JP2015232614A - Antireflection film and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film and a display excellent in antistatic property while preventing a problem of coloring even in the presence of illumination (particularly LED illumination) or even when conductive particles such as ITO and ATO are used.SOLUTION: The antireflection film includes high refractive index layers 4, 5 comprising conductive high refractive index particles and a low refractive index layer 6, in this order. The film has an average spectral reflectance of 0.05 to 0.40% in a wavelength region λ(450 nm≤λ≤680 nm) and a spectral reflectance of 0.05 to 1.30% in a wavelength region λ(430 nm≤λ<500 nm), which monotonously decreases from 430 nm to 500 nm; and the film has an average spectral reflectance of 0.03% or more and less than 0.15% in a wavelength region λ(500 nm≤λ≤600 nm) and a spectral reflectance of 0.05 to 1.50% in a wavelength region λ(600 nm<λ≤730 nm), which monotonously increases from 600 nm to 730 nm.

Description

  The present invention relates to an antireflection film and a display.

In recent years, the display is compatible with so-called 4K2K (screen: horizontal 4,000 x vertical 2,000 resolution), which can shift from analog broadcasting to BS and terrestrial digital broadcasting, etc., and display higher resolution images. With the development and commercialization of displays, it has become possible to display images with higher quality.
As the display quality of the display main body is improved, in order to observe the image display on the display with high quality, the influence of the light existing on the viewer side becomes a problem more than before.

  Generally, a display is used in an environment where various lights having various wavelengths and intensities exist without depending on a place such as indoors or outdoors. In order to prevent deterioration of display quality due to reflection of these various lights on the display surface, an antireflection film as in Patent Document 1 is installed on the display surface.

On the other hand, in recent years, indoor lighting has been changed from fluorescent lamp illumination (combination of mercury visible emission line and phosphor emission), which has been conventionally used, to LED illumination (mainly used as a white light source, blue LED and yellow phosphor). It may be replaced by a combination of the above and the influence on the visibility on the display resulting from the difference in the spectral distribution between these illuminations may be different from the conventional case. Specifically, the problem of coloring due to the difference in illumination occurs.
However, Patent Document 1 does not consider any color due to a difference in illumination.

Further, when dust or dirt adheres to the antireflection film installed on the surface of the display, the display quality of the display is impaired. Further, when foreign matter such as dust or dust adheres to the antireflection film during the production process of the antireflection film, a coating film defect occurs from the foreign matter as a starting point, and the yield decreases. For this reason, in recent years, it is also required to impart antistatic properties to the antireflection film.
In order to impart antistatic properties to the antireflection film, it is conceivable to add conductive particles such as ITO or ATO to the antireflection film. However, when conductive particles are used, display quality may be deteriorated by coloring. In this regard, Patent Document 1 does not consider any problem of coloring when conductive particles are used.

JP 2010-152111 A

  The present invention provides an antireflection film and a display which do not cause a coloring problem when used in the presence of illumination (particularly under LED illumination), or when conductive particles such as ITO and ATO are used, and have excellent antistatic properties. The purpose is to provide.

The present inventors have intensively studied, and the spectral reflectance curve of the conventional antireflection film has a large change rate of the spectral reflectance near the wavelength of 550 nm (green wavelength band) where human visibility is strongest, which is the cause. As a result, it has been found that a coloring problem that makes humans feel uncomfortable in the presence of illumination (particularly in the presence of an LED light source) has been found. The inventors of the present invention have further studied diligently, and conductive metal oxides such as ITO and ATO have free electrons whose plasma frequency is in the near infrared region, and visible light is caused by the plasma vibration of the free electrons. It was found that light in the region was also partially absorbed or reflected, causing a coloring problem.
Then, the inventors have further intensively studied to solve the above problems.

In order to solve the above problems, the present invention provides the following antireflection films and displays of [1] to [9].
[1] An antireflection film having a high refractive index layer and a low refractive index layer in this order on at least one surface of a transparent substrate, the high refractive index layer containing conductive high refractive index particles. The average spectral reflectance of the antireflection film surface in the wavelength region λ ₁ (450 nm ≦ λ ₁ ≦ 680 nm) is 0.05 to 0.40%, and the wavelength region λ _a (430 ≦ λ _a <500 nm), The spectral reflectance of the antireflection film surface in the wavelength region λ _b (500 nm ≦ λ _b ≦ 600 nm) and the wavelength region λ _c (600 nm <λ _c ≦ 730 nm) satisfies the following conditions (a) to (c). Antireflection film.
(A) The spectral reflectance in the wavelength region λ _a is 0.05 to 1.30%, and monotonously decreases from 430 nm to 500 nm.
(B) The average spectral reflectance in the wavelength region λ _b is 0.03% or more and less than 0.15%.
(C) The spectral reflectance in the wavelength region λ _c is 0.05 to 1.50% and monotonously increases from 600 nm to 730 nm.
[2] The reflection according to [1] above, wherein the ratio (R _max / R _min ) between the maximum value R _max and the minimum value R _min of the spectral reflectance in the wavelength band λ _b is 1.00 to 2.90. Prevention film.
[3] The high refractive index layer includes a high refractive index layer (A) located on the transparent substrate side and a high refractive index layer (B) located on the low refractive index layer side, and the high refractive index layer The refractive index of the high refractive index layer (B) is higher than the refractive index of the refractive index layer (A), and further, at least one of the high refractive index layer (A) and the high refractive index layer (B) The antireflection film according to the above [1] or [2], comprising conductive high refractive index particles.
[4] The high refractive index layer (A) has a refractive index of 1.50 to 1.75, the high refractive index layer (B) has a refractive index of 1.60 to 1.80, and the high refractive index layer The antireflection film as described in [3] above, wherein the total thickness of (A) and the high refractive index layer (B) is 100 to 200 nm.

[5] The above-mentioned [3], wherein the high refractive index layer (A) contains the conductive high refractive index particles, and the high refractive index layer (B) contains nonconductive high refractive index particles. ] Or the antireflection film as described in [4].
[6] Ratio of the thickness of the high refractive index layer (A) to the thickness of the high refractive index layer (B) ([thickness of the high refractive index layer (A) / the thickness of the high refractive index layer (B) Thickness]) is 0.40-0.90, The antireflection film as described in [5] above.
[7] The antireflective film according to any one of [1] to [6], wherein the low refractive index layer has a refractive index of 1.27 to 1.35 and a thickness of 80 to 120 nm.
[8] The antireflection film according to any one of [1] to [7], wherein the antireflection film has a surface resistivity of 1.0 × 10 ¹² Ω / □ or less.
[9] A display having an antireflection film on the outermost surface, wherein the antireflection film according to any one of [1] to [8] is used as the antireflection film.

  The antireflection film and display of the present invention are excellent in antistatic properties without causing coloring problems in the presence of illumination (particularly under LED illumination) or when conductive particles such as ITO and ATO are used. As a result, no dust or dirt adheres to the surface, so that a high-quality image can be provided.

