WO2015186753A1 - Chemically toughened glass plate with function film, method for producing same, and article - Google Patents

Abstract

Provided are: a method for producing a chemically toughened glass plate with a function film, which is capable of reliably performing chemical toughening of a glass plate after the formation of a function film; a chemically toughened glass plate with a function film, which is obtained by the production method; and an article which is provided with the chemically toughened glass plate with a function film. A chemically toughened glass plate with a function film, which is a chemically toughened glass plate that is provided with a function film on at least one surface, and wherein a part having the functional film containing a silica matrix has a wear resistance that is expressed as the difference between the specular gloss at 60˚ before a wear resistance test and the specular gloss at 60˚ after the wear resistance test, said difference being 20 or less. A method for producing a chemically toughened glass plate with a function film (1) comprising a chemically toughened glass plate (3) and a function film (5), which comprises: a step wherein a coating liquid that contains a silica precursor and a liquid medium so that the content of the silica precursor is 15% by mass or more relative to the solid content in terms of oxides in the coating liquid and the content of hollow silica particles is less than 10% by mass relative to the solid content in terms of oxides in the coating liquid is applied over a glass plate and dried thereon, thereby forming a function film (5); and a step wherein the glass plate, which has been provided with the function film (5), is subjected to chemical toughening, thereby obtaining a chemically toughened glass plate with a function film (1). In this connection, the step for forming the function film (5) is carried out at a temperature of 450°C or less.

Description

Chemically tempered glass plate with functional film, manufacturing method thereof and article

The present invention relates to a chemically strengthened glass plate with a functional film, a method for producing a chemically strengthened glass plate with a functional film, a chemically strengthened glass plate with a functional film obtained by the production method, and an article comprising the chemically strengthened glass plate with the functional film. .

Conventionally, functional films such as an antiglare film and a low reflection film have been formed on the surface of a glass plate. As one method for forming a functional film, there is a method in which a coating solution containing a silica precursor such as alkoxysilane is applied on a glass plate and dried or baked. This method has a simple process, and the performance of the functional film can be controlled by the composition of the coating solution and the coating method. For example, when a material having a low refractive index is blended in the coating solution, a functional film having low reflectivity is formed. Moreover, when a coating liquid is applied so that irregularities are formed on the surface, a functional film having an antiglare property is formed.

On the other hand, the glass plate is strengthened by a chemical strengthening method. In the chemical strengthening method, a glass plate is immersed in a molten salt at a temperature lower than the strain point temperature of the glass, and ions (for example, sodium ions) on the surface of the glass plate are exchanged for ions having a larger ion radius (for example, potassium ions). To do. Thereby, compressive stress arises in a glass plate surface layer, and the tolerance with respect to a crack and an impact improves.

When chemical strengthening is performed after the formation of the functional film, there is a concern that ion exchange is inhibited by the functional film and the glass plate cannot be sufficiently strengthened. Therefore, when manufacturing the glass plate chemically strengthened and the functional film was formed, the method of chemically strengthening a glass plate and forming a functional film after that is considered suitable. However, forming a functional film after chemical strengthening is troublesome in optimizing the firing conditions of the functional film so that the strengthening stress does not decrease, or a process requiring heating is required multiple times. Therefore, it is not desirable in terms of productivity.
Then, after forming a low reflection film on the surface of a glass plate, the method of performing a chemical strengthening process and manufacturing the tempered glass plate with a low reflection film is proposed (refer patent document 1). In the method described in Patent Document 1, ion exchange through the low-reflection film can be performed by using a coating solution containing a specific silicon compound, a hollow silica sol, and a metal chelate compound in a specific weight ratio for forming the low-reflection film. It is possible to perform chemical strengthening treatment effectively.

JP 2011-88765 A

However, the method described in Patent Document 1 is not suitable for forming a functional film other than the low reflection film because the composition of the coating solution is limited. Further, the material for forming the functional film is expensive because it needs to contain a relatively expensive hollow silica sol at a predetermined ratio. Furthermore, the chemical strengthening effect of the glass plate is not sufficient.

The present invention has been made in view of the above circumstances, and a method for producing a chemically tempered glass plate with a functional film that can satisfactorily chemically strengthen the glass plate after forming the functional film, and a chemical tempering with a functional film obtained by the production method. It aims at providing the articles | goods provided with a glass plate and this chemically strengthened glass plate with a functional film.
It is another object of the present invention to provide a chemically strengthened glass plate with a functional film in which physical deterioration due to contact with an object is suppressed by chemical strengthening after forming the functional film.

The present invention has the following aspects.

[1] A chemically strengthened glass plate provided with a functional film containing a silica-based matrix on at least one surface, wherein the portion having the functional film containing the silica-based matrix is before and after the abrasion resistance test. A chemically strengthened glass plate with a functional film, having a wear resistance of 20 or less as a difference in 60 ° specular gloss in each.
[2] The chemically strengthened glass plate with a functional film according to [1], wherein the silica-based matrix contains 50% or more of silica in the matrix.
[3] The portion having the functional film has an abrasion resistance of 10 or less as a difference in 60 ° specular gloss before and after the abrasion resistance test, according to [1] or [2] The chemically strengthened glass plate with a functional film as described.
[4] The chemically strengthened glass plate with a functional film according to any one of [1] to [3], wherein the surface compressive stress is 400 MPa or more and the compressive stress thickness is 5 μm or more.
[5] The chemically strengthened glass plate is expressed in terms of a molar percentage based on oxide, and includes SiO ₂ of 56 to 75%, Al ₂ O ₃ of 1 to 20%, Na ₂ O of 8 to 22%, and K ₂ O of The chemically strengthened glass with a functional film according to any one of [1] to [4], containing 0 to 10%, MgO 0 to 14%, ZrO ₂ 0 to 5%, and CaO 0 to 10%. Board.
[6] The chemically strengthened glass plate with a functional film according to any one of [1] to [5], wherein the functional film is an antiglare film.
[7] The chemically strengthened glass plate with a functional film according to any one of [1] to [6], wherein the functional film further includes solid inorganic particles.
[8] A method for producing a chemically strengthened glass plate with a functional film in which a functional film is formed on a glass plate, and the glass plate is subjected to a chemical strengthening treatment,
Applying the following coating solution on a glass plate and drying to form a functional film;
Chemically strengthening the glass plate on which the functional film is formed to obtain a chemically strengthened glass plate with a functional film, and
A method for producing a chemically strengthened glass plate with a functional film, wherein the step of forming the functional film is performed at a temperature of 450 ° C. or lower.
Coating solution: at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, and the content of the silica precursor However, it is 15 mass% or more with respect to the oxide conversion solid content in the said coating liquid.
[9] A method for producing a chemically strengthened glass plate with a functional film in which a functional film is formed on a glass plate, and the glass plate is subjected to a chemical strengthening treatment,
A functional film is formed from the following coating solution at a temperature of 450 ° C. or lower, and then a glass plate that has not been heat-treated at a temperature higher than 450 ° C. is chemically strengthened to obtain a chemically strengthened glass plate with a functional film. A method for producing a chemically strengthened glass plate with a functional film, which is characterized.
Coating solution: at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, and the content of the silica precursor However, it is 15 mass% or more with respect to the oxide conversion solid content in the said coating liquid.
[10] The method for producing a chemically strengthened glass plate with a functional film according to [8] or [9], wherein the glass plate has the following composition.
Glass composition: expressed in terms of mole percentage on oxide basis, SiO ₂ 56-75%, Al ₂ O ₃ 1-20%, Na ₂ O 8-22%, K ₂ O 0-10%, MgO 0-14%, ZrO ₂ 0-5% and CaO 0-10%.
[11] The coating liquid further contains solid inorganic particles, and the content of the solid inorganic particles is 10 to 85% by mass with respect to the oxide-converted solid content in the coating liquid. [8] Thru | or the manufacturing method of the chemically strengthened glass plate with a functional film as described in any one of [10].
[12] A chemically strengthened glass plate with a functional film obtained by the method for producing a chemically strengthened glass plate with a functional film according to any one of [8] to [11].
[13] An article comprising the chemically strengthened glass plate with a functional film according to any one of [1] to [7] and [12].

