CN105319616A - Anti-dazzle film substrate and article - Google Patents

Abstract

The present invention provides a base material with an anti-glare film excellent in the anti-glare effect against incident light having a large incident angle, and an article using the base material. The base material 10 with an anti-glare film has a base material 12 and an anti-glare film 14, the anti-glare film 14 has a refractive index of 1.2 or more and less than 1.4, an arithmetic mean roughness Ra of the surface of 0.112-0.700 μm, and an 85° specular gloss. 70% or less, or the refractive index is 1.4 to 1.5, the arithmetic mean roughness Ra of the surface is 0.158 to 0.500 μm, and the 85° specular gloss is 70% or less.

Description

Substrates and articles with anti-glare film

technical field

The present invention relates to a base material with an anti-glare film and an article using the base material.

Background technique

External light sources such as indoor lighting (fluorescent lamps, etc.), sunlight, etc., in image display devices (liquid crystal displays, organic EL displays, plasma displays, etc.) When projected on the display surface, the visibility is reduced due to the reflection of the image.

Therefore, anti-glare treatment or low-reflection treatment is applied to the surface of a substrate (such as a glass plate) constituting the display surface of an image display device in order to suppress reflection of an external light source.

In recent years, in order to reduce the reflection of sunlight and improve power generation efficiency, the light incident surface of the cover glass of the solar cell module has been treated with low reflection, or the surface of the cover glass has been anti-glare in order to prevent light pollution caused by reflected light. deal with.

The anti-glare treatment is a process of providing unevenness on the surface, and the incident light is scattered by the unevenness to make the reflected image unclear. As an anti-glare treatment, methods of roughening the surface of a base material by etching, sandblasting, or the like have been known so far. In addition, a method of forming a light-diffusing layer (anti-glare film) by applying and firing a treatment solution obtained by hydrolyzing a silicate ester, alcohol, water, and acid (hydrochloric acid/nitric acid, etc.) has been proposed (Patent Document 1) .

Low-reflection processing is processing that suppresses reflection itself of incident light. As a low-reflection 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 low-reflection film is designed based on the optical path length based on the vertical incidence angle, so there are disadvantages that the optical path length deviates from the design, the reflectivity increases, and the low-reflection effect is lost depending on the incident angle of the external light source or the position of the person watching the screen.

The anti-glare film diffuses and reflects the external light source, so it does not depend on the incident angle of the external light source or the position of the person viewing the screen to achieve the anti-glare effect, which is more advantageous than the low-reflection film in terms of suppressing the external light source.

The anti-glare effect of the anti-glare film is usually evaluated by the glossiness at an incident angle of 60° (60° specular gloss). Therefore, the anti-glare film is usually designed as a film that reduces the glossiness of the 60° specular surface.

However, even in the antiglare film, there is a problem that the antiglare effect cannot be fully exhibited when the incident angle is larger than 60°, especially close to 90°.

When a solar cell module is installed on a sloping roof, sunlight may enter the cover glass at an incident angle close to 90°. In this case, even if an anti-glare film is provided on the surface of the cover glass, the reflected light reflected on the surface of the cover glass may enter a nearby building and cause light pollution.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 60-109134

Contents of the invention

The technical problem to be solved by the invention

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

Technical solutions adopted to solve technical problems

The present invention includes the following technical contents.

[1] A substrate with an antiglare film, comprising a substrate and an antiglare film formed on the substrate,

The antiglare film has a refractive index of not less than 1.2 and less than 1.4,

The arithmetic average roughness Ra of the surface of the antiglare film is 0.112 to 0.700 μm,

The 85° specular gloss of the surface of the anti-glare film is 70% or less.

[2] A substrate with an antiglare film, comprising a substrate and an antiglare film formed on the substrate,

The antiglare film has a refractive index of not less than 1.4 and not more than 1.5,

The arithmetic average roughness Ra of the surface of the antiglare film is 0.158 to 0.500 μm,

The 85° specular gloss of the surface of the anti-glare film is 70% or less.

[3] The substrate with an antiglare film according to [1] or [2], wherein the antiglare film contains either 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 solution 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 anti-glare film according to [6], wherein the tempered glass plate is a chemically strengthened glass plate and has a thickness of 0.4 to 1.1 mm.

[8] An article comprising the base material with an antiglare film according to any one of [1] to [7].

[9] The article according to [8], which is a solar cell module.

The effect of the invention

According to the present invention, a base material with an anti-glare film excellent in an anti-glare effect against incident light having a large incident angle, and an article using the base material can be provided.

Description of drawings

FIG. 1 is a cross-sectional view schematically showing an embodiment of a substrate with an antiglare film of the present invention.

detailed description

The following definitions of terms apply to this specification and claims.

The "silicon dioxide precursor" refers to a substance capable of forming a matrix containing silica as a main component.

"Containing silicon dioxide as a main component" means containing 90% by mass or more of SiO ₂ .

"Containing titanium oxide as a main component" means containing 90% by mass or more of TiO ₂ .

"Solid" means no voids inside.

"Hollow" means having a void 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" respectively pass the method described in JISZ8741: 1997 (ISO2813: 1994), and the anti-glare film is pasted on the side opposite to the side on which the anti-glare film is formed. The base material with anti-glare film of black tape was measured.

"Arithmetic mean roughness Ra" is measured by the method described in JISB0601:2001 (ISO4287:1997).

"Haze" is measured by the method described in JISK7136:2000 (ISO14782:1999).

〔Substrate with anti-glare film〕

FIG. 1 is a cross-sectional view schematically showing an embodiment of a substrate with an antiglare film of the present invention.

The base material 10 with an antiglare film of this embodiment includes a base material 12 and an antiglare film 14 formed on the base material 12 .

(Substrate)

As the form of the base material 12, a plate, a film, etc. are mentioned, for example.

As a material of the base material 12, glass, resin, etc. are mentioned, for example.

As glass, soda lime glass, borosilicate glass, aluminosilicate glass, non-alkali glass, etc. are mentioned, for example.

The resin may, for example, be polyethylene terephthalate, polycarbonate, triacetyl cellulose or polymethyl methacrylate.

Substrate 12 is preferably transparent. Transparency in the base material 12 means that the average transmission of light in the wavelength range of 400 to 1100 nm is 80% or more.

As the base material 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 a decorative glass (Japanese: type plate garas) having unevenness on the surface formed by a rolling method or the like. In addition, not only flat glass but also glass having a curved shape is possible.

The thickness of the glass plate is not particularly limited. For example, a glass plate with a thickness of 10 mm or less can be used. Since the light absorption can be suppressed at a low level as the thickness is thinner, it is preferable for the purpose of improving the transmittance.

When the glass is soda lime glass, it preferably has the following composition.

Expressed as a mass percentage on an oxide basis, it contains:

SiO ₂ : 65-75%,

Al ₂ O ₃ : 0-10%,

CaO: 5-15%,

MgO: 0～15%,

Na2O _: 10-20%,

K2O _: 0-3%,

_Li2O : 0-5%,

Fe ₂ O ₃ : 0~3%,

TiO ₂ : 0-5%,

CeO ₂ : 0-3%,

BaO: 0-5%,

SrO: 0~5%,

B ₂ O ₃ : 0-15%,

ZnO: 0~5%,

ZrO ₂ : 0-5%,

SnO ₂ : 0-3%,

SO ₃ : 0 to 0.5%.

