JP2016018068A - Substrate with anti-glare film, and articles having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate with an anti-glare film that exhibits a superior anti-glare effect on incident light coming in at large angles, and to provide articles using the same.SOLUTION: An anti-glare-filmed substrate 10 comprises a substrate 12 and an anti-glare film 14, where the anti-glare film 14 is either a film having a refractive index of no less than 1.2 and less than 1.4, an arithmetic mean surface roughness Ra of 0.112-0.700 μm, and an 85° specular gloss of no greater than 70%, or a film having a refractive index of no less than 1.4 and no greater than 1.5, an arithmetic mean surface roughness Ra of 0.158-0.500 μm, and an 85° specular gloss of no less than 70%.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a base material with an antiglare 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 the solar cell module has been subjected to a low reflection treatment in order to reduce the reflection of sunlight and increase the power generation efficiency, and the light damage caused by the reflected light reflected from the surface of the cover glass has been reduced. In order to prevent this, an antiglare treatment is also performed.

The anti-glare treatment is a treatment that makes the reflected image unclear by providing unevenness on the surface and scattering incident light by the unevenness. As an anti-glare treatment, a method of roughening the surface of a substrate by erosion, sand blasting or the like has been conventionally known. Further, a method has been proposed in which a treatment liquid composed of hydrolyzed silicate ester, alcohol, water and acid (hydrochloric acid, nitric acid, etc.) is applied and baked to form a light diffusion layer (antiglare film) (Patent Literature). 1).
The low reflection processing is processing for suppressing reflection of incident light itself. As the low reflection treatment, a method of providing a low reflection film has been 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 low-reflection film is designed based on the optical path length due to the normal incidence angle, so depending on the incident angle of external light or the position of the person viewing the screen, the optical path length may deviate from the design, increasing the reflectivity. There is a disadvantage that the low reflection effect is impaired.
The anti-glare film diffuses and reflects external light, so the anti-glare effect is exhibited regardless of the incident angle of the external light or the position of the person viewing the screen, and it is less than the low-reflective film in terms of suppressing the reflection of external light. Is also advantageous.
The antiglare effect of the antiglare film is generally evaluated by the glossiness at an incident angle of 60 ° (60 ° specular glossiness). Therefore, the antiglare film is usually designed to reduce the 60 ° specular gloss.

However, the antiglare film also has a problem that the antiglare effect is not sufficiently exhibited when the incident angle is larger than 60 °, particularly close to 90 °.
When a solar cell module is installed on an inclined roof, sunlight may enter the cover glass at an incident angle close to 90 °. In this case, even if an antiglare film is provided on the surface of the cover glass, there is a concern that the reflected light reflected by the surface of the cover glass may enter a neighboring building and cause light damage.

JP-A-60-109134

  An object of this invention is to provide the base material with an anti-glare film excellent in the anti-glare effect with respect to incident light with a large incident angle, and an article | item using this.

The present invention has the following aspects.
[1] A base material and an antiglare film formed on the base material,
The refractive index of the antiglare film is 1.2 or more and less than 1.4,
The arithmetic average roughness Ra of the surface of the antiglare film is 0.112 to 0.700 μm,
A substrate with an antiglare film, characterized in that the 85 ° specular gloss on the surface of the antiglare film is 70% or less.
[2] A base material and an antiglare film formed on the base material,
The refractive index of the antiglare film is 1.4 or more and 1.5 or less,
The arithmetic average roughness Ra of the surface of the antiglare film is 0.158 to 0.500 μm,
A substrate with an antiglare film, characterized in that the 85 ° specular gloss on the surface of the antiglare film is 70% or less.
[3] The substrate with an antiglare film according to [1] or [2], wherein the antiglare film includes one or both of solid silica particles and hollow silica particles.
[4] The substrate with an antiglare 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. .
[5] The substrate with an antiglare film according to any one of [1] to [4], wherein the substrate is a glass plate.
[6] The substrate with an antiglare film according to [5], wherein the glass plate is a tempered glass plate.
[7] The substrate with an antiglare film according to [6], wherein the tempered glass plate is a chemically tempered glass plate and the plate thickness is 0.4 to 1.1 mm.
[8] An article comprising the substrate with an antiglare film according to any one of [1] to [7].
[9] The article according to [8], which is a solar cell module.

  ADVANTAGE OF THE INVENTION According to this invention, the base material with an anti-glare film excellent in the anti-glare effect with respect to incident light with a large incident angle, and articles | goods using the same can be provided.

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

The following definitions of terms apply throughout this specification and the claims.
“Silica precursor” means a substance capable of forming a matrix mainly composed of silica.
“Containing silica as a main component” means containing 90 mass% or more of SiO ₂ .
“Mainly containing titania” means containing 90% by mass or more of TiO ₂ .
“Solid” indicates that there is no cavity inside.
“Hollow” indicates that there is a cavity inside.
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.
“85 ° specular gloss” and “60 ° specular gloss” are the surfaces opposite to the side where the antiglare film is formed by the method described in JIS Z 8741: 1997 (ISO 2813: 1994). It measures about the base material with an anti-glare film which stuck the black tape to.
The “arithmetic average roughness Ra” is measured by the method described in JIS B0601: 2001 (ISO 4287: 1997).
“Haze” is measured by the method described in JIS K 7136: 2000 (ISO 14782: 1999).

