WO2015163330A1

WO2015163330A1 - Anti-glare-layer substrate and article

Info

Publication number: WO2015163330A1
Application number: PCT/JP2015/062142
Authority: WO
Inventors: 敏本谷; 義美大谷
Original assignee: 旭硝子株式会社
Priority date: 2014-04-23
Filing date: 2015-04-21
Publication date: 2015-10-29
Also published as: JP2017106944A; TW201606356A

Abstract

Provided are: an anti-glare-layer substrate provided with an anti-glare layer that is excellent in terms of the balance among an antiglare effect, a transmittance improvement effect, and mechanical strength; and an article using the anti-glare-layer substrate. An anti-glare-layer substrate (10) is provided with a transparent substrate (12) and an anti-glare layer (14) and is characterized in that the refractive index of the anti-glare layer (14) is 1.25-1.45, that an arithmetic mean roughness (Ra) of a surface of the anti-glare layer (14) is 0.05-0.25 μm, and that the anti-glare layer (14) contains solid silica particles in the form of chains.

Description

Substrates and articles with antiglare layers

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

In an image display device (for example, a liquid crystal display, an organic EL display, a plasma display, etc.) provided in various devices (for example, a television, a personal computer, a smartphone, a mobile phone, etc.), indoor lighting (for example, a fluorescent lamp), When external light such as sunlight is reflected on the display surface, the visibility decreases due to the reflected image.

In order to suppress the reflection of external light, an anti-glare treatment (anti-glare treatment) is performed on the transparent base material constituting the display surface of the image display device. As an anti-glare treatment, conventionally, a treatment for forming irregularities on the light incident surface of a transparent substrate is known. However, in this process, if the unevenness is increased in order to increase the antiglare effect (that is, the surface is roughened), the resolution of the image decreases, the haze increases, and the contrast of the image decreases. There is.

To solve the above problem, a coating liquid containing a hydrolyzate of alkoxysilane and hollow SiO ₂ fine particles is applied on a substrate by a spray method, and has a refractive index of 1.45 or less and a surface roughness of 0.04 to 0. A method of manufacturing an article having an antiglare layer of .17 μm has been proposed (see Patent Document 1). The antiglare layer described in Patent Document 1 is said to have an excellent antiglare effect even if the surface roughness is small because the matrix has a low refractive index.

JP 2009-058640 A

However, in patent document 1, it is not considered about making the improvement of the transmittance | permeability of a base material and sufficient anti-glare effect compatible.
In order to obtain the effect of improving the transmittance in the method of Patent Document 1, the present inventors have studied about increasing the content of hollow SiO ₂ fine particles to lower the refractive index of the antiglare layer. _When the content of the _two fine particles is increased, there is a problem that mechanical strength such as wear resistance is lowered. Further, the hollow SiO ₂ fine particles are relatively expensive as a low refractive index material, and an increase in the content causes an increase in material cost.

An object of the present invention is to provide a base material with an antiglare layer having an antiglare layer excellent in balance between an antiglare effect, a transmittance improvement effect and mechanical strength, and an article using the same.

The present invention has the following aspects.
[1] A transparent substrate and an antiglare layer formed on the transparent substrate,
The antiglare layer has a refractive index of 1.25 to 1.45,
The arithmetic average roughness Ra of the surface of the antiglare layer is 0.05 to 0.25 μm,
The base material with an antiglare layer, wherein the antiglare layer contains chain solid silica particles.
[2] The substrate with an antiglare layer according to [1], wherein the content of the chain solid silica particles in the antiglare layer is 50 to 80% by mass with respect to the total mass of the antiglare layer.
[3] The substrate with an antiglare layer according to [1] or [2], wherein the chain solid silica particles have an average aggregate particle diameter of 5 to 300 nm.
[4] Any one of [1] to [3], wherein the antiglare layer is a layer formed from a coating liquid containing the chain solid silica particles, a silica-based matrix precursor, and a liquid medium. The base material with an anti-glare layer according to item.
[5] The substrate with an antiglare layer according to [4], wherein the coating solution further contains a terpene compound.
[6] An article comprising the substrate with an antiglare layer according to any one of [1] to [5].

According to the present invention, it is possible to provide a substrate with an antiglare layer provided with an antiglare layer having an excellent balance of antiglare effect, transmittance improvement effect and mechanical strength, and an article using the same.

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

[Base material with anti-glare layer]
FIG. 1 is a cross-sectional view schematically showing an embodiment of a substrate with an antiglare (hereinafter abbreviated as AG) layer of the present invention.
The substrate 10 with an AG layer of the present embodiment includes a transparent substrate 12 and an AG layer 14 formed on the transparent substrate 12.

