JP2016041481A - Transparent base material with antiglare antireflection film, and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent base material with an antiglare antireflection film that is excellent in both antiglare and antireflection properties, and an article prepared therewith.SOLUTION: A transparent base material with an antiglare antireflection film 10 comprises a transparent base material 12, and an antiglare antireflection film 18. The antiglare antireflection film 18 comprises a low reflective film 14 formed on the transparent base material 12, and an antiglare film 16 formed on the low reflective film 14. The low reflective film 14 has a refractive index of 1.24-1.35 and a thickness of 20-140 nm. The antiglare film 16 has a refractive index of 1.40-1.50 and the antiglare film 16 has the surface with its arithmetic mean roughness Ra of 0.04-0.14 μm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transparent substrate with an antiglare antireflection film and an article using the same.

In image display devices (liquid crystal displays, organic EL displays, plasma displays, etc.) provided in various devices (TVs, personal computers, smartphones, mobile phones, etc.), room lights (fluorescent lamps, etc.), external light such as sunlight Is reflected on the display surface, the visibility decreases due to the reflected image. Therefore, in order to suppress the reflection of external light, an anti-glare treatment or a low reflection treatment is performed on the surface of a base material (glass plate or the like) constituting the display surface of the image display device.
In recent years, the light incident surface of the cover glass of a solar cell module has been subjected to antireflection treatment to reduce sunlight reflection and increase power generation efficiency, and light damage caused by reflected light reflected on the cover glass surface has been reduced. In order to prevent this, an antiglare treatment is also performed.

The antireflection process is a process for suppressing reflection of incident light itself. By suppressing the reflection of incident light, image resolution, contrast, light transmittance, and the like are improved. As an antireflection treatment, a method of providing a low reflection film is conventionally known. As the low reflection film, a single layer film made of a low refractive index material, a multilayer film in which a layer made of a low refractive index material and a layer made of a high refractive index material are combined are known.
The antiglare treatment is a treatment in which irregularities are provided on the surface and incident light is scattered by the irregularities. When the incident light is diffusely reflected, the reflected image becomes unclear and the reflection of external light is suppressed. Conventionally known anti-glare treatments include a method of roughening the surface of a substrate by erosion, sand blasting, or the like, and a method of providing an anti-glare film having irregularities on the surface.

As an antiglare and antireflection film having the same antiglare and antireflection film, the following antiglare antireflection film (1) has been proposed (Patent Document 1).
(1) An uneven antiglare layer having a fine surface is formed directly on the transparent substrate film or via another layer, and the refractive index lower than that of the antiglare layer is formed on the antiglare layer. In the antireflection film in which a low refractive index layer having a refractive index is formed, the low refractive index layer is formed by laminating two different types of first low refractive index layers and second low refractive index layers in this order. And the refractive index of the antiglare layer is higher than the refractive index of the layer of the antiglare layer that is in contact with the surface opposite to the surface that is in contact with the low refractive index layer. Antireflection film.

JP 7-325203 A

However, with the antiglare antireflection film of (1), it is difficult to achieve both antiglare and antireflection properties at a high level. The low reflection film is usually designed so that the average transmittance of light in an arbitrarily set wavelength range is maximized based on the optical path length depending on the vertical incident angle. In the antiglare antireflection film of (1), since the surface of the low refractive index layer (low reflective film) has irregularities, it is difficult to design as described above, and the transmittance improvement effect by the low refractive index layer. Is insufficient.
In general, when the surface roughness of the antiglare film increases, the haze increases and the antiglare property increases. However, as the haze increases, the light transmittance is lowered, and in some cases, the transmittance is lower than in the case of the transparent substrate alone. In the antiglare antireflection film of (1), the same problem arises if the surface irregularities of the antiglare layer become large. Moreover, antifouling property, abrasion resistance, etc. also fall by the unevenness | corrugation of a surface becoming large.

  An object of this invention is to provide the transparent base material with an anti-glare antireflection film which is excellent in both anti-glare property and anti-reflection property, and an article using the same.

The present invention has the following aspects.
[1] A transparent substrate and an antiglare antireflection film are provided,
The antiglare antireflection film comprises a low reflection film formed on the transparent substrate and an antiglare film formed on the low reflection film,
The low reflective film has a refractive index of 1.24 to 1.35, and the low reflective film has a thickness of 20 to 140 nm.
A transparent base material with an antiglare antireflection film, wherein the antiglare film has a refractive index of 1.40 to 1.50 and an arithmetic average roughness Ra of the surface of the antiglare film is 0.04 to 0.14 μm.
[2] The transparent base material with an antiglare antireflection film according to [1], wherein the low reflection film contains one or both of solid silica particles and hollow silica particles.
[3] The transparent base material with an antiglare antireflection film according to [1] or [2], wherein the matrix of the antiglare film has silica as a main component.
[4] The antiglare antireflection film according to any one of [1] to [3], wherein the antiglare film is formed from a coating liquid containing a silica precursor and a liquid medium. Transparent base material with
[5] The transparent base material with an antiglare antireflection film according to [3] or [4], wherein the antiglare film includes one or both of solid silica particles and scale-like silica particles.
[6] The transparent substrate with an antiglare antireflection film according to any one of [1] to [5], wherein the transparent substrate is a chemically strengthened glass plate.
[7] An article comprising the transparent base material with an antiglare antireflection film according to any one of [1] to [6].
[8] The article according to [7], which is a solar cell module.

  ADVANTAGE OF THE INVENTION According to this invention, the transparent base material with an anti-glare antireflection film which is excellent in both anti-glare property and antireflection property, and an article using the same can be provided.

It is sectional drawing which shows typically one Embodiment of the transparent base material with an anti-glare antireflection film of this invention.

The following definitions of terms apply throughout this specification and the claims.
“Containing silica as a main component” means containing 90 mass% or more of SiO ₂ .
“Silica precursor” means a substance capable of forming a matrix mainly composed of silica.
The “hydrolyzable group bonded to a silicon atom” means a group that can be converted into an OH group bonded to a silicon atom by hydrolysis.
“Solid” indicates that there is no cavity inside.
“Hollow” indicates that there is a cavity inside.
“Scaly” means having a flat shape.

The refractive index and film thickness of the low reflection film are determined by the following measurement method.
Only the low reflection film is formed on the transparent substrate, and the reflectance in the wavelength range of 380 to 780 nm on the surface of the low reflection film is measured with a spectrophotometer. The incident angle of light is 5 °.
From the minimum reflectance (so-called bottom reflectance) R _min within the wavelength range of 380 to 780 nm and the refractive index ns of the transparent substrate 12, the refractive index n of the low reflective film is calculated by the following equation (1).
R _min = (n−ns) ² / (n + ns) ² (1).
From the obtained refractive index n and the wavelength λ (nm) at the bottom reflectance R _min , the film thickness d (nm) of the low reflective film is calculated by the following equation (2).
n × d = λ / 4 (2).

The refractive index of the antiglare film is determined by the same measurement method as that of the low reflective film except that only the antiglare film is formed on the transparent substrate instead of the low reflective film.
The arithmetic average roughness Ra of the surface of the antiglare film is measured by the method described in JIS B 0601: 2001 (ISO 4287: 1997).

[Transparent substrate with antiglare antireflection film]
FIG. 1 is a cross-sectional view schematically showing an embodiment of a transparent substrate with an antiglare antireflection film of the present invention.
The transparent base material 10 with the antiglare antireflection film of the present embodiment includes a transparent base material 12 and an antiglare antireflection film 18.
The antiglare antireflection film 18 includes a low reflection film 14 formed on the transparent substrate 12 and an antiglare film 16 formed on the low reflection film 14.

(Transparent substrate)
The transparency in the transparent substrate 12 means that 80% or more of light in the wavelength region of 400 to 1100 nm is averaged.

Examples of the material of the transparent substrate 12 include glass and resin.
Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass.
Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethyl methacrylate, and the like.

Examples of the form of the transparent substrate 12 include a plate and a film.
The shape of the transparent substrate 12 is not limited to a flat shape as illustrated, but may be a shape having a curved surface. In recent years, various devices including an image display device (televisions, personal computers, smartphones, car navigation systems, etc.) in which the display surface of the image display device is curved have appeared. The transparent base material 10 with an antiglare antireflection film in which the transparent base material 12 has a curved surface is useful for such an image display device.
When the transparent substrate 12 has a curved surface, the entire surface of the transparent substrate 12 may be configured by a curved surface, or may be configured by a curved surface portion and a flat portion. As an example of the case where the entire surface is configured by a curved surface, for example, a case where the cross section of the transparent substrate is arcuate.