It is sectional drawing which shows an example of the antireflection film of this invention. It is a figure which shows the spectral reflectance curve of the antireflection film of Example 1. It is a figure which shows the spectral reflectance curve of the antireflection film of Example 2. It is a figure which shows the spectral reflectance curve of the antireflection film of Example 3. It is a figure which shows the spectral reflectance curve of the antireflection film of Example 4. It is a figure which shows the spectral reflectance curve of the antireflection film of Example 5. It is a figure which shows the spectral reflectance curve of the antireflection film of the comparative example 1. It is a figure which shows the spectral reflectance curve of the antireflection film of the comparative example 2. It is a figure which shows the spectral reflectance curve of the antireflection film of the comparative example 3. It is a figure which shows the spectral reflectance curve of the antireflection film of the comparative example 4. It is a figure which shows the spectral reflectance curve of the antireflection film of the comparative example 5. It is a figure which shows the spectral reflectance curve of the antireflection film of the comparative example 6.

[Antireflection film]
The antireflective film of the present invention is an antireflective film having a high refractive index layer and a low refractive index layer in this order on at least one surface of a transparent substrate, the high refractive index layer comprising conductive high refractive index particles. The average spectral reflectance of the antireflection film surface in the wavelength region λ ₁ (450 nm ≦ λ ₁ ≦ 680 nm) is 0.05 to 0.40%, and the wavelength region λ _a (430 ≦ λ The spectral reflectance of the surface of the antireflection film in _a <500 nm), wavelength region λ _b (500 nm ≦ λ _b ≦ 600 nm) and wavelength region λ _c (600 nm <λ _c ≦ 730 nm) is determined by the following conditions (a) to ( An antireflection film satisfying c).
(A) The spectral reflectance in the wavelength region λ _a is 0.05 to 1.30%, and monotonously decreases from 430 nm to 500 nm.
(B) The average spectral reflectance in the wavelength region λ _b is 0.03% or more and less than 0.15%.
(C) The spectral reflectance in the wavelength region λ _c is 0.05 to 1.50% and monotonously increases from 600 nm to 730 nm.
The spectral reflectance refers to the spectral reflectance of each wavelength measured with a spectrophotometer, and can be measured by, for example, the method described in the examples. The average spectral reflectance refers to the average spectral reflectance of each wavelength in the wavelength range for which the average value is calculated, and can be measured by, for example, the method described in the examples.

(Spectral reflectance, etc.)
The antireflection film of the present invention has an average spectral reflectance of 0.05 to 0.40% on the surface of the antireflection film (surface on the low refractive index layer side) in the wavelength region λ ₁ (450 nm ≦ λ ₁ ≦ 680 nm). It needs to be.
The wavelength region λ ₁ (450 nm ≦ λ ₁ ≦ 680 nm) is a wavelength region where human visibility is high. If the average spectral reflectance in the wavelength region λ ₁ is less than 0.05%, it may be impossible to suppress coloring of reflected light, which will be described later. In addition, when the average spectral reflectance in the wavelength region λ ₁ exceeds 0.40%, a sufficient antireflection function cannot be obtained. On the other hand, if the average spectral reflectance in the wavelength region λ ₁ is within the above range, it has a sufficient antireflection function, leading to suppression of coloring of reflected light.
The average spectral reflectance of the wavelength region λ ₁ on the antireflection film surface is preferably 0.05 to 0.30%, and more preferably 0.10 to 0.25%.

The ratio (450 nmR / 680 nmR) of the spectral reflectance (450 nmR) of 450 nm and the spectral reflectance of 680 nm (680 nmR) in the wavelength region λ ₁ is preferably 0.75 to 1.50, 0.80 It is more preferable that it is -1.25, and it is further more preferable that it is 0.90-1.10. If 450 nmR / 680 nmR is within this range, it is difficult to recognize the coloration of the reflected light in a wavelength range where human visibility is extremely high.

Further, the antireflection film of the present invention has a reflection in a wavelength region λ _a (430 nm ≦ λ _a <500 nm), a wavelength region λ _b (500 nm ≦ λ _b ≦ 600 nm) and a wavelength region λ _c (600 nm <λ _c ≦ 730 nm). The spectral reflectance of the surface of the prevention film (the surface on the low refractive index layer side) needs to satisfy the conditions (a) to (c).
(A) The spectral reflectance in the wavelength region λ _a is 0.05 to 1.30%, and monotonously decreases from 430 nm to 500 nm.
(B) The average spectral reflectance in the wavelength region λ _b is 0.03% or more and less than 0.15%.
(C) The spectral reflectance in the wavelength region λ _c is 0.05 to 1.50% and monotonously increases from 600 nm to 730 nm.

Condition (a) requires that the spectral reflectance in the wavelength region λ _a (430 nm ≦ λ _a <500 nm) be 0.05 to 1.30% and monotonously decrease from 430 nm to 500 nm.
When the spectral reflectance in the wavelength region lambda _a is less than 0.05%, it becomes difficult to suppress the spectral reflectance in the wavelength region lambda _b in the lower range, and it is difficult to suppress the coloring of the reflected light in the wavelength range lambda _b Become. If the spectral reflectance in the wavelength region λ _a exceeds 1.30%, it is difficult to suppress coloring of reflected light in the wavelength region λ _a . On the other hand, the spectral reflectance in the wavelength region lambda _a If the above range, it is possible to suppress the coloring of the reflected light. In addition, when the spectral reflectance does not monotonously decrease from 430 nm to 500 nm, the change rate of the spectral reflectance for each wavelength in the wavelength region λ _a is larger than when monotonously decreasing, and the color of reflected light is easily noticeable. Tend to be.
The spectral reflectance in the wavelength region λ _a is preferably 0.05 to 1.20%, and more preferably 0.05 to 1.00%.
Further, when the spectral reflectance does not monotonously decrease in the wavelength band λ _a , it is difficult to suppress the spectral reflectance in the wavelength band λ _b to a low range, and it is difficult to suppress coloring of reflected light in the wavelength band λ _b . . For example, as in Comparative Examples 3, 4 and 6, if the changes to increase after the spectral reflectivity monotonically decreases in the wavelength region lambda _a, it is difficult to suppress the spectral reflectance in the wavelength region lambda _b in the lower range, wavelength It becomes difficult to suppress coloring of reflected light in the region λ _b .

The average spectral reflectance in the wavelength region λ _a is preferably 0.10 to 0.70%, and more preferably 0.20 to 0.50%.

Condition (b) is that the average spectral reflectance in the wavelength region λ _b (500 ≦ λ _b ≦ 600 nm) is 0.03% or more and less than 0.15%. The wavelength range λ _b is a wavelength range where human visibility is extremely high.
In order to make the average spectral reflectance in the wavelength region λ _b less than 0.03%, it is necessary to make the antireflection layer into at least three layers, which leads to an increase in tact time and cost of materials. Therefore, it is not preferable. When the average spectral reflectance in the wavelength region λ _b exceeds 0.15%, the reflectance in the wavelength region with extremely high visibility is increased, and the reflected light is colored. On the other hand, _if the average spectral reflectance in the wavelength band λ _b is in the above range, the spectral reflectance is reduced and the color of the reflected light is suppressed at the same time in a wavelength range where human visibility is extremely high without increasing the cost. Can be satisfied.
The average spectral reflectance in the wavelength region λ _b is preferably 0.03% or more and 0.14% or less, and more preferably 0.03% or more and 0.13% or less.
The spectral reflectance in the wavelength band λ _b is preferably 0.02 to 0.30%, more preferably 0.02 to 0.25%, and 0.02 to 0.20%. Is more preferable.
The minimum value of the spectral reflectance in the wavelength region 430 to 730 nm is preferably located in the wavelength region λ _b .