[Base material with antiglare film]
FIG. 1 is a cross-sectional view schematically showing one embodiment of a substrate with an antiglare film of the present invention.
The base material 10 with an antiglare film of the present embodiment includes a base material 12 and an antiglare film 14 formed on the base material 12.

(Base material)
Examples of the form of the substrate 12 include a plate and a film.
Examples of the material of the base material 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.
The substrate 12 is preferably transparent. The transparency in the base material 12 means that 80% or more of light in the wavelength region of 400 to 1100 nm is averaged.

As the substrate 12, a glass plate is preferable.
The glass plate may be a smooth glass plate formed by a float method, a fusion method, or the like, or may be a template glass having irregularities on the surface formed by a roll-out method or the like. Further, not only flat glass but also glass having a curved surface shape 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.

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 base material 10 with a glare-proof 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 strain point of glass is lower than the softening point.

When the glass plate is thin (for example, 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. The 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 compositions can be used. For example, soda lime glass, aluminosilicate glass, borate Examples thereof include glass, lithium aluminosilicate glass, borosilicate glass, alkali-free glass, and other various 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 0.4 to 1.1 mm, particularly preferably 0.5 to 1.0 mm. If the thickness of the chemically strengthened glass plate is less than or equal to the upper limit of the above range, the substrate 10 with an antiglare film is lightweight, and if it is greater than or equal to the lower limit of the above range, the substrate 10 with an antiglare film is excellent in 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).

(Anti-glare film)
The antiglare film 14 is the following (α) or (β).
(Α) Antiglare having a refractive index of 1.2 or more and less than 1.4, a surface arithmetic average roughness Ra of 0.112 to 0.700 μm, and a 85 ° specular gloss on the surface of 70% or less. film.
(Β) Antiglare having a refractive index of 1.4 to 1.5, an arithmetic average roughness Ra of 0.158 to 0.500 μm, and an 85 ° specular gloss on the surface of 70% or less film.

Here, the surface of the antiglare film 14 means the surface opposite to the substrate 12 side, that is, the surface on the antiglare film 14 side of the substrate 10 with the antiglare film.
Arithmetic average roughness Ra is an index indicating the average height of the irregularities on the surface.
If the refractive index of the antiglare film 14 is the same, the larger the arithmetic average roughness Ra of the surface, the smaller the 85 ° specular gloss, and the incident light having an incident angle greater than 60 ° (hereinafter also referred to as oblique incident light). .) Tends to have an excellent antiglare effect. Further, if the arithmetic average roughness Ra of the surface of the antiglare film 14 is the same, the smaller the refractive index, the smaller the 85 ° specular gloss, and the better the antiglare effect against oblique incident light.

If the refractive index of the antiglare film 14 is 1.5 or less, particularly less than 1.4, the reflectance on the surface of the antiglare film 14 is low, and even when Ra is 0.700 μm or less, and even 0.500 μm or less. A sufficient antiglare effect can be obtained.
If the refractive index of the anti-glare film 14 is 1.2 or more, particularly 1.4 or more, the anti-glare film 14 is sufficiently dense and has excellent adhesion to the substrate 12 such as a glass plate. In addition, when the arithmetic average roughness Ra of the surface increases, the mechanical strength such as wear resistance of the antiglare film 14 tends to decrease. However, the arithmetic average roughness of the antiglare film 14 is high due to high density. Even if Ra is large, the mechanical strength of the antiglare film 14 is sufficiently excellent.

The refractive index of the antiglare film (α) is preferably 1.25 or more and less than 1.4.
The arithmetic average roughness Ra of the antiglare film (α) is preferably 0.113 to 0.650 μm. When the arithmetic average roughness Ra of the surface of the antiglare film (α) is not less than the lower limit of the above range, the antiglare effect is sufficiently exhibited. If the arithmetic average roughness Ra of the surface of the antiglare film (α) is not more than the upper limit of the above range, the mechanical strength of the antiglare film 14 is excellent and the haze of the substrate 10 with the antiglare film is sufficient. Becomes smaller.

  The 85 ° specular gloss of the antiglare film (α) is preferably 65% or less, and more preferably 60% or less. The lower limit of the 85 ° specular gloss is not particularly limited in terms of the antiglare effect against obliquely incident light, but is preferably 15% or more and more preferably 20% or more from the viewpoint of the mechanical strength of the antiglare film 14.

  The 60 ° specular gloss on the surface of the antiglare film (α) is preferably 60% or less, and more preferably 50% or less. When the 60 ° specular gloss is 60% or less, an excellent antiglare effect is exhibited even for incident light other than oblique incident light (incident light with an incident angle of 0 to 60 °).