As the transparent substrate 12, a glass plate is preferable.
The glass plate may be a smooth glass plate formed by a float method, a fusion method, a downdraw method, or the like, or may be a template glass having irregularities on the surface formed by a roll-out method or the like. In addition to a flat glass plate, a glass plate having a curved surface may be used.
The thickness of the glass plate is not particularly limited. For example, a glass plate having a thickness of 10 mm or less can be used. The thinner the thickness, the lower the light absorption, which is preferable for the purpose of improving the transmittance. Moreover, it contributes to the weight reduction of the transparent base material 10 with an anti-glare antireflection film, so that thickness is thin.

When glass is soda-lime glass, what has the following composition is preferable.
In mass percentage display based on oxide,
SiO _2: 65~75%,
Al ₂ O _3: 0~10%,
CaO: 5 to 15%,
MgO: 0 to 15%,
Na ₂ O: 10~20%,
K ₂ O: 0 to 3%,
Li ₂ O: 0 to 5%,
Fe ₂ O ₃ : 0 to 3%,
TiO _2: 0~5%,
CeO ₂ : 0 to 3%,
BaO: 0 to 5%,
SrO: 0 to 5%,
B ₂ O _3: 0~15%,
ZnO: 0 to 5%,
ZrO ₂ : 0 to 5%,
SnO ₂ : 0 to 3%,
SO ₃ : 0 to 0.5%.

When glass is aluminosilicate glass, what has the following composition is preferable.
In mole percentage display on oxide basis,
SiO _2: 62~68%,
Al ₂ O ₃ : 6 to 20%,
MgO: 7-13%,
Na ₂ O: 9~17%,
K ₂ O: 0~7%,
ZrO ₂ : 0 to 8%.

The glass plate is preferably a tempered glass plate. The tempered glass plate is a glass plate that has been tempered. By the strengthening treatment, the strength of the glass is improved, and for example, it is possible to reduce the plate thickness while maintaining the strength.
However, in this invention, glass plates other than a tempered glass plate can also be used, and it can set suitably according to the use etc. of the transparent base material 10 with an anti-glare antireflection film.

As the strengthening treatment, a treatment for forming a compressive stress layer on the glass plate surface is generally known. The compressive stress layer on the surface of the glass plate improves the strength of the glass plate against scratches and impacts. Typical methods for forming a compressive stress layer on the surface of the glass plate include an air cooling strengthening method (physical strengthening method) and a chemical strengthening method.
In the air cooling strengthening method, the glass plate surface heated to near the softening point temperature of glass (for example, 600 to 700 ° C.) is rapidly cooled by air cooling or the like. Thereby, a temperature difference arises between the surface of a glass plate, and the inside, and a compressive stress arises in a glass plate surface layer.
In the chemical strengthening method, a glass plate is immersed in a molten salt at a temperature lower than the strain point temperature of the glass, and ions (for example, sodium ions) on the surface of the glass plate are exchanged for ions having a larger ion radius (for example, potassium ions). To do. Thereby, compressive stress arises in a glass plate surface layer.
The physical strengthening treatment and chemical strengthening treatment of the glass described above may be performed before or after the antiglare antireflection film is formed on the glass plate surface.

When the thickness of the glass plate is thin (for example, 2.5 mm or less, particularly less than 2 mm), the air cooling strengthening method is unlikely to cause a temperature difference between the inside of the glass plate and the surface layer. Therefore, the chemical strengthening method is preferably used.
The glass plate subjected to the chemical strengthening treatment is not particularly limited as long as it has a composition that can be chemically strengthened, and various glass compositions can be used, for example, soda lime glass, aluminosilicate glass, borate glass. , Lithium aluminosilicate glass, borosilicate glass, and various other glasses. In terms of easy chemical strengthening, the glass composition is expressed in terms of mole percentages based on oxides, SiO ₂ is 56 to 75%, Al ₂ O ₃ is 1 to 20%, Na ₂ O is 8 to 22%, K ₂ O. 0-10%, MgO 0-14%, ZrO ₂ 0-5% and CaO 0-10%. Of these, aluminosilicate glass is preferred.
The plate thickness of the glass plate subjected to the chemical strengthening treatment is preferably 0.1 to 2.5 mm, particularly preferably 0.1 to 2.0 mm. If the plate thickness is less than or equal to the upper limit of the above range, the transparent base material 10 with an antiglare antireflection film is lightweight, and if it is greater than or equal to the lower limit of the above range, the transparent base material 10 with antiglare antireflection film is Excellent strength.
There is no change in the plate thickness before and after chemical strengthening. That is, the plate thickness of the glass plate subjected to the chemical strengthening treatment is the thickness of the chemically strengthened glass plate (the glass plate after the chemical strengthening treatment is performed).

(Low reflective film)
The refractive index of the low reflection film 14 is 1.24 to 1.35, preferably 1.24 to 1.30.
The film thickness of the low reflection film 14 is 20 to 140 nm, and preferably 40 to 120 nm.
When the refractive index and film thickness of the low reflection film 14 are within the above ranges, the antireflection property is excellent.

  The refractive index of the low reflective film 14 can be adjusted by the matrix material of the low reflective film 14, the porosity of the low reflective film 14, the addition of a substance having an arbitrary refractive index into the matrix, and the like. For example, as the content of silica particles (I) described later increases, the porosity of the low reflective film 14 increases and the refractive index tends to decrease.

The low-reflection film 14 is not particularly limited as long as the refractive index and the film thickness are satisfied. From the viewpoint of easy adjustment of the refractive index, excellent chemical stability, and the like, solid silica particles and hollow silica particles Those containing either one or both (hereinafter also referred to as silica particles (I)) are preferred.
The membrane containing silica particles (I) typically further includes a matrix that fills the voids between the silica particles (I). The matrix may cover the upper side (the side opposite to the transparent substrate 12 side) of the silica particles (I).
The low reflection film 14 may further include particles other than the silica particles (I).
The low reflection film 14 may further include a terpene compound.
The low reflection film 14 may further include other components (hereinafter, also referred to as “other optional components”) other than the silica particles (I), the matrix, other particles, and the terpene compound.

Silica particles (I):
Examples of the shape of the solid silica particles include a spherical shape, an elliptical shape, a needle shape, a plate shape, a rod shape, a conical shape, a cylindrical shape, a cubic shape, a rectangular shape, a diamond shape, a star shape, and an indefinite shape. The solid silica particles may exist in a state where each particle is independent, each particle may be linked in a chain, or each particle may be aggregated.
The shape of the particles can be confirmed using a transmission electron microscope.
Solid silica particles may be used alone or in combination of two or more.

The solid silica particles are preferably chain solid silica particles in terms of easy reduction in refractive index.
The chain solid silica particles are solid silica particles having a chain shape. For example, the thing of the shape which the solid silica particle which has a shape of a some spherical ellipse shape, a needle shape, etc. connected in the shape of a chain | strand is mentioned. The shape of the chain solid silica particles can be confirmed by an electron microscope.
The chain solid silica particles can be easily obtained as a commercial product. Moreover, you may use what was manufactured by the well-known manufacturing method. Examples of commercially available products include Snowtex ST-OUP manufactured by Nissan Chemical Industries, Ltd.

The average aggregate particle diameter of the solid silica particles is preferably 5 to 300 nm, more preferably 5 to 200 nm. When the average aggregate particle diameter of the solid silica particles is equal to or greater than the lower limit of the above range, the reflectance of the low reflective film 14 is sufficiently low. When the average aggregate particle diameter of the solid silica particles is not more than the upper limit of the above range, the mechanical strength of the low reflective film 14 is increased. Moreover, the surface roughness of the low reflection film 14 is reduced, and the antifouling property of the transparent base material 10 with the antiglare antireflection film is improved.
The average agglomerated particle diameter can be measured using a dynamic light scattering particle size analyzer (for example, Microtrack UPA manufactured by Nikkiso Co., Ltd.).

Since the hollow silica particle has a cavity inside, the refractive index is lower than that of the solid silica particle. Therefore, there is an advantage that the effect of reducing the refractive index can be obtained in a small amount as compared with the solid silica particles.
Examples of the hollow silica particles include those having an outer shell of silica (SiO ₂ ) and having a hollow inside. The hollow silica particles may be present in an independent state, the particles may be linked in a chain, or the particles may be aggregated.