The ratio (λ _b R _max / λ _b R _min ) between the maximum value λ _b R _max and the minimum value λ _b R _min of the spectral reflectance in the wavelength band λ _b is 1.00 to 2.90. Preferably, it is 1.20 to 2.80, more preferably 1.40 to 2.50. If λ _b R _max / λ _b R _min is within this range, the color of reflected light is not conscious at all in a wavelength range where human visibility is extremely high, and an excellent antireflection function is provided.
The difference between λ _b R _max and λ _b R _min (λ _b R _max −λ _b R _min ) is preferably 0.15 or less, and more preferably 0.01 to 0.13. More preferably, it is 0.01 to 0.10.

Condition (c) requires that the spectral reflectance in the wavelength region λ _c (600 <λ _c ≦ 730 nm) is 0.05 to 1.50% and monotonously increases from 600 nm to 730 nm.
If the spectral reflectance in the wavelength region λ _c is less than 0.05%, it is difficult to suppress the spectral reflectance in the wavelength region λ _b to a low range, and it is difficult to suppress coloring of reflected light in the wavelength region λ _b . Become. If the spectral reflectance in the wavelength region λ _c exceeds 1.50%, it is difficult to suppress coloring of reflected light in the wavelength region λ _c . On the other hand, if the spectral reflectance in the wavelength region λ _c is set to the above range, coloring of reflected light can be suppressed. Further, when the spectral reflectance does not increase monotonously from 600 nm to 730 nm, the change rate of the spectral reflectance for each wavelength in the wavelength region λ _c tends to increase, and the color of the reflected light becomes conspicuous.
The spectral reflectance in the wavelength region λ _c is preferably 0.05 to 1.20%, more preferably 0.06 to 1.00%, and 0.07 to 0.90%. Is more preferable.

In the antireflection film of the present invention, the ratio of [average spectral reflectance of wavelength region λ _c / average spectral reflectance of wavelength region λ _a ] is preferably 1.50 or less, and 1.00 to 1.30. More preferably, it is more preferably 1.00 to 1.25.

The surface resistivity (surface resistivity on the low refractive index layer side) of the antireflection film of the present invention is preferably 1.0 × 10 ¹² Ω / □ or less, more preferably 1.0 × 10 ¹¹ Ω / □. It is as follows. If the surface resistivity is in the above range, it not only prevents dust and dirt from adhering to the surface of the antireflection film, but also suppresses liquid crystal orientation disturbance caused by static electricity that occurs when the protective sheet for the antireflection film is peeled off. It is possible to obtain an antireflection film excellent in antistatic properties.

The arithmetic average roughness Ra (JIS B0601: 2001) of the surface of the antireflection film (the surface on the low refractive index layer side) is preferably 1 to 10 nm, and more preferably 1 to 8 nm. The ten-point average roughness Rz (JIS B0601: 2001) of the surface of the antireflection film (the surface on the low refractive index layer side) is preferably 50 to 160 nm, and more preferably 55 to 155 nm.
When Ra and Rz are within the above ranges, the surface is smooth and the scratch resistance is improved.

The antireflection film of the present invention preferably has a total light transmittance (JIS K7361-1: 1997) of 90% or more, and more preferably 92% or more. In the antireflection film of the present invention, haze (JIS K7136: 2000) is preferably 1.0% or less, more preferably 0.5% or less, and 0.3% or less. Further preferred.
The light incident surface for measuring the total light transmittance and haze is on the transparent substrate side.

(Basic configuration)
FIG. 1 is a cross-sectional view showing an embodiment of the antireflection film of the present invention. In FIG. 1, the antireflection film 1 is formed by laminating a hard coat layer 3, a high refractive index layer (A) 4, a high refractive index layer (B) 5, and a low refractive index layer 6 in this order on a transparent substrate 2. It is a thing.
The hard coat layer 3, the high refractive index layer (A) 4, the high refractive index layer (B) 5, and the low refractive index layer 6 may be provided on one surface of the transparent substrate 2 as shown in FIG. However, they may be provided on both sides.

<Transparent substrate>
The transparent substrate used in the present invention is not particularly limited as long as it is generally used as a substrate for an antireflection film, but is preferably a plastic film or plastic sheet from the viewpoint of material cost, productivity, and the like. Etc. can be appropriately selected depending on the application.

  As a plastic film or a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include cellulose resins such as triacetyl cellulose resin (TAC), diacetyl cellulose, acetate butyrate cellulose, cellophane; polyethylene terephthalate resin (PET), polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polyester Polyester resins such as thermoplastic elastomers; low density polyethylene resins (including linear low density polyethylene resins), medium density polyethylene resins, high density polyethylene resins, ethylene-α olefin copolymers, polypropylene resins, polymethylpentene resins, Polyolefin resins such as polybutene resins, ethylene-propylene copolymers, propylene-butene copolymers, olefinic thermoplastic elastomers or mixtures thereof; T) Acrylic resins such as methyl acrylate resin, poly (meth) ethyl acrylate resin, poly (meth) butyl acrylate resin; polyamide resin represented by nylon 6 or nylon 66; polystyrene resin; polycarbonate resin; polyarylate A resin; or a polyimide resin is preferable.

As the transparent substrate, it can be used alone or in the form of a mixture of two or more of the above-described plastic film and plastic sheet. From the viewpoint of flexibility, toughness, transparency, and the like, a cellulose resin, A polyester resin is more preferable, and triacetyl cellulose resin (TAC) and polyethylene terephthalate resin are more preferable.
Although there is no restriction | limiting in particular about the thickness of a transparent base material, Although it selects suitably according to a use, Usually, it is 5-130 micrometers, and when considering durability, handling property, etc., 20-100 micrometers is preferable.

<Hard coat layer>
The antireflection film of the present invention preferably has a hard coat layer between the transparent substrate and the high refractive index layer for the purpose of improving the scratch resistance. Here, a hard coat means what shows hardness more than "H" in the pencil hardness test prescribed | regulated by JISK5600-5-4: 1999.
The hard coat layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, and from the viewpoint of improving scratch resistance, an ionizing radiation curable resin. More preferably, it contains a cured product of the composition.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group, an epoxy group, and an oxetanyl group. As the ionizing radiation curable compound, a compound having an ethylenically unsaturated bond group is preferable, a compound having two or more ethylenic unsaturated bond groups is more preferable, and among them, having two or more ethylenically unsaturated bond groups, Polyfunctional (meth) acrylate compounds are more preferred. As the polyfunctional (meth) acrylate compound, any of a monomer and an oligomer can be used.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

Among the polyfunctional (meth) acrylate compounds, bifunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, 1,6-hexane. Examples thereof include diol diacrylate.
Examples of the tri- or higher functional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di Examples include pentaerythritol tetra (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate.
The (meth) acrylate-based monomer may be modified by partially modifying the molecular skeleton, and is modified with ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, alkyl, cyclic alkyl, aromatic, bisphenol, or the like. Can also be used.