When the glass is aluminosilicate glass, it preferably has the following composition.

Expressed as a mole percent on an oxide basis, containing

SiO ₂ : 62-68%,

Al ₂ O ₃ : 6-20%,

MgO: 7-13%,

Na2O: ₉ ～17%,

K2O _: 0-7%,

ZrO ₂ : 0 to 8%.

The glass plate is preferably a tempered glass plate. A tempered glass plate is a glass plate subjected to tempering treatment. The strengthening treatment increases the strength of the glass, and it is possible to reduce the thickness of the glass while maintaining the strength, for example.

However, in the present invention, a glass plate other than a tempered glass plate may be used, and it may be appropriately set according to the application of the base material 10 with an antiglare film.

As a strengthening treatment, a treatment of forming a compressive stress layer on the surface of a glass plate is generally known. The compressive stress layer on the surface of the glass sheet increases the strength of the glass sheet to damage or impact. As a method of forming a compressive stress layer on the surface of a glass plate, an air-cooling strengthening method (physical strengthening method) and a chemical strengthening method are typified.

In the air-cooling tempering method, the surface of a glass plate heated to a temperature near the softening point of glass (for example, 600 to 700° C.) is rapidly cooled by air cooling or the like. Thereby, a temperature difference is generated between the surface and the inside of the glass sheet, and compressive stress is generated on the surface layer of the glass sheet.

In the chemical strengthening method, the glass plate is immersed in molten salt at a temperature below the deformation point temperature of the glass, and the ions (such as sodium ions) on the surface of the glass plate are exchanged with ions (such as potassium ions) with a larger ionic radius. Thereby, compressive stress is generated on the surface layer of the glass sheet. In addition, the deformation point of glass is lower than the softening point.

If the thickness of the glass sheet becomes thin (for example, less than 2mm), it is difficult to generate a temperature difference between the inside and the surface of the glass sheet in the air-cooling strengthening method and the glass sheet cannot be sufficiently strengthened. Therefore, it is preferable to use a chemical strengthening method.

As long as it has a composition that can be chemically strengthened, the glass plate with a composition that can be chemically strengthened is not particularly limited, and glass plates with various compositions can be used, such as soda lime glass, aluminosilicate glass, boron glass, etc. Salt glass, lithium aluminosilicate glass, borosilicate glass, alkali-free glass, and various other glasses. From the viewpoint of ease of chemical strengthening, the glass composition preferably contains 56 to 75% of SiO ₂ , 1 to 20% of Al ₂ O ₃ , 8 to 22% of Na ₂ O , and K ₂ O0 in terms of mole percent based on oxides. ～10%, MgO 0～14%, ZrO ₂ 0～5%, CaO 0～10%. Among them, aluminosilicate glass is preferable.

The thickness of the glass plate to be chemically strengthened 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 below the upper limit of the above range, 10 parts of the substrate with antiglare film will be light, and if it is above the lower limit of the above range, the substrate with antiglare film 10 will have excellent strength.

In addition, there was no change in plate thickness before and after chemical strengthening. That is, the plate thickness of the chemically strengthened glass plate is the plate thickness of the chemically strengthened glass plate (the chemically strengthened glass plate).

(anti-glare film)

The antiglare film 14 is the following (α) or (β).

(α) An antiglare film having a refractive index of not less than 1.2 and not more than 1.4, an arithmetic average surface roughness Ra of 0.112 to 0.700 μm, and a surface 85° specular gloss of not more than 70%.

(β) An antiglare film having a refractive index of 1.4 to 1.5, an arithmetic mean surface roughness Ra of 0.158 to 0.500 μm, and a surface 85° specular gloss of 70% or less.

Here, the surface of the antiglare film 14 refers to the surface opposite to the substrate 12 , that is, the surface of the antiglare film-attached substrate 10 on the antiglare film 14 side.

The arithmetic mean roughness Ra is an index showing the average height of the undulations (Japanese: valleys) of surface irregularities.

In the case of the same refractive index of the anti-glare film 14, the larger the arithmetic mean roughness Ra of the surface, the smaller the 85° specular glossiness becomes, and there is an incident light with an incident angle greater than 60° (hereinafter referred to as oblique incidence) Light) tends to be excellent in the antiglare effect. In addition, when the arithmetic mean roughness Ra of the surface of the antiglare film 14 is the same, the smaller the refractive index is, the smaller the 85° specular gloss is, and the antiglare effect against obliquely incident light tends to be excellent.

If the refractive index of the antiglare film 14 is less than 1.5, especially less than 1.4, the reflectance of the surface of the antiglare film 14 becomes low, and even if Ra is less than 0.700 μm, further less than 0.500 μm, sufficient antiglare can be obtained. Effect.

If the antiglare film 14 has a refractive index of 1.2 or more, especially 1.4 or more, the antiglare film 14 will have sufficiently high density and excellent adhesion to substrates 12 such as glass plates. In addition, if the arithmetic mean roughness Ra of the surface becomes larger, the mechanical strength such as abrasion resistance of the antiglare film 14 tends to be lowered, but since the antiglare film 14 is dense, even if the arithmetic mean roughness Ra becomes The mechanical strength of the anti-glare film 14 is also sufficiently excellent.

(α) The antiglare film preferably has a refractive index of 1.25 or more and less than 1.4.

(α) The arithmetic average roughness Ra of the antiglare film is preferably 0.113 to 0.650 μm. If the arithmetic mean roughness Ra of the surface of the anti-glare film of (α) is more than the lower limit of the above-mentioned range, the anti-glare effect can fully be exhibited. If the arithmetic mean roughness Ra of the surface of the antiglare film (α) is below the upper limit of the above-mentioned range, the mechanical strength of the antiglare film 14 is excellent, and in addition, the haze of the base material 10 with the antiglare film becomes low. small enough.

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

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

(β) The antiglare film preferably has a refractive index of 1.40 or more and 1.46 or less.

(β) The arithmetic average roughness Ra of the antiglare film is preferably 0.200 to 0.500 μm. If the arithmetic mean roughness Ra of the surface of the anti-glare film of (β) is more than the lower limit value of the said range, an anti-glare effect can fully be exhibited. If the arithmetic average roughness Ra of the surface of the antiglare film (β) is below the upper limit of the above-mentioned range, the mechanical strength of the antiglare film 14 is excellent, and in addition, the haze of the base material 10 with the antiglare film becomes low. small enough.

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

The 85° specular glossiness and the 60° specular glossiness of the surface of the antiglare film 14 can be adjusted according to the refractive index of the antiglare film 14 , the arithmetic mean roughness Ra of the surface of the antiglare film 14 , and the like.

The refractive index of the anti-glare film 14 can be adjusted by the matrix material of the anti-glare film 14, the porosity of the anti-glare film 14, adding a substance with an arbitrary refractive index to the matrix, and the like. For example, the refractive index can be lowered by increasing the porosity of the anti-glare film 14 . The refractive index of the antiglare film 14 can also be lowered by adding a substance with a low refractive index (solid silica particles, hollow silica particles, etc.) to the matrix.

The method of adjusting the arithmetic mean roughness Ra of the surface of the antiglare film 14 will be described in detail later.