The average primary particle diameter of the hollow silica particles is preferably 40 to 150 nm, and more preferably 50 to 100 nm. When the average primary particle diameter of the hollow silica particles is equal to or greater than the lower limit of the above range, the reflectance of the low reflective film 14 is sufficiently low. If the average primary particle diameter of the hollow silica particles is not more than the upper limit of the above range, the hollow silica particles are densely packed and the refractive index is lowered. Moreover, the surface roughness of the low reflection film 14 is reduced, and the antifouling property of the transparent base material 10 with the antiglare antireflection film is improved.
The average primary particle diameter of the hollow silica particles is determined as follows.
The hollow silica particles are observed with a scanning electron microscope (hereinafter referred to as SEM) or a transmission electron microscope (hereinafter referred to as TEM), and 100 hollow silica particles are randomly selected and each hollow silica particle is selected. The particle diameters of the 100 hollow silica particles are averaged to determine the particle diameter.

matrix:
Examples of the matrix of the low reflection film 14 include a silica matrix and a titania matrix.
“Silica-based matrix” refers to a matrix mainly composed of silica.
The “titania matrix” refers to a matrix mainly composed of titania.
“Mainly containing titania” means containing 90% by mass or more of TiO ₂ .

As a matrix of the low reflection film 14, a silica-based matrix is preferable. If the matrix is a silica-based matrix, the refractive index (reflectance) of the low reflective film 14 tends to be low. In addition, chemical stability, wear resistance and the like are improved. When the transparent substrate 12 is glass, the adhesion is particularly good.
The silica-based matrix may contain a small amount of components other than silica. The components include Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Sr. , Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi and compounds such as one or more ions and oxides selected from lanthanoid elements .
As the silica-based matrix, those substantially consisting of silica are preferable. The phrase “consisting essentially of silica” means that it is composed only of silica excluding inevitable impurities.
Examples of the silica-based matrix include those formed from a coating solution containing a silica precursor and a liquid medium. The silica precursor will be described in detail later.

Other particles:
Examples of other particles include metal oxide particles, metal particles, pigment-based particles, and resin particles. Other particles may have a hollow structure or a solid structure.

As the material of the metal oxide particles, Al ₂ O ₃ , SiO ₂ , SnO ₂ , TiO ₂ , ZrO ₂ , ZnO, CeO ₂ , Sb-containing SnO _X (ATO), Sn-containing In ₂ O ₃ (ITO), RuO ₂ etc. are mentioned.
Examples of the material of the metal particles include metals (Ag, Ru, etc.), alloys (AgPd, RuAu, etc.) and the like.
Examples of pigment-based particles include inorganic pigments (titanium black, carbon black, etc.) and organic pigments.
Examples of the resin particle material include polystyrene and melanin resin.

Examples of other particle shapes include scales, spheres, ellipses, needles, plates, rods, cones, columns, cubes, cuboids, diamonds, stars, and irregular shapes. . The other particles may be present in an independent state, the particles may be linked in a chain, or the particles may be aggregated.
Other particles may be used alone or in combination of two or more.

As the other particles, scaly silica particles are preferable in that cracks and film peeling of the low reflective film 14 can be suppressed.
The flaky silica particles are flaky silica primary particles or silica secondary particles formed by laminating and laminating a plurality of flaky silica primary particles in parallel with each other. The silica secondary particles usually have a particle form of a laminated structure. The scaly silica particles may be either one of the silica primary particles and the silica secondary particles, or both.
As the flaky silica particles, commercially available ones may be used, or those produced may be used. Examples of the method for producing the scale-like silica particles include a production method described in Japanese Patent No. 4063464, a production method described in Japanese Patent Application Laid-Open No. 2014-94845, and the like.

Terpene compounds:
The terpene compound will be described in detail later.

Other optional ingredients:
Other optional components in the low reflection film 14 will be described in detail later.

The content of the silica particles (I) in the low reflection film 14 can be appropriately set in consideration of the refractive index of the low reflection film 14, the type of silica particles (I), and the like.
When the silica particles (I) are solid silica particles, the content of the solid silica particles in the low reflective film 14 is preferably 60 to 80% by mass with respect to the total mass of the low reflective film 14, 70-80 mass% is especially preferable. If the content of the solid silica particles is within the above range, the refractive index of the low reflective film 14 is likely to be within the above range. If the content of the solid silica particles is within the above range, the refractive index of the low reflective film 14 tends to decrease as the content of the solid silica particles increases.
When the silica particles (I) are hollow silica particles, the content of the hollow silica particles in the low reflection film 14 is preferably 21 to 80% by mass with respect to the total mass of the low reflection film 14, and 30 to 70% by mass is particularly preferred. If the content of the hollow silica particles is within the above range, the refractive index of the low reflective film 14 tends to be within the above range. If the content of the hollow silica particles is within the above range, the refractive index of the low reflective film 14 tends to decrease as the content of the hollow silica particles increases.

  In the low reflection film 14, the total content of the silica particles (I) and the matrix is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, with respect to the total mass of the low reflection film 14. 100% by mass is particularly preferred. When the total content of the silica particles (I) and the matrix is not less than the lower limit of the above range, the antiglare antireflection film 18 has more excellent wear resistance.

(Anti-glare film)
The refractive index of the antiglare film 16 is 1.40 to 1.50, preferably 1.40 to 1.48.
If the refractive index of the antiglare film 16 is not more than the upper limit of the above range, the reflection of light at the surface of the antiglare film 16 and the reflection of light at the interface between the antiglare film 16 and the low reflection film 14 are sufficiently suppressed. And antireflection properties are excellent. Further, by suppressing the reflection of light on the surface of the antiglare film 16, a sufficient antiglare effect can be obtained even when the arithmetic average roughness Ra of the surface is 0.14 μm or less.
If the refractive index of the antiglare film 16 is not less than the lower limit of the above range, the antiglare film 16 is sufficiently dense and has excellent adhesion to the low reflective film 14. Further, when the arithmetic average roughness Ra of the surface of the antiglare film 16 is increased, the mechanical strength such as wear resistance tends to be lowered. However, the arithmetic average roughness is high because the antiglare film 16 is highly dense. Even if Ra is large, the mechanical strength of the antiglare film 16 is sufficiently excellent.

  The refractive index of the antiglare film 16 can be adjusted by the matrix material of the antiglare film 16, the porosity of the antiglare film 16, the addition of a substance having an arbitrary refractive index into the matrix, and the like. For example, the refractive index can be lowered by increasing the porosity of the antiglare film 16. Moreover, the refractive index of the anti-glare film 16 can be lowered by adding a substance having a low refractive index (solid silica particles, hollow silica particles, etc.) to the matrix.

The arithmetic average roughness Ra of the surface of the antiglare film 16 is 0.04 to 0.14 μm, and preferably 0.05 to 0.09 μm.
Here, the surface of the antiglare film 16 means the surface opposite to the transparent base material 12 side, that is, the surface of the antiglare film 16 side of the transparent base material 10 with the antiglare antireflection film. Arithmetic average roughness Ra is an index indicating the average height of the irregularities on the surface.
When the arithmetic average roughness Ra of the surface of the antiglare film 16 is not less than the lower limit of the above range, the glossiness (60 ° specular glossiness) on the surface is small and the antiglare property is excellent. If the arithmetic average roughness Ra of the surface of the antiglare film 16 is not more than the upper limit of the above range, the haze of the transparent base material 10 with the antiglare antireflection film is sufficiently small, and high transmittance is obtained. The antiglare film 16 is excellent in antifouling property, wear resistance and the like.
The arithmetic average roughness Ra of the surface of the antiglare film 16 can be adjusted by, for example, the conditions for forming the antiglare film 16 (for example, the composition of the antiglare film coating solution used in the production method described later, the coating conditions, etc.).

The 60 ° specular gloss on the surface of the antiglare film 16 is preferably 52% or less, and more preferably 50% or less. If the 60 ° specular gloss is not more than the above upper limit value, excellent antiglare properties are exhibited.
The 60 ° specular gloss on the surface of the antiglare film 16 can be adjusted by the refractive index of the antiglare film 16, the arithmetic average roughness Ra of the surface of the antiglare film 16, and the like.

The antiglare film 16 is not particularly limited as long as the refractive index and the arithmetic average roughness Ra are satisfied, but the matrix is silica because it is easy to make the refractive index within the above range and excellent in chemical stability. The main component is preferred. That is, the matrix is preferably a silica matrix.
The antiglare film 16 may include particles as necessary.
The antiglare film 16 may further contain a terpene compound.
The antiglare film 16 may further include other components (hereinafter, also referred to as “other optional components”) other than the matrix, the particles, and the terpene compound.