Moreover, examples of the polyfunctional (meth) acrylate oligomer include acrylate polymers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate.
Urethane (meth) acrylate is obtained by reaction of polyhydric alcohol and organic diisocyanate with hydroxy (meth) acrylate, for example.
A preferable epoxy (meth) acrylate is a (meth) acrylate obtained by reacting (meth) acrylic acid with a tri- or higher functional aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like. (Meth) acrylates obtained by reacting the above aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins and the like with polybasic acids and (meth) acrylic acid, and bifunctional or higher functional aromatic epoxy resins, It is a (meth) acrylate obtained by reacting an alicyclic epoxy resin, an aliphatic epoxy resin or the like with a phenol and (meth) acrylic acid.
The ionizing radiation curable compounds can be used alone or in combination of two or more.

When the ionizing radiation curable compound is an ultraviolet curable compound, the ionizing radiation curable composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like. These photopolymerization initiators preferably have a melting point of 100 ° C. or higher. By setting the melting point of the photopolymerization initiator to 100 ° C. or higher, the photopolymerization initiator remaining due to the heat of the transparent conductive film formation or the crystallization process is sublimated to prevent the low resistance of the transparent conductive film from being impaired. can do. The same applies to the case where a photopolymerization initiator is used in the hard coat layer B described later.
The photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more selected may be mentioned.

The thickness of the hard coat layer is preferably in the range of 0.1 to 100 μm, and more preferably in the range of 0.8 to 20 μm. If the thickness of the hard coat layer is within the above range, sufficient hard coat performance can be obtained, and it is difficult to break without occurrence of cracks or the like with respect to external impact.
The thickness of the hard coat layer can be calculated, for example, by measuring the thickness of 20 locations from a cross-sectional image taken using a transmission electron microscope (TEM) and calculating the average value of the 20 locations. The thicknesses of the high refractive index layer and the low refractive index layer to be described later can be calculated in the same manner.

  The refractive index of the hard coat layer is preferably smaller than the refractive index of the high refractive index layer described later. The refractive index of the hard coat layer is preferably in the range of 1.45 to 1.70, more preferably in the range of 1.45 to 1.60. If the refractive index of the hard coat layer is within such a range, there will be no difficulty in controlling the refractive index of the high refractive index layer. From the viewpoint of suppressing interference fringes, it is preferable to reduce the difference between the refractive index of the hard coat layer and the refractive index of the transparent substrate.

The refractive index of the hard coat layer can be measured by an Abbe refractometer or an ellipsometer after forming a single layer of the hard coat layer.
Moreover, the following (1) and (2) are mentioned as a method of measuring a refractive index after forming a hard-coat layer on a transparent base material. The refractive indexes of the high refractive index layer and the low refractive index layer described later can also be calculated by the following methods (1) and (2).
(1) A method of calculating by fitting a reflection spectrum measured by a reflection photometer and a reflection spectrum calculated from an optical model of a multilayer thin film using a Fresnel coefficient. In this calculation, the refractive index in the wavelength range of 380 to 780 nm was constant.
(2) A method in which a hard coat layer is scraped off with a cutter to prepare a powder sample and calculated by the Becke method according to JIS K7142: 2008 method B (for powder or granular transparent material).
[Becke method]
Using a Cargill reagent having a known refractive index, a powder sample is placed on a slide glass or the like, the reagent is dropped on the sample, and the sample is immersed in the reagent. This state is observed by microscopic observation, and the refractive index of the reagent that makes it impossible to visually observe the bright line (Becke line) generated in the sample outline due to the difference in refractive index between the sample and the reagent is defined as the refractive index of the sample.

  The hard coat layer is prepared by adjusting the coating liquid for forming the hard coat layer with the above-described resin composition, additives such as an ultraviolet absorber and a leveling agent and a diluent solvent to be blended as necessary, and applying the coating liquid on the transparent substrate. It can be formed by coating, drying, and curing by irradiating with ionizing radiation, if necessary, by a conventionally known coating method.

<High refractive index layer>
The high refractive index layer needs to contain conductive high refractive index particles.
By containing conductive high-refractive-index particles in the high-refractive-index layer, the antireflection film is imparted with antistatic properties, dust and dust can be prevented from adhering to the surface, and high-quality images can be provided. Can do. In addition, the conductive high refractive index particles are preferable in that they are not affected by the humidity environment unlike quaternary ammonium salts widely used as antistatic agents.
Note that conductive high refractive index particles such as ITO and ATO have free electrons whose plasma frequency is in the near infrared region, and part of the light in the visible light region is also absorbed or caused by the plasma vibration of the free electrons. Reflected and may cause coloring problems. However, since the antireflection film of the present invention uses conductive high refractive index particles so as to satisfy the above-described spectral reflectance conditions, coloring problems can be suppressed.

The high refractive index layer preferably has a two-layer structure of a high refractive index layer (A) located on the transparent substrate side and a high refractive index layer (B) located on the low refractive index layer side. At that time, it is preferable to make the refractive index of the high refractive index layer (B) higher than the refractive index of the high refractive index layer (A).
By configuring the high refractive index layer as described above, it is easy to adjust the optical distance while imparting antistatic properties to the antireflection film, and the spectral reflectance of the antireflection film can easily satisfy the above-described conditions. . Further, by configuring the high refractive index layer as described above, the refractive index difference from the low refractive index layer can be increased, and the reflectance can be decreased. Furthermore, by using the high refractive index layer as the configuration, the refractive index difference between the high refractive index layer and the hard coat layer can be reduced, and the generation of interference fringes can be suppressed.

Examples of conductive high refractive index particles include antimony pentoxide (Sb ₂ O ₅ ; 1.79), antimony-doped tin oxide (ATO; 1.80), tin-doped indium oxide (ITO; 1.95), and gallium-doped zinc oxide. (GZO; 1.9 to 2.2). Among these, antimony-doped tin oxide (ATO) having excellent conductivity is preferable. In addition, the numerical value in the said parenthesis shows the refractive index of the material of each particle | grain.

The conductive high refractive index particles may be contained in at least one of the high refractive index layer (A) and the high refractive index layer (B). The degree tends to increase. For this reason, it is preferable that the conductive highly refractive particles are contained in the layer on the side where the amount of the high refractive index particles added is small (in other words, the layer on the side where the refractive index is lowered). More specifically, the high refractive index layer (A) contains conductive high refractive index particles, and the high refractive index layer (B) has a nonconductive high refractive index higher than that of the conductive high refractive index particles. It is preferable to contain refractive index particles. With this configuration, it is possible to make the spectral reflectance of the antireflection film easily satisfy the above-described conditions while imparting antistatic properties to the antireflection film.
The high refractive index layer (A) contains non-conductive high refractive index particles, and the high refractive index layer (B) contains conductive high refractive index particles having a higher refractive index than the non-conductive high refractive index particles. You may make it contain. According to this configuration, it is possible to easily satisfy the above-described conditions for the spectral reflectance of the antireflection film while imparting antistatic properties to the antireflection film. However, in the case of this configuration, it is preferable to use particles having a sufficiently high refractive index as the conductive high refractive particles and suppress the addition amount of the conductive high refractive particles.