As the anti-glare film 14, it is preferable to contain either or both of solid silica particles and hollow silica particles (hereinafter also referred to as silica particles) from the viewpoint of easy adjustment of the refractive index, arithmetic surface roughness Ra, and excellent chemical stability. silicon particles (I)).

A film containing silica particles (I) typically further contains a matrix that fills voids between the silica particles (I). The matrix may cover the upper side of the silica particles (I) (the side opposite to the substrate 12 side) so as not to expose the silica particles (I).

As the anti-glare film 14, a film made of a matrix and not containing silica particles (I) can also be used.

The anti-glare film 14 may contain particles other than the silica particles (I).

The antiglare film 14 may also contain a terpene compound.

The antiglare film 14 may further contain components other than silica particles (I), a matrix, other particles, and terpene compounds (hereinafter also referred to as “other optional components”).

Matrix:

The matrix of the anti-glare film 14 may, for example, be a silica-based matrix or a titanium oxide-based matrix.

"Silica-based substrate" means a substrate containing silica as a main component.

The "titanium oxide-based substrate" refers to a substrate containing titanium oxide as a main component.

As the matrix of the antiglare film 14, a silica-based matrix is preferable. If the matrix is a silica-based matrix, the refractive index (reflectance) of the anti-glare film 14 is easily lowered. In addition, chemical stability, abrasion resistance, and the like are also good. When the base material 12 is glass, the adhesiveness is particularly good.

The silica-based matrix may contain a small amount of components other than silica. As this component, there may be mentioned, for example, those selected from Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn , Ga, Sr, Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi, and one or more ions and/or oxides of lanthanum.

The silica-based matrix is preferably substantially composed of silica. "Consisting substantially of silica" means consisting only of silica except for unavoidable impurities.

As the silica-based matrix, for example, a matrix formed from a coating solution containing a silica precursor and a liquid medium may be mentioned. The silica precursor will be described in detail later.

Silica particles (I):

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

The shape of the solid silica particles may, for example, be spherical, oval, acicular, plate, rod, conical, cylindrical, cubic, cuboid, diamond, star, or irregular. The solid silica particles may exist in a state where each particle is independent, each particle may be connected in a chain, or each particle may be aggregated.

As the solid silica particles, chain-shaped solid silica particles are preferable from the viewpoint of ease of lowering the refractive index.

Chain-like solid silica particles are solid silica particles having a chain-like shape. For example, solid silica particles having a shape in which a plurality of solid silica particles having shapes such as spherical, elliptical, and acicular shapes are connected in a chain can be exemplified. The shape of the chain-like solid silica particles can be confirmed with an electron microscope.

Chain-like solid silica particles can be easily obtained as a commercial item. In addition, particles produced by known production methods can also be used. As a commercial item, Nissan Chemical Industry Co., Ltd. (Nissan Chemical Industry Co., Ltd.) SNOWTEXST-OUP etc. are mentioned, for example.

The average aggregated particle size of the solid silica particles is preferably 5 to 300 nm, more preferably 5 to 200 nm. If the average aggregated particle diameter of the solid silica particles is within the above-mentioned range, the arithmetic mean roughness Ra of the surface of the anti-glare film 14 is likely to be within the above-mentioned range.

The average aggregated particle size can be measured using a dynamic light scattering particle size analyzer (manufactured by Nikkiso Co., Ltd. (Nikkiso Co., Ltd., MICROTRACUPA).

Since hollow silica particles have voids inside, they have a lower refractive index than solid silica particles. Therefore, there is an advantage that the effect of lowering the refractive index can be obtained with a smaller amount than solid silica particles.

Examples of hollow silica particles include particles having a silica (SiO ₂ ) shell and hollows formed in the shell.

The average primary particle diameter of the hollow silica particles is preferably 40 to 150 nm, more preferably 50 to 100 nm. If the average primary particle diameter of the hollow silica particles is within the above-mentioned range, the arithmetic mean roughness Ra of the surface of the anti-glare film 14 is likely to be within the above-mentioned range.

The average primary particle diameter of the hollow silica particles was determined as follows.

Observe the hollow silica particles with a scanning electron microscope (hereinafter referred to as SEM) or a transmission electron microscope (hereinafter referred to as TEM), randomly select 100 hollow silica particles, and measure the particle diameter of each hollow silica particle , Calculate the average value of the particle diameters of 100 hollow silica particles.

Other particles:

As other particles, metal oxide particles, metal particles, pigment particles, resin particles and the like may, for example, be mentioned. Other particles can be of hollow or solid configuration.

As the material of the metal oxide particles, Al ₂ O ₃ , SiO ₂ , SnO ₂ , TiO ₂ , ZrO ₂ , ZnO, CeO ₂ , SnO _x (ATO) containing Sb, In ₂ O ₃ ( ITO), RuO ₂ and so on.

As a material of the metal particles, metals (Ag, Ru, etc.), alloys (AgPd, RuAu, etc.) and the like may, for example, be mentioned.

As the pigment particles, inorganic pigments (titanium black, carbon black, etc.) and organic pigments may, for example, be mentioned.

As a material of the resin particle, polystyrene, a melamine resin, etc. are mentioned.

Other particle shapes include scales, spheres, ellipses, needles, plates, rods, cones, columns, cubes, cuboids, diamonds, stars, and irregular shapes. The other particles may exist in a state where each particle is independent, each particle may be connected in a chain, or each particle may be aggregated.

Other particles may be used alone or in combination of two or more.

As other particles, scale-like particles are preferable from the viewpoint of being able to suppress cracking or film peeling of the anti-glare film 14 . "Scaly particles" mean particles having a flat shape. The shape of the particles can be confirmed using TEM.

The flaky particles include flaky silica particles, flaky alumina particles, flaky titanium oxide, and flaky zirconia particles. From the viewpoint of suppressing the increase in the refractive index of the film and reducing the reflectance, flaky particles are preferable. shaped silica particles.

As the flaky silica particles, those produced by the production method described in JP-A-2014-94845 are preferable.

Terpenes:

The terpene compound will be described in detail later.

Any other 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, particularly preferably 30 to 100% by mass, based on the total mass of the antiglare film 14. . When the total content of the matrix and the silica particles (I) is at least 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 antiglare film 14 is the above (α) antiglare film, and the silica particles (I) are solid silica particles, the content of the solid silica particles in the antiglare film 14 is relative to that of the antiglare film. The total mass of 14 is preferably more than 0% by mass and not more than 70% by mass, more preferably more than 0% by mass and not more than 60% by mass, particularly preferably more than 0% by mass and not more than 50% by mass. If the content of the solid silica particles is within the above range, the larger the content of the solid silica particles, the lower the refractive index of the anti-glare film 14 and the larger the arithmetic surface roughness Ra will tend to be. . If the content of the solid silica particles is not more than the upper limit of the above range, the refractive index of the anti-glare film 14 will be more than the lower limit of the above range, and the arithmetic surface roughness Ra will be not more than the upper limit of the above range. .

For the same reason, when the anti-glare film 14 is the above-mentioned (β) anti-glare film and the silica particles (I) are solid silica particles, the content of the solid silica particles in the anti-glare film 14 Preferably it is 60-80 mass % with respect to the total mass of the anti-glare film 14, More preferably, it is 70-80 mass %.