(Transparent substrate)
The transparency in the transparent substrate 12 means that 80% or more of light in the wavelength region of 400 to 1100 nm is transmitted on average.
Examples of the form of the transparent substrate 12 include a plate and a film.
Examples of the material of the transparent substrate 12 include glass and resin.
Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, and alkali-free glass.
Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, polymethyl methacrylate, and the like.

As the transparent substrate 12, a glass plate is preferable.
The glass plate may be a smooth glass plate formed by a float method, a fusion method, 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 to 75%,
Al ₂ O ₃ : 0 to 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 to 5%,
CeO ₂ : 0 to 3%
BaO: 0 to 5%,
SrO: 0-5%
B ₂ O ₃ : 0 to 15%,
ZnO: 0 to 5%,
ZrO ₂ : 0 to 5%,
SnO ₂ : 0 to 3%
SO ₃ : 0 to 0.5%.

When glass is an alkali free glass, what has the following composition is preferable.
In mass percentage display based on oxide,
SiO ₂ : 39 to 70%,
Al ₂ O ₃ : 3 to 25%,
B ₂ O ₃ : 1-30%,
MgO: 0 to 10%,
CaO: 0 to 17%,
SrO: 0 to 20%,
BaO: 0 to 30%.

When glass is aluminosilicate glass, what has the following composition is preferable.
In mole percentage display on oxide basis,
SiO ₂ : 62 to 68%,
Al ₂ O ₃ : 6 to 12%,
MgO: 7-13%,
Na ₂ O: 9-17%,
K ₂ O: 0-7%,
ZrO ₂ : 0 to 8%.

The glass plate may be tempered in advance. 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.
The strengthening treatment includes physical strengthening in which the glass plate is air-cooled after being exposed to a high temperature, or an alkali with a small atomic diameter present on the outermost surface of the glass substrate by immersing the glass plate in a molten salt containing an alkali metal. Examples include chemical strengthening in which metal ions (for example, Na ions) are replaced with alkali metal ions (for example, K ions) having a large atomic diameter present in the molten salt. In the case of subjecting a glass plate to chemical strengthening treatment, it is particularly preferable to use an aluminosilicate glass.

(AG layer)
The AG layer 14 is a layer that includes chain solid silica particles and has irregularities on the surface.
The AG layer 14 typically further includes a matrix that fills the voids between the chain solid silica particles. The matrix may cover the upper side of the chain solid silica particles (that is, the side opposite to the transparent substrate 12 side) so that the chain solid silica particles are not exposed.
The AG layer 14 may further include particles other than the chain solid silica particles.
The AG layer 14 may be formed using a coating solution further containing a terpene compound.
The AG layer 14 may further include a chain solid silica particle, a matrix, other particles, and other components other than the terpene compound (hereinafter also referred to as “other optional components”).

Chain solid silica particles:
The chain solid silica particles are solid silica particles having a chain shape. For example, solid silica particles having a plurality of spheres, ellipses, needles, plates, rods, cones, cylinders, cubes, cuboids, diamonds, stars, etc. in a chain shape The thing of the connected shape is mentioned. The shape of the chain solid silica particles can be confirmed by an electron microscope.
“Solid” indicates that there is no cavity inside.

The average aggregate particle diameter of the chain solid silica particles is preferably 5 to 300 nm, and more preferably 5 to 200 nm. If the average agglomerated particle diameter of the chain solid silica particles is not less than the lower limit of the above range, the refractive index reduction effect is excellent, and if it is not more than the upper limit, the wear resistance is excellent.

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 content of the chain solid silica particles in the AG layer 14 is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, and more preferably 60 to 70% by mass with respect to the total mass of the AG layer 14. Is particularly preferred. If the content of the chain solid silica particles is not less than the lower limit of the above range, the refractive index of the AG layer 14 is lowered, and a sufficient transmittance improving effect is obtained. If the content of the chain solid silica particles is not more than the upper limit of the above range, the mechanical strength of the AG layer is excellent.

Matrix:
Examples of the matrix of the AG layer 14 include a silica matrix and a titania matrix.
As the matrix of the AG layer 14, a silica-based matrix is preferable. If the matrix is a silica-based matrix, the refractive index (that is, the reflectance) of the AG layer 14 tends to be low. In addition, chemical stability, wear resistance and the like are improved. When the transparent substrate is glass, adhesion is particularly good.