  In addition, electroconductive high refractive index particle | grain can make electroconductivity so high that electroconductive high refractive index particle | grains contact and form a network. That is, when conductive high refractive index particles and nonconductive high refractive index particles are used in the same layer, the formation of the network is hindered. In addition, when only the conductive high refractive index particles are used in the same layer, the formation of the network becomes smooth, and the conductivity can be improved with a small addition amount and a small thickness. For this reason, it is preferable that the conductive high refractive index particles and the nonconductive high refractive particles are not used in the same layer. For example, it is preferable that the high refractive index layer containing conductive high refractive index particles does not substantially contain nonconductive high refractive particles. Moreover, it is preferable that the high refractive index layer containing non-conductive high refractive index particles does not substantially contain conductive high refractive particles. “Substantially not contained” means 0.5% by mass or less of the total solid content in the high refractive index layer, preferably 0.1% by mass or less, and more preferably 0% by mass.

Non-conductive high refractive index particles include zinc oxide (ZnO; 1.90), titanium oxide (TiO ₂ ; 2.3 to 2.7), cerium oxide (CeO ₂ ; 1.95), yttrium oxide (Y ₂ O ₃ ; 1.87), zirconium oxide (ZrO ₂ ; 2.0) and the like, and can be appropriately selected depending on the application. In addition, the numerical value in the said parenthesis shows the refractive index of the material of each particle | grain.

The average particle diameter of primary particles of the high refractive index particles (conductive high refractive index particles and nonconductive high refractive index particles) is preferably 5 to 200 nm, more preferably 5 to 100 nm, and even more preferably 10 to 80 nm.
If the average particle diameter of the primary particles of the high refractive index particles is within the above range, the transparency of the high refractive index layer is not impaired, a good dispersion state of fine particles can be obtained, and a desired refractive index can be obtained. . Moreover, in this invention, if an average particle diameter exists in the said range, microparticles | fine-particles may be formed in a chain form. In particular, when conductive highly refractive particles are connected in a chain, it is preferable in that the conductivity can be increased with a small amount.
In addition, the average particle diameter of the primary particles of the high refractive index particles and the low refractive index particles described later can be measured by a laser scattering method. In addition, the average particle diameter of the primary particles of the high refractive index particles in the high refractive index layer is obtained by taking a photograph of the cross section of the high refractive index layer with a scanning transmission electron microscope (STEM), and high refraction without aggregation from the screen. The operation is repeated until particles are extracted and a total of 20 high-refractive particles can be extracted, and can be calculated from the number average of the primary particle diameters of the total 20 high-refractive particles. The average particle diameter of the primary particles of the low refractive index particles in the low refractive index layer can be calculated by the same means.

  The content of the high refractive index particles can be adjusted within a range that satisfies the refractive index described later. Usually, the content of the high refractive index particles is preferably 50 to 500 parts by mass and more preferably 60 to 400 parts by mass with respect to 100 parts by mass of the curable resin composition.

The refractive index of the high refractive index layer is such that the refractive index of the high refractive index layer (A) is 1.50 to 1.75 and the high refractive index layer (B) The refractive index is preferably 1.60 to 1.80. More preferably, the refractive index of the high refractive index layer (A) is 1.55 to 1.73, the refractive index of the high refractive index layer (B) is 1.61 to 1.78, and more preferably, The refractive index of the high refractive index layer (A) is 1.57 to 1.70, and the refractive index of the high refractive index layer (B) is 1.62 to 1.75.
The refractive index difference between the high refractive index layer (A) and the high refractive index layer (B) [refractive index of the high refractive index layer (A) −refractive index of the high refractive index layer (B)] is 0.10. Or less, more preferably from 0.01 to 0.08, and even more preferably from 0.02 to 0.07.

The thickness of the high refractive index layer is preferably 100 to 200 nm in total thickness of the high refractive index layer (A) and the high refractive index layer (B) in order to easily satisfy the above-described spectral reflectance conditions. More preferably, it is 130-190 nm.
Further, in order to easily satisfy the above-described spectral reflectance condition, the thickness of the layer containing conductive high refractive index particles in the high refractive index layer (A) and the high refractive index layer (B) is non-conductive. It is preferable that the thickness of the layer containing conductive high refractive index particles is smaller.
Specifically, when the high refractive index layer (A) contains conductive high refractive particles and the high refractive index layer (B) contains nonconductive high refractive particles, the thickness of the high refractive index layer (A). And the ratio of the thickness of the high refractive index layer (B) ([the thickness of the high refractive index layer (A) / the thickness of the high refractive index layer (B)]) is preferably 0.40 to 0.90. More preferably, it is 0.50 to 0.80. Moreover, when satisfy | filling this ratio, it is preferable that the refractive index of the high refractive index layer (B) is higher than the high refractive index layer (A). By satisfying these conditions, the above-described spectral reflectance can be satisfied and the antistatic property can be easily improved.
Conversely, when the high refractive index layer (A) contains non-conductive high refractive particles and the high refractive index layer (B) contains conductive high refractive particles, the thickness of the high refractive index layer (B), The ratio with respect to the thickness of the high refractive index layer (A) ([thickness of high refractive index layer (B) / thickness of high refractive index layer (A)]) is preferably 0.40 to 0.90. More preferably, it is 50 to 0.80. Moreover, when satisfy | filling this ratio, it is preferable that the refractive index of the high refractive index layer (B) is higher than the high refractive index layer (A).

The high refractive index layer is prepared by adjusting the coating liquid for forming a high refractive index layer with a high refractive index particle, a curable resin composition, an additive such as an ultraviolet absorber or a leveling agent and a diluent solvent, if necessary. The coating liquid can be formed by coating and drying by a conventionally known coating method, and curing by irradiating ionizing radiation as necessary.
As the curable resin composition for forming the high refractive index layer, the same as those exemplified for the hard coat layer can be used, and an ionizing radiation curable resin composition is suitable.

<Low refractive index layer>
The low refractive index layer is a layer provided on the high refractive index layer.
Methods for forming the low refractive index layer can be broadly classified into wet methods and dry methods. As the wet method, a method of forming by a sol-gel method using a metal alkoxide, a method of forming by applying a low refractive index resin such as a fluororesin, and a low low refractive index particle in a resin composition. A technique of coating and forming a coating solution for forming a refractive index layer is exemplified. Examples of the dry method include a method in which particles having a desired refractive index are selected from low-refractive-index particles described later and formed by physical vapor deposition or chemical vapor deposition.
The wet method is excellent in terms of production efficiency. In the present invention, among the wet methods, the wet method is preferably formed by a coating solution for forming a low refractive index layer in which low refractive index particles are contained in a resin composition.

  The low refractive index particles are preferably used for the purpose of reducing the refractive index, that is, for the purpose of improving the antireflection property. The low refractive index particles can be used without limitation whether they are inorganic or organic such as silica and magnesium fluoride, but the viewpoint of improving the antireflection properties and ensuring good surface hardness. Therefore, particles having a structure having voids themselves are preferably used.

  A particle having a structure having a void itself has a fine void inside, and is filled with a gas such as air having a refractive index of 1.0, so that its own refractive index is low. It has become. Examples of such particles having voids include inorganic or organic porous particles, hollow particles, and the like. For example, porous polymer particles using porous silica, hollow silica particles, acrylic resin, or the like. And hollow polymer particles. As inorganic particles, silica particles having voids prepared by using the technology disclosed in Japanese Patent Application Laid-Open No. 2001-233611 are used, and as organic particles, technology disclosed in Japanese Patent Application Laid-Open No. 2002-80503. As a preferred example, hollow polymer particles prepared using Silica having voids as described above, or porous silica has a refractive index in the range of 1.20 to 1.44, and the refractive index is higher than that of general silica particles having a refractive index of about 1.45. Is low from the viewpoint of reducing the refractive index of the low refractive index layer.

