to the transparent resin film 11 and the hard coat layer 12 tends to be insufficient, which is not preferable. Specific examples of the aliphatic wax include carnauba wax, candelilla wax, rice wax, wood wax, palm wax, montan wax, ozokerite, ceresin wax, paraffin wax, polyethylene glycol, polypropylene glycol, water dispersible or water soluble Waxes are preferred.

In order to provide the adhesive layer 14 on the transparent resin film 11, the coating liquid is applied to one or both sides of the transparent resin film 11. The application can be carried out at an arbitrary stage, but it is preferable that it is carried out during the production process of the transparent resin film 11 with good efficiency. As the coating method, any known coating method can be employed. For example, a gravure coating method, a roll brush method, a spray coating method, an air knife method, a coil bar method, a dip coating method and the like can be mentioned.
(Reducing reflection layer 13)
Next, the antireflection layer 13 will be described. The reduced reflection layer 13 includes 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 higher than that of the hard coat layer 12 and the second optical interference layer 13b, and the refractive index difference between the first optical interference layer 13a and the hard coat layer 12 is 0.01 to 0.05. Set to The refractive index difference is preferably 0.01 to 0.03. When this difference in refractive index is smaller than 0.01, the reflected light at the interface between the hard coat layer 12 and the first optical interference layer 13a becomes too weak, which is not preferable. On the other hand, when the difference in refractive index is larger than 0.05, the reflected light at the interface between the hard coat layer 12 and the first optical interference layer 13a becomes too strong, and flattening of the reflectance can be achieved. Since it disappears, it is not preferable.

  Furthermore, 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 is preferably 1.28 to 1.45. When the refractive index is less than 1.28, it is difficult to form a sufficiently hard layer. On the other hand, when the refractive index exceeds 1.45, a sufficient antireflection effect can be obtained particularly by the wet coating method. Is difficult.

  Subsequently, 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 the film thickness of the first optical interference layer 13a / the film thickness of the second optical interference layer 13b = 1.6 to It is set 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 film thickness fluctuation becomes large, and flattening of the reflectance cannot be achieved.

  The method for forming the antireflection layer 13 is not particularly limited, and for example, a dry coating method, a wet coating method, or the like can be employed. Among these methods, the wet coating method is particularly preferable in terms of productivity and production cost. A known method is employed as the wet coating method, and examples thereof include a roll coating method, a spin coating method, and a dip coating method. Among these, a method capable of continuously forming the antireflection layer 13 such as a roll coating method is preferable from the viewpoint of productivity.

  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, tantalum oxide, yttrium oxide, ytterbium oxide, zirconium oxide, indium tin oxide, and antimony-containing tin oxide. In particular, the use of conductive fine particles such as indium tin oxide and antimony-containing tin oxide is preferable because the surface resistivity can be lowered and the antistatic ability can be imparted. On the other hand, as the organic material, for example, a material obtained by polymerizing and curing a composition containing a polymerizable monomer having a fluorene skeleton can be used.

  As a material constituting the second optical interference layer 13b, an inorganic substance such as silicon oxide, lanthanum fluoride, magnesium fluoride, cerium fluoride, a fluorine-containing organic compound alone or a mixture, or a polymer of a fluorine-containing organic compound is used. Compositions containing can be used. Further, a monomer containing no fluorine (abbreviated as a non-fluorine monomer) or a polymer can be used as a binder. Among these, silicon oxide-based fine particles, particularly hollow silicon oxide-based fine particles and fluorine-containing organic compounds are particularly preferable because of their low refractive index.

  Examples of the hollow silicon oxide fine particles include those having cavities inside the outer shell and porous silica fine particles. The average particle diameter of the fine particles preferably does not greatly exceed the film thickness of the second optical interference layer 13b, and is particularly preferably 0.1 μm or less. When the average particle size is increased, scattering occurs and the haze value increases, so that it is not suitable as the antireflection material 10. Further, the surface of the fine particles can be modified with various coupling agents as required. Examples of the various coupling agents include organically substituted silicon compounds, metal alkoxides such as aluminum, titanium, zirconium, and antimony, and organic acid salts. In particular, a film having high hardness can be formed by modifying the surface with a reactive group such as a (meth) acryloyl group.

  The fluorine-containing organic compound is not particularly limited. For example, fluorine-containing monofunctional (meth) acrylate, fluorine-containing polyfunctional (meth) acrylate, fluorine-containing itaconic acid ester, fluorine-containing maleic acid ester, fluorine-containing silicon compound And the like, and polymers thereof. Among these, fluorine-containing (meth) acrylate is preferable from the viewpoint of reactivity, and fluorine-containing polyfunctional (meth) acrylate is particularly preferable from the viewpoint of hardness and refractive index. By curing these fluorine-containing organic compounds, the second optical interference layer 13b having a low refractive index and high hardness can be formed.

  Examples of the fluorine-containing monofunctional (meth) acrylate include 1- (meth) acryloyloxy-1-perfluoroalkylmethane, 1- (meth) acryloyloxy-2-perfluoroalkylethane, and the like. Examples of the perfluoroalkyl group include linear, branched or cyclic groups having 1 to 8 carbon atoms.