The refractive index of the antiglare film (β) is preferably 1.40 or more and 1.46 or less.
The arithmetic average roughness Ra of the antiglare film (β) is preferably 0.200 to 0.500 μm. When the arithmetic average roughness Ra on the surface of the antiglare film (β) is not less than the lower limit of the above range, the antiglare effect is sufficiently exhibited. If the arithmetic average roughness Ra of the surface of the antiglare film (β) is not more than the upper limit of the above range, the mechanical strength of the antiglare film 14 is excellent and the haze of the substrate 10 with the antiglare film is sufficient. Becomes smaller.

  The preferable range of the 85 ° specular glossiness and the preferable range of the 60 ° specular glossiness of the antiglare film (β) are the same as those of the antiglare film (α).

The 85 ° specular glossiness and the 60 ° specular glossiness on the surface of the antiglare film 14 can be adjusted by the refractive index of the antiglare film 14, the arithmetic average roughness Ra of the surface of the antiglare film 14, and the like.
The refractive index of the antiglare film 14 can be adjusted by the matrix material of the antiglare film 14, the porosity of the antiglare film 14, 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 14. Moreover, the refractive index of the anti-glare film 14 can be lowered by adding a substance having a low refractive index (solid silica particles, hollow silica particles, etc.) to the matrix.
A method for adjusting the arithmetic average roughness Ra of the surface of the antiglare film 14 will be described in detail later.

As the anti-glare film 14, either one or both of solid silica particles and hollow silica particles (hereinafter referred to as silica particles) because it is easy to adjust the refractive index and arithmetic surface roughness Ra, and is excellent in chemical stability. (I) is also preferable.
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 substrate 12 side) of the silica particles (I) so that the silica particles (I) are not exposed.
As the anti-glare film 14, a film made of a matrix and containing no silica particles (I) can also be used.
The antiglare film 14 may further include particles other than the silica particles (I).
The antiglare film 14 may further contain a terpene compound.
The anti-glare film 14 may further include silica particles (I), a matrix, other particles, and other components (hereinafter, also referred to as “other optional components”) other than the terpene compound.

Matrix:
Examples of the matrix of the antiglare 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.

As a matrix of the anti-glare film 14, a silica-based matrix is preferable. If the matrix is a silica-based matrix, the refractive index (reflectance) of the antiglare film 14 tends to be low. In addition, chemical stability, wear resistance and the like are improved. In the case where the 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.
As a silica type matrix, what was formed from the coating liquid containing a silica precursor and a liquid medium is mentioned, for example. The silica precursor will be described in detail later.

Silica particles (I):
The silica particles (I) are either one or both of solid silica particles and hollow silica particles.

  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.

As the solid silica particles, chain-shaped solid silica particles are preferable 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 within the above range, the arithmetic average roughness Ra of the surface of the antiglare film 14 is easily set within the above range.
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 compared to 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 average primary particle diameter of the hollow silica particles is preferably 40 to 150 nm, and more preferably 50 to 100 nm. If the average primary particle diameter of the hollow silica particles is within the above range, the arithmetic average roughness Ra of the surface of the antiglare film 14 is easily set within the above range.
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.

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 other particles, scaly particles are preferable because cracks and peeling of the antiglare film 14 can be suppressed. “Scaly particle” means a particle having a flat shape. The shape of the particles can be confirmed using TEM.
Examples of the scaly particles include scaly silica particles, scaly alumina particles, scaly titania, scaly zirconia, etc., and scaly silica particles from the point that the increase in the refractive index of the film can be suppressed and the reflectance can be lowered. Is preferred.
As the flaky silica particles, those produced by the production method described in JP-A-2014-94845 are preferable.

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

Other optional ingredients:
Other optional components will be described in detail later.

  In the antiglare film 14, the total content of the matrix and the silica particles (I) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, with respect to the total mass of the antiglare film 14, and 30 to 30%. 100% by mass is particularly preferred. When the total content of the matrix and the silica particles (I) is not less than the lower limit of the above range, the wear resistance is excellent.

The content of the silica particles (I) in the antiglare film 14 can be appropriately set in consideration of the refractive index of the antiglare film 14, the arithmetic surface roughness Ra, the type of the silica particles (I), and the like.
When the anti-glare film 14 is the anti-glare film (α) and the silica particles (I) are solid silica particles, the content of the solid silica particles in the anti-glare film 14 is The total mass is preferably more than 0% by mass and less than 70% by mass, more preferably more than 0% by mass and less than 60% by mass, and particularly preferably more than 0% by mass and less than 50% by mass. 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 14 and the higher the arithmetic surface roughness Ra. If the content of the solid silica particles is not more than the upper limit value of the above range, the refractive index of the antiglare film 14 is likely to be not less than the lower limit value of the above range and the arithmetic surface roughness Ra is not more than the upper limit value of the above range.
For the same reason, when the antiglare film 14 is the anti-glare film (β) and the silica particles (I) are solid silica particles, the content of the solid silica particles in the antiglare film 14 is: It is preferable that it is 60-80 mass% with respect to the total mass of the anti-glare film 14, and 70-80 mass% is more preferable.