  The hollow silica particles are particles having a function of lowering the refractive index while maintaining the coating strength of the low refractive index layer. The hollow silica particles used in the present invention are silica particles having a structure having a cavity inside. The hollow silica particles are silica particles whose refractive index decreases in inverse proportion to the occupancy of the internal cavities as compared with the original refractive index of silica particles (refractive index n = 1.46 or so). For this reason, the refractive index of the hollow silica particles as a whole is 1.20 to 1.45.

  The hollow silica particles are not particularly limited, and are, for example, particles that have an outer shell and are porous or hollow inside, and are disclosed in JP-A-6-330606, JP-A-7-013137, and JP-A-7. -133105 and the silica particle prepared using the technique currently disclosed by Unexamined-Japanese-Patent No. 2001-233611.

  The average particle diameter of the primary particles of the low refractive index particles is preferably 5 to 200 nm, more preferably 5 to 100 nm, and further preferably 10 to 80 nm. If the average particle diameter of the particles is within the above range, the transparency of the low refractive index layer is not impaired, and a good dispersion state of the particles can be obtained. Moreover, in this invention, if an average particle diameter exists in the said range, particle | grains may be formed in a chain form.

  The low refractive index particles used in the present invention are preferably surface-treated. As the surface treatment of the low refractive index particles, a surface treatment using a silane coupling agent is more preferable, and among these, a surface treatment using a silane coupling agent having a (meth) acryloyl group is preferably performed. By applying surface treatment to the low refractive index particles, the affinity with the binder resin described later is improved, the dispersion of the particles becomes uniform, and the particles are less likely to agglomerate. The decrease in the transparency of the refractive index layer, the applicability of the composition for forming a low refractive index layer, and the decrease in the coating strength of the composition are suppressed.

  In addition, when the silane coupling agent has a (meth) acryloyl group, the silane coupling agent has ionizing radiation curability, and therefore easily reacts with a binder resin described later. Therefore, the composition for forming a low refractive index layer In the coating film, the low refractive index particles are satisfactorily fixed to the binder resin. That is, the low refractive index particles have a function as a crosslinking agent in the binder resin. Thereby, the tightening effect of the whole coating film is obtained, and it is possible to impart excellent surface hardness to the low refractive index layer while leaving the flexibility inherent to the binder resin. Therefore, since the low refractive index layer is deformed by utilizing its own flexibility, it has the ability to absorb and restore external impacts, so that the generation of scratches is suppressed and the surface hardness is excellent with excellent scratch resistance. It will have.

  Examples of the silane coupling agent preferably used in the surface treatment of the low refractive index particles include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3- (meth) acryloxypropyl. Examples thereof include methyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 2- (meth) acryloxypropyltrimethoxysilane, 2- (meth) acryloxypropyltriethoxysilane and the like.

The content of the low refractive index particles in the low refractive index layer is preferably 80 to 160 parts by mass, more preferably 85 to 155 parts by mass, and further 90 to 150 parts by mass with respect to 100 parts by mass of the resin of the low refractive index layer. preferable. If the content of the fine particles is within the above range, good antireflection characteristics and surface hardness can be obtained.
The proportion of hollow particles and / or porous particles in all the low refractive index particles contained in the low refractive index layer is preferably 65 to 97 mass%, more preferably 67 to 95 mass%, and 69 to 93 mass%. Is more preferable.

As a resin composition contained in the coating solution for forming a low refractive index layer, first, a curable resin composition is exemplified. As a curable resin composition, the thing similar to what was illustrated by the hard-coat layer can be used, and an ionizing radiation curable resin composition is suitable.
Further, as the resin composition, a fluorine-containing polymer that itself exhibits a low refractive index property is also preferably used. The fluorine-containing polymer is a polymer of a polymerizable compound containing at least a fluorine atom in the molecule, and is preferable in that it can impart antifouling property and slipperiness. The fluoropolymer preferably has a reactive group in the molecule and functions as a curable resin composition, and has an ionizing radiation curable reactive group and functions as an ionizing radiation curable resin composition. More preferred.

  As the fluorine-containing polymer, not only repels dirt on the surface of the low refractive index layer, but also preferably contains silicon together with fluorine in order to impart wiping property of the repelled dirt. For example, a silicone component is added to the copolymer. Preferred is a silicone-containing vinylidene fluoride copolymer. Examples of silicone components in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl-modified (poly) dimethylsiloxane, azo group-containing (poly) dimethylsiloxane, , Dimethyl silicone, phenylmethyl silicone, alkyl aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, methyl hydrogen silicone, silanol group containing silicone, alkoxy group containing silicone, phenol group containing silicone, methacryl modified silicone, Acrylic modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone Corn, fluorine-modified silicones, polyether-modified silicone, and the like. Of these, those having a dimethylsiloxane structure are preferred.

  The refractive index of the low refractive index layer is preferably 1.27 to 1.35, more preferably 1.28 to 1.33 in order to easily satisfy the above-described spectral reflectance condition. More preferably, it is 1.29 to 1.32.

  The thickness of the low refractive index layer is preferably 80 to 120 nm, more preferably 85 to 110 nm, and still more preferably 90 to 105 nm in order to easily satisfy the above-described spectral reflectance conditions. .

  The low refractive index layer is prepared, for example, by adjusting the coating solution for forming a low refractive index layer with low refractive index particles, a resin composition, additives such as an ultraviolet absorber and a leveling agent, and a diluent solvent, if necessary. The coating liquid can be formed on the high refractive index layer by coating and drying by a conventionally known coating method, and curing by irradiation with ionizing radiation as necessary.

[display]
The display of the present invention is a display having an antireflection film on the outermost surface, and the antireflection film of the present invention described above is used as the antireflection film.

Examples of the display include a liquid crystal display (LCD), a plasma display panel (PDP), a cathode ray tube display (CRT), an inorganic and organic electroluminescence display, a rear projection display, a fluorescent display tube (VFD), and the like. Can be mentioned.
The display of the present invention can be produced by attaching the above-described antireflection film of the present invention to the surface plate of these displays via an adhesive layer.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.

1. Physical properties and evaluation The following measurements and evaluations were performed on the antireflection films obtained in Examples and Comparative Examples. The results are shown in Table 1.