“Silica-based matrix” refers to a matrix mainly composed of silica. To have silica as a main component means that the proportion of silica is 90% by mass or more in the matrix (100% by mass).
The silica matrix is more preferably substantially composed of silica. The phrase “consisting essentially of silica” means that it is composed only of silica excluding inevitable impurities.

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 one or more ions selected from the group consisting of lanthanoid elements, and / or this group And compounds such as oxides having one or more elements selected from:

Examples of the silica matrix include a fired product of a silica matrix precursor. The silica-based matrix precursor will be described in detail later.
The layer containing the chain solid silica particles and the silica-based matrix can be formed from, for example, a coating solution containing chain solid silica particles, a silica-based matrix precursor, and a liquid medium. The method for forming the coating solution and the AG layer 14 will be described in detail later.

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

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

Examples of other particle shapes include spherical, elliptical, needle-like, plate-like, rod-like, conical, cylindrical, cubic, rectangular, diamond-like, star-like, and indefinite 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.
The content of other particles in the AG layer 14 is preferably up to 30% by mass with respect to the total mass of the AG layer 14.
The average aggregate particle diameter of the other particles is preferably about the same as that of the chain solid silica particles.
As other particles, hollow silica particles are preferable in that they are excellent in the effect of reducing the refractive index.

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

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

The refractive index of the AG layer 14 is 1.25 to 1.45, preferably 1.25 to 1.40. When the refractive index of the AG layer 14 is less than or equal to the upper limit of the above range, the reflectance on the surface of the AG layer 14 is sufficiently low, and the transmittance is improved as compared with the case of the transparent substrate 12 alone. Further, the AG layer 14 having a refractive index equal to or higher than the lower limit of the above range is dense, and has excellent mechanical strength, adhesion to the transparent substrate 12 such as a glass plate, and the like. A method for measuring the refractive index will be described later.

The arithmetic average roughness Ra of the surface of the AG layer 14 (that is, the surface on the AG layer 14 side of the substrate 10 with the AG layer) is 0.05 to 0.25 μm, preferably 0.07 to 0.25 μm, and 0 10 to 0.25 μm is particularly preferable.
Arithmetic average roughness Ra is an index indicating the average height of the irregularities on the surface. If the arithmetic average roughness Ra of the surface of the AG layer 14 is equal to or greater than the lower limit of the above range, the antiglare effect is sufficiently exhibited. When the arithmetic average roughness Ra of the surface of the AG layer 14 is not more than the upper limit of the above range, the mechanical strength of the AG layer 14 is excellent, and the haze of the base material 10 with the AG layer is sufficiently small.
The arithmetic average roughness Ra of the surface of the AG layer is a value measured according to the method described in JIS B0601: 2001.

The 60 ° specular gloss on the surface of the AG layer 14 is preferably 50% or less, and more preferably 45% or less. The 60 ° specular gloss on the surface of the AG layer 14 is an index of the antiglare effect. When the 60 ° specular gloss is 50% or less, the antiglare effect is sufficiently exhibited.
The lower limit of the 60 ° specular gloss is not particularly limited in terms of the antiglare effect, but is preferably 5% or more and more preferably 10% or more in terms of the transmittance improvement effect.
The 60 ° specular gloss is a value measured according to the method defined in JIS Z8741: 1997.

(Haze)
The haze of the substrate 10 with an AG layer is preferably 5 to 20%, more preferably 5 to 15%. If the haze is less than or equal to the upper limit of the above range, the image contrast when the substrate 10 with an AG layer is used in a display device and the power generation efficiency when the substrate 10 with an AG layer is used in a solar cell module are good. It is. If the haze is equal to or higher than the lower limit of the above range, the antiglare effect is easily exhibited.
The haze is a value measured according to a method defined in JIS K7136: 2000.

<Method for producing substrate with AG layer>
As a manufacturing method of the base material 10 with an AG layer, for example, a coating liquid (hereinafter referred to as an AG layer) containing a chain solid silica particle, a silica-based matrix precursor, and a liquid medium on the transparent base material 12. And a method of forming a coating film and baking it.
The coating liquid for AG layer will be described in detail later.

(Application)
As a coating method of the AG layer coating liquid, known wet coating methods (for example, 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 coating method, flexo coating method, slit coating method, roll coating 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 coating liquid droplets ejected 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 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 and 60 ° specular glossiness of the surface of the AG layer can be adjusted by applying time, that is, the number of coated surfaces (number of overcoating) by a spray method under a certain application condition. For example, as the number of coated surfaces increases, the arithmetic average roughness Ra of the surface of the AG layer increases, and as a result, the 60 ° specular gloss decreases (that is, the antiglare effect increases) and the haze tends to increase. There is.