When the anti-glare film 14 is the anti-glare film of the above (α), and the silica particles (I) are hollow silica particles, the content of the hollow silica particles in the anti-glare film 14 is relative to the anti-glare film. The total mass of 14 is preferably more than 0% by mass and not more than 20% by mass, more preferably more than 0% by mass and not more than 15% by mass, particularly preferably more than 0% by mass and not more than 20% by mass. If the content of the hollow silica particles is within the above range, the larger the content of the hollow silica particles, the lower the refractive index of the anti-glare film 14 and the larger the arithmetic surface roughness Ra will tend to be. . If the content of the hollow silica particles is not more than the upper limit of the above range, the refractive index of the anti-glare film 14 will be more than the lower limit of the above range, and the arithmetic surface roughness Ra will be not more than the upper limit of the above range. .

For the same reason, when the anti-glare film 14 is the above-mentioned (β) anti-glare film and the silica particles (I) are hollow silica particles, the content of the hollow silica particles in the anti-glare film 14 Preferably it is 21-80 mass % with respect to the total mass of the anti-glare film 14, More preferably, it is 30-70 mass %.

(haze)

The haze of the anti-glare film-attached substrate 10 is preferably 5 to 20%, more preferably 5 to 15%. If the haze is below the upper limit of the above range, the contrast of the image when the base material 10 with an antiglare film is used for a display device, or the power generation efficiency when the base material 10 with an antiglare film is used for a solar cell module good. The antiglare effect will be exhibited easily as haze is more than the lower limit of the said range.

<Manufacturing method of base material with anti-glare film>

As the manufacturing method of the anti-glare film substrate 10, for example,

For example, a method of coating a coating solution containing a silica precursor and a liquid medium (hereinafter also referred to as a coating solution for an anti-glare film) on the substrate 12 and drying it to form the anti-glare film 14 .

The coating liquid for an antiglare film may contain silica particles (I), other particles, a terpene compound, other optional components, and the like as needed. The coating liquid for an antiglare film will be described in detail later.

When forming the anti-glare film 14 , the application and drying of the anti-glare film coating solution are carried out under conditions such that the arithmetic average roughness Ra of the surface of the anti-glare film 14 falls within a predetermined range.

(coating)

As the coating method of the coating liquid for anti-glare film, known wet coating method (spray coating method, spin coating method, dip coating method, die coating method, curtain coating method, screen printing coating method, spray coating method, etc.) ink method, flow coating method, gravure coating method, bar coating method, flexo coating method, slit coating method, roll coating method) and the like.

As a coating method, a spray coating method is preferable from the viewpoint of easily forming sufficient unevenness.

The nozzle used in the spraying method may, for example, be a two-fluid nozzle or a one-fluid nozzle.

The droplet diameter of the coating liquid discharged from the nozzle is usually 0.1 to 100 μm, preferably 1 to 50 μm. If the particle size of the droplets is 1 μm or more, it is possible to form irregularities in a short time that can fully exert the antiglare effect. When the droplet size is 50 μm or less, it is easy to form unevenness that can sufficiently exert the antiglare effect.

The droplet size can be appropriately adjusted by the type of nozzle, spraying pressure, liquid volume, etc. For example, in a two-fluid nozzle, the higher the spraying pressure, the smaller the droplets, and the larger the liquid volume, the larger the droplets.

The particle diameter of the liquid droplet is a Sauter average particle diameter measured with a laser measuring device.

The arithmetic mean roughness Ra of the surface of the anti-glare film can be determined according to the composition of the coating solution for the anti-glare film (solid content concentration, type, size, content, etc. of silica particles (I) or other particles), Coating conditions of the coating liquid (spray pressure, liquid volume, substrate temperature, number of times of coating, etc. when coating the coating liquid) and the like are adjusted.

For example, when the conditions other than the solid content concentration of the coating liquid for antiglare films are the same, the arithmetic mean roughness Ra tends to increase as the solid content concentration increases.

When the coating solution for an antiglare film contains silica particles (I), and the conditions are the same except for the average particle diameter (average primary particle diameter, average aggregated particle diameter, etc.) of the silica particles (I), there is The larger the average particle diameter of the silica particles (I), the larger the arithmetic average roughness Ra tends to be.

In the case where the coating liquid for anti-glare film contains silica particles (I), and the conditions are the same except for the content of silica particles (I), the more content of silica particles (I) exists, the arithmetic The average roughness Ra tends to be larger.

When the conditions other than the spraying pressure at the time of coating the coating liquid for anti-glare films are the same, the lower the spraying pressure, the larger the arithmetic mean roughness Ra tends to be.

When the conditions other than the liquid amount at the time of coating the coating liquid for anti-glare films are the same, the arithmetic mean roughness Ra tends to increase as the liquid amount increases.

When the conditions other than the substrate temperature at the time of coating the coating liquid for anti-glare films are the same, the arithmetic mean roughness Ra tends to become larger as the substrate temperature is higher.

In the case of the same conditions except the number of times of coating when coating the coating liquid for anti-glare film, the more the number of times of coating, that is, the number of coated surfaces (number of repeated coatings) by the spray coating method, the arithmetic mean There is a tendency that the roughness Ra becomes larger.

Furthermore, as the arithmetic average roughness Ra increases, the 85° specular glossiness tends to decrease, the antiglare effect against obliquely incident light tends to increase, and the haze tends to increase.

When coating the coating liquid for an anti-glare film by a spray coating method, it is preferable to heat the substrate 12 to 30 to 90° C. in advance. If the temperature of the substrate 12 is 30° C. or higher, sufficient unevenness is easily formed due to rapid evaporation of the liquid medium. When the temperature of the base material 12 is 90° C. or lower, the adhesion between the base material 12 and the anti-glare film 14 is good. When the base material 12 is a glass plate with a thickness of 5 mm or less, a thermal insulation board set to a temperature equal to or higher than the temperature of the base material 12 may be placed under the base material 12 to suppress a drop in temperature of the base material 12 .

(dry)

The coating film of the coating liquid for an anti-glare film formed on the substrate 12 by applying the coating liquid for an anti-glare film is dried. Thereby, the liquid medium in the coating film is removed, and the conversion of the silicon dioxide precursor remaining in the coating film to a silicon dioxide matrix (for example, the silicon dioxide precursor has a hydrolyzability bonded to a silicon atom) In the case of the silane compound of the group, the hydrolyzable group is basically decomposed, and the condensation of the hydrolyzate proceeds), and at the same time, the film is densified to form the anti-glare film 14 .

Drying may be performed by heating or without heating (natural drying, air drying, etc.).

The heating of the coating film may be carried out simultaneously with the application by heating the substrate 12 when the coating solution for the antiglare film is coated on the substrate 12, or may be performed after the coating solution for the antiglare film is coated on the substrate 12. 12 After application, it is carried out by heating the coating film.

The drying temperature is preferably 30° C. or higher, and can be appropriately determined according to the material of the substrate 12 , the material of the coating liquid for an anti-glare film, and the like.

When the silica precursor is a silane compound having a hydrolyzable group bonded to a silicon atom (silane compound (A) described later), the drying temperature is preferably 80°C or higher, more preferably 100°C or higher. If the drying temperature is 80° C. or higher, the film can be densified to improve durability such as the mechanical strength of the anti-glare film 14 .