When the anti-glare film 14 is the anti-glare film (α) and the silica particles (I) are hollow silica particles, the content of the hollow silica particles in the anti-glare film 14 is the total mass of the anti-glare film 14. On the other hand, it is preferably more than 0% by mass and 20% by mass or less, more preferably more than 0% by mass and 15% by mass or less, and particularly preferably more than 0% by mass and 20% by mass or less. If the content of the hollow silica particles is within the above range, the higher the content of the hollow silica particles, the lower the refractive index of the antiglare film 14 and the higher the arithmetic surface roughness Ra. If the content of the hollow silica particles is less than or equal to the upper limit of the range, the refractive index of the antiglare film 14 is likely to be greater than or equal to the lower limit of the range and the arithmetic surface roughness Ra is less than or equal to the upper limit of the range.
For the same reason, when the antiglare film 14 is the anti-glare film (β) and the silica particles (I) are hollow silica particles, the content of the hollow silica particles in the antiglare film 14 is antiglare. It is preferable that it is 21-80 mass% with respect to the total mass of the film | membrane 14, and 30-70 mass% is more preferable.

(Haze)
5-20% is preferable and, as for the haze of the base material 10 with an anti-glare film, 5-15% is more preferable. If the haze is less than or equal to the upper limit of the above range, the image contrast when the substrate 10 with antiglare film is used in a display device, and the power generation efficiency when the substrate 10 with antiglare film is used in a solar cell 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.

<Method for producing substrate with antiglare film>
As a manufacturing method of the base material 10 with an antiglare film, for example,
A method of forming an antiglare film 14 by applying a coating liquid containing a silica precursor and a liquid medium (hereinafter also referred to as an antiglare film coating liquid) on the substrate 12 and drying it. It is done.
The antiglare film coating solution may contain silica particles (I), other particles, a terpene compound, other optional components, and the like as necessary. The coating solution for antiglare film will be described in detail later.
When the antiglare film 14 is formed, the antiglare film coating solution is applied and dried so that the arithmetic average roughness Ra of the surface of the antiglare film 14 is within a predetermined range.

(Application)
As a coating method of the coating solution for the antiglare film, known wet coating methods (spray coating method, spin coating method, dip coating method, die coating method, curtain coating method, screen coating method, ink jet method, flow coating method, gravure coating) Method, bar coat method, flexo coat method, slit coat method, roll coat method, etc.).
As a coating method, a 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 arithmetic average roughness Ra of the surface of the antiglare film 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), for the antiglare film It can be adjusted according to the application conditions of the application liquid (spray pressure, application amount, substrate temperature, number of applications, etc. when applying the application 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 silica particles (I) and the conditions other than the average particle size (average primary particle size, average aggregated particle size, etc.) of the silica particles (I) are the same, the silica particles (I) There is a tendency that the arithmetic average roughness Ra is larger as the average particle size of is larger.
When the coating solution for the antiglare film contains the silica particles (I) and the conditions other than the content of the silica particles (I) are the same, the arithmetic average roughness Ra is increased as the content of the silica particles (I) is increased. There is a big tendency.
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 base material temperature at the time of applying the antiglare film coating solution are the same, the arithmetic average roughness Ra tends to increase as the base material temperature increases.
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 85 ° specular gloss decreases, the antiglare effect against oblique incident light tends to increase, and the haze tends to increase.

  When applying the coating solution for the antiglare film by the spray method, the substrate 12 is preferably heated to 30 to 90 ° C. in advance. If the temperature of the base material 12 is 30 ° C. or higher, the liquid medium evaporates quickly, so that sufficient unevenness is easily formed. If the temperature of the base material 12 is 90 degrees C or less, the adhesiveness of the base material 12 and the anti-glare film 14 will become favorable. When the base material 12 is a glass plate having a thickness of 5 mm or less, a heat insulating plate that is set to a temperature equal to or higher than the temperature of the base material 12 in advance may be disposed under the base material 12 to suppress the temperature drop of the base material 12.

(Dry)
The coating film of the antiglare film coating solution formed on the substrate 12 by applying the antiglare film coating solution is dried. Thereby, the liquid medium in the coating film is removed, and the conversion of the silica precursor remaining in the coating film into a silica-based matrix proceeds (for example, a hydrolyzable group in which the silica precursor is bonded to a silicon atom). When the silane compound has a hydrolyzable group, the hydrolyzable group is substantially decomposed and the condensation of the hydrolyzate proceeds), and the film is densified to form the antiglare film 14.

Drying may be performed by heating or may be performed without heating (natural drying, air drying, etc.).
The coating film may be heated simultaneously with the application by heating the substrate 12 in advance when the coating solution for the antiglare film is applied onto the substrate 12, and the coating solution for the antiglare film is applied to the substrate 12. After coating, the coating film may be heated.