ADVANTAGE OF THE INVENTION According to this invention, after forming a functional film, the manufacturing method of the chemically strengthened glass plate with a functional film which can chemically strengthen a glass plate, the chemically strengthened glass plate with a functional film obtained by this manufacturing method, and with this functional film An article comprising a chemically strengthened glass plate can be provided. In particular, by chemically strengthening after the functional film is formed, the functional film is cured, and physical deterioration due to contact with an object is suppressed.

It is sectional drawing which shows typically an example of the chemically strengthened glass plate with a functional film manufactured by the manufacturing method of the chemically strengthened glass plate with a functional film of this invention.

The following definitions of terms apply throughout this specification and the claims.
The “chemically tempered glass plate” is a glass plate tempered (chemically strengthened) by a chemical strengthening method.
The chemical strengthening method is one of the methods for forming a compressive stress layer on the surface of the glass plate. The glass plate is immersed in a molten salt at a temperature equal to or lower than the strain point temperature of the glass, and ions on the surface of the glass plate (for example, sodium). This is a method of exchanging ions) for ions having a larger ion radius (for example, potassium ions). Thereby, compressive stress arises in a glass plate surface layer. The strain point of glass is lower than the softening point.
The “compressive stress layer” is a layer (chemical strengthening layer) having a desired surface compressive stress.
The surface compressive stress of the chemically strengthened glass plate and the thickness of the compressive stress layer are measured by a surface stress meter (for example, FSM-6000LE manufactured by Orihara Seisakusho).

“Silica precursor” means a substance capable of forming a matrix mainly composed of silica.
“Containing silica as a main component” means containing 90 mass% or more of SiO ₂ .
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.
Oxide conversion solid content means the sum total of the oxide conversion (metal oxide conversion) content of the component containing a metal element among the components contained in a coating liquid.
Content shown as a ratio with respect to oxide conversion solid content is content of oxide conversion. For example, the content of the silica precursor is an amount equivalent to SiO ₂ . That is, the content when all Si contained in the silica precursor is converted to SiO ₂ .

<Chemical tempered glass plate with functional film>
FIG. 1 is a cross-sectional view schematically showing an example of a chemically strengthened glass plate with a functional film of the present invention.
The chemically strengthened glass plate 1 with a functional film in this example includes a functional film 5 and a chemically strengthened glass plate 3 having the functional film 5 on the surface. A glass plate on which the functional film 5 is formed (a glass plate before chemical strengthening: an unstrengthened glass plate) may be referred to as a glass plate 3.
The functional film 5 may be a single layer film or a multilayer film.

(Chemical tempered glass plate)
The thickness of the chemically strengthened glass plate 3 is preferably less than 2 mm, more preferably 0.33 mm to 1.1 mm, and particularly preferably 0.7 mm to 1.1 mm.
A glass plate having a thickness of less than 2 mm is difficult to strengthen by the air-cooling strengthening method. Therefore, the usefulness of this invention is high when the thickness of the glass plate to strengthen is less than 2 mm. Further, the thinner the chemically strengthened glass plate 3 is, the lower the light absorption is, and it is preferable for the purpose of improving the transmittance. Moreover, the mass of the chemically strengthened glass plate 1 with a functional film per unit area becomes light, and an article provided with the chemically strengthened glass plate 1 with a functional film can be reduced in weight.
When the thickness of the chemically strengthened glass plate 3 is 0.33 mm or more, even when the chemically strengthened glass plate 1 with a functional film is large (for example, the long side is 300 mm or more), the deflection is small and easy to handle.

The chemically strengthened glass plate 3 preferably has a surface compressive stress of 400 MPa or more and a compressive stress layer thickness of 5 μm or more. If the surface compressive stress is 400 MPa or more and the thickness of the compressive stress layer is 5 μm or more, the chemically strengthened glass plate 3 is excellent in durability against physical impacts such as scratches.
The surface compressive stress of the chemically strengthened glass plate 3 is more preferably 500 MPa or more, and further preferably 600 MPa or more, depending on the application. Typically, the surface compressive stress is 800 MPa or less.
The thickness of the compressive stress layer is more preferably 10 μm or more, even more preferably 20 μm or more, and even more preferably more than 25 μm. Further, typically, the thickness of the compressive stress layer is 70 μm or less.
The glass plate before chemical strengthening (unstrengthened glass plate) will be described in detail later.

(Functional membrane)
The chemically strengthened glass plate 3 includes a functional film 5 on at least one surface. The functional film 5 is provided on at least a part of the glass plate 3. The functional film 5 may be provided on a part of one surface of the glass plate 3 or may be provided so as to cover the entire surface of the one surface.
The functional film 5 is applied with a coating solution containing at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, It is formed by drying. Therefore, the functional film 5 includes a matrix mainly composed of silica (hereinafter also referred to as a silica-based matrix) formed from a silica precursor. A silica-based matrix is one in which 50% or more of silica is contained in the matrix.