When applying the coating solution for the AG layer by spraying, it is preferable to heat the transparent substrate 12 to 30 to 90 ° C. in advance. If the temperature of the transparent substrate 12 is 30 ° C. or higher, the liquid medium evaporates quickly, so that sufficient unevenness can be easily formed. If the temperature of the transparent base material 12 is 90 degrees C or less, the adhesiveness of the transparent base material 12 and AG layer 14 will become favorable. When the transparent substrate 12 is a glass plate having a thickness of 5 mm or less, a heat insulating plate set in advance at a temperature equal to or higher than the temperature of the transparent substrate 12 is arranged under the transparent substrate 12 to suppress the temperature drop of the transparent substrate 12. May be.

(Baking)
By baking the coating film formed by applying the coating solution for the AG layer, the liquid medium is removed, the remaining hydrolyzable groups are substantially decomposed, and the film is densified to form the AG layer 14. The

In the present invention, firing includes heating and curing a coating film obtained by applying a coating composition.
The baking may be performed simultaneously with the application by heating when the AG layer coating liquid is applied on the transparent substrate 12, or by applying the coating liquid to the substrate and then heating the coating film. Also good.

The firing temperature is preferably 30 ° C. or higher, and may be appropriately determined according to the material of the transparent substrate 12, the material of the coating solution for the AG layer, and the like.
When the silica matrix precursor is a silane compound (A), the firing temperature is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher. When the firing temperature is 80 ° C. or higher, the fired product is densified and durability is improved.
When the material of the transparent substrate 12 is a resin, the firing temperature is equal to or lower than the heat resistant temperature of the resin. When the material of the transparent substrate 12 is glass, the firing temperature is preferably equal to or lower than the softening point temperature of the glass.
When the transparent substrate 12 is a chemically strengthened glass plate, the firing temperature is preferably 80 to 450 ° C.
When the transparent substrate 12 is a glass plate that is not chemically strengthened, it can also serve as a firing step for forming the AG layer 14 and a physical strengthening step for the glass plate. In the physical strengthening step, the glass plate is heated to near the softening temperature of the glass. In this case, the firing 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 or calcination temperature to a temperature setting near room temperature if there is no restriction on time.

(AG layer coating solution)
The coating liquid for AG layer contains chain solid silica particles, a silica-based matrix precursor, and a liquid medium.
The AG layer coating solution may further contain other particles, a terpene compound, other optional components, and the like, if necessary.

Chain solid silica particles:
The description of the chain solid silica particles is the same as described above.

Silica-based matrix precursor:
The “silica-based matrix precursor” means a substance that can form a silica-based matrix by firing.
Examples of the silica-based matrix precursor include a silane compound having a hydrolyzable group bonded to a silicon atom (hereinafter also referred to as silane compound (A)), a hydrolysis condensate (sol-gel silica) of silane compound (A), and silazane. From the viewpoint of each characteristic of the AG layer 14, one or both of the silane compound (A) and the hydrolysis condensate thereof are preferable, and the hydrolysis condensate of the 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 selected from —O—, —S—, —CO— and —NR′— (wherein R ′ is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms, or You may have group which combined 2 or more.

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.
Examples of the hydrolyzable group 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 the alkoxy group, an alkoxy group having 1 to 3 carbon atoms 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) And 3-glycidoxypropyltriethoxysilane) and alkoxysilanes having an acryloyloxy group (such as 3-acryloyloxypropyltrimethoxysilane).

The silane compound (A1) is preferably a compound represented by the following formula (I) from the viewpoint of the mechanical strength of the AG layer 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) Or a group formed by combining two or more of them.). 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 viewpoints of mechanical strength and availability of the AG layer 14.

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 tetraalkoxysilane, it is carried out using 4 times or more water of tetraalkoxysilane and 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 fine particles such as chain solid silica particles is preferable.

As a silica type matrix precursor, 1 type may be used independently and 2 or more types may be used in combination.
The silica-based matrix precursor includes silane compound (A1) and / or its hydrolytic condensate, tetraalkoxysilane and its It is particularly preferred that one or both of the hydrolysis condensates are included.
The ratio of the silane compound (A1) and the hydrolysis condensate thereof in the silica matrix precursor is preferably 5 to 30% by mass with respect to the solid content (100% by mass) in terms of SiO ₂ of the silica matrix precursor.