The drying temperature is preferably 30 ° C. or higher, and may be appropriately determined according to the material of the substrate 12, the material of the antiglare film coating liquid, and the like.
In the case where the silica precursor 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 more preferably 100 ° C. or higher. When the drying temperature is 80 ° C. or higher, the film is densified and durability such as mechanical strength of the antiglare film 14 is improved.
When the material of the substrate 12 is a resin, the drying temperature is equal to or lower than the heat resistant temperature of the resin. When the material of the base material 12 is glass, the drying temperature is preferably equal to or lower than the softening point temperature of the glass.
When the base material 12 is a chemically strengthened glass plate, the drying temperature is preferably 80 to 450 ° C.
When the base material 12 is a glass plate that is not chemically strengthened, the drying step when forming the antiglare film 14 and the physical strengthening (wind cooling strengthening) step of the glass plate can also be performed. 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.

(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 silica particles (I), other particles, a terpene compound, other optional components, and the like, if necessary.

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. From the point of each characteristic of the anti-glare film | membrane 14, any 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 hydrolyzable groups may be the same group or different groups, and it is easy to obtain that they are the same group. This is preferable.

  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 antiglare film 14.
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, more preferably an alkylene group having 2 to 6 carbon atoms, from the viewpoint of mechanical strength of the antiglare film 14, ease of 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.
From the viewpoint of preventing cracks and film peeling of the antiglare film 14, the silica precursor preferably contains one or both of the silane compound (A1) and the hydrolysis condensate thereof.
From the viewpoint of the abrasion resistance strength of the antiglare film 14, the silica precursor preferably contains one or both of tetraalkoxysilane and its hydrolysis condensate.
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. When the coating liquid for antiglare film contains particles such as silica particles and other particles, the liquid medium may have a function as a dispersion medium for dispersing the particles.
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.

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

Other fine particles:
The explanation for the other fine particles is the same as described above.

Terpene compounds:
When the coating solution for antiglare 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:
Examples of other optional components include surfactants for improving leveling properties, metal compounds for improving durability of the antiglare film 14, ultraviolet absorbers, infrared reflection / infrared absorbers, antireflection agents, and the like. It is done.
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 precursor in the antiglare film coating solution (in terms of SiO ₂ ) is the solid content (100% by mass) in the antiglare film coating solution (however, the silica precursor is in terms of SiO ₂ ). On the other hand, 20 mass% or more is preferable and 25 mass% or more is more preferable. When the content of the silica-based matrix precursor is not less than the above lower limit value, the antiglare film 14 is excellent in mechanical strength. Moreover, sufficient adhesion strength is obtained between the base material 12 and the antiglare film 14.
The upper limit of the content (SiO ₂ conversion) of the silica precursor with respect to the solid content is not particularly limited, and may be 100% by mass. It can set suitably according to content of the other component mix | blended as needed with the coating liquid for anti-glare films.
For example, when the coating liquid for antiglare film contains silica particles (I), the content of the silica precursor relative to the solid content (in terms of SiO ₂ ) is based on the solid content (100% by mass) in the coating liquid for antiglare film. 50 mass% or less is preferable, and 45 mass% or less is more preferable.

The content of the liquid medium in the coating solution is an amount corresponding to the solid content concentration of the coating solution.
2-7 mass% is preferable and, as for the solid content density | concentration of the coating liquid for anti-glare films, 3-5 mass% is more preferable. When the solid content concentration is within the above range, the antiglare film 14 having the arithmetic average roughness Ra of the surface 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 .

The content of the silica particles (I) in the coating solution for the antiglare film can be appropriately set in consideration of the content of the silica particles (I) in the antiglare film 14 described above.
Silica particles (I) with respect to the content of silica particles (I) in the antiglare film 14 and the solid content (100% by mass) in the coating solution for the antiglare film (where the silica precursor is converted to SiO ₂ ). ) Content is almost the same.

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.

  The antiglare film coating solution is prepared, for example, by preparing a solution in which a silane precursor is dissolved in a liquid medium, and if necessary, an additional liquid medium, a dispersion of silica particles (I), a dispersion of other particles, a terpene It can be prepared by mixing a compound and other optional components.

(Function and effect)
In the base material 10 with the antiglare film, since the antiglare film 14 is the above (α) or (β), the antiglare effect with respect to oblique incident light close to the horizontal is excellent as compared with the conventional one.
Moreover, in the base material 10 with an anti-glare film, the anti-glare effect with respect to light other than near horizontal oblique incident light is also favorable.
The surface roughness characteristics of the film include arithmetic mean roughness Ra, average length RSm of roughness curve elements, maximum height roughness Rz, roughness curve kurtosis Rku, roughness curve skewness Rsk, and the like. Various things are known. The present inventors have high correlation between the arithmetic average roughness Ra and the 85 ° specular gloss on the surface of the antiglare film 14, but other surface roughness characteristics are 85 ° on the surface of the antiglare film 14. It has been confirmed that the correlation with the specular gloss is low (see [Example] described later).