The silica-based matrix may contain components other than silica. The components include Li, B, C, N, F, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, and Sr. , Y, Zr, Nb, Ru, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, Bi and compounds such as one or more ions and / or oxides selected from the group of lanthanoid elements Is mentioned.

The functional film 5 may be composed of only a silica-based matrix, or may further include components other than the silica-based matrix. For example, particles dispersed in a silica-based matrix may be included. The type of particles and the like will be described in detail in the section of the coating liquid for producing the functional film.

The functional film 5 is not particularly limited as long as it can be formed from a coating solution containing the silica precursor and a liquid medium. For example, an antiglare film, a low reflection film, a glass anti-glare film, an alkali barrier film, Examples thereof include a flaw prevention film and an antifouling film. Among these, an antiglare film or a low reflection film is preferable because it is highly necessary in many applications in which chemically strengthened glass is used.
The antiglare film is a film having an antiglare property. The antiglare film may be an antiglare film having low reflectivity (that is, a low reflectivity antiglare film).
The low reflection film is a film having low reflectivity (that is, antireflection property).

When the functional film 5 is an antiglare film, the 60 ° specular gloss on the surface of the functional film 5 is preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less. If the 60 ° specular gloss on the surface of the functional film 5 is 80% or less, the antiglare effect is sufficiently exhibited.

When the functional film 5 is an antiglare film, the arithmetic average roughness Ra of the surface of the functional film 5 is preferably 0.04 to 1.00 μm, more preferably 0.06 to 1.00 μm, and more preferably 0.1 to 0 More preferably, it is 8 μm. If the arithmetic average roughness Ra of the surface of the functional film 5 is not less than the lower limit of the above range, the antiglare effect is sufficiently exhibited. If the arithmetic average roughness Ra of the surface of the functional film 5 is less than or equal to the upper limit of the above range, when the chemically strengthened glass plate 1 with the functional film is provided on the viewing side of the image display device body as a protective plate or various filters, A decrease in image contrast is sufficiently suppressed.

When the functional film 5 is an antiglare film having low reflectivity, the refractive index of the functional film 5 is preferably 1.23 to 1.47, and more preferably 1.25 to 1.40. When the refractive index of the functional film 5 is not more than the upper limit of the above range, reflection on the surface of the functional film 5 is suppressed, and the light transmittance is improved as compared with the case of the chemically strengthened glass plate 3 alone. When the refractive index of the functional film 5 is equal to or higher than the lower limit of the above range, the functional film 5 is dense and excellent in mechanical strength such as wear resistance of the functional film 5 and adhesion to the chemically strengthened glass plate 3. Moreover, when the chemically strengthened glass plate 1 with a functional film is provided as a cover crow on the light incident side of the solar cell, the power generation efficiency of the solar cell is good.

When the functional film 5 is a low reflection film, the thickness of the functional film 5 is preferably 30 to 300 nm, and more preferably 40 to 200 nm. If the film thickness of the functional film 5 is 30 nm or more, light interference occurs and low reflection performance is exhibited. If the film thickness of the functional film 5 is 300 nm or less, the film can be formed without generating cracks.
The film thickness of the functional film 5 is measured by the reflectance measured by a spectrophotometer.

When the functional film 5 is a low reflection film, the reflectance of the functional film 5 is the lowest value (so-called bottom reflectance) in the wavelength range of 300 to 1200 nm, preferably 2.6% or less, and 1.0% The following is more preferable.
The portion provided with the functional film 5 (hereinafter also referred to as a functional film surface) has a 60 ° specular gloss difference before and after the abrasion resistance test of 60 or less, more preferably 55 or less, and even more preferably 50 or less. Have The abrasion resistance test can be performed with an abrasion resistance tester (hereinafter also referred to as a rubbing tester) in which a friction element such as an eraser, steel wool, felt, or the like is attached to the tip, and reciprocation is possible under a constant load. The 60 ° specular glossiness on the functional film surface side is measured based on JIS Z8741 after being prevented from the influence of reflection from the surface opposite to the functional film surface of the chemically strengthened glass plate 3. As the surface wear progresses, the specular reflection component from the surface with respect to the incident light from the predetermined incident angle increases. Therefore, the smaller the change in the 60 ° specular gloss, the better the wear resistance.
In particular, the functional film 5 has a 60 ° specular gloss difference of 20 or less before and after the abrasion resistance test because physical deterioration due to contact with an object is suppressed and a functional film excellent in long-term durability can be obtained. It is preferable that it has abrasion resistance, More preferably, it is 15 or less, More preferably, it is 10 or less. When there is substantially no change in 60 ° specular gloss, that is, when the difference in 60 ° specular gloss before and after the abrasion resistance test is 0, the abrasion resistance is most preferable.

<Method for producing chemically strengthened glass plate with functional film>
The chemically strengthened glass plate 1 with a functional film is, for example,
A step of applying the following coating solution onto a glass plate and drying to form the functional film 5 (hereinafter also referred to as “functional film forming step”);
The glass plate on which the functional film 5 is formed can be chemically strengthened to obtain a chemically strengthened glass plate 1 with a functional film (hereinafter also referred to as “chemical strengthening step”).
You may perform the process of giving a well-known post-process with respect to the chemically strengthened glass plate 1 with a functional film after a chemical strengthening process as needed.
When the functional film is a chemically strengthened glass plate with a functional film provided in a part of the chemically strengthened glass plate 3, for example, the portion of the surface of the chemically strengthened glass plate 3 that does not form the functional film is masked. A film may be formed.

(Coating solution)
The coating liquid contains at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium. The coating solution may further contain particles, a terpene compound, an additive, and the like as necessary.

Silica precursor:
As the silica precursor, a silane compound having a hydrocarbon group bonded to a silicon atom and a hydrolyzable group (hereinafter also referred to as A1), a hydrolysis condensate thereof, and alkoxysilane (however, a silane compound (A1) is excluded). And its hydrolyzed condensate (sol-gel silica).

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 selected from the group consisting of —O—, —S—, —CO— and —NR′— (wherein R ′ is a hydrogen atom or a monovalent hydrocarbon group) between carbon atoms. One or a combination of two or more may be included.

Examples of the hydrolyzable group bonded to the silicon atom include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen atom. Among these, an alkoxy group, an isocyanate group, and a halogen atom (particularly a chlorine atom) are preferable from the viewpoint of the balance between the stability of the silane compound (A1) and the ease of hydrolysis.
As 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).