  As the fluorine-containing polyfunctional (meth) acrylate, fluorine-containing bifunctional (meth) acrylate, fluorine-containing trifunctional (meth) acrylate and fluorine-containing tetrafunctional (meth) acrylate are preferable. Examples of the fluorine-containing bifunctional (meth) acrylate include 1,2-di (meth) acryloyloxy-3-perfluoroalkylbutane, 2-hydroxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′. , 2′-bis {(meth) acryloyloxymethyl} propionate, α, ω-di (meth) acryloyloxymethyl perfluoroalkane and the like. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms, and the perfluoroalkane group is preferably a linear group. These fluorine-containing bifunctional (meth) acrylates can be used alone or as a mixture when used.

  Examples of the fluorine-containing trifunctional (meth) acrylate include, for example, 2- (meth) acryloyloxy-1H, 1H, 2H, 3H, 3H-perfluoroalkyl-2 ′, 2′-bis {(meth) acryloyloxy Methyl} propionate. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 11 carbon atoms.

  Examples of fluorine-containing tetrafunctional (meth) acrylates include α, β, ψ, ω-tetrakis {(meth) acryloyloxy} -αH, αH, βH, γH, γH, χH, χH, ψH, ωH, ωH- Perfluoroalkane and the like are preferable. The perfluoroalkane group is preferably a linear one having 1 to 14 carbon atoms. In use, the fluorine-containing tetrafunctional (meth) acrylate can be used alone or as a mixture.

  As a specific example of the fluorine-containing silicon compound, (1H, 1H, 2H, 2H-perfluoroalkyl) trimethoxysilane and the like are preferable. The perfluoroalkyl group is preferably a linear, branched or cyclic group having 1 to 10 carbon atoms. Examples of the polymer of the fluorinated organic compound or the polymer of the other fluorinated monomer include a homopolymer, a copolymer, or a copolymer with a non-fluorinated monomer of the fluorinated monomer. Linear polymers such as, polymers containing carbocycles or heterocycles in the chain, cyclic polymers, comb polymers, and the like. A conventionally well-known thing can be used as said non-fluorine-type monomer. Examples thereof include silicon compounds such as monofunctional or polyfunctional (meth) acrylates and tetraethoxysilane.

  The antireflection layer 13 may contain other components as long as the effects of the present invention are not impaired in addition to the above compounds. Other components are not particularly limited, and for example, inorganic or organic pigments, polymers, polymerization initiators, photopolymerization initiators, polymerization inhibitors, antioxidants, dispersants, surfactants, light stabilizers, leveling Additives such as an agent. Further, any amount of solvent can be added as long as it is dried after film formation in the wet coating method. The anti-reflection layer 13 is formed by performing a curing reaction by irradiation with an active energy ray such as an ultraviolet ray or an electron beam or heating, if necessary, after being formed by wet coating. The curing reaction using active energy rays is preferably performed in an inert gas atmosphere such as nitrogen or argon.

In the antireflection material 10, an adhesive layer can be formed on the surface of the transparent resin film 11 opposite to the hard coat layer 12 and the antireflection layer 13. Although it does not restrict | limit especially as a material used for this adhesion layer, For example, an acrylic resin adhesive, a silicone adhesive, a ultraviolet curable adhesive, a thermosetting adhesive, etc. are mentioned. This adhesive layer can be provided with one or more functions such as blocking light in a specific wavelength range, improving contrast, and correcting color tone. For example, if the transmitted light color of the anti-reflective material 10 is yellowish or the like, it is possible to correct the color tone by adding a dye or the like.
[Electronic image display device]
The anti-reflective member 10 of the present embodiment can be suitably used for applications that require an effect of improving color reproducibility, an effect of suppressing unevenness of light interference, and an effect of reducing reflection. In particular, the electronic image display device is used in front of the display. Examples of the electronic image display device include a plasma display, a liquid crystal display, and a cathode ray tube. And it can be made to adhere to the board arrange | positioned directly on the display (screen) surface or the front surface of a display through an adhesion layer.
[Summary of Effects and Effects of Embodiment]
In the reduced reflection material 10 according to the present embodiment, the refractive index of the first optical interference layer 13a is higher than the refractive index of the hard coat layer 12, the refractive index difference is 0.01 to 0.05, and the second optical The refractive index of the interference layer 13b is set lower than the refractive index of the first optical interference layer 13a, and the ratio of the film thickness of the first optical interference layer 13a / the film thickness of the second optical interference layer 13b is 1.6 to 1.8. Is set to For this reason, the flatness of the reflectance in the visibility wavelength range of the anti-reflection material 10 can be achieved. Accordingly, the colors in the flat wavelength range appear to be mixed and appear not to be colored whitish. When the reflection spectrum becomes V-shaped, a complementary color having a wavelength at the bottom of the V-shape can be seen. For this reason, when the reflection spectrum fluctuates due to fluctuations in the film thickness of the first optical interference layer 13a and the second optical interference layer 13b, and the wavelength at the bottom of the V shape shifts, various colors appear depending on the location, and uneven coloring is observed. Occurs. Therefore, in the reduced reflection material 10, the reflectance can be made constant in the visibility wavelength range, and coloring unevenness due to the film thickness variation of the coating layer can be suppressed.