When the material of the base material 12 is resin, the drying temperature is not higher than the heat-resistant temperature of the resin. When the material of the base material 12 is glass, the drying temperature is preferably not higher than the softening point temperature of 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 has not been chemically strengthened, a drying process for forming the anti-glare film 14 and a physical strengthening (air-cooling strengthening) process for the glass plate may also be combined. In the physical strengthening process, glass is heated to around the softening temperature of glass. In this case, the drying temperature is typically set at about 600 to 700°C.

A certain degree of polymerization occurs even in natural drying, so if there is no time limit, the drying temperature can theoretically be set to a temperature around room temperature.

(Coating solution for anti-glare film)

The coating solution for an antiglare film includes a silica precursor and a liquid medium.

The coating liquid for an antiglare film may further contain silica particles (I), other particles, a terpene compound, other optional components, and the like as necessary.

Silica precursor:

As a silica precursor, a silane compound (hereinafter also referred to as a silane compound (A)) having a hydrolyzable group bonded to a silicon atom, a hydrolytic condensate of a silane compound (A) (sol-gel bismuth Silicon oxide), silazane, etc. From the viewpoint of the properties of the anti-glare film 14, either or both of the silane compound (A) and its hydrolysis condensate are preferred, and the hydrolysis condensate of the silane compound (A) is more preferred.

The silane compound (A) may, for example, be a silane compound (A1) or an alkoxysilane (excluding the silane compound (A1)) having a hydrocarbon group bonded to a silicon atom and a hydrolyzable group.

In the silane compound (A1), the hydrocarbon group bonded to a silicon atom may be a monovalent hydrocarbon group bonded to one silicon atom or a divalent hydrocarbon group bonded to two silicon atoms. As a monovalent hydrocarbon group, an alkyl group, an alkenyl group, an aryl group etc. are mentioned. As a divalent hydrocarbon group, an alkylene group, an alkenylene group, an arylene group etc. are mentioned.

The hydrocarbon group may have one or more combinations of carbon atoms selected from -O-, -S-, -CO-, and -NR'- (wherein R' is a hydrogen atom or a monovalent hydrocarbon group) group.

The hydrolyzable group bonded to the silicon atom may, for example, be an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminooxy group, an amide group, an isocyanate group, or a halogen atom. Among these groups, alkoxy groups, isocyanate groups, and halogen atoms (especially chlorine atoms) are preferred from the viewpoint of the balance between the stability of the silane compound (A1) and the easiness of hydrolysis.

The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably a methoxy group or an ethoxy group.

When there are a plurality of hydrolyzable groups in the silane compound (A1), the hydrolyzable groups may be the same group or different groups, but the same group is preferred from the viewpoint of ease of acquisition. .

The silane compound (A1) may, for example, be a compound represented by the formula (I) described later, an alkoxysilane having an alkyl group (methyltrimethoxysilane, ethyltriethoxysilane, etc.), a vinyl group-containing Alkoxysilanes (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilanes with epoxy groups (2-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldiethoxysilane, 3-Glycidoxypropyltriethoxysilane, etc.), Alkoxysilanes having an acryloyloxy group (3-acryloyloxypropyltrimethoxysilane, etc.) and the like.

As the silane compound (A1), a compound represented by the following formula (I) is preferable 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 formula (I), Q is a divalent hydrocarbon group (can be selected from -O-, -S-, -CO- and -NR'- (wherein, R' is a hydrogen atom or a 1-valent hydrocarbon group) between carbon atoms) A group formed by a combination of 1 or 2 or more of them). As the divalent olefin, the above-mentioned divalent olefin may, for example, be mentioned.

As Q, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable from the viewpoints of the mechanical strength of the antiglare film 14 and ease of acquisition.

In formula (I), L is a hydrolyzable group. As a hydrolyzable group, the above-mentioned hydrolyzable group is mentioned, and a preferable aspect is also the same.

R is a hydrogen atom or a monovalent hydrocarbon group. As the monovalent olefin, the above-mentioned monovalent olefin may, for example, be mentioned.

p is an integer of 1-3. p is preferably 2 or 3, particularly preferably 3, from the viewpoint of not slowing down the reaction rate too much.

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

The hydrolysis and condensation of a silane compound (A) can be performed by a well-known method.

For example, when the silane compound (A) is a tetraalkoxysilane, it carries out using 4 times mole or more water of tetraalkoxysilane, and the acid or alkali which are catalysts.

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.). The base may, for example, be ammonia, sodium hydroxide or potassium hydroxide. As a catalyst, an acid is preferable from the viewpoint of the long-term storage property of the hydrolysis-condensation product of a 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 the silica precursor, one type may be used alone, or two or more types may be used in combination.

The silica precursor preferably contains either or both of the silane compound (A1) and its hydrolytic condensate from the viewpoint of preventing cracks or film peeling of the antiglare film 14 .

From the viewpoint of the abrasion resistance strength of the antiglare film 14, the silica precursor preferably contains either or both of tetraalkoxysilane and its hydrolytic condensate.

It is particularly preferable that the silica precursor contains either or both of a silane compound (A1) and its hydrolytic condensate, and either or both of a tetraalkoxysilane and its hydrolytic condensate.

The proportion of the silane compound (A1) and its hydrolysis condensate in the silica precursor is preferably 5 to 30 mass % relative to the solid content (100 mass %) of the silica precursor in terms of SiO ₂ .

Liquid medium:

The liquid medium is a liquid for dissolving or dispersing a silica precursor. When the coating liquid for an antiglare film contains particles such as silica particles and other particles, the liquid medium may function as a dispersion medium for dispersing the particles.

As a liquid medium, water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds, etc. are mentioned, for example.

The alcohols may, for example, be methanol, ethanol, isopropanol, butanol or diacetone alcohol.

As ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned.

Examples of ethers include tetrahydrofuran, 1,4-bis alkanes etc.

As cellosolves, methyl cellosolve, ethyl cellosolve, etc. are mentioned.

The esters may, for example, be methyl acetate or ethyl acetate.

As glycol ethers, ethylene glycol monoalkyl ether etc. are mentioned.

The nitrogen-containing compound may, for example, be N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidone.

Dimethyl sulfoxide etc. are mentioned as a sulfur compound.

The liquid medium may be used alone or in combination of two or more.

Since water is required for hydrolysis of alkoxysilane and the like in the silica precursor, the liquid medium contains at least water when the liquid medium is not replaced after hydrolysis.

In this case, the liquid medium may be water alone, or a mixed liquid of water and other liquids. Examples of other liquids include alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, sulfur-containing compounds, and the like. Among other liquids, alcohols are preferable as the solvent for the silica precursor, and methanol, ethanol, isopropanol, and butanol are particularly preferable.

The liquid medium may contain an acid or a base. The acid or base may be added as a catalyst for hydrolysis and condensation of raw materials (alkoxysilane, etc.) when preparing the solution of the silica precursor, or may be added after preparing the solution of the silica precursor.

Silica particles (I):

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

Other particles:

The description of other microparticles is the same as above.

Terpenes:

If the coating solution for anti-glare film contains particles such as silica particles (I) and further contains terpene compounds, voids will be formed around the particles, and the refraction will be reduced compared with the case of not containing terpene compounds. tendency to decrease.