As the silane compound (A1), a compound represented by the following formula (I) is preferable from the viewpoint that even if the film thickness is large, the functional film is not easily cracked or peeled off.
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) And a group obtained by combining one or two or more selected from the group consisting of: What was mentioned above is mentioned as a bivalent hydrocarbon.
Q is preferably an alkylene group having 2 to 8 carbon atoms, and is preferably an alkylene group having 2 to 6 carbon atoms from the viewpoint that it is easily available, and even if the film thickness is large, the functional film is less likely to crack or peel off. Further preferred.

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 (A1) and alkoxysilane (excluding the silane compound (A1)) can be carried out by a known method.
For example, in the case of tetraalkoxysilane, the reaction is carried out using 4 times or more moles of 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 a silica precursor, 1 type may be used independently and 2 or more types may be used in combination.
It is preferable that a silica precursor contains either one or both of a silane compound (A1) and its hydrolysis condensate from a viewpoint of preventing the crack of a functional film, and film | membrane peeling.
The silica precursor preferably contains either one or both of tetraalkoxysilane and its hydrolysis condensate from the viewpoint of the wear resistance strength of the functional film.
It is particularly preferable that the silica precursor contains one or both of the silane compound (A1) and the hydrolysis condensate thereof, and one or both of the tetraalkoxysilane and the hydrolysis condensate thereof.

Liquid medium:
The liquid medium dissolves or disperses the silica precursor, and is preferably a solvent that dissolves the silica precursor. When the coating liquid contains particles, the liquid medium may also have a function as a dispersion medium for dispersing the particles.
Examples of the liquid medium include water, alcohols, ketones, ethers, cellosolves, esters, glycol ethers, nitrogen-containing compounds, and sulfur-containing compounds.

Examples of alcohols include methanol, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 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 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, 1-butanol, 2-butanol, and isobutanol are particularly preferable.

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

particle:
When the coating liquid contains particles, the characteristics of the functional film 5 (refractive index, transmittance, reflectance, color tone, conductivity, wettability, physical durability, chemical durability, etc.) depend on the type and amount of particles. Can be adjusted.
Examples of the particles include inorganic particles and organic particles.

Examples of the material for the inorganic particles include metal oxides, metals, alloys, and inorganic pigments.
Examples of the metal oxide include 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 and the} like. Can be mentioned.
Examples of the metal include Ag and Ru.
Examples of the alloy include AgPd and RuAu.
Examples of inorganic pigments include titanium black and carbon black.

Examples of the organic particle material include organic pigments and resins.
Examples of the resin include polystyrene and melanin resin.

Examples of the particle shape include a spherical shape, an elliptical shape, a needle shape, a plate shape, a rod shape, a cone shape, a columnar shape, a cube shape, a rectangular shape, a diamond shape, a star shape, and an indefinite shape.
The particles may be solid particles, hollow particles, or perforated particles such as porous particles. “Solid” indicates that there is no cavity inside. “Hollow” indicates that there is a cavity inside. The solid inorganic particles may exist in a state where each particle is independent, each particle may be linked in a chain shape, or each particle may be aggregated.
The particles may be used alone or in combination of two or more.

As the particles, solid inorganic particles are preferable from the viewpoint of cost and availability, and solid metal oxide particles are more preferable from the viewpoint of chemical durability.
Solid inorganic particles and other particles may be used in combination.

In the case of forming a functional film (low-reflective antiglare film, low-reflective film, etc.) having low reflectivity (antireflection property) as the functional film 5, solid silica particles may be included as solid inorganic particles. preferable.
As the solid silica particles, chain solid silica particles are preferable. The chain solid silica particles are solid silica particles having a chain shape. For example, the thing of the shape which the solid silica particle which has a shape of a some spherical ellipse shape, a needle shape, etc. connected in the shape of a chain | strand is mentioned. The shape of the chain solid silica particles can be confirmed by an electron microscope.
The chain solid silica particles can be easily obtained as a commercial product. Moreover, you may use what was manufactured by the well-known manufacturing method. Examples of commercially available products include Snowtex ST-OUP manufactured by Nissan Chemical Industries, Ltd.

The average aggregate particle diameter of the particles is preferably 5 to 300 nm, more preferably 5 to 200 nm. If the average agglomerated particle diameter of the particles is equal to or greater than the lower limit value of the above range, the effect of blending the particles is easily exhibited. If the average aggregate particle diameter is equal to or smaller than the upper limit value, the functional film 5 is excellent in mechanical properties such as wear resistance.
The average aggregate particle diameter of the particles is measured on a volume basis by a laser diffraction type particle size distribution measuring apparatus.

Terpene compounds:
The terpene compound is preferably used when the coating solution contains particles. When the coating liquid contains the terpene compound together with the particles, voids are formed around the particles in the functional film 5, and the refractive index of the functional film 5 tends to be lower than when the terpene compound is not included.
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.

Additive:
As the additive, various known additives can be used. For example, a surfactant for improving leveling properties, a metal compound for improving durability of the functional film 5, an ultraviolet absorber, an infrared reflector, an infrared ray Absorbers, antireflection agents and the like can be mentioned.
Examples of the surfactant include silicone oil and acrylic.
As the metal compound, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound and the like are preferable. Examples of the zirconium chelate compound include zirconium tetraacetylacetonate and zirconium tributoxy systemate.

composition:
The content of the silica precursor in the coating solution (in terms of SiO ₂ ) is 15% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more based on the oxide-converted solid content in the coating solution. preferable.
Adhesive strength sufficient between the chemically strengthened glass plate 3 and the functional film 5 is obtained when the content of the silica precursor (in terms of SiO ₂ ) is 15% by mass or more with respect to the oxide-converted solid content.
The upper limit of the silica precursor content (SiO ₂ equivalent) relative to the oxide equivalent solid content is not particularly limited, and may be 100% by mass. Content of a silica precursor can be suitably set according to content of the other component mix | blended as needed with a coating liquid.

The content of the liquid medium in the coating solution is an amount corresponding to the solid content concentration of the coating solution.
The solid content concentration of the coating solution is preferably 1 to 6% by mass and more preferably 2 to 5% by mass in the total amount (100% by mass) of the coating solution. If the solid content concentration is not less than the lower limit of the above range, the amount of the coating solution used for forming the functional film 5 can be reduced. If solid content concentration is below the upper limit of the said range, the uniformity of the film thickness of the functional film 5 will improve.
The solid content concentration of the coating solution is the total content of all components other than the liquid medium in the coating solution. However, content of the component containing a metal element is oxide conversion.