Silica matrix:
The silica-based matrix is the same as that mentioned for the low reflection film 14, and the preferred embodiment is also the same.

particle:
When the anti-glare film 16 contains particles, the refractive index of the anti-glare film 16 can be adjusted by the type and content of the particles. For example, when silica particles are contained, the refractive index is lower than in the case of using only a silica-based matrix. When particles having a refractive index higher than that of silica (for example, alumina particles, zirconia particles, titania particles, etc.) are contained, the refractive index is higher than in the case of using only a silica-based matrix.

Examples of the particles include metal oxide particles, metal particles, pigment-based particles, and resin particles. As materials for the metal oxide particles, metal particles, pigment-based particles, and resin particles, the same materials as those described for the low reflective film 14 may be used.
The particles may have a hollow structure or a solid structure.

Examples of the shape of the particles include scales, spheres, ellipses, needles, plates, rods, cones, cylinders, cubes, cuboids, diamonds, stars, and indefinite shapes. In the antiglare film 16, the particles may be present in an independent state, the particles may be linked in a chain shape, or the particles may be aggregated.
The particles may be used alone or in combination of two or more.

The antiglare film 16 preferably includes one or both of solid silica particles and scaly silica particles (hereinafter also referred to as silica particles (II)) as particles. By including the silica particles (II), the refractive index and arithmetic average roughness Ra of the antiglare film 16 can be easily adjusted. Further, the antiglare film 16 is excellent in mechanical strength such as wear resistance. Silica particles (II) are also excellent in chemical stability.
Examples of the solid silica particles and the scaly silica particles are the same as those described for the low reflective film 14.
The silica particles (II) preferably contain solid silica particles in terms of easier reduction in the refractive index of the antiglare film 16, and scaly in terms of suppressing cracks and film peeling of the antiglare film 16. It is preferable to contain silica particles.
Silica particles (II) and other particles other than silica particles (II) may be used in combination. For example, other flaky particles other than flaky silica may be used. Examples of other scaly particles include scaly alumina particles, scaly titania, and scaly zirconia.

Terpene compounds:
The terpene compound will be described in detail later.

Other optional ingredients:
Other optional components in the antiglare film 16 will be described in detail later.

  In the antiglare film 16, the content of the silica-based matrix is preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more with respect to the total mass of the antiglare film 16. An upper limit is not specifically limited, 100 mass% may be sufficient. When the content of the silica-based matrix is not less than the lower limit of the above range, the antiglare film 16 has better wear resistance, chemical durability, and the like.

In the antiglare film 16, the content of the particles can be appropriately set in consideration of the refractive index of the antiglare film 16, the arithmetic average roughness Ra, the type of particles, and the like.
When the solid silica particles are included as the particles, the content of the solid silica particles in the antiglare film 16 is preferably more than 0 mass% and not more than 85 mass% with respect to the total mass of the antiglare film 16. More than 80% by mass and more preferably 80% by mass or less, more preferably more than 0% by mass and 70% by mass or less. If the content of solid silica particles is within the above range, the higher the content of solid silica particles, the lower the refractive index of the antiglare film 16 and the higher the arithmetic average roughness Ra. If the content of the solid silica particles is less than or equal to the upper limit of the range, the refractive index of the antiglare film 16 is likely to be greater than or equal to the lower limit of the range and the arithmetic average roughness Ra is less than or equal to the upper limit of the range.

(Haze)
1-10% is preferable and, as for the haze of the transparent base material 10 with an anti-glare antireflection film, 2-7% is more preferable. If the haze is less than or equal to the upper limit of the above range, the contrast of the image when the transparent base material 10 with an antiglare antireflection film is used in an image display device, or the transparent base material 10 with an antiglare antireflection film is The power generation efficiency when used in a battery module is good. If the haze is equal to or higher than the lower limit of the above range, the antiglare effect is easily exhibited.
Haze is measured by the method described in JIS K 7136: 2000 (ISO 14782: 1999).

<Method for producing transparent base material with antiglare antireflection film>
As a manufacturing method of the transparent base material 10 with an anti-glare antireflection film, for example, a coating liquid (hereinafter referred to as “low”) containing a silica particle (I), a silica precursor, and a liquid medium on the transparent base material 12. And a coating solution containing a silica precursor and a liquid medium (hereinafter also referred to as an anti-glare coating solution) by a wet coating method, and if necessary. The method of preheating and baking is mentioned.
The coating solution for a low reflection film may contain other particles, a terpene compound, other optional components, and the like as necessary. The coating liquid for low reflection film will be described in detail later.
The antiglare film coating solution may contain particles, a terpene compound, other optional components, and the like, if necessary. The antiglare coating solution will be described in detail later.

  In the above method, after the coating liquid for the low reflection film is applied, the formed coating film is baked, and then the coating liquid for the antiglare film may be applied thereon. After the coating, the anti-glare film coating solution may be coated on the formed coating film in a wet state without firing.

Application:
As a method for applying the coating solution for the low reflection film, a known wet coating method can be employed.
Wet coating methods include spin coating, spray coating, dip coating, die coating, curtain coating, screen coating, inkjet coating, flow coating, gravure coating, bar coating, flexo coating, and slit coating. Method, roll coat method and the like.
Among them, the roll coating method is preferable because it can cope with a wide transparent substrate 12, the transfer speed of the transparent substrate 12 can be relatively fast, and the amount of coating liquid required is relatively small, and optical design is possible. The reverse roll coating method is more preferable from the viewpoint of easily forming a coating film having an arbitrary film thickness with a uniform film thickness (excelling in film thickness controllability).
The coating temperature (atmosphere) of the coating solution for low reflection film is preferably room temperature to 80 ° C, more preferably room temperature to 60 ° C.
The coating amount of the coating liquid for low reflection film is an amount corresponding to the film thickness of the low reflection film 14.

As a coating method of the antiglare film coating solution, a known wet coating method can be adopted as in the coating method of the low reflection film coating solution.
Of these, the spray method is preferable because sufficient unevenness can be easily formed.
Examples of the nozzle used in the spray method include a two-fluid nozzle and a one-fluid nozzle.
The particle size of the droplets of the coating liquid discharged from the nozzle is usually 0.1 to 100 μm, and preferably 1 to 50 μm. If the particle size of the droplets is 1 μm or more, it is possible to form irregularities that sufficiently exhibit the antiglare effect in a short time. If the particle size of the droplet is 50 μm or less, it is easy to form moderate unevenness that sufficiently exhibits the antiglare effect.

The particle size of the droplets can be adjusted as appropriate according to the type of nozzle, spray pressure, liquid volume, and the like. For example, in a two-fluid nozzle, the higher the spray pressure, the smaller the droplet, and the larger the liquid volume, the larger the droplet.
The particle size of the droplet is the Sauter average particle size measured by a laser measuring device.

The application of the antiglare film coating solution is performed such that the arithmetic average roughness Ra of the surface of the antiglare film 16 is within a predetermined range.
The arithmetic average roughness Ra of the surface of the antiglare film 16 is the composition of the coating solution for the antiglare film (solid content concentration, type, size, content, etc. of silica particles (I) and other particles), antiglare film. It can be adjusted according to the application conditions of the coating liquid (spray pressure, liquid volume, substrate temperature, number of times of application, etc. when applying the coating liquid).

For example, when the conditions other than the solid content concentration of the coating solution for the antiglare film are the same, the higher the solid content concentration, the larger the arithmetic average roughness Ra tends to be.
When the coating solution for the antiglare film contains particles such as solid silica particles, and the conditions other than the average particle size (average primary particle size, average aggregated particle size, etc.) are the same, the average particle size of the particles is large. As shown, the arithmetic average roughness Ra tends to be large.
When the coating solution for the antiglare film contains particles and the conditions other than the content of the particles are the same, the arithmetic average roughness Ra tends to increase as the content of the particles increases.
When the conditions other than the spray pressure when applying the antiglare film coating solution are the same, the arithmetic average roughness Ra tends to increase as the spray pressure decreases.
When the conditions other than the liquid amount at the time of applying the antiglare film coating solution are the same, the arithmetic average roughness Ra tends to increase as the liquid amount increases.
When conditions other than the temperature of the transparent base material when applying the antiglare film coating solution are the same, the higher the temperature of the transparent base material, the higher the arithmetic average roughness Ra tends to be.
When conditions other than the number of times of application when applying the coating solution for the antiglare film are the same, the arithmetic average roughness Ra tends to increase as the number of times of application, that is, the number of coated surfaces (number of times of overcoating) by the spray method increases. is there.
When the arithmetic average roughness Ra increases, the 60 ° specular gloss decreases, the antiglare effect tends to increase, and the haze tends to increase.