A terpene refers to 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. Terpene compounds refer to terpenes having functional groups derived from terpenes. Terpene compounds also include terpene compounds having different degrees of unsaturation.

In addition, although there are substances that function as liquid media among terpene compounds, "hydrocarbons having a composition of (C ₅ H ₈ ) _n having isoprene as a structural unit" correspond to terpene derivatives and are not Equivalent to a liquid medium.

As the terpene compound, terpene derivatives described in International Publication No. 2010/018852 and the like can be used.

Any other ingredients:

Other optional components include, for example, 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.

As surfactants, silicone oils, acrylics, and the like may, for example, be mentioned.

As a metal compound, zirconium chelate, titanium chelate, aluminum chelate, etc. are preferable. The zirconium chelate compound may, for example, be zirconium tetraacetylacetonate or zirconium tributoxystearate.

composition:

The content of the silica precursor in the coating liquid for antiglare film ( _SiO2 conversion) is relative to the solid content (100% by mass) in the coating liquid for antiglare film (wherein, the silica precursor is _SiO2 converted) is preferably 20% by mass or more, more preferably 25% by mass or more. When the content of the silica-based matrix precursor is more than the above lower limit, the anti-glare film 14 has excellent mechanical strength. In addition, sufficient adhesion strength can be obtained between the base material 12 and the antiglare film 14 .

The upper limit of the content (SiO ₂ conversion) of the silica precursor to the solid content is not particularly limited, and may be 100% by mass. The content of other components to be blended can be appropriately set according to the needs of the coating liquid for an antiglare film.

For example, when the coating liquid for an anti-glare film contains silica particles (I), the content of the silica precursor relative to the solid content ( _SiO2 conversion) relative to the solid content of the coating liquid for an anti-glare film Components (100% by mass) are preferably 50% by mass or less, more preferably 45% by mass or less.

The content of the liquid medium in the coating liquid is set according to the solid content concentration of the coating liquid.

The solid content concentration of the coating liquid for an antiglare film is preferably 2 to 7% by mass, more preferably 3 to 5% by mass. If the solid content concentration is within the above-mentioned range, it will be easy to obtain the anti-glare film 14 in which the arithmetic mean roughness Ra of the surface is within the above-mentioned range.

The solid content of the coating liquid for an anti-glare film is the total content of all components other than the liquid medium in the coating liquid for an anti-glare film. The content of the silicon dioxide precursor is calculated as SiO ₂ .

The content of the silica particles (I) in the coating solution for an anti-glare film can be appropriately set in consideration of the content of the silica particles (I) in the anti-glare film 14 as described above.

The content of the silica particles (I) in the antiglare film 14 and the solid content (100% by mass) of the silica particles (I) relative to the coating solution for the antiglare film (wherein the silica precursor is SiO ₂ conversion) content is basically the same.

When the coating liquid for antiglare film contains a terpene compound, the content of the terpene compound in the coating liquid for antiglare film is relative to the solid content (100% by mass) in the coating liquid for antiglare film (wherein , the silica precursor is SiO ₂ conversion), preferably 0.05 to 0.25% by mass, more preferably 0.1 to 0.15% by mass. When content of a terpene compound is more than the lower limit of the said range, the effect by containing a terpene compound will be acquired easily. When content of a terpene compound is below the upper limit of the said range, it will be excellent in mechanical strength.

The coating solution for the anti-glare film can be prepared, for example, by dissolving a solution of a silane precursor in a liquid medium, adding as needed a liquid medium, a dispersion of silica particles (I), a dispersion of other particles, a terpene Compounds, other optional components, etc. are mixed and prepared.

(Effect)

Since the antiglare film 14 of the base material 10 with an antiglare film is the above-mentioned (α) or (β), the antiglare effect with respect to obliquely incident light close to the horizontal is excellent compared with conventional ones.

In addition, in the base material 10 with an anti-glare film, the anti-glare effect with respect to light other than obliquely incident light close to the horizontal is also good.

In addition, as the surface roughness characteristics of the film, in addition to the arithmetic mean roughness Ra, the average length RSm of the roughness curve element, the maximum height roughness Rz, the kurtosis (Japanese: クルトシス) Rku of the roughness curve, Various elements such as the skewness (Japanese: スキューネス) Rsk of the roughness curve. The present inventors have confirmed that the correlation between the arithmetic mean roughness Ra and the 85° specular gloss of the surface of the antiglare film 14 is high, while the correlation of other surface roughness characteristics and the 85° specular gloss of the surface of the antiglare film 14 is low (Refer to the "Example" described later).

(use)

The use of the antiglare film-attached substrate 10 is not particularly limited. Specific examples include automotive transparent parts (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, etc.), automotive transparent parts (dashboard surfaces, etc.), measuring tools , architectural windows, shop windows, displays (notebook computers, monitors, LCDs, PDPs, ELDs, CRTs, PDAs, etc.), LCD color filters, substrates for touch panels, camera lenses, optical lenses, spectacle lenses, camera parts, camcorders Components, CCD cover substrates, optical fiber end faces, projector components, copier components, transparent substrates for solar cells (cover glass, etc.), mobile phone windows, backlight unit components (light guide plates, cold cathode tubes, etc.), backlight unit components Liquid crystal brightness improvement Films (prisms, semi-permeable films, etc.), liquid crystal brightness enhancement films, organic EL light-emitting element parts, inorganic EL light-emitting element parts, phosphor light-emitting element parts, optical filters, end faces of optical parts, lighting lamps, covers for lighting fixtures, Magnifying laser light source, anti-reflection film, polarizing film, agricultural film, etc.

The anti-glare film-attached substrate 10 is preferably a transparent substrate for solar cells from the viewpoint of excellent anti-glare effect against obliquely incident light.

In the solar cell module, in order to protect the solar cell, a transparent substrate (cover glass, etc.) is arranged on the front surface of the solar cell. Depending on the installation place, light pollution may be generated due to reflected light reflected on the surface of the transparent substrate. In particular, if the solar cell module is installed on an inclined surface such as a sloping roof, light may be incident at an incident angle close to 90°, and strong reflected light may be generated. By using the anti-glare film-attached substrate 10 as a transparent substrate for a solar cell, the occurrence of light pollution due to reflected light as described above can be suppressed.

As mentioned above, although one Embodiment of the base material with an antiglare film of this invention was shown and demonstrated, this invention is not limited to the said embodiment. The respective configurations and combinations thereof in the above-described embodiments are examples, and additions, omissions, substitutions, and other changes to configurations are possible without departing from the technical idea of the present invention.

For example, a functional layer such as AFP (fingerprint removal layer) may be provided on the upper side (the side opposite to the substrate 12 side) of the anti-glare film 14 . Functional layers such as an alkali metal barrier layer, a reflectance waveform adjustment layer, and an infrared shielding layer may be provided between the substrate 12 and the antiglare film 14 . The functional layer can be formed by a known method such as a coating method.

The form of the base material 12 is not limited to sheets such as plates and films. For example, a shape such as a rectangle or a curved surface may also be used.

The production method of the base material with an anti-glare film is not limited to the method of forming the anti-glare film 14 by coating the above-mentioned coating liquid for an anti-glare film on the base material and drying it.