When the coating liquid contains solid inorganic particles, the content of the solid inorganic particles in the coating liquid (as oxide) is 10 to 85 mass with respect to the oxide-based solid content (100 mass%) in the coating liquid. %, More preferably 20 to 80% by mass, particularly preferably 30 to 75% by mass. If the content of the solid inorganic particles is not less than the lower limit of the above range, the blending effect of the solid inorganic particles can be sufficiently obtained. For example, in the case of solid silica particles, the refractive index of the functional film 5 is lowered, and a sufficient transmittance improvement effect is obtained. If the content of the solid inorganic particles is not more than the upper limit of the above range, the functional film 5 is excellent in mechanical strength such as wear resistance.

The coating liquid may or may not contain hollow silica particles as particles, but the content of the hollow silica particles in the coating liquid (in terms of SiO ₂ ) is based on the oxide-converted solid content in the coating liquid. Less than 10% by mass. Preferably it is less than 7 mass%, More preferably, it is less than 5 mass%. If the content of the hollow silica particles is less than 10% by mass with respect to the oxide-converted solid content, unreinforced glass through the functional film 5 in the chemical strengthening step after forming the functional film on the unreinforced glass plate surface. The plate can be sufficiently chemically strengthened, and the chemically strengthened glass plate 1 with a functional film can be produced at low cost.
That is, the content (in terms of SiO ₂ ) of the hollow silica particles in the coating solution is 0% by mass or more and less than 10% by mass, preferably 0% by mass or more and 7% by mass with respect to the oxide-converted solid content in the coating solution. %, More preferably 0% by mass or more and less than 5% by mass.

The coating liquid can be prepared, for example, by preparing a solution in which a silane precursor is dissolved in a liquid medium, and mixing an additional liquid medium, a dispersion of particles, a terpene compound, and other optional components as necessary.

(Glass plate)
The glass plate that forms a functional film and is chemically strengthened (hereinafter referred to as “unstrengthened glass plate”) is not particularly limited as long as it has a composition that can be chemically strengthened, and has various compositions. be able to. For example, soda lime glass and aluminosilicate glass can be suitably used. In view of easy chemical strengthening, aluminosilicate glass is preferable.
As a glass composition that is easy to chemically strengthen, SiO ₂ is 56 to 75%, Al ₂ O ₃ is 1 to 20%, Na ₂ O is 8 to 22%, and K ₂ O is 0 to 0 in terms of mole percentage based on oxide. It is preferable to contain 10%, MgO 0 to 14%, ZrO ₂ 0 to 5%, and CaO 0 to 10%.
In addition, a glass plate that is easily chemically strengthened is expressed in terms of a molar percentage based on oxide as a glass composition, SiO ₂ is 60 to 75%, Al ₂ O ₃ is 2 to 25%, Na ₂ O is 10 to 20%, K It is preferable to contain 0 to 7% ₂ O, 0 to 10% MgO, and 0 to 15% CaO.
Further, a glass plate that is easily chemically strengthened is expressed in terms of a molar percentage based on oxide as a glass composition, SiO ₂ is 50 to 74%, Al ₂ O ₃ is 2 to 8%, Na ₂ O is 8 to 18%, K ₂ O 0 ~ 8% MgO 2 to 15% of ZrO ₂ 0 ~ 4% of CaO 0 ~ 10% of SrO 0-3%, it is preferable that the BaO containing 0-3%.
Further, a glass plate that is easily chemically strengthened is expressed in terms of a molar percentage based on oxide as a glass composition, SiO ₂ is 50 to 74%, Al ₂ O ₃ is 8 to 25%, Na ₂ O is 8 to 18%, K ₂ O 0 ~ 8% MgO 2 to 15% of ZrO ₂ 0 ~ 4% of CaO 0 ~ 10% of SrO 0-3%, it is preferable that the BaO containing 0-3%.
For example, “containing 0 to 10% of K ₂ O” means not necessarily essential but may contain up to 10%. The same applies to MgO, ZrO ₂ and CaO.

The thickness of the untempered glass plate is the same as the thickness of the chemically strengthened glass plate 3.
The unstrengthened glass plate may be a smooth glass plate formed by a float method or the like, or a template glass plate having irregularities on the surface. Moreover, not only a flat glass plate but the glass plate which has a curved surface shape may be sufficient.
A commercially available thing may be used for an unstrengthened glass plate, and what was manufactured by the well-known manufacturing method may be used.
The unstrengthened glass plate is prepared by, for example, preparing various amounts of various raw materials constituting the glass, heating and melting, and then homogenizing by defoaming or stirring, a well-known float method, down draw method (for example, fusion method), Or it can manufacture by shape | molding in plate shape by the press method etc., and cutting | disconnecting to a desired size after slow cooling. Further, a glass ribbon may be used on-line during glass forming by a float method or a downdraw method (for example, a fusion method).

(Functional film formation process)
In the functional film formation step, the functional film 5 is formed by applying the coating liquid on an unstrengthened glass plate and drying it. Drying may be performed by heating, or may be performed without heating (natural drying, air drying, etc.).

In the present invention, the functional film forming step is performed at a temperature of 450 ° C. or lower. As for the temperature which performs a functional film formation process, 400 degrees C or less is more preferable.
By performing the functional film forming step at a temperature of 450 ° C. or less, even if the content of the hollow silica particles in the coating liquid is less than 10% by mass with respect to the oxide-converted solid content, in the subsequent chemical strengthening step, The unstrengthened glass plate can be sufficiently chemically strengthened through the functional film 5.
The minimum of the temperature which performs a functional film formation process will not be specifically limited if it is the temperature which can apply | coat a coating liquid and dry a coating film.

Performing the functional film forming step at a temperature of 450 ° C. or less means that the coating solution (coating film) is applied between the time when the coating solution is applied on the unstrengthened glass plate and the time when chemical strengthening is performed in the next chemical strengthening step. This means that the functional film 5 is not exposed to a temperature higher than 450 ° C.
Specifically, the temperature of the atmosphere in which the coating solution is applied, the temperature of the unstrengthened glass plate to which the coating solution is applied, the temperature of the coating film after application and drying, the drying temperature, and the chemical strengthening after drying The temperature and the like of the functional film 5 until the process is all 450 ° C. or lower.