When applying the antiglare film coating solution by the spray method, it is preferable to heat the transparent substrate 12 after the application of the low reflection film coating solution to 30 to 90 ° C. in advance. If the temperature of the transparent substrate 12 is 30 ° C. or higher, the liquid medium contained in the coating liquid droplets quickly evaporates, so that sufficient unevenness can be easily formed. When the temperature of the transparent substrate 12 is 90 ° C. or lower, the adhesion between the low reflective film 14 and the antiglare film 16 is good.
When the transparent substrate 12 is a glass plate having a thickness of 5 mm or less, a heat insulating plate set in advance at a temperature equal to or higher than the temperature of the transparent substrate 12 is disposed under the transparent substrate 12 to suppress the temperature drop of the transparent substrate 12. Also good.

Firing:
When the coating film formed on the transparent substrate 12 by applying the coating solution for the low reflection film or the antiglare film is baked, the liquid medium in the coating film is removed, and the silica precursor silica in the coating film is removed. Conversion to a system matrix proceeds (for example, when the silica precursor is a silane compound having a hydrolyzable group bonded to a silicon atom, the hydrolyzable group is substantially decomposed, and condensation of the hydrolyzate proceeds. ), The low-reflection film 14 and the antiglare film 16 are formed.
Firing may be performed by applying a low reflection film coating solution or an antiglare film coating solution, followed by heating. The transparent substrate 12 is heated in advance to the firing temperature, and the transparent substrate 12 ( You may carry out by apply | coating the coating liquid for glare-proof films to the surface of the transparent base material 12 or the coating film surface of the coating liquid for low reflection films.

The baking temperature is preferably 30 ° C. or higher, and may be appropriately determined according to the material of the transparent substrate 12, the material of the coating solution for the low reflection film or the coating solution for the antiglare film, and the like.
When the silica precursor contained in the coating solution is a silane compound having a hydrolyzable group bonded to a silicon atom (a silane compound (A) described later), the drying temperature is preferably 80 ° C. or higher, and 100 ° C. or higher. More preferred. When the drying temperature is 80 ° C. or higher, the film becomes dense and durability such as mechanical strength is improved.
When the material of the transparent substrate 12 is a resin, the firing temperature is equal to or lower than the heat resistant temperature of the resin. When the material of the transparent substrate 12 is glass, the firing temperature is preferably equal to or lower than the softening point temperature of the glass.
When the transparent substrate 12 is a chemically strengthened glass plate, the firing temperature is preferably 80 to 450 ° C.
When the transparent substrate 12 is a glass plate that is not chemically strengthened, the firing step can also serve as a physical strengthening (wind cooling strengthening) step of the glass plate. In the physical strengthening step, the glass plate is heated to near the softening temperature of the glass. In this case, the drying temperature is typically set to about 600 to 700 ° C.
Since the polymerization proceeds to some extent even in natural drying, it is theoretically possible to set the drying temperature to a temperature setting near room temperature if there is no time limit.

(Coating solution for low reflection film)
The coating liquid for antiglare film contains silica particles (I), a silica precursor, and a liquid medium.
The antiglare film coating solution may further contain other particles, a terpene compound, other optional components, and the like, if necessary.

Silica particles (I):
The description of the silica particles (I) is the same as described above.

Silica precursor:
Examples of the silica precursor include a silane compound having a hydrolyzable group bonded to a silicon atom (hereinafter also referred to as a silane compound (A)), a hydrolysis condensate of silane compound (A) (sol-gel silica), silazane, and the like. Can be mentioned. From the point of each characteristic of the film | membrane formed, either one or both of a silane compound (A) and its hydrolysis-condensation product are preferable, and the hydrolysis-condensation product of a silane compound (A) is more preferable.

  Examples of the silane compound (A) include a silane compound (A1) having a hydrocarbon group and a hydrolyzable group bonded to a silicon atom, and alkoxysilane (however, excluding the silane compound (A1)).

In the silane compound (A1), the hydrocarbon group bonded to the silicon atom may be a monovalent hydrocarbon group bonded to one silicon atom, or a divalent hydrocarbon group bonded to two silicon atoms. There may be. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group.
The hydrocarbon group is one or two selected from —O—, —S—, —CO— and —NR′— (wherein R ′ is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms. You may have the group which combined two or more.

Examples of the hydrolyzable group bonded to the silicon atom include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen atom. Among these, an alkoxy group, an isocyanate group, and a halogen atom (particularly a chlorine atom) are preferable from the viewpoint of the balance between the stability of the silane compound (A1) and the ease of hydrolysis.
As an alkoxy group, a C1-C3 alkoxy group is preferable and a methoxy group or an ethoxy group is more preferable.
When a plurality of hydrolyzable groups are present in the silane compound (A1), the plurality of hydrolyzable groups may be the same group or different groups, respectively, and in terms of availability, The same group is preferred.

  Examples of the silane compound (A1) include a compound represented by the formula (I) described later, an alkoxysilane having an alkyl group (methyltrimethoxysilane, ethyltriethoxysilane, etc.), an alkoxysilane having a vinyl group (vinyltrimethoxysilane). , Vinyltriethoxysilane, etc.), alkoxysilanes having an epoxy group (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane) , 3-glycidoxypropyltriethoxysilane, etc.), alkoxysilanes having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.) and the like.

The silane compound (A1) is preferably a compound represented by the following formula (I) from the viewpoint of the mechanical strength of the film.
R _3-p L _p Si-Q-SiL _p R _3-p (I)

In the formula (I), Q is a divalent hydrocarbon group (-O—, —S—, —CO— and —NR′— (where R ′ is a hydrogen atom or a monovalent hydrocarbon). A group that is a combination of one or two or more selected from: What was mentioned above is mentioned as a bivalent hydrocarbon.
Q is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms from the viewpoint of mechanical strength of the film, availability, and the like.

In formula (I), L is a hydrolyzable group. Examples of the hydrolyzable group include those described above, and preferred embodiments are also the same.
R is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon include those described above.
p is an integer of 1 to 3. p is preferably 2 or 3, particularly preferably 3, from the viewpoint that the reaction rate does not become too slow.

  Examples of the alkoxysilane (excluding the silane compound (A1)) include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.), alkoxysilane having a perfluoropolyether group ( Perfluoropolyether triethoxysilane and the like), alkoxysilanes having a perfluoroalkyl group (perfluoroethyltriethoxysilane and the like), and the like.

Hydrolysis and condensation of the silane compound (A) can be performed by a known method.
For example, when the silane compound (A) is a tetraalkoxysilane, it is carried out using 4 or more moles of water of tetraalkoxysilane and an acid or alkali as a catalyst.
Examples of the acid include inorganic acids (HNO ₃ , H ₂ SO ₄ , HCl, etc.) and organic acids (formic acid, oxalic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, etc.). Examples of the alkali include ammonia, sodium hydroxide, potassium hydroxide and the like. As the catalyst, an acid is preferable from the viewpoint of long-term storage stability of the hydrolysis condensate of the silane compound (A).
As the catalyst used for the hydrolysis of the silane compound (A), a catalyst that does not hinder the dispersion of particles such as silica particles (I) is preferable.

As a silica precursor, 1 type may be used independently and 2 or more types may be used in combination.
It is preferable that a silica precursor contains either one or both of a silane compound (A1) and its hydrolysis condensate from a viewpoint of preventing the crack and peeling of a film | membrane.
The silica precursor preferably contains one or both of tetraalkoxysilane and its hydrolysis condensate from the viewpoint of the abrasion resistance strength of the film.
It is particularly preferable that the silica precursor contains one or both of the silane compound (A1) and the hydrolysis condensate thereof, and one or both of the tetraalkoxysilane and the hydrolysis condensate thereof.
The ratio of the silane compound (A1) and the hydrolysis condensate thereof in the silica precursor is preferably 5 to 30% by mass with respect to the SiO ₂ equivalent solid content (100% by mass) of the silica precursor.

Liquid medium:
The liquid medium is a liquid that dissolves or disperses the silica precursor. The liquid medium may have a function as a dispersion medium for dispersing particles such as silica particles (I).
Examples of the liquid medium include water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds, and the like.

Examples of alcohols include methanol, ethanol, isopropanol, butanol, diacetone alcohol and the like.
Examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Examples of ethers include tetrahydrofuran and 1,4-dioxane.
Examples of cellosolves include methyl cellosolve and ethyl cellosolve.
Examples of esters include methyl acetate and ethyl acetate.
Examples of glycol ethers include ethylene glycol monoalkyl ether.
Examples of nitrogen-containing compounds include N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone and the like.
Examples of the sulfur-containing compound include dimethyl sulfoxide.
A liquid medium may be used individually by 1 type, and may be used in combination of 2 or more type.