Further, in the anti-reflection material 10, the maximum value of the difference in the amplitude of the reflectance in the light wavelength region of 500 to 650 nm is 1% or less, and the ab chroma is based on JIS Z8729 against the CIE standard illuminant D65 based on JIS Z8720. Cab * = {(a *) 2 + (b *) 2 } 1/2 is 5 or less. For this reason, while being able to suppress effectively the interference nonuniformity resulting from the refractive index difference of the transparent resin film 11 and the hard-coat layer 12, the antireflection layer 13 which consists of the 1st optical interference layer 13a and the 2nd optical interference layer 13b. The coloring derived from the structure of can be suppressed.

  Furthermore, in the anti-reflective material 10, the visibility reflectance Y based on JIS Z8701 with respect to the CIE standard illuminant D65 based on JIS Z8720 is 1.5% or less. Thus, since the visibility reflectance is low, it is possible to provide the reduced reflection material 10 with more excellent visibility.

  -An electronic image display apparatus equips the front surface of a display with the said low reflection material 10. FIG. Therefore, in the electronic image display device, the effect of the above-described antireflection material 10 can be exhibited. Therefore, the antireflection material 10 can be suitably applied to a plasma display or a liquid crystal display.

Hereinafter, although the said embodiment is described more concretely, giving a manufacture example, an Example, and a comparative example, this invention is not limited to the range of these Examples. In addition, the refractive index of the hardened | cured material of the coating liquid for the antireflection layers 13 prepared by the manufacture example was measured by the method shown below.
(1) An acrylic resin plate having a refractive index of 1.49 (trade name: “Delagrass A”, manufactured by Asahi Kasei Chemicals Corporation) and a dip coater (manufactured by Sugiyama Genroku Riki Co., Ltd.) for the antireflection layer 13 The coating liquid was applied with the layer thickness adjusted so that the optical film thickness was about 550 nm with a dry film thickness.
(2) After drying the solvent, if necessary, use a 120 W high-pressure mercury lamp in a nitrogen atmosphere with an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) to irradiate 400 mJ of ultraviolet light to form a coating solution for the antireflection layer 13. Cured.
(3) The back of the acrylic resin plate is roughened with sandpaper, and the black paint is applied to the spectrophotometer [“U-Best V560”, manufactured by JASCO Corporation] at 5 ° to −5 ° at 400 to 650 nm. The regular reflectance was measured, and the minimum or maximum value of the reflectance was read.
(4) The refractive index was calculated from the extreme value of the reflectance using the following formula.

The physical properties of the obtained antireflection material 10 were evaluated by the following methods.

  1) Spectral reflectance: A spectrophotometer ["U-Best V560", manufactured by JASCO Corporation, the back surface of the anti-reflective material 10 (the back surface of the transparent resin film 11) roughened with sandpaper and painted with black paint. ], 5 ° and −5 ° regular reflection spectra of light having a wavelength of 380 to 780 nm were measured. Thereby, the reflection spectrum of the reduced reflection layer 13 can be measured.

  2) Visibility reflectance Y: XYZ color specification defined in JIS Z8701 using the spectral reflectance of the above-measured light wavelength of 380 to 780 nm and the relative spectral distribution of CIE standard illuminant D65 based on JIS Z8720 The tristimulus value Y (%) of the object color due to reflection in the system was calculated.

  3) Maximum value of difference in amplitude of reflectance at light wavelength of 500 to 650 nm: Difference in amplitude of reflectance (%) at wavelength of light from 500 to 650 nm from reflection spectrum obtained by spectral reflectance measurement The maximum value of was read.

4) ab chroma Cab *: color space CIE 1976L defined in JIS Z8729 using the spectral reflectance of light of 380 to 780 nm measured in 1) above and the relative spectral distribution of CIE standard illuminant D65 based on JIS Z8720. * a * b * color system was calculated, and ab chroma Cab * = {(a *) 2 + (b *) 2 } 1/2 was calculated from the obtained a * value and b * value.