The temperature of a coating film and the drying temperature of a coating film shall mean the temperature of the unstrengthened glass plate in which the coating film was formed, respectively. Moreover, the temperature of the functional film 5 shall mean the temperature of the non-tempered glass plate in which the functional film 5 was formed.
The temperature of the unstrengthened glass plate can be measured with a thermocouple, a radiation thermometer, or the like. For example, it can measure by attaching a thermocouple to the chemically tempered glass surface.

Application method:
As a coating method of the coating liquid, known wet coating methods (spin coating method, spray 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) Method, flexo coat method, slit coat method, roll coat method, etc.).

In the case of forming an antiglare film as the functional film 5, a spray method is preferable as a coating method of the coating solution from the viewpoint that 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 droplet is the Sauter average particle size measured by a laser measuring device. 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.
Under a certain coating condition, the arithmetic average roughness Ra and 60 ° specular gloss of the surface of the functional film 5 to be formed can be adjusted by the coating time, that is, the number of coated surfaces by spraying (number of overcoating). For example, as the number of coated surfaces increases, the arithmetic average roughness Ra of the surface of the functional film 5 increases and the 60 ° specular gloss tends to decrease (that is, the antiglare effect increases).
An electrostatic coating method may be used as an application method of the application liquid when an antiglare film is formed as the functional film 5. As an application method by the electrostatic coating method, for example, there is a method of charging and spraying the coating liquid using an electrostatic coating gun having a rotary atomizing head.

In the case of forming a low reflection film as the functional film 5, the coating liquid can be applied to a wide unstrengthened glass plate, the transport speed of the unstrengthened glass plate can be made relatively fast, and the required coating liquid In terms of a relatively small amount, the roll coating method is preferable, the functional film 5 having a uniform film thickness can be formed, and the functional film 5 having an arbitrary film thickness that can be optically designed can be easily formed (that is, the film thickness). From the viewpoint of excellent controllability, the reverse roll coating method is more preferable. On the other hand, from the viewpoint of the appearance of the product, a die coating method and an ink jet method are preferable.

The temperature of the atmosphere when applying the coating solution is preferably room temperature to 50 ° C., more preferably room temperature to 40 ° C.
The temperature of the unstrengthened glass plate when applying the coating solution may be the same as or different from the temperature of the atmosphere.
When an antiglare film is formed as the functional film 5, it is preferable to apply the coating liquid after heating the unreinforced glass plate to 30 to 90 ° C. in advance. If the temperature of the unstrengthened glass plate is 30 ° C. or higher, the liquid medium evaporates quickly, so that sufficient unevenness can be easily formed. If the temperature of an unstrengthened glass plate is 90 degrees C or less, the adhesiveness of an unstrengthened glass plate and the functional film 5 will become favorable. When the unstrengthened glass plate is 5 mm or less in thickness, a heat insulating plate set in advance at a temperature equal to or higher than the temperature of the unstrengthened glass plate may be disposed under the unstrengthened glass plate to suppress the temperature drop of the unstrengthened glass plate. .

In the functional film forming step, a plurality of coating liquids having different compositions may be sequentially applied onto the unstrengthened glass plate. Thereby, a multilayer film can be formed as the functional film 5.
For example, first, a coating solution containing no particles may be applied, and then a coating solution containing particles may be applied. Moreover, you may apply | coat the coating liquid containing particle | grains, and may apply | coat the coating liquid which is different in the kind and content of the particle | grains which contain particle | grains and contain previously after that.
When applying a plurality of coating solutions sequentially, after applying one of the plurality of coating solutions, the next coating solution may be applied as it is on the formed coating film. The coating film may be dried before coating. The drying at this time may be performed so that the liquid medium in the coating film is completely removed, or may be performed so that the liquid medium remains in the coating film.

Drying method:
As described above, drying when applying the coating liquid on the glass plate surface to form the functional film may be performed by heating or may be performed without heating.
The heating may be performed simultaneously with the application by heating the unreinforced glass plate when applying the coating solution to the unreinforced glass plate, and the coating film is heated after the coating solution is applied to the unreinforced glass plate. You may go by.

The preferable upper limit of the drying temperature is the same as the preferable upper limit of the temperature at which the functional film forming step is performed. That is, the upper limit temperature is 450 ° C.
The lower limit of the drying temperature is not particularly limited. Since the polymerization of the silane precursor proceeds to some extent even in the case of natural drying, it is theoretically possible to set the drying temperature to a temperature around room temperature if there is no restriction on time.
The drying temperature is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoint that sufficient drying conditions can be secured.
From the viewpoint of chemical strengthening efficiency, the drying temperature is preferably 25 to 400 ° C, particularly preferably 30 to 400 ° C.
The drying time varies depending on the drying temperature, but is typically about 0.5 to 30 minutes, and preferably 1 to 5 minutes.

(Chemical strengthening process)
In the chemical strengthening step, the unstrengthened glass plate on which the functional film 5 is formed in the functional film forming step is chemically strengthened. Thereby, the unstrengthened glass plate becomes the chemically strengthened glass plate 3, and the chemically strengthened glass plate 1 with a functional film is obtained.

Chemical strengthening can be performed by a known method.
For example, as an example in a case where the unstrengthened glass plate contains Na ₂ O, there is a method of immersing the unstrengthened glass plate on which the functional film 5 is formed in a heated potassium nitrate (KNO ₃ ) molten salt. . In this method, Na ions on the surface layer of the unstrengthened glass plate and K ions in the molten salt are exchanged to generate surface compressive stress and form a compressive stress layer. KNO ₃ molten salt, in addition to KNO _3, for example, NaNO ₃ may be one which contained about 5%.

The chemical strengthening is preferably performed so that a compressive stress layer having a desired surface compressive stress is formed on the unstrengthened glass plate. The preferable ranges of the surface compressive stress and the thickness of the compressive stress layer are as described above.
The chemical strengthening treatment conditions for forming a compressive stress layer having a desired surface compressive stress on the unstrengthened glass plate vary depending on the glass composition of the unstrengthened glass plate, the thickness of the unstrengthened glass plate, etc., but the glass strain point temperature. It is typically immersed in the following 350 to 550 ° C. KNO ₃ molten salt for 2 to 20 hours. From an economical point of view, the chemical strengthening treatment conditions are preferably immersed in KNO ₃ molten salt at 350 to 500 ° C. for 2 to 16 hours, and immersed in KNO ₃ molten salt at 350 to 500 ° C. for 2 to 10 hours. More preferred.

As described above, the chemically strengthened glass plate 1 with the functional film including the chemically strengthened glass plate 3 and the functional film 5 is obtained.