Liquid medium:
The liquid medium is a dispersion medium for dispersing the chain solid silica particles. The liquid medium may be a solvent that dissolves the silica-based matrix precursor.
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 the nitrogen-containing compound 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 matrix 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-based matrix precursor, alcohols are preferable, and methanol, ethanol, isopropyl alcohol, and butanol are particularly preferable.

The liquid medium may contain acid or 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 matrix precursor solution. It may be added later.

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

Terpene compounds:
When the coating solution for the AG layer further contains a terpene compound, voids are formed around the chain solid silica particles, and the refractive index is lower than when no terpene compound is contained, and the transmittance improvement effect tends to increase. 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 AG layer 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 chain solid silica particles in the AG layer coating solution is based on the solid content (100% by mass) in the AG layer coating solution (however, the silica-based matrix precursor is converted to SiO ₂ ). 50 to 80% by mass is preferable, 55 to 75% by mass is more preferable, and 60 to 70% by mass is particularly preferable. If the content of the chain solid silica particles is not less than the lower limit of the above range, the refractive index of the AG layer 14 is lowered, and a sufficient transmittance improving effect is obtained. If the content of the chain solid silica particles is not more than the upper limit of the above range, the mechanical strength of the AG layer is excellent.

The content of the silica-based matrix precursor in the AG layer coating solution (in terms of SiO ₂ ) is preferably 20 to 50% by mass, preferably 25 to 45%, based on the solid content (100% by mass) in the AG layer coating solution. The mass% is more preferable. When the content of the silica-based matrix precursor is not less than the lower limit of the above range, the mechanical strength is excellent.

When the coating solution for AG layer contains a terpene compound, the content of the terpene compound in the coating solution for AG layer is the solid content (100% by mass) in the coating solution for AG layer (however, the silica-based matrix precursor is and in terms of SiO _2.) to, preferably 0.05 to 0.25 mass%, more preferably from 0.1 to 0.15 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 solid content concentration of the coating solution for the AG layer is preferably 1 to 8% by mass, and more preferably 2 to 5% by mass. When the solid content concentration is at least the lower limit of the above range, the antiglare effect is improved. If solid content concentration is below the upper limit of the said range, mechanical strength will improve.
The solid content concentration of the coating solution for AG layer is the total content of all components other than the liquid medium in the coating solution for AG layer. However, the content of the silica-based matrix precursor is in terms of SiO ₂ .

The coating liquid for the AG layer includes, for example, a chain solid silica particle dispersion, a silica-based matrix precursor solution, an additional liquid medium, a dispersion of other particles, a terpene compound, and other optional liquids as necessary. It is prepared by mixing ingredients and the like.

(Function and effect)
In the base material 10 with the AG layer, the refractive index of the AG layer 14 is 1.25 to 1.45, the arithmetic average roughness Ra of the surface of the AG layer 14 is 0.05 to 0.25 μm, Since the AG layer 14 includes chain solid silica particles, the balance between the antiglare effect, the transmittance improvement effect, and the mechanical strength is excellent as compared with the conventional one. In addition, it is easy to obtain materials.
When lowering the refractive index with solid silica particles, it is necessary to increase the content as compared with the case of using hollow silica particles. Conventionally, it is known that when the content of fine particles increases, mechanical strength such as wear resistance decreases and haze tends to increase. However, in the substrate 10 with an AG layer of the present invention, surprisingly, by using chain solid silica particles as fine particles, even when the content is large (for example, 70% by mass), the AG layer 14 Has sufficient mechanical strength, and the haze of the substrate 10 with the AG layer is sufficiently low.

(Use)
The use of the base material 10 with the AG layer is not particularly limited. Specific examples include transparent parts for vehicles (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, instrument panel surface plates, etc.), meters, architectural windows, show windows, displays (notebooks) PC, monitor, LCD, PDP, ELD, CRT, PDA, etc.), LCD color filter, touch panel substrate, pickup lens, optical lens, eyeglass lens, camera component, video component, CCD cover substrate, optical fiber end face, projector Parts, copier parts, transparent substrates for solar cells (cover glass, etc.), mobile phone windows, backlight unit parts (light guide plates, cold cathode tubes, etc.), backlight unit parts, LCD brightness enhancement films (prisms, half Transmissive film, etc.), organic EL light emitting device parts, inorganic EL light emitting device Goods, phosphor emitting element part, an optical filter, the end face of the optical component, the illumination lamp, the cover of the luminaire, amplified laser light source, an antireflection film, a polarizing film, agricultural film, and the like.