5) Coloring suppression effect: A sample in which a low reflection film was bonded to one side of a glass plate having a size of 10 cm in length and 10 cm in width using an acrylic resin-based adhesive sheet and a black film was bonded to the other side was prepared. . The sample is observed under a fluorescent lamp that is not a three-wavelength fluorescent lamp (for example, Palook (FL20SS D / 18) manufactured by Matsushita Electric Industrial Co., Ltd.), and the color unevenness due to the film thickness variation of the coating layer is observed. Moreover, it observed under three wavelength fluorescent lamp [For example, Matsushita Electric Industrial Co., Ltd. product Palook (FL20SS EX-N / 18)], and the appearance of interference nonuniformity was evaluated, respectively. As evaluation criteria, the case where no interference unevenness or coloring unevenness was seen was evaluated as ◎, the case where interference unevenness was visible but the color unevenness was not visible was evaluated as ○, and the case where coloring unevenness was observed regardless of the interference unevenness was evaluated as ×.
[Production Example 1, Preparation of Coating Solution Forming Adhesive Layer 14 (hereinafter referred to as Adhesive Layer Coating Solution)]
(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 5-sodium sulfoisophthalate, 36 parts by mass of ethylene glycol, and 3 parts by mass of diethylene glycol were charged into the reactor. 0.05 part by mass of tetrabutoxytitanium was added, the temperature was adjusted to 230 ° C. and heated in a nitrogen atmosphere, and the produced methanol was distilled off to conduct a transesterification reaction. Subsequently, the temperature of the reaction system was gradually raised to 255 ° C., and the inside of the system was reduced in pressure to 133 Pa (1 mmHg) to carry out a polycondensation reaction to obtain polyester 1 (Tg = 71 ° C., mass average molecular weight 16000).
(2) Synthesis of Acrylic Resin Aqueous Dispersion In a four-necked flask, 302 parts by mass of ion-exchanged water was charged and heated to 60 ° C. in a nitrogen stream, and then 0.5 parts by mass of ammonium persulfate as a polymerization initiator, 0.2 part by mass of sodium hydrogen nitrate was added, and further, as a monomer, 23.3 parts by mass of methyl methacrylate, 22.6 parts by mass of 2-isopropenyl-2-oxazoline, polyethylene oxide (n = 10) methacrylic acid A mixture of 40.7 parts by mass and 13.3 parts by mass of acrylamide was added dropwise over 3 hours while adjusting the liquid temperature to 60 to 70 ° C. The reaction was continued with stirring while maintaining the same temperature range for 2 hours after the completion of the dropping, and then cooled to obtain an acrylic resin aqueous dispersion (Tg = 50 ° C.) having a solid content of 25% by mass.
(3) Synthesis of Composite Inorganic Particles of Silica and Titania 140 parts by mass of methanol, 260 parts by mass of isopropanol and 100 parts by mass of aqueous ammonia (25% by mass) were charged in a 4 liter glass reaction vessel with a stirring blade. A liquid was prepared and stirred while maintaining the temperature of the reaction liquid at 40 ° C. Next, 542 parts by mass of silicon tetramethoxide [Si (OMe) 4 , Colcoat Co., Ltd., trade name; methyl silicate 39] was charged into a 3 liter Erlenmeyer flask, and 195 parts by mass of methanol and 0. 28 mass parts of 1 mass% hydrochloric acid aqueous solution [35 mass% hydrochloric acid, Wako Pure Chemical Industries, Ltd. diluted to 1/1000 with water] was added and stirred for about 10 minutes.

Subsequently, a solution obtained by diluting 300 parts by mass of titanium tetraisopropoxide [Ti (Oi-Pr) 4 , Nippon Soda Co., Ltd., product name: A-1 (TPT)] with 634 parts by mass of isopropanol was added, and transparent A uniform solution (co-condensate of silicon tetraalkoxide and titanium tetraalkoxide) was obtained. Add 1699 parts by mass of the homogeneous solution and 480 parts by mass of aqueous ammonia (25% by mass) to the reaction solution at the beginning by decreasing the dropping rate and gradually increasing the rate toward the end, and simultaneously dropping over 2 hours. did. After completion of the dropwise addition, the obtained cohydrolyzate is filtered, the organic solvent is dried at 50 ° C., then dispersed in water, and silica and titania composite inorganic particles having a concentration of 10% by mass and a refractive index of 1.56 ( Average particle diameter: 100 nm) was obtained.
(4) Preparation of Adhesive Layer Coating Solution 67 parts by weight of polyester 1, 20 parts by weight of an acrylic resin aqueous dispersion, 3 parts by weight of silica and titania composite inorganic particles, carnauba wax [manufactured by Chukyo Yushi Co., Ltd. 5 parts by mass of name Cerozol 524] and 5 parts by mass of polyoxyethylene (n = 7) lauryl ether [manufactured by Sanyo Chemical Industries, Ltd., trade name NAROACTY N-70] as a wetting agent are mixed and coated with an adhesive layer. A liquid was obtained.
[Production Example 2, preparation of coating liquid (N-1)]
70 parts by mass of dipentaerythritol hexaacrylate, 30 parts by mass of 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane, photopolymerization initiator [product name “IRGACURE184”, manufactured by Ciba Japan Co., Ltd.] 4 A coating liquid (N-1) was prepared by mixing 100 parts by mass of isopropanol and 100 parts by mass of isopropanol. The refractive index of the polymerized cured product (cured with ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere) of the coating liquid (N-1) was 1.52.
[Production Example 3, Preparation of coating liquid (N-2)]
Dipentaerythritol hexaacrylate 50 parts by mass, organosilica sol [trade name: “IPA-ST”, manufactured by Nissan Chemical Industries, Ltd.] 166 parts by mass, methyl ethyl ketone 20 parts by mass and photopolymerization initiator [trade name: “IRGACURE 184”, Ciba Japan Co., Ltd.] 4 parts by mass were mixed to prepare a coating liquid (N-2). The refractive index of the polymerized cured product (cured with ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere) of the coating liquid (N-2) was 1.49.
[Production Example 4, Preparation of Coating Liquid (N-3)]
Antimony-doped tin oxide 30 mass% methyl ethyl ketone dispersion (trade name: “SNS-10M”, manufactured by Ishihara Sangyo Co., Ltd.) 233 mass parts, dipentaerythritol hexaacrylate 30 mass parts and photopolymerization initiator [trade name: “ IRGACURE 184 ”, manufactured by Ciba Japan Co., Ltd.] was mixed to prepare a coating liquid (N-3). The refractive index of the polymerized cured product of the coating liquid (N-3) (cured by ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere) was 1.64.
[Production Example 5, preparation of coating liquid (N-4)]
Antimony-doped tin oxide 30 mass% methyl ethyl ketone dispersion [trade name: “SNS-10M”, manufactured by Ishihara Sangyo Co., Ltd.] 100 mass parts, tetramethylol methane triacrylate 70 mass parts, photopolymerization initiator [trade name: “ “KAYACURE BMS” (manufactured by Nippon Kayaku Co., Ltd.) 5 parts by mass and 830 parts by mass of butyl alcohol were mixed to prepare a coating liquid (N-4). The refractive index of the polymerized cured product of the coating liquid (N-4) (cured by ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere) was 1.54.
[Production Example 6, Preparation of coating liquid (N-5)]
Zirconia [trade name: “Nanouse ZR-30AL”, manufactured by Nissan Chemical Industries, Ltd.] 283 parts by mass, tetramethylolmethane triacrylate 15 parts by mass, photopolymerization initiator [trade name: “KAYACURE BMS”, Nippon Kayaku ( Co., Ltd.] 5 parts by mass and 702 parts by mass of butyl alcohol were mixed to prepare a coating solution (N-5). The refractive index of the polymerized cured product (cured by ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere) of the coating liquid (N-5) was 1.68.
[Production Example 7, preparation of coating liquid (N-6)]
40 parts by mass of dipentaerythritol hexaacrylate, hollow silica sol [trade name: “NY-1016SIV”, solid content concentration 20% by mass, average particle size 60 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd.] 300 parts by mass, photopolymerization initiator [ [Product name: “KAYACURE BMS”, manufactured by Nippon Kayaku Co., Ltd.] 5 parts by mass were mixed to prepare a coating liquid (N-6). The refractive index of the polymerized cured product (cured by ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere) of the coating liquid (N-6) was 1.35.
[Production Example 8, Preparation of coating liquid (N-7)]
1,10-Diacryloyloxy-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane 40 parts by mass, hollow silica sol [Trade name: “NY-1016SIV”, solid content concentration 20% by mass, average particle size 60 nm, manufactured by Catalyst Kasei Kogyo Co., Ltd.] 300 parts by mass, photopolymerization initiator [trade name: “KAYACURE BMS”, Nippon Kayaku Co., Ltd.] 5 parts by mass were mixed to prepare a coating liquid (N-7). The refractive index of the polymerized cured product (cured with ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere) of the coating liquid (N-7) was 1.32.
Example 1
On the surface of the polyethylene terephthalate (PET) film (trade name: “A4100”, manufactured by Toyobo Co., Ltd.) having a film thickness of 100 μm on which the easy adhesion layer is not formed, the adhesive layer coating solution of Production Example 1 is gravure-coated. The coating was applied by adjusting the thickness of the layer so that the thickness of the adhesive layer 14 was 40 nm.