(1) Spectral reflectance A black tape is applied to the surface of the transparent substrate opposite to the side on which the hard coat layer is formed to prevent back reflection, and the low refractive index layer side of the antireflection film is used as the light source. The spectral reflectance was measured at 1 nm intervals in the wavelength range of 380 to 780 nm using a spectrophotometer (manufactured by Shimadzu Corporation, model number: UV-2450). The measurement conditions at this time were a C light source, a 2-degree field of view, and an incident angle of 5 °.
(2) Visibility About the antireflection film, the light of the fluorescent lamp (three-wavelength fluorescent lamp tube) and the light of the white LED are respectively reflected from the front (0 degree) of the observation surface, and the reflected light of the front (0 degree) The difference in color from the reflected light at 45 degrees to the left and right was evaluated visually.
Color is almost the same: ○
Feel the difference in color: △
There is a big difference in color: ×

(3) Surface resistivity Reflection using a surface resistance meter (Mitsubishi Chemical Co., Ltd., Loresta MCP: Four-terminal probe) based on JIS R1637 (Fine ceramic thin film resistivity test method: 4-probe method measurement method) The surface resistivity (Ω / □) of the surface of the prevention film on the low refractive index layer side was measured.
Surface resistivity 1.0 × 10 ¹² Ω / □ or less: ○ Surface resistivity 1.0 × 10 ¹² Ω / □ or more: ×
(4) Interference fringes A black tape is attached to the surface of the transparent substrate opposite to the side where the hard coat layer is formed to prevent back reflection, and a three-wavelength tube fluorescent lamp is irradiated from the low refractive index layer side. Then, the presence or absence of interference fringes was visually evaluated.
Interference fringes are not visible: ○ Interference fringes are visible: ×

2. Preparation of coating solution Preparation Example 1: Preparation of coating solution for forming a hard coat layer The following components were mixed at the following mass ratio to prepare a coating solution for forming a hard coat layer.
<Coating liquid for forming hard coat layer>
-Urethane acrylate ^{* 11} : 12.0 parts by mass-Isocyanuric acid EO-modified triacrylate ^{* 12} : 4.0 parts by mass-Polymerization initiator ^{* 13} : 0.6 parts by mass-Methyl ethyl ketone: 5.6 parts by mass * 11: " “UV1700B (trade name)”, manufactured by Nippon Synthetic Chemical Co., Ltd. * 12: “M315 (trade name)”, manufactured by Toagosei Co., Ltd. * 13: “Irgacure 184 (trade name)”, manufactured by BASF Japan

Preparation Example 2: Preparation of Coating Solution 1 for Forming High Refractive Index Layer (A) The following components were mixed at the following mass ratio to prepare Coating Solution 1 for forming a high refractive index layer (A).
<Coating liquid 1 for forming a high refractive index layer (A)>
-ATO particle dispersion ^{* 21} : 0.97 parts by mass-Binder resin ^{* 22} : 0.31 parts by mass-Photopolymerization initiator ^{* 23} : 0.007 parts by mass-Propylene glycol monomethyl ether: 13 parts by mass * 21: " ELCOM V-3560 (trade name), manufactured by JGC Catalysts & Chemicals, ATO particle primary particle size: 5 to 11 nm, solid content 20%
* 22: “KAYARAD DPHA (trade name)” manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate * 23: “Irgacure 127 (trade name)”, manufactured by BASF Japan

Preparation Example 3: Preparation of Coating Solution 2 for Forming High Refractive Index Layer (A) The following components were mixed at the following mass ratio to prepare Coating Solution 2 for forming a high refractive index layer (A).
<High refractive index layer (A) forming coating solution 2>
-Zirconia particle dispersion ^{* 31} : 0.8 parts by mass-Binder resin ^{* 22} : 0.1 parts by mass-Photopolymerization initiator ^{* 23} : 0.007 parts by mass-Propylene glycol monomethyl ether: 10.3 parts by mass * 31 : “ZRPGM15WT% -F04 (trade name)”, manufactured by CIK Nanotech, primary particle size of zirconia particles: 20 nm, solid content 15%

Preparation Example 4: Preparation of coating solution 3 for forming a high refractive index layer (A) The following components were mixed in the following mass ratio to prepare coating solution 3 for forming a high refractive index layer (A).
<Coating liquid 3 for forming a high refractive index layer (A)>
-Antimony pentoxide particle dispersion ^{* 41} : 0.84 parts by mass-Binder resin ^{* 22} : 0.085 parts by mass-Photopolymerization initiator ^{* 23} : 0.007 parts by mass-Propylene glycol monomethyl ether: 11.3 parts by mass * 41: “ELCOM V-4564 (trade name)”, manufactured by JGC Catalysts & Chemicals, solid content of 40%

Preparation Example 5: Preparation of coating solution 1 for forming high refractive index layer (B) The following components were mixed in the following mass ratio to prepare coating solution 1 for forming a high refractive index layer (B).
<Coating liquid 1 for forming a high refractive index layer (B)>
-Zirconia particle dispersion ^{* 51} : 0.8 parts by mass-Binder resin ^{* 52} : 0.1 parts by mass-Photopolymerization initiator ^{* 53} : 0.007 parts by mass-Propylene glycol monomethyl ether: 10.3 parts by mass * 51 : “ZRPGM15WT% -F04 (trade name)”, manufactured by CIK Nanotech, primary particle size of zirconia particles: 20 nm, solid content 15%
* 52: “KAYARAD DPHA (trade name)” manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate * 53: “Irgacure 127 (trade name)”, manufactured by BASF Japan

Preparation Example 6: Preparation of coating solution 2 for forming high refractive index layer (B) The following components were mixed in the following mass ratio to prepare coating solution 2 for forming a high refractive index layer (B).
<High refractive index layer (B) forming coating solution 2>
-GZO particle dispersion ^{* 61} : 1.25 parts by mass-Binder resin ^{* 52} : 0.31 parts by mass-Photopolymerization initiator ^{* 53} : 0.007 parts by mass-Methyl isobutyl ketone: 12.5 parts by mass * 61: “GZO MIBK 15 WT% (trade name)”, manufactured by CIK Nanotech, primary particle size of GZO particles: about 30 nm, solid content 15%

Preparation Example 7: Preparation of coating solution for forming low refractive index layer The following components were mixed at the following mass ratio to obtain a coating solution for forming a low refractive index layer.
<Coating liquid for forming a low refractive index layer>
Pentaerythritol triacrylate (PETA): 0.015 parts by mass Hollow silica particle dispersion ^{* 71} : 0.8 parts by mass Solid silica particle dispersion ^{* 72} : 0.05 parts by mass Fluoropolymer ^{* 73} : 0.6 parts by mass, fluorine-containing monomer ^{* 74} : 0.06 parts by mass, photopolymerization initiator ^{* 75} : 0.008 parts by mass, methyl isobutyl ketone: 9.0 parts by mass, propylene glycol monomethyl ether acetate: 1.2 Mass part * 71: The content of hollow silica particles in the dispersion is 20.5% by mass, and the content of solvent (methyl isobutyl ketone) is 79.5% by mass. Moreover, the average particle diameter of hollow silica particles is 60 nm, and has a photocurable reactive group by surface treatment.
* 72: “MIBK-SD (trade name)”, average primary particle size: 12 nm, solid content: 30% by mass, solvent: methyl isobutyl ketone, silica particle-containing reactive functional group: methacryloyl group * 73: “OPSTAR TU2224 ( Product name) ”, manufactured by JSR, 20% by mass solution (solvent: methyl isobutyl ketone)
* 74: “LINC3A (trade name)”: manufactured by Kyoeisha Chemical Co., Ltd., fluorine-containing monomer having a pentaerythritol skeleton, 20% by mass solution (solvent: methyl isobutyl ketone)
* 75: “Irgacure 127 (trade name)” manufactured by BASF Japan