It is preferable that the base material 10 with an AG layer is 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. Moreover, the sunlight transmittance of the transparent substrate affects the power generation efficiency of the solar cell module. Also, mechanical strength is required to protect the solar cell. The base material 10 with an AG layer of the present invention is useful as a transparent substrate for solar cells because it has an excellent balance of antiglare effect, transmittance improvement effect and mechanical strength.

While the present invention has been described with reference to the embodiment, the present invention is not limited to the above embodiment. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
For example, a functional layer such as an AFP (fingerprint removal layer) may be provided on the upper side of the AG layer 14 (the side opposite to the transparent substrate 12 side). You may have functional layers, such as an alkali barrier layer, a reflectance waveform adjustment layer, and an infrared shielding layer, between the transparent base material 12 and the AG layer 14. The functional layer can be formed by a known method such as a coating method.

[Goods]
The article of the present invention includes the substrate with the AG layer.
The article of the present invention may be composed of the base material with an AG layer, or may further include a member other than the base material with an AG layer.
Examples of the article of the present invention include those mentioned above for the use of the substrate 10 with an AG layer, 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 above-mentioned base material with an AG layer 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.
Of examples 1 to 7 described later, examples 2 to 5 are examples, and examples 1, 6 and 7 are comparative examples.
The evaluation methods and materials used in each example are shown below.

〔Evaluation methods〕
(Average aggregated particle size)
The average aggregate particle diameter of the fine particles (chain solid silica particles, hollow silica particles) was measured using a dynamic light scattering particle size analyzer (manufactured by Nikkiso Co., Ltd., Microtrac UPA).

(Refractive index of AG layer)
The refractive index n of the AG layer was measured by the following method.
A single layer smooth film of a layer whose refractive index is desired to be obtained is formed on the surface of a transparent substrate with a spin coater, black vinyl tape is formed on the surface of the transparent substrate opposite to the single layer film, and no bubbles are contained. Pasted like so. Thereafter, the reflectance of the single layer film was measured in the wavelength range of 300 to 780 nm with a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., instantaneous multi-photometry system MCPD-3000). In measuring the reflectance, the incident angle of light was set to 2 °. From the lowest reflectance (bottom reflectance R _min ) in the wavelength range of 300 to 780 nm and the refractive index n _s of the transparent substrate, the refractive index n was calculated by the following equation (1).
R _min = (n−n _s ) ² / (n + n _s ) ² (1)

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

(Transmissivity difference Td)
About each of the transparent base material before forming the AG layer and the base material with the AG layer obtained in each example, using a spectrophotometer (manufactured by JASCO Corporation, V670), light transmittance at a wavelength of 400 nm to 1100 nm ( %) And the average transmittance (%) was determined. From the result, transmittance difference Td (%) was calculated by the following equation (2). The incident angle of light was 0 ° (incident perpendicular to the transparent substrate). It shows that the transmittance | permeability improvement effect is so high that the transmittance | permeability difference Td is large.
Td = T1-T2 (2)
However, T1 is the average transmittance (%) of the substrate with the AG layer, and T2 is the average transmittance (%) of only the transparent substrate.

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

(Haze)
Haze was measured at a substantially central portion of the AG layer by a method defined in JIS K7136: 2000 (ISO 14782: 1999) using a haze meter (manufactured by Murakami Color Research Laboratory, HM150L2 type).

(Abrasion resistance)
The following wear test was performed as an evaluation of wear resistance. A felt with an opening diameter of 1 cm × 2 cm (manufactured by Shin-Korika Kogyo Co., Ltd., polishing puff AM-1) is attached to a rubbing tester (manufactured by Ohira Rika Kogyo Co., Ltd.), and the felt is attached to the AG layer as a base material with an AG layer under a 1 kg load The felt was reciprocated 40 times in contact with the surface on the side, and reciprocated horizontally.
Before and after the abrasion test, the glossiness of the surface of each AG layer was measured according to the procedure described above. From the results, the gloss change ΔG (%) before and after the abrasion test was calculated by the following equation (3). It shows that it is excellent in abrasion resistance, so that glossiness change (DELTA) G is small.
ΔG = G1-G2 (3)
However, G1 is the glossiness (%) of the surface of the AG layer before the wear test, and G2 is the glossiness (%) of the surface of the AG layer after the wear test.