The coating liquid (N-1) is applied to the coating liquid with a bar coater by adjusting the layer thickness so that the film thickness becomes 3 μm, and after drying, it is cured by ultraviolet rays of 400 mJ / cm 2 in the atmosphere. A hard coat layer was obtained. Next, on the hard coat layer 12, as the first optical interference layer 13a, the coating liquid (N-4) is applied by adjusting the layer thickness so that the film thickness becomes 170 nm by a spin coater, and dried. Then, it hardened | cured with the ultraviolet-ray of 400mJ / cm < 2 > in nitrogen atmosphere.

Further, as a second optical interference layer 13b, a coating liquid (N-6) is applied by adjusting the thickness of the layer so that the film thickness becomes 100 nm by a spin coater, and after drying, under a nitrogen atmosphere Was cured by ultraviolet rays of 400 mJ / cm 2 to produce a reduced reflection material 10. As shown in FIG. 1, the obtained antireflection material 10 is provided with a hard coat layer 12 on a transparent resin film 11, and a first optical interference layer as a dereflection layer 13 on the surface of the hard coat layer 12. 13a and a second optical interference layer 13b are provided.

Table 1 shows the results of evaluating the visibility reflectance of the obtained anti-reflection material 10, the maximum value of the difference in the amplitude of the reflectance at a light wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect. . The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG. In FIG. 3A, the maximum value of the difference in the amplitude of the reflectance is shown as X. In FIG. 3A, a line connecting the centers of the waves indicating the reflectance spectrum is indicated by a one-dot chain line, and the degree of flattening is determined by the one-dot chain line. As a result, as shown in FIG. 3A, in Example 1, the center of the spectrum is larger in the visibility wavelength range (light wavelength 500 to 650 nm) than in Comparative Example 1 (shown in FIG. 3B). It became clear that the line was flattened sufficiently.
(Example 2)
On the surface of the polyethylene terephthalate (PET) film (trade name: “A4100”, manufactured by Toyobo Co., Ltd.) having a film thickness of 100 μm on which the easy adhesion layer is not formed, the adhesive layer coating solution of Production Example 1 is gravure-coated. The coating was applied by adjusting the thickness of the layer so that the film thickness was 85 nm.