〔thing〕

The article of the present invention includes the above-mentioned substrate with an antiglare film of the present invention.

The article of the present invention may be composed of the base material with an antiglare film of the present invention, or may include other members in addition to the base material with an antiglare film of the present invention.

Examples of the article of the present invention include the article exemplified above as the use of the antiglare film-attached substrate 10 , a device including any one or more of these articles, and the like.

As a device, a solar cell module, a display device, a lighting device, etc. are mentioned, for example.

As a solar cell module, it is preferable to use the base material with an anti-glare film of the present invention as the transparent substrate provided with a solar cell and a transparent substrate (cover glass, etc.) respectively arranged on the front and back of the solar cell for protecting the solar cell A solar cell module with at least one transparent substrate (preferably at least the transparent substrate on the front side).

Examples of the display device include mobile phones, smartphones, tablet PCs, car navigation systems, and the like.

Examples of lighting devices include organic EL (electroluminescence) lighting devices, LED (light emitting diode) lighting devices, and the like.

Example

Next, the present invention will be described in detail by showing 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 and evaluation methods and materials (acquisition sources or preparation methods) used in each example are as follows.

<Measurement and evaluation method>

(Gloss)

As the glossiness of the surface of the antiglare film, the 60° specular glossiness and the 85° specular glossiness were measured. Each specular gloss was measured near the center of the anti-glare film using a gloss meter (GM-268plus, manufactured by Konica Minolta, Inc.) according to the method specified in JISZ8741:1997. In addition, each specular glossiness was measured by sticking black tape on the back surface (surface opposite to the anti-glare film) of a glass plate, and not being affected by the reflection of the back surface of a glass plate. The smaller the glossiness, the better the anti-glare property.

(surface roughness)

The surface roughness of the anti-glare film (arithmetic average roughness Ra, average length RSm of roughness curve elements, maximum height roughness Rz, kurtosis Rku of roughness curve, skewness Rsk of roughness curve) using a surface roughness meter (Tokyo Precision Co., Ltd. (Tokyo Precision Co., Ltd., SURFCOM (registered trademark) 1500DX)) Measured according to the method described in JISB0601:2001. The reference length lr (boundary value λc) for the thickness curve was set to 0.08 mm.

(refractive index of anti-glare film)

The refractive index n of the antiglare film was measured by the following method.

A single-layer smooth film of the desired refractive index is formed on the surface of a glass plate by spin coating, and a black polyvinyl chloride tape is pasted on the single-layer film and the opposite surface of the glass plate without air bubbles. . Thereafter, the reflectance of the single-layer film was measured in a wavelength range of 300 to 780 nm with a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (Otsuka Electronics Co., Ltd., instantaneous multi-point photometry system MCPD-3000). When measuring the reflectance, the incident angle of light was set to 2°. The refractive index n was calculated by the following formula (1) from the minimum reflectance (minimum reflectance R _min ) in the wavelength range of 300 to 780 nm and the refractive index n _s of the glass plate.

R _min ＝(nn _s ) ² /(n+n _s ) ² …(1)

<Materials used>

(Preparation of Silica Precursor Solution (a-1))

While stirring 69.0 g of modified ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., trade name "SOLMIXAP-11", a mixed solvent with ethanol as the main agent, the same below), add 11.9 g A mixed solution of ion-exchanged water and 0.1 g of 61% by mass nitric acid was stirred for 5 minutes. To this, 19.0 g of tetraethoxysilane (SiO ₂ conversion solid content concentration: 29 mass %) was added, and stirred at room temperature for 30 minutes to prepare a SiO ₂ conversion solid content concentration of 5.5 mass % silica precursor solution (a -1).

In addition, here, the SiO ₂ converted solid content concentration is the solid content concentration when all the Si in tetraethoxysilane is converted into SiO ₂ .

(Preparation of Silica Precursor Solution (a-2))

A mixed solution of 7.9 g of ion-exchanged water and 0.2 g of 61% by mass nitric acid was added while stirring 80.3 g of modified ethanol, and stirred for 5 minutes. Next, 11.6 g of 1,6-bis(trimethoxysilyl)hexane (manufactured by Shin-Etsu Silicone Co., Ltd. (Shin-Etsu Silicone Co., Ltd.), trade name "KBM3066" was added, and the solid content concentration in terms of SiO ₂ was 37% by mass. ), stirred in a 60° C. water bath for 15 minutes, and prepared a silica precursor solution (a-2) having a solid content concentration of 4.3% by mass in terms of SiO ₂ .

In addition, here, the solid content concentration in terms of SiO ₂ is the solid content concentration when all the Si in 1,6-bis(trimethoxysilyl)hexane is converted into 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 modified ethanol was added and stirred at room temperature for 30 minutes to obtain a silica precursor solution (a) having a SiO ₂ -equivalent solid content concentration of 5.0% by mass.

(Preparation of Silica Precursor Solution (b))

A mixed solution of 1.2 g of ion-exchanged water and 0.4 g of 36% by mass hydrochloric acid was added while stirring 91.1 g of modified ethanol, and stirred for 5 minutes. Add 7.3 g of ethyl silicate 40 (Tama Chemical Industry Co., Ltd. (Tama Chemical Industry Co., Ltd.), polytetraethoxysilane, SiO ₂ conversion solid content concentration: 40% by mass) to this, and stir at room temperature for 30 minutes to prepare A silica precursor solution (b) having a solid content concentration of 3.0% by mass in terms of SiO ₂ .

(Solid silica particle dispersion (c))

Chain-like SiO ₂ fine particle dispersion liquid of Nissan Chemical Industry Co., Ltd. (Nissan Chemical Industry Co., Ltd.), trade name: "SNOWTEXOUP", SiO ₂ converted solid content concentration: 15.5% by mass, average primary particle size: 10-20 nm, average aggregated particle size Diameter: 40~100nm.

(Hollow silica particle dispersion (d))

Nikki Catalyst Chemicals Co., Ltd. (Nichika Catalyst Chemicals Co., Ltd.) hollow _SiO2 fine particle dispersion, trade name: Suluria 4110, _SiO2 conversion solid content concentration: 20.5% by mass, average primary particle diameter: 60nm.

(Preparation of Coating Solution (A))

Next, while stirring 60.0 g of the silica precursor solution (a), 40.0 g of modified ethanol was added, and stirred at room temperature for 30 minutes to obtain a coating liquid having a solid content concentration of 3.0% by mass in terms of SiO ₍ A).

(Preparation of Coating Solution (B))

The silica precursor solution (a) was used as it is to obtain a coating liquid (B) having a SiO ₂ -equivalent 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 modified ethanol was added, and stirred at room temperature for 30 minutes to obtain a coating solution (C) having a solid content concentration of 4.0% by mass in terms of _SiO2 .

(Preparation of Coating Solution (D))

While stirring 47.4 g of modified ethanol, add 30.0 g of the silica precursor solution (a), and then add 22.6 g of the solid silica particle dispersion (c), and stir at room temperature for 30 minutes to obtain A coating solution (D) having a solid content concentration of 5.0% by mass in terms of SiO ₂ .

(Preparation of Coating Solution (E))

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

(Preparation of Coating Solution (F))

While stirring 37.8 g of modified ethanol, add 50.0 g of silica precursor solution (a), then add 12.2 g of hollow silica particle dispersion (d), and stir at room temperature for 30 minutes to obtain A coating solution (D) having a solid content concentration of 5.0% by mass in terms of SiO ₂ .