[Materials used]
(Preparation of silica-based matrix precursor solution (a-1))
75. Denatured ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., trade name “SOLMIX (registered trademark) AP-11”. Mixed solvent containing ethanol as a main component. The same applies to denatured ethanol used in the following preparation). While stirring 8 g, a mixed solution of 11.9 g of ion-exchanged water and 0.1 g of 61% by mass nitric acid was added and stirred for 5 minutes. To this, 12.2 g of tetraethoxysilane (SiO ₂ equivalent solid content concentration: 29% by mass) is added and stirred at room temperature for 30 minutes, and the silica-based matrix precursor having a SiO ₂ equivalent solid content concentration of 3.5% by mass is added. Solution (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-based matrix 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. Subsequently, 11.6 g of 1,6-bis (trimethoxysilyl) hexane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name “KBM3066”, solid content concentration of SiO ₂ : 37 mass%) was added, and the mixture was added at 15 ° C. in a water bath at 60 ° C. The mixture was stirred for 5 minutes to prepare a silica-based matrix 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 coating solution (A))
While stirring 77.1 g of the silica-based matrix precursor solution (a-1), 7.0 g of the silica-based matrix precursor solution (a-2) was added and stirred for 30 minutes. Subsequently, 15.9 g of denatured ethanol was added, and the mixture was stirred at room temperature for 30 minutes to obtain a coating solution (A) having a solid content concentration of SiO ₂ of 3.0% by mass.

(Preparation of coating solution (B))
12. 30.0 g of coating solution (A) is added while stirring 56.5 g of denatured ethanol, and then a chain solid silica sol (manufactured by Nissan Chemical Industries, Ltd., “Snowtex (registered trademark) ST-OUP”). 5 g was added and stirred at room temperature for 30 minutes to obtain a coating solution (B) having a solid content concentration of SiO ₂ of 3.0% by mass.
Incidentally, in terms of SiO ₂ solid content concentration herein is the sum of the terms of SiO ₂ solids, calculated as SiO ₂ solid content in the chain solid silica sol (solid silica particles chain) of the coating solution (A) .
The content of the coating solution (B) chain in solid silica particles in is 70 mass% with respect to SiO ₂ in terms the solid content of the coating solution (B).
The average aggregate particle diameter of the chain solid silica particles in the coating liquid (B) was 70 nm.

(Preparation of coating solution (C))
12. 50.0 g of the coating solution (A) was added while stirring 36.5 g of denatured ethanol, and then a chain solid silica sol (manufactured by Nissan Chemical Industries, Ltd., “Snowtex (registered trademark) ST-OUP”). 5 g was added, and the mixture was stirred at room temperature for 30 minutes to obtain a coating solution (C) having a solid content concentration in terms of SiO ₂ of 5.0% by mass.

(Preparation of coating solution (D))
While stirring 5.5 g of denatured ethanol, 50.0 g of the coating solution (A) was added, and then a chain solid silica sol (manufactured by Nissan Chemical Industries, “Snowtex (registered trademark) ST-OUP)” 13. 5 g, 20.0 g of isobutyl alcohol, 10.0 g of diacetone alcohol and 1.0 g of α-terpineol were added, and the mixture was stirred at room temperature for 30 minutes to obtain a coating solution (D) having a solid content concentration of 5.0 mass% in terms of SiO _2. Obtained.

(Preparation of coating solution (E))
While stirring 25.6 g of denatured ethanol, 70.0 g of the coating liquid (A) was added, and then 4.4 g of hollow silica sol (manufactured by JGC Catalysts & Chemicals, “Thruria (registered trademark) 4110)” was added at room temperature. and stirred for 30 minutes to obtain in terms of SiO ₂ solid content concentration of 3.0 mass% of the coating solution (E).

(Preparation of coating solution (F))
While stirring 59.8 g of denatured ethanol, 30.0 g of the coating solution (A) was added, and then 10.2 g of hollow silica sol (JGC Catalysts & Chemicals Thruria (registered trademark) 4110) was added and stirred at room temperature for 30 minutes. to obtain in terms of SiO ₂ solid content concentration of 3.0 mass% of the coating solution (F).

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

(Production of base material with AG layer)
The transparent substrate was preheated in a preheating furnace (manufactured by ISUZU, VTR-115). Next, with the surface temperature of the transparent substrate kept at 90 ° C., the coating liquid (A) was applied on the transparent substrate so as to have the arithmetic average roughness Ra shown in Table 1 under the following conditions. .
・ 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 base material with AG layer.
For application by the spray method, a 6-axis coating robot (manufactured by Kawasaki Robotics, JF-5) was used. As the nozzle 20, a VAU nozzle (manufactured by Spraying System Japan) was used.