On top of that, the coating liquid (N-1) was applied with a bar coater by adjusting the thickness of the layer so that the film thickness was 3 μm, dried, and then cured by ultraviolet rays of 400 mJ / cm 2 in the air. As a result, a hard coat layer 12 was obtained. Next, as the first optical interference layer 13a, the coating liquid (N-4) is applied onto the hard coat layer 12 with a spin coater so that the film thickness is adjusted to 170 nm and dried. Then, it hardened | cured with the ultraviolet-ray of 400mJ / cm < 2 > in nitrogen atmosphere. Furthermore, as a second optical interference layer 13b, a coating liquid (N-7) is applied by adjusting the thickness of the layer so that the film thickness becomes 100 nm by a spin coater, and after drying, under a nitrogen atmosphere Was cured by ultraviolet rays of 400 mJ / cm 2 to obtain a reduced reflection material 10. As shown in FIG. 2, the obtained anti-reflection material 10 is provided with a hard coat layer 12 on a transparent resin film 11 through an adhesive layer 14, and the anti-reflection layer 13 on the surface of the hard coat layer 12. As shown, a first optical interference layer 13a and a second optical interference layer 13b are provided.

Table 1 shows the results of evaluating the visibility reflectance of the obtained anti-reflection material 10, the maximum value of the difference in the amplitude of the reflectance at a light wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect. . The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG. In FIG. 3C, the maximum value of the difference in the amplitude of the reflectance is indicated as X. As shown in FIG. 3C, in Example 2, the center line of the spectrum is sufficiently flattened in the visibility wavelength range as compared with Comparative Example 2 [shown in FIG. 3D]. It was revealed.
(Example 3)
On the triacetyl cellulose (TAC) film (trade name: “KC8UY”, manufactured by Konica Minolta Opto Co., Ltd.) having a film thickness of 80 μm, the coating liquid (N-2) is made to be 3 μm by a bar coater. The thickness of the layer was adjusted and applied, and cured with ultraviolet rays of 400 mJ / cm 2 to obtain a hard coat layer 12. Next, on the hard coat layer 12, as the first optical interference layer 13a, the coating liquid (N-4) is applied by adjusting the layer thickness so that the film thickness becomes 160 nm by a spin coater, and dried. Then, it hardened | cured with the ultraviolet-ray of 400mJ / cm < 2 > in nitrogen atmosphere. Furthermore, as a second optical interference layer 13b, a coating liquid (N-6) is applied by adjusting the thickness of the layer so that the film thickness becomes 95 nm by a spin coater, and after drying, under a nitrogen atmosphere It hardened | cured by the ultraviolet ray of 400mJ / cm < 2 >, and produced the antireflection material 10. FIG. Table 1 shows the results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG. As shown in FIG. 3 (e), the spectrum in Example 3 is higher than that in Comparative Example 3 (shown in FIG. 3 (f)) or Comparative Example 4 (shown in FIG. 3 (h)) in the visibility wavelength range. The center line has been further flattened.
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 results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG. As shown in FIG. 3G, in Example 4, the center line of the spectrum is more in the visibility wavelength range (light wavelength 500 to 650 nm) than in Comparative Example 4 (shown in FIG. 3H). Flattened.
(Example 5)
On the surface of the polyethylene terephthalate (PET) film (trade name: “A4100”, manufactured by Toyobo Co., Ltd.) having a film thickness of 100 μm on which the easy-adhesion layer is not formed, the adhesive layer coating solution is formed by a gravure coating method. The thickness of the layer was adjusted so that the thickness was 10 nm.

On top of that, the coating liquid (N-3) was applied with a bar coater by adjusting the layer thickness so that the film thickness was 3 μm, and after drying, it was cured by ultraviolet rays of 400 mJ / cm 2 in the atmosphere. A hard coat layer 12 was obtained. Next, on the hard coat layer 12, as the first optical interference layer 13a, the coating liquid (N-5) is applied by adjusting the thickness of the layer so that the film thickness becomes 155 nm by a spin coater, and dried. Then, it hardened | cured with the ultraviolet-ray of 400mJ / cm < 2 > in nitrogen atmosphere. Further, as a second optical interference layer 13b, a coating liquid (N-7) is applied by adjusting the thickness of the layer so that the film thickness becomes 96 nm by a spin coater, and after drying, under a nitrogen atmosphere Was cured by ultraviolet rays of 400 mJ / cm 2 to produce a reduced reflection material 10. Table 1 shows the results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG. As shown in FIG. 3 (i), in Example 5, the spectral centerline is better in the visibility wavelength range (light wavelength 500 to 650 nm) than in Comparative Example 5 (shown in FIG. 3 (j)). It was flattened.
(Comparative Example 1)
A coating liquid (N-2) is applied onto the surface of the polyethylene terephthalate (PET) film (trade name: “A4100”, manufactured by Toyobo Co., Ltd.) having a film thickness of 100 μm on which the easy adhesion layer is not formed. Thus, the thickness of the layer was adjusted so as to be 3 μm, applied, dried, and then cured with 400 mJ / cm 2 ultraviolet rays in the atmosphere to obtain the hard coat layer 12. Next, on the hard coat layer 12, as the first optical interference layer 13a, the coating liquid (N-4) is applied by adjusting the thickness of the layer so that the film thickness becomes 100 nm by a spin coater, and dried. Then, it hardened | cured with the ultraviolet-ray of 400mJ / cm < 2 > in nitrogen atmosphere.