Since water is required for hydrolysis of alkoxysilane or the like in the silica precursor, the liquid medium contains at least water unless the liquid medium is replaced after hydrolysis.
In this case, the liquid medium may be water alone or a mixed liquid of water and another liquid. Examples of other liquids include alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds. Among the other liquids, as the solvent for the silica precursor, alcohols are preferable, and methanol, ethanol, isopropyl alcohol, and butanol are particularly preferable.

  The liquid medium may contain an acid or an alkali. The acid or alkali may be added as a catalyst for the hydrolysis and condensation of the raw material (alkoxysilane, etc.) during the preparation of the silica precursor solution, and is added after the preparation of the silica precursor solution. It may be a thing.

Other particles:
The description of the other particles is the same as described above.

Terpene compounds:
When the coating liquid for low reflective film contains particles such as silica particles (I), if it further contains a terpene compound, voids are formed around the particles, and the refractive index tends to be lower than when no terpene compound is contained. There is.
The terpene means a hydrocarbon having a composition of (C ₅ H ₈ ) _n (where n is an integer of 1 or more) having isoprene (C ₅ H ₈ ) as a structural unit. The terpene compound means terpenes having a functional group derived from terpene. Terpene compounds also include those with different degrees of unsaturation.
Although some terpene compounds function as a liquid medium, those having “a hydrocarbon having a composition of (C ₅ H ₈ ) _n having isoprene as a structural unit” fall under the category of terpene derivatives. Shall not apply.
As the terpene compound, terpene derivatives described in International Publication No. 2010/018852 can be used.

Other optional ingredients:
Other arbitrary components in the coating liquid for low reflection film are other components other than the silica particles (I), the silica precursor, other particles, and the terpene compound.
Examples of other optional components include a surfactant for improving leveling properties, a metal compound for improving film durability, an ultraviolet absorber, an infrared reflection / infrared absorber, and an antireflection agent.
Examples of the surfactant include silicone oil and acrylic.
As the metal compound, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound and the like are preferable. Examples of the zirconium chelate compound include zirconium tetraacetylacetonate and zirconium tributoxy systemate.

composition:
The content of the silica particles (I) in the coating solution for low reflection film and the total content of the silica particles (I) and the silica precursor are the same as those of the silica particles (I) in the low reflection film 14 described above. The content is set according to the total content of the silica particles (I) and the matrix.
Silica particles (I) with respect to the content of the silica particles (I) in the low reflection film 14 and the solid content (100% by mass) in the coating solution for antiglare film (however, the silica precursor is converted to SiO ₂ ). ) Content is almost the same.
The total content of the silica particles (I) and the matrix in the low reflection film 14 and the solid content (100% by mass) in the coating solution for the low reflection film (however, the silica precursor is converted to SiO ₂ ). The total content of the silica particles (I) and the silica precursor is substantially the same.

The content of the liquid medium in the coating liquid for low reflection film is an amount corresponding to the solid content concentration of the coating liquid for low reflection film.
0.2-4 mass% is preferable and, as for the solid content concentration of the coating liquid for low reflection films, 0.8-3 mass% is more preferable. If solid content concentration is more than the lower limit of the said range, it will be easy to control the film thickness of the coating film of the coating liquid for low reflection films. If solid content concentration is below the upper limit of the said range, it will be easy to make the film thickness of the coating film of the coating liquid for low reflection films uniform.
The “solid content” of the coating solution for low reflection film is the total content of all components other than the liquid medium in the coating solution for low reflection film. However, the content of the silica precursor is in terms of SiO ₂ .

When the coating solution for low reflection film contains a terpene compound, the content of the terpene compound in the coating solution for low reflection film is the solid content (100% by mass) in the coating solution for low reflection film (however, a silica precursor) Is in terms of SiO ₂ ), preferably 0.05 to 0.25% by mass, more preferably 0.1 to 0.15% by mass. The effect by including a terpene compound is easy to be acquired as content of a terpene compound is more than the lower limit of the said range. When the content of the terpene compound is not more than the upper limit of the above range, the mechanical strength is excellent.

  The coating solution for the low reflection film is prepared, for example, by preparing a solution in which a silane precursor is dissolved in a liquid medium, a dispersion of the silica particles (I), an additional liquid medium as required, and other particles. And a terpene compound, other optional components, and the like can be mixed.

(Anti-glare coating solution)
The coating solution for antiglare film contains a silica precursor and a liquid medium.
The antiglare film coating solution may further contain particles, a terpene compound, other optional components, and the like, if necessary.

Silica precursor:
As a silica precursor, the same thing as the silica precursor in the coating liquid for low reflection films is mentioned. The preferred embodiment is also the same.

Liquid medium:
Examples of the liquid medium include the same liquid medium as in the low reflection film coating liquid.

particle:
The particles are the same as the particles mentioned in the description of the antiglare film 16. The preferred embodiment is also the same.

Terpene compounds:
Examples of the terpene compound include those similar to the terpene compound in the coating liquid for low reflection film.

Other optional ingredients:
Other optional components in the antiglare coating solution are components other than the silica precursor, particles, and terpene compound.
Examples of other optional components include those similar to the other optional components in the coating liquid for low reflection film.

composition:
The content of the silica precursor (in terms of SiO ₂ ) and the content of the particles in the coating solution for the antiglare film depend on the content of the silica matrix in the antiglare film 16 and the content of the particles, respectively. Is set.
Content of the silica-based matrix in the anti-glare film 16 and content of the silica precursor with respect to the solid content (100% by mass) in the coating solution for the anti-glare film (where the silica precursor is converted to SiO ₂ ). It is almost the same as (SiO ₂ equivalent).
The content of the particles in the antiglare film 16 and the content of the particles relative to the solid content (100% by mass) in the antiglare film coating solution (however, the silica precursor is converted to SiO ₂ ) are almost the same. It is.

The content of the liquid medium in the antiglare film coating liquid is set according to the solid content concentration of the antiglare film coating liquid.
1-5 mass% is preferable and, as for the solid content density | concentration of the coating liquid for anti-glare films, 2-4 mass% is more preferable. When the solid content concentration is within the above range, the antiglare film 16 having a surface arithmetic average roughness Ra within the above range is easily obtained.
The “solid content” of the antiglare film coating liquid is the total content of all components other than the liquid medium in the antiglare film coating liquid. However, the content of the silica precursor is in terms of SiO ₂ .

When the coating liquid for anti-glare film contains a terpene compound, the content of the terpene compound in the coating liquid for anti-glare film is the solid content (100% by mass) in the coating liquid for anti-glare film (however, the silica precursor) Is in terms of SiO ₂ ), preferably 0.05 to 0.25% by mass, more preferably 0.1 to 0.15% by mass. The effect by including a terpene compound is easy to be acquired as content of a terpene compound is more than the lower limit of the said range. When the content of the terpene compound is not more than the upper limit of the above range, the mechanical strength is excellent.

  For the antiglare coating solution, for example, a solution in which a silane precursor is dissolved in a liquid medium is prepared, and if necessary, an additional liquid medium, a dispersion of particles, a terpene compound, and other optional components are mixed. Can be prepared.

(Function and effect)
In the transparent base material 10 with an antiglare antireflection film, an antiglare antireflection film 18 has a low reflection film 14 formed on the transparent base material 12 and an antireflection film formed on the low reflection film 14. The low-reflection film 14 has a refractive index of 1.24 to 1.35, a low-reflection film 14 has a thickness of 20 to 140 nm, and the anti-glare film 16 has a refractive index of 1.40 to 40. Since the arithmetic average roughness Ra of the surface of the antiglare film 16 is 0.04 to 0.14 μm at 1.50, both the antiglare property and the antireflection property are excellent. For example, generation of strong reflected light can be suppressed when light such as sunlight is incident. Moreover, the light transmittance is improved as compared with the case of the transparent substrate 12 alone.
Further, since the arithmetic average roughness Ra of the surface of the antiglare film 16, that is, the surface of the transparent base material 10 with the antiglare and antireflection film on the antiglare film 16 side is 0.14 μm or less, wear resistance and the like Excellent mechanical strength and antifouling property (hardness of dirt adhering, easy removal of adhering dirt).