(Function and effect)
In the manufacturing method of the chemically strengthened glass plate 1 with a functional film of the present invention described above, a predetermined amount of hollow silica particles are obtained as in Patent Document 1 by performing the functional film forming step at a temperature of 450 ° C. or lower. Even if it does not contain, the unstrengthened glass plate can be sufficiently chemically strengthened through the functional film 5 in the subsequent chemical strengthening step. For example, in the case of an aluminosilicate glass, a compressive stress layer having a compressive stress of 500 MPa or more can be formed in a thickness of 20 μm or more on the surface layer of the surface of the unreinforced glass plate in contact with the functional film 5.
This is because the functional matrix formation step is performed at a temperature of 450 ° C. or lower, so that the silica matrix constituting the functional membrane 5 can pass ions, and the ion exchange through the functional membrane 5 is performed in the chemical strengthening step. This is considered to be done well. The reason why it is necessary to include the hollow silica sol at a certain ratio or more in the above-mentioned Patent Document 1 is that the matrix is dense because the low-reflection film is baked at a high temperature, and ions are contained therein. It is thought that it cannot pass.
Therefore, in the production method of the present invention, even if a relatively expensive hollow silica particle is not used as a material for the functional membrane, for example, even when a coating liquid composed of a silica precursor and a liquid medium is used, the function is achieved. A chemically strengthened glass plate with a functional film can be obtained by performing chemical strengthening after the film is formed.

In addition, although the example which performs a functional film formation process and a chemical strengthening process one by one was shown here, the manufacturing method of the chemically strengthened glass plate with a functional film of this invention is a functional film at the temperature of 450 degrees C or less from the said coating liquid. After that, a glass plate that is not heat-treated at a temperature higher than 450 ° C. is used as a starting material, and the method may include a step of chemically strengthening the glass plate.

The chemically strengthened glass plate with a functional film obtained by the method for producing a chemically strengthened glass plate with a functional film of the present invention can be used for various applications depending on the type of the functional film. Specific examples include transparent parts for vehicles (headlight covers, side mirrors, front transparent substrates, side transparent substrates, rear transparent substrates, instrument panel surfaces, etc.), meters, architectural windows, show windows, displays (notebook type) PC, monitor, LCD, PDP IV, 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 surface, projector component , Copier parts, transparent substrates for solar cells (cover glass, etc.), mobile phone windows, backlight unit parts (light guide plates, cold cathode tubes, etc.), LCD brightness enhancement films, organic EL light-emitting element parts, inorganic EL light emission Element parts, phosphor light emitting element parts, optical filters, end faces of optical parts, lighting A lamp, a cover of a lighting fixture, an amplified laser light source, and the like can be given.

<Article>
The article of the present invention includes the above-described chemically strengthened glass plate with a functional film or the chemically strengthened glass plate with a functional film obtained by the above-described manufacturing method.
The article of the present invention may be composed of the chemically strengthened glass plate with the functional film, or may further include other members other than the chemically strengthened glass plate with the functional film. Further, a functional film may be provided on a part of the chemically strengthened glass plate.
Examples of the article of the present invention include those mentioned above as the uses of the chemically strengthened glass plate with a functional film, devices provided with any one or more of them.
Examples of the device include a solar cell module, a display device, and a lighting device as an example in which the functional film is an antiglare film (may or may not have low reflectivity) or a low reflection film. Is mentioned.

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 chemically strengthened glass plate with a functional film as 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
Of the following examples, Examples 3 to 11 and Examples 14 and 15 are examples, and Examples 1, 2, 12, 13, and 16 are comparative examples.
The measurement / evaluation method and materials (source or preparation method) used in each example are shown below.

<Measurement and evaluation method>
(Surface compressive stress, compressive stress layer thickness)
The surface compressive stress of the chemically strengthened glass plate and the thickness of the compressive stress layer were measured with a surface stress meter (manufactured by Orihara Seisakusho: FSM-6000LE).
For chemically tempered glass plate after functional tempered glass plate with functional film (antiglare film, low reflection film), the surface compressive stress on the side where the functional film is formed, the thickness of the compressive stress layer are the same as above And measured.

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

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

(Transmissivity difference Td)
Transmission of light at a wavelength of 400 nm to 1100 nm using a spectrophotometer (manufactured by JASCO Corporation, V670) for each of the glass plate before forming the low reflection film and each chemically strengthened glass plate with the low reflection film obtained in each example The rate (%) was measured and the average transmittance (%) was determined. From the result, the transmittance difference Td (%) was calculated by the following formula (1). The incident angle of light was 0 ° (incident perpendicular to the glass plate). It shows that the transmittance | permeability improvement effect is so high that the transmittance | permeability difference Td is large.
Td = T1-T2 (1)
However, T1 is the average transmittance (%) of the chemically strengthened glass plate with a low reflection film, and T2 is the average transmittance (%) of the glass plate before forming the low reflection film.

(Film thickness)
The film thickness d (nm) of the low-reflection film is a spectrophotometer (Otsuka Electronics Co., Ltd.) with a black vinyl tape attached to the back surface (surface opposite to the low-reflection film) of the chemically tempered glass plate with the low-reflection film. The reflectance of the low-reflection film is measured in the wavelength range of 300 to 780 nm using an instantaneous multi-metering system MCPD-3000), and the lowest reflectance (bottom reflectance R _min ) obtained and the low-reflection film The refractive index n is calculated by the following formula (2) from the refractive index n _s of the glass plate before forming, and the following formula is calculated from the obtained refractive index n and the wavelength λ (nm) at the bottom reflectance R _min . Calculated according to (3).
R _min = (n−n _s ) ² / (n + n _s ) ² (2)
n × d = λ / 4 (3)

(Surface compressive stress, compressive stress layer thickness)
The surface compressive stress of the chemically strengthened glass plate with a functional film and the thickness of the compressive stress layer were measured with a surface stress meter (manufactured by Orihara Seisakusho: FSM-6000LE).

(Abrasion resistance)
The abrasion resistance of the surface of the anti-glare film was determined by attaching an eraser (Lion Secretariat, GAZA1K, length 18 mm × width 11 mm) to a rubbing tester (Ohira Rika Kogyo Co., Ltd.) and attaching the eraser to 9.8 × 10 ^−2. Horizontal reciprocation was performed on the surface of the antiglare film at a pressure of MPa. The difference (absolute value) in 60 ° specular gloss on the surface of the antiglare film before and after reciprocating the eraser 200 times was determined as wear resistance ΔG. The smaller the difference in 60 ° specular gloss, the better the wear resistance. The 60 ° specular gloss was measured on an article with an antiglare film in which a black tape was not attached to the surface opposite to the side on which the antiglare film was formed.