Further, as a second optical interference layer 13b, a coating liquid (N-6) is applied by adjusting the thickness of the layer so that the film thickness becomes 100 nm by a spin coater, and after drying, under a nitrogen atmosphere Was cured by ultraviolet rays of 400 mJ / cm 2 to produce a reduced reflection material 10. Table 1 shows the results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG.
(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 for the first optical interference layer 13a. Table 1 shows the results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG.
(Comparative Example 3)
The antireflection material 10 was produced in the same manner as in Example 3 except that the thickness of the first optical interference layer 13a was adjusted so as to be 100 nm. Table 1 shows the results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectrum of the spectral reflectance of the anti-reflection material 10 is shown in FIG.
(Comparative Example 4)
The antireflection material 10 was produced in the same manner as in Example 3 except that the thickness of the first optical interference layer 13a was adjusted so as to be 260 nm. Table 1 shows the results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectral reflectance of the anti-reflection material 10 is shown in FIG.
(Comparative Example 5)
On the triacetyl cellulose (TAC) film (trade name: “KC8UY”, manufactured by Konica Minolta Opto Co., Ltd.) having a film thickness of 80 μm, the coating liquid (N-1) is made to be 3 μm by a bar coater. The thickness of the layer was adjusted and applied, and cured with ultraviolet rays of 400 mJ / cm 2 to obtain a hard coat layer 12. Next, a coating liquid (N-3) is applied as a first optical interference layer 13a on the hard coat layer 12 by a spin coater so that the film thickness is adjusted to 100 nm, and dried. And cured with ultraviolet rays of 400 mJ / cm 2 in a nitrogen atmosphere. Furthermore, as the second optical interference layer 13b, a coating liquid (N-6) is applied by adjusting the thickness of the layer so that the film thickness becomes 100 nm, and after drying, it is 400 mJ / cm under a nitrogen atmosphere. Curing was performed with the ultraviolet rays of No. 2 , and the antireflection material 10 was produced. Table 1 shows the results of evaluating the visibility reflectance, the maximum value of the difference in the amplitude of the reflectance at a wavelength of 500 to 650 nm, the ab chroma Cab *, and the coloring suppression effect of the reduced reflection material 10 obtained. The spectrum of the spectral reflectance of the antireflection material 10 is shown in FIG.

From the results shown in Table 1, the antireflective material 10 produced in Example 1 controls the refractive index and film thickness of the hard coat layer 12, the first optical interference layer 13a, and the second optical interference layer 13b. The reflectance was constant in the visibility wavelength range, and the uneven coloring due to the film thickness variation of the coating layer was not noticeable. Furthermore, in Examples 2 and 5, the adhesive layer 14 and the hard coat layer 12 having an appropriate refractive index and film thickness are provided. In Examples 3 and 4, the refractive index is (the refractive index of the TAC film) ± 0.02. The hard coat layer 12 was used. Therefore, the maximum value of the difference in the amplitude of the reflectance of the light having a wavelength of 500 to 650 nm is 0.5% or less, and in addition to flattening the reflectance, it is possible to reduce interference unevenness, Coloring unevenness due to film thickness variation could be reduced more effectively. Each of the anti-reflective materials had an ab chroma Cab * of 5 or less and a luminous reflectance Y of 1.5% or less with respect to the CIE standard illuminant D65, and had an excellent appearance and low reflectance.

  On the other hand, in Comparative Example 2, since the refractive index of the first optical interference layer 13a is lower than that of the hard coat layer 12, in Comparative Example 1 and Comparative Examples 3 to 5, the film thickness of the first optical interference layer 13a / second Since the ratio of the thickness of the optical interference layer 13b is outside the range of 1.6 to 1.8, the spectrum is not flat in the visibility wavelength range, and the value of the ab chroma Cab * exceeds 5. . In addition, in Comparative Example 1, since the adhesive layer 14 is not provided, the maximum value of the difference in the amplitude of the reflectance at the light wavelength of 500 to 650 nm exceeds 1.0%, and the interference unevenness of the hard coat layer 12 occurs. The pattern of oil floating on the surface of the anti-reflection layer 13 was intense. Furthermore, in any of the comparative examples, the uneven coloring due to the variation in the thickness of the coating layer was a conspicuous result.

It should be noted that the above embodiment can be modified as follows.
-The composition which forms the said hard-coat layer 12 can also be mix | blended with the monomer which has a carboxyl group, an amino group, etc., and it can also comprise so that the adhesiveness of the hard-coat layer 12 with respect to the transparent resin film 11 may be improved. .

  -The composition for forming a hard coat layer contains a near-infrared absorber, an ultraviolet absorber, etc., and the hard coat layer 12 exhibits a near-infrared absorption effect or an ultraviolet absorption effect, or the transparent resin film 11 has a near-infrared absorber, An ultraviolet absorber or the like can be contained to exhibit a near infrared absorption effect or an ultraviolet absorption effect.

Furthermore, the technical idea grasped from the embodiment will be described below.
The reduced reflection material according to any one of claims 1 to 3, wherein the transparent resin film is formed of a polyester resin or acetyl cellulose. In this case, in addition to the effects of the invention according to any one of claims 1 to 3, the molding is easy and easy to obtain, and the refractive index of the transparent resin film is set to be high or low. be able to.

  The reduced reflection material according to any one of claims 1 to 3, wherein an adhesive layer is formed between the transparent resin film and the hard coat layer. When comprised in this way, in addition to the effect of the invention which concerns on any one of Claims 1-3, while being able to improve the adhesiveness between a transparent resin film and a hard-coat layer, an anti-reflective material Interference unevenness can be reduced.