(Use)
The use of the base material 10 with the antiglare 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.

Since the base material 10 with an anti-glare film is excellent in the anti-glare effect against oblique incident light, it is preferably a transparent substrate for solar cells.
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. In particular, when a solar cell module is installed on an inclined surface such as on an inclined roof, there is a concern that light is incident at an incident angle close to 90 ° and strong reflected light is generated. By using the base material 10 with an antiglare film as a transparent substrate for solar cells, it is possible to suppress the occurrence of light damage due to reflected light as described above.

As mentioned above, although one embodiment was shown and demonstrated about the base material with an anti-glare film of this invention, this invention is not limited to the said 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, you may have functional layers, such as AFP (fingerprint removal layer), on the upper side (the side opposite to the base material 12 side) of the antiglare film 14. You may have functional layers, such as an alkali barrier layer, a reflectance waveform adjustment layer, and an infrared shielding layer, between the base material 12 and the anti-glare film 14. The functional layer can be formed by a known method such as a coating method.
The form of the 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 base material with an anti-glare film is not limited to the method of forming the anti-glare film 14 by apply | coating the said coating liquid for anti-glare films on a base material, and drying.

[Goods]
The article of the present invention comprises the substrate with an antiglare film of the present invention.
The article of the present invention may be composed of the substrate with an antiglare film of the present invention, or may further comprise other members other than the substrate with an antiglare film of the present invention.
Examples of the article of the present invention include those mentioned above as applications of the base material 10 with an antiglare film, and devices including any one or more of them.
Examples of the device include a solar cell module, a display device, and a lighting device.

The solar cell module includes a solar cell and a transparent substrate (cover glass or the like) disposed on each of the front and back surfaces of the solar cell in order to protect the solar cell, and at least one of the transparent substrates (preferably a transparent substrate) Are preferably those using the substrate with an antiglare film of the present invention as at least a transparent substrate on the front side.
Examples of the display device include a mobile phone, a smartphone, a tablet, and a car navigation.
Examples of the illumination device include an organic EL (electroluminescence) illumination device and an LED (light emitting diode) illumination device.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description.
Among Examples 1 to 16 described later, Examples 1 to 4 and 10 to 15 are examples, and Examples 5 to 9 and 16 are comparative examples.
The measurement / evaluation method and materials (source or preparation method) used in each example are shown below.

<Measurement and evaluation method>
(Glossiness)
As the glossiness of the surface of the antiglare film, 60 ° specular glossiness and 85 ° specular glossiness were measured. Each specular gloss was measured at a substantially central portion of the antiglare film by a method defined in JIS Z8741: 1997 using a gloss meter (GM-268plus, manufactured by Konica Minolta). Moreover, each mirror glossiness was measured in the state which eliminated the influence of the back surface reflection of a glass plate by sticking a black tape on the back surface (surface on the opposite side to an anti-glare film) in a glass plate. It shows that it is excellent in anti-glare property, so that glossiness is small.

(Surface roughness)
Surface roughness of the antiglare film (arithmetic average roughness Ra, average length RSm of roughness curve element, maximum height roughness Rz, kurtosis Rku of roughness curve, skewness Rsk of roughness curve) Using a meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom (registered trademark) 1500DX), it was measured by the method described in JIS B0601: 2001. The reference length lr (cut-off value λc) for the roughness curve was 0.08 mm.

(Refractive index of antiglare film)
The refractive index n of the antiglare film was measured by the following method.
A single layer smooth film of the layer whose refractive index is to be obtained is formed on the surface of the glass plate by a spin coater, and a black vinyl tape is formed on the surface of the glass plate opposite to the single layer film so as not to contain bubbles. Pasted. Then, the reflectance of the said single layer film was measured in the wavelength range of 300-780 nm with the spectrophotometer (The Otsuka Electronics company make, instantaneous multiphotometry system MCPD-3000). In measuring the reflectance, the incident angle of light was set to 2 °. From the lowest reflectance in the wavelength range of 300~780nm and (bottom reflectivity _{R min)} and the refractive index _{n s} of the glass plate, it was calculated refractive index n by the following equation (1).
R _min = (n−n _s ) ² / (n + n _s ) ² (1)

<Materials used>
(Preparation of silica precursor solution (a-1))
While stirring 69.0 g of denatured ethanol (trade name “Solmix AP-11”, manufactured by Nippon Alcohol Sales Co., Ltd., a mixed solvent containing ethanol as a main ingredient, the same shall apply hereinafter), 11.9 g and 61 mass of ion-exchanged water are stirred. A mixed solution with 0.1 g of% nitric acid was added and stirred for 5 minutes. To this, 19.0 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 5.5% by mass ( a-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 (a-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 5 minutes to prepare a silica precursor solution (a-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 silica precursor solution (a))
While stirring 81.8 g of the silica precursor solution (a-1), 11.7 g of the silica precursor solution (a-2) was added and stirred for 30 minutes. Next, 6.5 g of denatured ethanol was added and stirred at room temperature for 30 minutes to obtain a silica precursor solution (a) having a solid content concentration in terms of SiO ₂ of 5.0% by mass.