[Examples 2 and 3]
A substrate with an AG layer was obtained in the same manner as in Example 1 except that the coating solution (A) was changed to the coating solution (B) and coated so as to have the arithmetic average roughness Ra shown in Table 1.

[Example 4]
A substrate with an AG layer was obtained in the same manner as in Example 1 except that the coating solution (A) was changed to the coating solution (C) and coated so as to have the arithmetic average roughness Ra shown in Table 1.

[Example 5]
A substrate with an AG layer was obtained in the same manner as in Example 1 except that the coating solution (A) was changed to the coating solution (D) and coated so as to have an arithmetic average roughness Ra shown in Table 1.

[Example 6]
A substrate with an AG layer was obtained in the same manner as in Example 1 except that the coating solution (A) was changed to the coating solution (E) and coated so as to have an arithmetic average roughness Ra shown in Table 1.

[Example 7]
A substrate with an AG layer was obtained in the same manner as in Example 1 except that the coating solution (A) was changed to the coating solution (F) and coated so as to have an arithmetic average roughness Ra shown in Table 1.

About the base material with an AG layer obtained in each example, the particle ratio (mass%) in the AG layer, the refractive index of the AG layer and the arithmetic average roughness Ra of the surface, the transmittance difference Td, the glossiness (%), the haze ( %) And abrasion resistance (gloss change ΔG (%)) are shown in Table 1.
The particle ratio is the ratio of silica particles (chain solid silica particles, hollow silica particles) to the solid content of SiO _{2 in} the coating liquid used for forming the AG layer in each example, and the silica particles relative to the total mass of the AG layer Is equal to

As shown in the above results, in Example 1 in which the particle ratio in the AG layer is 0, the transmittance difference Td is 0.0% (same as the case of the transparent base material alone), and the transmittance improving effect was not seen. .
In Examples 2 to 5 in which the AG layer contains chain solid silica particles, the transmittance was improved as compared with the case of the transparent substrate alone. Further, the antiglare property and the wear resistance were sufficiently good. Furthermore, although the particles were contained at a ratio of 70% by mass, the haze was smaller than that of Example 1 not containing particles.
In Example 4, since the solid content was high and voids were easily formed during film formation, the refractive index was lower than in Examples 2 and 3, and the transmittance was improved as compared with the case of a transparent substrate alone. Further, the antiglare property and the wear resistance were sufficiently good.
In Example 5, the refractive index was lower than those in Examples 2 to 4, and the transmittance was greatly improved as compared with the case of using a transparent substrate alone. It is thought that such a result was obtained by including a terpene derivative. Further, the antiglare property and the wear resistance were sufficiently good.
In Example 6 in which hollow silica particles were used at a particle ratio of 30% by mass and arithmetic average roughness Ra was 0.31 μm, the refractive index was the same as in Examples 2 to 5, but the transmittance was not improved.
Example 7 in which hollow silica particles were used at a particle ratio of 70% by mass had lower abrasion resistance than Examples 2-5.

ADVANTAGE OF THE INVENTION According to this invention, the base material with an anti-glare layer provided with the anti-glare layer excellent in the balance of an anti-glare effect, the transmittance | permeability improvement effect, and mechanical strength, and an article using the same can be provided, and it is used for various apparatus. It is useful as an antiglare substrate.
The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2014-089455 filed on April 23, 2014 are incorporated herein by reference. .

10: Substrate with an antiglare layer 12: Transparent substrate 14: Antiglare layer

Claims

A transparent base material, and an antiglare layer formed on the transparent base material,
The antiglare layer has a refractive index of 1.25 to 1.45,
The arithmetic average roughness Ra of the surface of the antiglare layer is 0.05 to 0.25 μm,
The base material with an antiglare layer, wherein the antiglare layer contains chain solid silica particles.
The substrate with an antiglare layer according to claim 1, wherein the content of the chain solid silica particles in the antiglare layer is 50 to 80% by mass with respect to the total mass of the antiglare layer.
3. The substrate with an antiglare layer according to claim 1 or 2, wherein the average particle diameter of the chain solid silica particles is 5 to 300 nm.
The antiglare layer according to any one of claims 1 to 3, wherein the antiglare layer is a layer formed from a coating liquid containing the chain solid silica particles, a silica-based matrix precursor, and a liquid medium. Layered substrate.
The substrate with an antiglare layer according to claim 4, wherein the coating solution further contains a terpene compound.
An article comprising the substrate with an antiglare layer according to any one of claims 1 to 5.