  The low-reflection material according to any one of claims 1 to 3, wherein the hard coat layer is a polymerized cured product of a monomer containing an ultraviolet curable polyfunctional acrylate. When comprised in this way, in addition to the effect of the invention according to any one of claims 1 to 3, the hardness of the hard coat layer can be increased and the productivity of the anti-reflection material can be improved. .

  O The refractive index of the said 2nd optical interference layer is 1.28-1.45, The antireflection material of any one of Claims 1-3 characterized by the above-mentioned. In this case, in addition to the effect of the invention according to any one of claims 1 to 3, the second optical interference layer can be made a sufficiently hard layer, and a sufficient antireflection effect is obtained. be able to.

The schematic sectional drawing which shows the structure of the low reflection material in embodiment. The schematic sectional drawing which shows another form of a low reflection material. (A) is a spectrum diagram showing the relationship between the wavelength of light and reflectance in Example 1, (b) is a spectrum diagram showing the relationship between the wavelength of light and reflectance in Comparative Example 1, and (c) is an example. 2 is a spectrum diagram showing the relationship between the wavelength of light and the reflectance in FIG. 2, (d) is a spectrum diagram showing the relationship between the wavelength of light and the reflectance in Comparative Example 2, and (e) is the wavelength of light in Example 3. The spectrum figure which shows the relationship with a reflectance, (f) is a spectrum figure which shows the relationship between the wavelength of the light in Comparative Example 3, and a reflectance, (g) is the relationship between the wavelength of the light in Example 4, and a reflectance. (H) is a spectrum diagram showing the relationship between the light wavelength and the reflectance in Comparative Example 4, (i) is a spectrum diagram showing the relationship between the light wavelength and the reflectance in Example 5, and (j ) Shows the relationship between the wavelength of light and the reflectance in Comparative Example 5. Spectrum diagram.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Decrease reflection material, 11 ... Transparent resin film, 12 ... Hard-coat layer, 13 ... Decrease reflection layer, 13a ... 1st optical interference layer, 13b ... 2nd optical interference layer.

Claims (4)

  1. In the anti-reflection material in which at least the hard coat layer, the first optical interference layer, and the second optical interference layer are laminated in this order on the transparent resin film,
    The refractive index of the first optical interference layer is higher than the refractive index of the hard coat layer, the refractive index difference is 0.01 to 0.05, and the refractive index of the second optical interference layer is that of the first optical interference layer. A reduced reflection material characterized in that the ratio of the film thickness of the first optical interference layer / the film thickness of the second optical interference layer is 1.6 to 1.8 lower than the refractive index.
  2. Ab chroma Cab * = {(a *) 2 based on JIS Z8729 with respect to CIE standard illuminant D65 based on JIS Z8720 having a maximum difference in reflectance amplitude in the wavelength range of 500 to 650 nm. The reduced reflection material according to claim 1, wherein + (b *) 2 } 1/2 is 5 or less.
  3. 3. The reduced reflection material according to claim 1, wherein the visibility reflectance Y based on JIS Z8701 for the CIE standard illuminant D65 based on JIS Z8720 is 1.5% or less.
  4. An electronic image display device comprising the antireflection material according to any one of claims 1 to 3 on a front surface of a display.
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CN 200910127646 CN101551475A (en) 2008-03-31 2009-03-19 Reflection-reducing material and electronic image display device having the same
TW098108980A TWI448720B (en) 2008-03-31 2009-03-19 Antireflection material and electronic image display apparatus having the antireflection material

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US6391161B1 (en) 1999-03-30 2002-05-21 Bayer Aktiengesellschaft Method for reducing the chlorine content of low molecular weight isocyanates
US6395925B1 (en) 1999-05-17 2002-05-28 Bayer Aktiengesellschaft Process for purifying organic isocyanates, the organic isocyanates so purified and their use

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EP2711742A4 (en) 2011-05-17 2014-10-29 Canon Denshi Kk Optical filter, optical device, electronic device, and antireflection complex
JP2012252305A (en) * 2011-06-07 2012-12-20 Nof Corp Antireflection film
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JP4314803B2 (en) * 2001-09-28 2009-08-19 日油株式会社 Anti-reflection film
JP2005043749A (en) * 2003-07-24 2005-02-17 Fuji Photo Film Co Ltd Antireflection coating, antireflection film, polarizing plate, image display device and hard-coated article
JP4887612B2 (en) * 2004-10-20 2012-02-29 日油株式会社 Anti-reflection material and electronic image display device using the same
JP2007133386A (en) * 2005-10-13 2007-05-31 Toray Ind Inc Antireflection film and optical filter provided therewith
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US6222066B1 (en) 1999-03-30 2001-04-24 Bayer Aktiengesellschaft Process for decreasing the chlorine content of organic isocyanates
US6391161B1 (en) 1999-03-30 2002-05-21 Bayer Aktiengesellschaft Method for reducing the chlorine content of low molecular weight isocyanates
US6395925B1 (en) 1999-05-17 2002-05-28 Bayer Aktiengesellschaft Process for purifying organic isocyanates, the organic isocyanates so purified and their use

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TWI448720B (en) 2014-08-11
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CN101551475A (en) 2009-10-07

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