(Use)
The use of the transparent base material 10 with the antiglare antireflection film is not particularly limited. As specific examples, transparent parts for vehicles (headlight covers, side mirrors, front transparent boards, side transparent boards, rear transparent boards, etc.), transparent parts for vehicles (instrument panel surfaces, etc.), meters, architectural windows , Show windows, displays (notebook computers, monitors, LCDs, PDPs, ELDs, CRTs, PDAs, etc.), LCD color filters, touch panel substrates, pickup lenses, optical lenses, eyeglass lenses, camera parts, video parts, CCD covers Substrate, optical fiber end face, projector part, copier part, transparent substrate for solar cell (cover glass, etc.), mobile phone window, backlight unit part (light guide plate, cold cathode tube, etc.), backlight unit part, liquid crystal brightness Improvement film (prism, transflective film, etc.), LCD brightness enhancement film Organic EL light-emitting element parts, inorganic EL light-emitting element parts, phosphor light-emitting element parts, optical filters, end faces of optical parts, illumination lamps, covers for lighting fixtures, amplified laser light sources, antireflection films, polarizing films, agricultural films, etc. Can be mentioned.

As a preferable use of the transparent base material 10 with an antiglare antireflection film, a transparent substrate for solar cells can be mentioned.
In the solar cell module, a transparent substrate (cover glass or the like) is disposed on the front surface of the solar cell to protect the solar cell. Depending on the installation location, light damage is caused by the reflected light reflected from the surface of the transparent substrate. Since the transparent base material 10 with an antiglare antireflection film is excellent in antiglare properties, the use of this as a transparent substrate for solar cells can suppress the occurrence of light damage due to reflected light.
In the solar cell module, the transmittance of sunlight or the like of the transparent substrate disposed on the front surface of the solar cell affects the power generation efficiency of the solar cell module. The transparent base material 10 with an antiglare antireflection film is excellent in antireflection properties and has high transmittance such as sunlight. Therefore, the power generation efficiency of the solar cell module can be improved by using this as a transparent substrate disposed on the front surface of the solar cell.
Moreover, in the manufacturing process of a solar cell module using a transparent substrate, dirt such as machine oil and fingerprints easily adheres to the transparent substrate. In addition, dirt is likely to adhere to the transparent substrate when the manufactured module is installed. Dirt on the transparent substrate is required to be removed because it impairs antiglare properties, antireflection properties, sunlight transmittance, appearance, and the like. A general anti-glare film takes time and effort to remove dirt once adhered, and it is difficult to completely remove dirt, and a dirt mark may remain after removal. In the transparent base material 10 with an antiglare and antireflection film, since the unevenness of the surface is small, dirt is difficult to adhere, and it is easy to remove even if it adheres, and this point is also useful as a transparent substrate for solar cells. .

Another preferred application of the transparent base material 10 with an antiglare antireflection film is an interior part of a transport aircraft.
Car interior articles are preferred as interior parts for transport aircraft. As the in-vehicle article, an in-vehicle system including an image display device (a car navigation system, an instrument panel, a head-up display, a dashboard, a center console, a shift knob, etc.) is preferable.

As mentioned above, although the transparent substrate with an antiglare antireflection film of the present invention has been described with reference to one embodiment, the present invention is not limited to the above embodiment. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
For example, a functional layer such as an AFP (fingerprint removal layer) may be provided on the antiglare antireflection film 18 (on the antiglare film 16). You may have functional layers, such as an alkali barrier layer, a reflectance waveform adjustment layer, and an infrared shielding layer, between the transparent base material 12 and the anti-glare antireflection film 18. The functional layer can be formed by a known method such as a coating method.
The form of the transparent substrate 12 is not limited to a sheet shape such as a plate or a film. For example, it may be in the form of a rectangle or a curved surface.
The manufacturing method of the transparent base material with an anti-glare antireflection film is not limited to the manufacturing method described above.

[Articles]
The article of the present invention comprises the transparent substrate with the antiglare antireflection film of the present invention.
The article of the present invention may be composed of the transparent substrate with an antiglare and antireflection film of the present invention, or may further comprise other members other than the transparent substrate with an antiglare and antireflection film of the present invention.
Examples of the article of the present invention include those mentioned above for the use of the transparent base material 10 with the antiglare and antireflection film, and devices including any one or more of them.
Examples of the device include a lighting device and a system including the same, an image display device and a system including the same, a solar cell module, and the like.
Examples of the illumination device or a system including the illumination device include an organic EL (electroluminescence) illumination device and an LED (light emitting diode) illumination device.
Examples of the image display device or a system including the image display device include a mobile phone, a smartphone, a tablet, and a car navigation system.

The article of the present invention is preferably a solar cell module, an image display device, or a system including the same.
When the article of the present invention is a solar cell module, the solar cell module includes a solar cell and transparent substrates (cover glass or the like) respectively disposed on the front and back surfaces of the solar cell to protect the solar cell. It is preferable that at least one transparent substrate (preferably at least the front transparent substrate) of the transparent substrate is the transparent base material with the antiglare antireflection film of the present invention.

When the article of the present invention is an image display device, the image display device includes an image display device main body for displaying an image, and a transparent with an antiglare antireflection film of the present invention provided on the viewing side of the image display device main body. What comprises a base material is preferable.
Examples of the image display device main body include a liquid crystal panel, an organic EL (electroluminescence) panel, and a plasma display panel.
The transparent base material with an antiglare antireflection film may be provided integrally with the image display device main body as a protective plate of the image display device main body, or may be disposed on the viewing side of the image display device main body as various filters. Good.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description.
Of Examples 1 to 9 described later, Examples 1 to 6 are examples, and Examples 7 to 9 are comparative examples.
The measurement / evaluation method and materials (source or preparation method) used in each example are shown below.

[Measurement and evaluation method]
(Refractive index and film thickness of low reflection film)
In each example, a transparent substrate with an antiglare antireflection film was prepared under the same conditions except that no antiglare film was formed (no coating liquid (B) was applied). Thereby, the transparent base material with a low reflection film in which the low reflection film was formed on the transparent base material was obtained. A black vinyl tape was attached to the surface of the transparent substrate with the low reflection film on the transparent substrate side to prepare a sample.
The reflectance in the wavelength range of 380 to 780 nm on the surface of the sample on the low reflection film side was measured with a spectrophotometer (Otsuka Electronics Co., Ltd., instantaneous multi-photometry system MCPD-3000). The incident angle of light was 5 °.
The refractive index n of the low reflective film was calculated from the bottom reflectance R _min within the wavelength range of 380 to 780 nm and the refractive index ns of the transparent substrate by the following equation (1).
R _min = (n−ns) ² / (n + ns) ² (1).
From the refractive index n and the wavelength λ (nm) at the bottom reflectance R _min , the film thickness d (nm) of the low reflective film was calculated by the following equation (2).
n × d = λ / 4 (2).

(Refractive index of antiglare film)
In each example, a transparent substrate with an antiglare antireflection film was produced under the same conditions except that a low reflection film was not formed (no coating liquid (A) was applied). Thereby, the transparent base material with an anti-glare film in which the anti-glare film was formed on the transparent base material was obtained. A black vinyl tape was attached to the surface of the transparent substrate with the antiglare film on the transparent substrate side to prepare a sample.
The reflectance in the wavelength range of 380 to 780 nm on the antiglare film side of the sample was measured in the same manner as described above, and the refractive index n of the antiglare film was calculated by the above formula (1).

(Arithmetic mean roughness Ra)
The arithmetic average roughness Ra of the surface of the antiglare film was measured by a method described in JIS B0601: 2001 using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom (registered trademark) 1500DX). The reference length lr (cut-off value λc) for the roughness curve was 0.08 mm.

(Glossiness)
As the glossiness of the surface of the antiglare film, 60 ° specular glossiness was measured. The 60 ° specular gloss was measured at a substantially central portion of the antiglare film using a gloss meter (PG-3D type, manufactured by Nippon Denshoku Industries Co., Ltd.) according to the method defined in JIS Z8741: 1997. Further, the glossiness of the surface of the antiglare film was measured in a state in which the influence of the back surface reflection of the glass plate was eliminated by applying a black tape to the back surface (surface opposite to the antiglare film) of the glass plate. It shows that it is excellent in anti-glare property, so that glossiness is small.