(Preparation of silica precursor solution (b))
While stirring 91.1 g of denatured ethanol, a mixed solution of 1.2 g of ion exchange water and 0.4 g of 36 mass% hydrochloric acid was added and stirred for 5 minutes. Thereto, ethyl silicate 40 (Tama Chemicals Co., Ltd., poly tetraethoxysilane, calculated as SiO ₂ solid content concentration: 40 mass%) 7.3 g was added and stirred for 30 minutes at room temperature, the SiO ₂ solid concentration in terms A 3.0% by mass silica precursor solution (b) was prepared.

(Solid silica particle dispersion (c))
A chain-like SiO ₂ fine particle dispersion manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex OUP, solid content concentration in terms of SiO ₂ : 15.5% by mass, average primary particle size: 10 to 20 nm, average aggregated particle size: 40 to 100 nm.

(Hollow silica particle dispersion (d))
Hollow SiO ₂ fine particle dispersion manufactured by JGC Catalysts & Chemicals, trade name: Thruglia 4110, solid content concentration in terms of SiO ₂ : 20.5% by mass, average primary particle size: 60 nm.

(Preparation of coating solution (A))
While stirring 60.0 g of the silica precursor solution (a), 40.0 g of denatured ethanol is added and stirred at room temperature for 30 minutes to obtain a coating solution (A) having a solid content concentration of SiO ₂ of 3.0% by mass. It was.

(Preparation of coating solution (B))
The silica precursor solution (a) was used as it was to obtain a coating solution (B) having a SiO ₂ converted solid content concentration of 5.0% by mass.

(Preparation of coating solution (C))
While stirring 80.0 g of the silica precursor solution (a), 20.0 g of denatured ethanol was added and stirred at room temperature for 30 minutes to obtain a coating solution (C) having a solid content concentration of SiO ₂ of 4.0% by mass. It was.

(Preparation of coating solution (D))
The 30.0g of the silica precursor solution (a) was added with stirring 47.4g of denatured ethanol, and then, the solid silica particle dispersion (c) 22.6 g was added, and stirred for 30 minutes at room temperature, SiO ₂ A coating liquid (D) having a converted solid content concentration of 5.0% by mass was obtained.

(Preparation of coating solution (E))
While stirring 7.4 g of denatured ethanol, 24.0 g of isobutyl alcohol, 15.0 g of diacetone alcohol, 1.00 g of α-terpineol, and 30.0 g of silica precursor solution (a) were added thereto. Then, 22.6 g of solid silica particle dispersion (c) was added and stirred at room temperature for 30 minutes to obtain a coating liquid (E) having a solid content concentration in terms of SiO ₂ of 5.0% by mass.

(Preparation of coating solution (F))
While stirring 37.8 g of denatured ethanol, 50.0 g of the silica precursor solution (a) was added, then 12.2 g of the hollow silica particle dispersion (d) was added, and the mixture was stirred at room temperature for 30 minutes, converted to SiO ₂ A coating liquid (D) having a solid content concentration of 5.0% by mass was obtained.

(Preparation of coating solution (G))
While stirring 76.3 g of denatured ethanol, 12.0 g of the silica precursor solution (a) was added, then 11.7 g of the hollow silica particle dispersion (d) was added, and the mixture was stirred at room temperature for 30 minutes, converted to SiO ₂ A coating solution (G) having a solid content concentration of 3.0% by mass was obtained.

(Preparation of coating solution (H))
Silica precursor solution 18.0g of (a) added with stirring 71.8g of denatured ethanol, and then, the hollow silica particle dispersion (d) 10.2 g was added, and stirred for 30 minutes at room temperature, SiO ₂ in terms of A coating liquid (H) having a solid content concentration of 3.0% by mass was obtained.

(Preparation of coating solution (I))
While stirring 22.8 g of denatured ethanol, 70.0 g of the silica precursor solution (a) was added, then 7.3 g of the hollow silica particle dispersion (d) was added, and the mixture was stirred at room temperature for 30 minutes, converted to SiO ₂ A coating liquid (I) having a solid content concentration of 5.0% by mass was obtained.

(Preparation of coating solution (J))
The silica precursor solution (b) was used as it was to obtain a coating solution (J) having a SiO ₂ equivalent solid content concentration of 3.0% by mass.

<Example 1>
(Washing glass plate)
As the glass plate, a chemically strengthened aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd., trade name “Leoflex”, size: 300 mm × 300 mm, thickness 0.85 mm) was prepared. The surface of the glass plate was washed with sodium hydrogen carbonate water, rinsed with ion-exchanged water, and dried.