(Preparation of Coating Solution (G))

While stirring 76.3 g of modified ethanol, add 12.0 g of the silica precursor solution (a), then add 11.7 g of the hollow silica particle dispersion (d), and stir at room temperature for 30 minutes to obtain A coating liquid (G) having a solid content concentration of 3.0% by mass in terms of SiO ₂ .

(Preparation of Coating Solution (H))

While stirring 71.8 g of modified ethanol, add 18.0 g of the silica precursor solution (a), then add 10.2 g of the hollow silica particle dispersion (d), and stir at room temperature for 30 minutes to obtain A coating solution (H) having a solid content concentration of 3.0% by mass in terms of SiO ₂ .

(Preparation of Coating Solution (I))

While stirring 22.8 g of modified ethanol, add 70.0 g of the silica precursor solution (a), then add 7.3 g of the hollow silica particle dispersion (d), and stir at room temperature for 30 minutes to obtain A coating liquid (I) having a solid content concentration of 5.0% by mass in terms of SiO ₂ .

(Preparation of Coating Solution (J))

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

<Example 1>

(cleaning of glass plate)

As a glass plate, a chemically strengthened aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd. (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 bicarbonate water, rinsed with ion-exchanged water, and dried.

(Manufacturing of glass panels with anti-glare film)

The above-mentioned glass plate was preheated with a preheating furnace (manufactured by Isuzu Corporation (ISUZU), VTR-115). Next, in the state where the surface temperature of the glass plate is kept at 90° C., the coating liquid (A) is applied on the above-mentioned glass plate by the spray coating method according to the following coating conditions so that the anti-glare formed by coating The arithmetic mean roughness Ra of the surface of the film was the value shown in Table 2. That is, the spraying pressure (air discharge pressure of the nozzle) was set to 0.2 MPa, and the following coating process was repeated so that the arithmetic average roughness Ra of the surface of the formed anti-glare film became 0.247 μm.

Coating process: Repeat the following operations: that is, make the nozzle move horizontally at a speed of 750 mm/min on the glass plate, then move forward 22 mm, and then move the nozzle horizontally at a speed of 750 mm/min on the glass plate The operation of moving up and down until the coating solution (A) is coated on the entire surface of the glass plate. (coating conditions)

Liquid volume of coating liquid: 40cm ³ /min,

Spraying pressure: 0.2MPa,

Nozzle moving speed: 750mm/min,

Spraying distance: 22mm.

Thereafter, heating and aging were performed at 200° C. for 3 minutes in the air to obtain a glass plate with an anti-glare film.

For coating by the spray coating method, a 6-axis coating robot (manufactured by Kawasaki Robotics, JF-5) was used. In addition, as a nozzle, a VAU nozzle (manufactured by Spraying System Japan Co., Ltd. (Spraying System Japan Co., Ltd.)) was used.

<Example 2-16>

A glass plate with an anti-glare film was obtained in the same manner as in Example 1, except that the type of coating liquid, the liquid volume of the coating liquid, and the spraying pressure were as shown in Table 1, and the arithmetic mean roughness Ra was changed as shown in Table 2. .

The glass plate with antiglare film obtained in each example was measured for the refractive index in the antiglare film, the glossiness (60° specular gloss, 85° specular gloss) at an incident angle of 60° or 85°, and the glossiness of the antiglare film. The results of surface roughness (arithmetic mean roughness Ra, average length RSm of roughness curve elements, maximum height roughness Rz, roughness curve kurtosis Rku, roughness curve skewness Rsk) are shown in Table 1 to 2.

[Table 1]

[Table 2]

As shown in the results in Table 1, the antiglare films of Examples 1 to 4 with a refractive index of not less than 1.4 and not more than 1.5 and an arithmetic average surface roughness Ra of 0.158 to 0.500 μm at an incident angle of 85° The glossiness is below 70%, and it has excellent anti-glare effect on oblique incident light.

On the other hand, the antiglare films of Examples 5 to 9 having an arithmetic average roughness Ra of less than 0.158 μm had a glossiness of more than 70% at an incident angle of 85°, and compared with the antiglare films of Examples 1 to 4, the glossiness for oblique incidence The anti-glare effect of light is poor. In particular, the anti-glare films of Examples 7 and 9 have a lower gloss than 1 at an incident angle of 60°, but a higher gloss than 1 at an incident angle of 85°.

As shown in the results in Table 2, the antiglare films of Examples 10 to 15 with a refractive index of 1.2 to less than 1.4 and an arithmetic average surface roughness Ra of 0.112 to 0.700 μm at an incident angle of 85° The glossiness is below 70%, and it has excellent anti-glare effect on oblique incident light.

In contrast, the antiglare film of Example 16 having an arithmetic average roughness Ra of less than 0.112 μm had a glossiness of over 70% at an incident angle of 85°, and had a poor antiglare effect on obliquely incident light compared with Examples 10 to 15. .

In addition, in the surface roughness characteristics of the surface of the anti-glare film, a high correlation can be seen between the arithmetic mean roughness Ra and the glossiness at an incident angle of 85°, while in other characteristics (the average length of the roughness curve element RSm, the maximum height roughness Rz, the kurtosis Rku of the roughness curve, and the skewness Rsk of the roughness curve), no correlation was found with the glossiness at an incident angle of 85°. From this, it was confirmed that the arithmetic mean roughness Ra is useful as an index of the anti-glare effect with respect to obliquely incident light.

Symbol Description

10 base material with anti-glare film

12 base material

14 anti-glare film

Claims (9)

1. be with an antiglare film base material, it is characterized in that,

The antiglare film possessing base material and formed on the substrate,

The refractive index of described antiglare film is more than 1.2 and lower than 1.4,

The arithmetic mean rugosity Ra on the surface of described antiglare film is 0.112 ~ 0.700 μm,

85 ° of mirror surface lusters on the surface of described antiglare film are less than 70%.

2. be with an antiglare film base material, it is characterized in that,

The antiglare film possessing base material and formed on the substrate,

The refractive index of described antiglare film is more than 1.4 and below 1.5,

The arithmetic mean rugosity Ra on the surface of described antiglare film is 0.158 ~ 0.500 μm,

85 ° of mirror surface lusters on the surface of described antiglare film are less than 70%.

3. as described in claim 1 or 2 band antiglare film base material, is characterized in that, described antiglare film contains either one or both of solid silicon dioxide granule and hollow silica particle.

4. the band antiglare film base material according to any one of claims 1 to 3, it is characterized in that, described antiglare film is formed by the coating fluid containing silica precursor and liquid medium.

5. the band antiglare film base material according to any one of Claims 1 to 4, is characterized in that, described base material is glass plate.

6. band antiglare film base material as claimed in claim 5, it is characterized in that, described glass plate is strengthening glass sheets.

7. band antiglare film base material as claimed in claim 6, it is characterized in that, described strengthening glass sheets is chemically reinforced glass plate, and thickness of slab is 0.4 ~ 1.1mm.

8. article, is characterized in that, possess the band antiglare film base material according to any one of claim 1 ~ 7.

9. article as claimed in claim 8, it is characterized in that, be solar module.