(Transmissivity difference Td)
A spectrophotometer (manufactured by JASCO Corporation, V670) was used for each of the transparent substrate before forming the antiglare antireflection film (low reflection film and antiglare film) and the transparent substrate with the antiglare antireflection film. Then, the transmittance (%) of light at a wavelength of 400 nm to 1100 nm was measured, and the average transmittance (%) was obtained. From the result, the transmittance difference Td (%) was calculated by the following formula (3). It shows that antireflection performance is so high that the transmittance | permeability difference Td is large.
Transmittance difference Td = average transmittance of transparent substrate with antiglare antireflection film−average transmittance of only transparent substrate (3)

[Materials used]
(Silica precursor solution (a))
What was prepared in the following procedures was used.
While stirring 77.6 g of denatured ethanol (manufactured by Japan Alcohol Sales Co., Ltd., Solmix AP-11, a mixed solvent mainly composed of ethanol, the same applies hereinafter), 11.9 g of ion-exchanged water and 61% by mass of nitric acid were added thereto. A mixed solution with 0.1 g was added and stirred for 5 minutes. To this, 10.4 g of tetraethoxysilane (SiO ₂ conversion solid content concentration: 29% by mass) is added and stirred at room temperature for 30 minutes to obtain a silica precursor solution having a SiO ₂ conversion solid content concentration of 3.0% by mass ( a) was prepared. Incidentally, SiO ₂ in terms of solids concentration here is solid concentration when all Si of tetraethoxysilane was converted to SiO _2.

(Preparation of silica precursor solution (b-1))
While stirring 75.8 g of denatured ethanol, a mixed solution of 11.9 g of ion exchange water and 0.1 g of 61 mass% nitric acid was added and stirred for 5 minutes. To this, 12.2 g of tetraethoxysilane (SiO ₂ equivalent solid content concentration: 29% by mass) was added and stirred at room temperature for 30 minutes to obtain a silica precursor solution having a SiO ₂ equivalent solid content concentration of 3.5% by mass ( b-1) was prepared. Incidentally, SiO ₂ in terms of solids concentration here is solid concentration when all Si of tetraethoxysilane was converted to SiO _2.

(Preparation of silica precursor solution (b-2))
While stirring 80.3 g of denatured ethanol, a mixed solution of 7.9 g of ion exchange water and 0.2 g of 61% by mass nitric acid was added and stirred for 5 minutes. Next, 11.6 g of 1,6-bis (trimethoxysilyl) hexane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name “KBM3066”, solid content concentration in terms of SiO ₂ : 37% by mass) was added, and the mixture was added at 60 ° C. in a water bath at 15 ° C. The mixture was stirred for minutes to prepare a silica precursor solution (b-2) having a solid content concentration in terms of SiO ₂ of 4.3% by mass. Here, the solid content concentration in terms of SiO ₂ is the solid content concentration when all Si of 1,6-bis (trimethoxysilyl) hexane is converted to SiO ₂ .

(Preparation of coating solution (A))
While stirring 59.8 g of denatured ethanol, 30.0 g of the silica precursor solution (a) was added. Stirring was performed for a minute to obtain a coating liquid (A) having a solid content concentration in terms of SiO ₂ of 3.0 mass%. Incidentally, in terms of SiO ₂ solid content concentration herein is the sum of the terms of SiO ₂ solids content of the silica precursor solution (a), in terms of SiO ₂ solid content of the hollow silica particle dispersion (the hollow silica particles).
The content of the hollow silica particles in the coating liquid (A) is a 70 wt% with respect to SiO ₂ in terms the solid content of the coating solution (A), the average primary particle size of the hollow silica particles in the coating liquid (A) Was 60 nm.

(Preparation of coating solution (B))
While stirring 77.1 g of the silica precursor solution (b-1), 7.0 g of the silica precursor solution (b-2) was added and stirred for 30 minutes. Subsequently, 15.9 g of denatured ethanol was added, and the mixture was stirred at room temperature for 30 minutes to obtain a coating liquid (B) having a solid content concentration of SiO ₂ of 3.0% by mass.

[Example 1]
(Cleaning transparent substrates)
A chemically strengthened aluminosilicate glass plate (trade name “Leoflex (registered trademark)” manufactured by Asahi Glass Co., Ltd., size: 300 mm × 300 mm, thickness 0.85 mm) was prepared as a transparent substrate. The surface of the transparent substrate was washed with sodium hydrogen carbonate water, rinsed with ion-exchanged water, and dried.

(Formation of antiglare antireflection film)
The transparent base material is preheated in a preheating furnace (VTR-115, manufactured by ISUZU Co., Ltd.), and the surface temperature of the transparent base material is kept at 30 ° C. The coating liquid (A) (low reflection film coating liquid) was applied with a coating roll manufactured by Seiki Co., Ltd. Next, the transparent base material is preheated in a preheating furnace (manufactured by ISUZU, VTR-115), and the surface temperature of the transparent base material is kept at 90 ° C. (A) The coating liquid (B) (antiglare film coating liquid) was coated on the surface coated with a coating by a spray method. Thereafter, it was cured by heating at 200 ° C. for 3 minutes in the atmosphere. Thereby, the transparent base material with the anti-glare antireflection film which laminated | stacked the transparent base material, the low reflection film, and the anti-glare film in this order was obtained.

The coating amount of the coating liquid (A) was set to an amount that gives the film thickness shown in Table 1.
The coating conditions were as follows: conveying speed of the template glass: 8.5 m / min, gap between the coating roll and the conveying belt: 2.9 mm, and indentation thickness between the coating roll and the doctor roll: 0.6 mm.
As the coating roll, a rubber lining roll lined with rubber (ethylene propylene diene rubber) having a surface hardness (JIS-A) of 30 was used.
As the doctor roll, a metal roll having lattice-like grooves formed on the surface thereof was used.

Application of the coating solution (B) by the spray method was performed under the following conditions so that the arithmetic average roughness Ra of the surface of the antiglare film was a value shown in Table 1.
Spray pressure: 0.2 MPa
Nozzle moving speed: 750 mm / min,
Spray pitch: 22 mm.
A 6-axis coating robot (manufactured by Kawasaki Robotics, JF-5) was used for application by the spray method. As the nozzle, a VAU nozzle (manufactured by Spraying System Japan) was used.

[Examples 2 to 9]
The coating liquid (A) was applied so as to have the thickness of the low reflection film shown in Table 1, and the coating liquid (B) was applied so as to have the arithmetic average roughness Ra of the antiglare film shown in Table 1. A transparent base material with an antiglare antireflection film was obtained in the same manner as Example 1 except for the above.

  Table 1 shows the refractive index and film thickness of the low reflection film, the refractive index of the antiglare film, the arithmetic average roughness Ra and glossiness of the surface of the antiglare film, and the transmittance difference Td in each example.

As shown in the above results, the transparent base materials with antiglare and antireflection films of Examples 1 to 6 had a glossiness of 50% or less and excellent antiglare properties. Further, the transmittance difference Td was 0.56% or more, and the antireflection property was excellent.
On the other hand, the transparent base material with an antiglare antireflection film of Example 7 in which the arithmetic average roughness Ra of the surface of the antiglare film is less than 0.04 μm is inferior in antiglare properties to Examples 1-6. It was.
The transparent base material with an antiglare antireflection film of Example 8 in which the film thickness of the low reflection film was more than 140 nm was inferior in both antiglare property and antireflection property as compared with Examples 1-6.
The transparent base material with an antiglare antireflection film of Example 9 in which the arithmetic average roughness Ra of the surface of the antiglare film is more than 0.14 μm was inferior in antireflection properties as compared with Examples 1-6.

DESCRIPTION OF SYMBOLS 10 Transparent base material with anti-glare antireflection film 12 Transparent base material 14 Low reflection film 16 Anti-glare film 18 Anti-glare anti-reflection film

Claims (8)

A transparent substrate and an antiglare antireflection film are provided,
The antiglare antireflection film comprises a low reflection film formed on the transparent substrate and an antiglare film formed on the low reflection film,
The low reflective film has a refractive index of 1.24 to 1.35, and the low reflective film has a thickness of 20 to 140 nm.
A transparent base material with an antiglare antireflection film, wherein the antiglare film has a refractive index of 1.40 to 1.50 and an arithmetic average roughness Ra of the surface of the antiglare film is 0.04 to 0.14 μm.   The transparent base material with an anti-glare antireflection film according to claim 1, wherein the low reflection film contains one or both of solid silica particles and hollow silica particles.   The transparent base material with an anti-glare antireflection film according to claim 1 or 2, wherein the matrix of the anti-glare film has silica as a main component.   The transparent base material with an anti-glare antireflection film according to any one of claims 1 to 3, wherein the anti-glare film is formed from a coating liquid containing a silica precursor and a liquid medium.   The transparent base material with an anti-glare antireflection film according to claim 3 or 4, wherein the anti-glare film includes one or both of solid silica particles and scaly silica particles.   The transparent base material with an anti-glare antireflection film according to any one of claims 1 to 5, wherein the transparent base material is a chemically strengthened glass plate.   An article comprising the transparent base material with an antiglare antireflection film according to any one of claims 1 to 6.   The article according to claim 7, which is a solar cell module.

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