(Preparation of glass plate with antiglare film)
The glass plate was preheated in a preheating furnace (manufactured by ISUZU, VTR-115). Next, the surface average temperature Ra of the antiglare film formed on the glass plate by the spray method under the following coating conditions with the surface temperature of the glass plate kept at 90 ° C. is shown in Table 2. The coating solution (A) was applied so as to have the value shown. That is, the spray pressure (nozzle air discharge pressure) was set to 0.2 MPa, and the following coating treatment was repeated so that the arithmetic average roughness Ra of the surface of the antiglare film to be formed was 0.247 μm.
Coating treatment: The operation of moving the nozzle laterally on the glass plate at a speed of 750 mm / min, then moving forward 22 mm, and then moving laterally on the glass plate at a speed of 750 mm / min. Repeat until the coating solution (A) is applied to the entire surface of the plate.
(Application conditions)
Liquid volume of coating solution: 40 cm ³ / min,
Spray pressure: 0.2 MPa
Nozzle moving speed: 750 mm / min,
Spray pitch: 22 mm.
Then, it heat-cured for 3 minutes at 200 degreeC in air | atmosphere, and obtained the glass plate with an anti-glare film.
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 16>
A glass plate with an antiglare film as in Example 1 except that the type of coating solution, the amount of coating solution, and the spray pressure were changed as shown in Table 1, and the arithmetic average roughness Ra was changed as shown in Table 2. Got.

  About the glass plate with an anti-glare film obtained in each example, the refractive index in the anti-glare film, the gloss at an incident angle of 60 ° or 85 ° (60 ° specular gloss, 85 ° specular gloss), Table 1 shows the results of measurement of the surface roughness (arithmetic average roughness Ra, average length RSm of roughness curve element, maximum height roughness Rz, roughness curve kurtosis Rku, roughness curve skewness Rsk). Shown in ~ 2.

As shown in the results of Table 1, the antiglare film of Examples 1 to 4 has a refractive index of 1.4 to 1.5 and an arithmetic average roughness Ra of 0.158 to 0.500 μm. The film had a glossiness of 70% or less at an incident angle of 85 °, and had an excellent antiglare effect against obliquely incident light.
On the other hand, the antiglare film of Examples 5 to 9 having an arithmetic average roughness Ra of less than 0.158 μm has a glossiness of more than 70% at an incident angle of 85 °. Compared to the anti-glare effect against obliquely incident light, it was inferior. In particular, the antiglare films of Examples 7 and 9 had higher glossiness at an incident angle of 85 ° than Example 1 although the glossiness at an incident angle of 60 ° was lower than that of Example 1.

As shown in the results of Table 2, the antiglare film of Examples 10 to 15 in which the refractive index of the antiglare film is 1.2 or more and less than 1.4 and the arithmetic average roughness Ra is 0.112 to 0.700 μm. The glossiness at an incident angle of 85 ° was 70% or less, and had an excellent antiglare effect against obliquely incident light.
On the other hand, the antiglare film of Example 16 having an arithmetic average roughness Ra of less than 0.112 μm has a glossiness of more than 70% at an incident angle of 85 °, and is obliquely incident as compared with Examples 10-15. It was inferior in the antiglare effect against light.

  Of the surface roughness characteristics of the surface of the antiglare film, the arithmetic average roughness Ra showed a high correlation with the glossiness at an incident angle of 85 °, but other characteristics (roughness) There is no correlation between the average length RSm of the curve element, the maximum height roughness Rz, the roughness curve kurtosis Rku, and the roughness curve skewness Rsk) with the glossiness at an incident angle of 85 °. It was. From this, it was confirmed that the arithmetic average roughness Ra is useful as an index of the antiglare effect against oblique incident light.

10 Base material with antiglare film 12 Base material 14 Antiglare film

Claims (9)

A base material, and an antiglare film formed on the base material,
The refractive index of the antiglare film is 1.2 or more and less than 1.4,
The arithmetic average roughness Ra of the surface of the antiglare film is 0.112 to 0.700 μm,
A substrate with an antiglare film, characterized in that the 85 ° specular gloss on the surface of the antiglare film is 70% or less. A base material, and an antiglare film formed on the base material,
The refractive index of the antiglare film is 1.4 or more and 1.5 or less,
The arithmetic average roughness Ra of the surface of the antiglare film is 0.158 to 0.500 μm,
A substrate with an antiglare film, characterized in that the 85 ° specular gloss on the surface of the antiglare film is 70% or less.   The base material with an antiglare film according to claim 1 or 2, wherein the antiglare film contains one or both of solid silica particles and hollow silica particles.   The substrate with an antiglare film according to any one of claims 1 to 3, wherein the antiglare film is formed from a coating solution containing a silica precursor and a liquid medium.   The base material with an anti-glare film according to any one of claims 1 to 4, wherein the base material is a glass plate.   The base material with an anti-glare film according to claim 5, wherein the glass plate is a tempered glass plate.   The substrate with an antiglare film according to claim 6, wherein the tempered glass plate is a chemically tempered glass plate and has a thickness of 0.4 to 1.1 mm.   An article comprising the substrate with an antiglare film according to any one of claims 1 to 7.   The article according to claim 8, which is a solar cell module.

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