[Example 1]
On the triacetyl cellulose (TAC) resin film having a thickness of 80 μm, the coating liquid for forming a hard coat layer obtained in Preparation Example 1 is bar-coated, dried at 50 ° C. for 1 minute, and the solvent is removed. Using a UV irradiation device (manufactured by Fusion UV System Japan, light source H bulb), UV irradiation was performed at an irradiation dose of 30 mJ / cm ² and cured to obtain a hard coat layer having a thickness of 5 μm and a refractive index of 1.51. .
Next, the coating liquid 1 for forming the high refractive index layer (A) obtained in Preparation Example 2 is bar-coated on the hard coat layer, cured by irradiation with ultraviolet rays at an irradiation dose of 40 mJ / cm ² , a thickness of 65 nm, A high refractive index layer (A) having a refractive index of 1.61 was formed.
Next, the coating solution 1 for forming the high refractive index layer (B) obtained in Preparation Example 5 is bar coated on the high refractive index layer (A), and cured by irradiation with ultraviolet rays at an irradiation dose of 40 mJ / cm ^2. A high refractive index layer (B) having a thickness of 105 nm and a refractive index of 1.65 was formed.
Furthermore, on the high refractive index layer (B), the coating solution for forming the low refractive index layer obtained in Preparation Example 7 is bar-coated, dried at 50 ° C. for 1 minute, and after removing the solvent, the irradiation dose It is cured by irradiation with ultraviolet rays at 200 mJ / cm ² to form a low refractive index layer having a thickness of 102 nm and a refractive index of 1.30. Transparent substrate / hard coat layer / high refractive index layer (A) / high refractive index An antireflection film having a layer (B) / low refractive index layer was obtained.

[Example 2]
An antireflection film was obtained in the same manner as in Example 1 except that the thickness of the high refractive index layer (A) in Example 1 was changed to 75 nm and the thickness of the high refractive index layer (B) was changed to 95 nm.

[Example 3]
An antireflection film was obtained in the same manner as in Example 1 except that the thickness of the high refractive index layer (A) in Example 1 was changed to 65 m and the thickness of the high refractive index layer (B) was changed to 120 nm.

[Example 4]
The coating liquid 1 for forming the high refractive index layer (A) in Example 1 was changed to the coating liquid 2 for forming the high refractive index layer (A), and the coating liquid 1 for forming the high refractive index layer (B) was changed to the high refractive index layer. (B) It changed into the forming coating liquid 2. Further, the thickness of the high refractive index layer (A) of Example 1 was changed to 68 nm, and the thickness of the high refractive index layer (B) was changed to 97 nm. An antireflection film was obtained in the same manner as in Example 1 except for these changes. In addition, the refractive index of the high refractive index layer (A) of Example 4 was 1.66, and the refractive index of the high refractive index layer (B) was 1.73.

[Example 5]
An antireflection film was obtained in the same manner as in Example 1 except that the thickness of the high refractive index layer (A) in Example 1 was changed to 70 nm and the thickness of the high refractive index layer (B) was changed to 110 nm.

[Comparative Example 1]
An antireflection film was obtained in the same manner as in Example 1, except that the thickness of the high refractive index layer (A) in Example 1 was changed to 110 nm and the thickness of the high refractive index layer (B) was changed to 70 nm.

[Comparative Example 2]
An antireflection film was obtained in the same manner as in Example 1 except that the thickness of the high refractive index layer (A) in Example 1 was changed to 45 nm and the thickness of the high refractive index layer (B) was changed to 125 nm.

[Comparative Example 3]
An antireflection film was obtained in the same manner as in Example 1 except that the thickness of the high refractive index layer (A) in Example 1 was changed to 125 nm and the thickness of the high refractive index layer (B) was changed to 45 nm.

[Comparative Example 4]
The coating liquid 1 for forming the high refractive index layer (A) in Example 1 was changed to the coating liquid 3 for forming the high refractive index layer (A), and the high refractive index layer (B) was not formed. An antireflection film was obtained in the same manner as in Example 1 except that the thickness of A) was changed to 170 nm.

[Comparative Example 5]
An antireflection film was obtained in the same manner as in Example 1 except that the high refractive index layer (B) of Example 1 was not formed and the thickness of the high refractive index layer (A) was changed to 170 nm.

[Comparative Example 6]
An antireflection film was obtained in the same manner as in Example 1 except that the high refractive index layer (A) of Example 1 was not formed and the thickness of the high refractive index layer (B) was changed to 170 nm.

  The antireflection film and display of the present invention are excellent in antistatic properties without causing coloring problems in the presence of illumination (particularly under LED illumination) or when conductive particles such as ITO and ATO are used. It is preferable in that a high-quality video can be provided.

1: Antireflection film 2: Transparent substrate 3: Hard coat layer 4: High refractive index layer (A)
5: High refractive index layer (B)
6: Low refractive index layer

Claims (9)

An antireflection film having a high refractive index layer and a low refractive index layer in this order on at least one surface of a transparent substrate, the high refractive index layer containing conductive high refractive index particles, and having a wavelength region The average spectral reflectance of the antireflection film surface at λ ₁ (450 nm ≦ λ ₁ ≦ 680 nm) is 0.05 to 0.40%, and the wavelength region λ _a (430 ≦ λ _a <500 nm), the wavelength region λ _The antireflection film in which the spectral reflectance of the antireflection film surface in _b (500 nm ≦ λ _b ≦ 600 nm) and wavelength region λ _c (600 nm <λ _c ≦ 730 nm) satisfies the following conditions (a) to (c) .
(A) The spectral reflectance in the wavelength region λ _a is 0.05 to 1.30%, and monotonously decreases from 430 nm to 500 nm.
(B) The average spectral reflectance in the wavelength region λ _b is 0.03% or more and less than 0.15%.
(C) The spectral reflectance in the wavelength region λ _c is 0.05 to 1.50% and monotonously increases from 600 nm to 730 nm. The antireflection film according to claim 1, wherein a ratio (R _max / R _min ) between the maximum value R _max and the minimum value R _min of the spectral reflectance in the wavelength region λ _b is 1.00 to 2.90.   The high refractive index layer comprises a high refractive index layer (A) located on the transparent substrate side and a high refractive index layer (B) located on the low refractive index layer side, and the high refractive index layer ( The refractive index of the high refractive index layer (B) is higher than the refractive index of A), and further, at least one of the high refractive index layer (A) and the high refractive index layer (B) has the conductivity high. The antireflection film according to claim 1 or 2, comprising refractive index particles.   The high refractive index layer (A) has a refractive index of 1.50 to 1.75, the high refractive index layer (B) has a refractive index of 1.60 to 1.80, and the high refractive index layer (A) The antireflection film according to claim 3, wherein the total thickness of the high refractive index layer (B) is 100 to 200 nm.   The high refractive index layer (A) contains the conductive high refractive index particles, and the high refractive index layer (B) contains nonconductive high refractive index particles. The antireflection film as described.   Ratio of the thickness of the high refractive index layer (A) and the thickness of the high refractive index layer (B) ([thickness of the high refractive index layer (A) / thickness of the high refractive index layer (B)]) The antireflection film according to claim 5, wherein is from 0.40 to 0.90.   The antireflection film according to claim 1, wherein the low refractive index layer has a refractive index of 1.27 to 1.35 and a thickness of 80 to 120 nm. The antireflection film according to any one of claims 1 to 7, wherein a surface resistivity of the antireflection film is 1.0 × 10 ¹² Ω / □ or less.   A display having an antireflection film on the outermost surface, wherein the antireflection film according to any one of claims 1 to 8 is used as the antireflection film.