[Materials used]
(Preparation of silica precursor solution (a-1))
While stirring 75.8 g of denatured ethanol (trade name “SOLMIX AP-11”, manufactured by Nippon Alcohol Sales Co., Ltd., a mixed solvent containing ethanol as a main ingredient, the same shall apply hereinafter), 11.9 g and 61 mass of ion-exchanged water are stirred. A mixed solution with 0.1 g of% nitric acid was added and stirred for 5 minutes. To this, 12.2 g of tetraethoxysilane (SiO ₂ equivalent solid content concentration: 29% by mass) was added and stirred at room temperature for 30 minutes to obtain a silica precursor solution having a SiO ₂ equivalent solid content concentration of 3.5% by mass ( a-1) was prepared.
Incidentally, SiO ₂ in terms of solids concentration here is solid concentration when all Si of tetraethoxysilane was converted to SiO _2.

(Preparation of silica precursor solution (a-2))
While stirring 80.3 g of denatured ethanol, a mixed solution of 7.9 g of ion exchange water and 0.2 g of 61% by mass nitric acid was added and stirred for 5 minutes. 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 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 .

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

(Preparation of coating solution (A))
While stirring 77.1 g of the silica precursor solution (a-1), 7.0 g of the silica 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))
30.0 g of the coating solution (A) was added while stirring 56.5 g of denatured ethanol, and then 13.5 g of a chain solid silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name “Snowtex ST-OUP”) In addition, the mixture was stirred at room temperature for 30 minutes to obtain a coating solution (B) having a solid content concentration in terms 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))
While stirring 0.3 g of denatured ethanol, 24.0 g of isobutyl alcohol, 15.0 g of diacetone alcohol (DAA), 30.0 g of coating solution (A), solid silica particle dispersion (b) Was added to prepare a coating solution (C) having a solid content concentration of 3.0% by mass.

[Example 1]
As a glass plate, a soda-lime glass plate (manufactured by Asahi Glass Co., Ltd., product name: FL1.1, size: 100 mm × 100 mm, thickness 1.1 mm, glass strain point temperature: 511 ° C.) was prepared.
The glass plate was subjected to ultrasonic cleaning treatment in pure water, air-dried, treated in a preheating furnace at 420 ° C. for 120 minutes, and then immersed in a KNO ₃ melting bath at 420 ° C. for 150 minutes. After the treatment, the glass plate was taken out and cooled at room temperature for 60 minutes, and a chemically strengthened glass plate was obtained by ultrasonic cleaning treatment and air drying in pure water.
Table 1 shows the surface compressive stress of the obtained chemically strengthened glass plate and the thickness of the compressive stress layer.

[Example 2]
Except for changing the glass plate to an aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd., product name: glass before strengthening of Leoflex. Size: 100 mm × 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.) In the same manner as in Example 1, a chemically strengthened glass plate was obtained.
Table 2 shows the surface compressive stress of the obtained tempered glass sheet and the thickness of the compressive stress layer.

[Example 3]
(Glass plate and its cleaning)
As a glass plate, a soda-lime glass plate (manufactured by Asahi Glass Co., Ltd., product name: FL1.1, size: 100 mm × 100 mm, thickness 1.1 mm, glass strain point temperature: 511 ° C.) was prepared. The surface of the glass plate was washed with sodium hydrogen carbonate water, rinsed with ion-exchanged water, and dried.

(Preparation of glass plate with antiglare film)
The glass plate was preheated in a preheating furnace (manufactured by ISUZU, VTR-115). Next, in a state where the surface temperature of the glass plate was kept at 89 ° C., the coating solution (A) was applied on the glass plate under the following conditions so that the arithmetic average roughness Ra shown in Table 1 was obtained. Other conditions at the time of application are as shown in Table 1.
・ Spray pressure: 0.2 MPa
・ Nozzle moving speed: 750 mm / min,
-Spray pitch: 22 mm.
Then, it dried for 30 minutes at 30 degreeC, and obtained the glass plate with an anti-glare film.
For application by the spray method, a 6-axis coating robot (manufactured by Kawasaki Robotics, JF-5) was used. As the nozzle, a VAU nozzle (manufactured by Spraying System Japan) was used.

(Chemical strengthening treatment of glass plate with antiglare film)
A chemically strengthened glass plate with an antiglare film was obtained by performing a chemical strengthening treatment in the same manner as in Example 1 except that the glass plate with an antiglare film was used instead of the glass plate of Example 1.
Table 1 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, and the arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.

[Examples 4 to 6]
A chemically strengthened glass plate with an antiglare film in the same manner as in Example 3 except that the coating solution (A) was applied so as to have the arithmetic average roughness Ra shown in Table 1 under the coating conditions and drying conditions shown in Table 1. Got.
Table 1 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, and the arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.

[Example 7]
The glass plate was changed to an aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd., product name: glass before strengthening of Leoflex. Size: 100 mm × 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.) A) was changed to the coating solution shown in Table 2, and the coating solution and drying conditions shown in Table 2 were applied in the same manner as in Example 3 except that the coating was applied so that the arithmetic average roughness Ra shown in Table 2 was obtained. A chemically strengthened glass plate with a glare film was obtained.
Table 2 shows the surface compressive stress, thickness of the compressive stress layer, glossiness, and arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.

[Examples 8 to 9]
A chemically strengthened glass plate with an antiglare film was applied in the same manner as in Example 7 except that the coating solution was applied so as to have the arithmetic average roughness Ra shown in Table 2 under the coating solution, coating conditions, and drying conditions shown in Table 2. Obtained.
Table 2 shows the surface compressive stress, thickness of the compressive stress layer, glossiness, and arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.

[Examples 10 to 11]
A chemically strengthened glass plate with an antiglare film was obtained in the same manner as in Example 3 except that the coating liquid was applied so as to have the arithmetic average roughness Ra shown in Table 1 at the coating liquid and drying temperature shown in Table 1.
Table 1 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, and the arithmetic average roughness Ra of the obtained chemically strengthened glass plate with an antiglare film.

[Example 12]
(Chemically strengthened glass plate and its cleaning)
As in Example 2, a chemically strengthened aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd., product name: Leoflex, size: 100 mm × 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.) was prepared in the same manner as in Example 2. . The surface of the glass plate was washed with sodium hydrogen carbonate water, rinsed with ion-exchanged water, and dried.

(Production of chemically strengthened glass plate with antiglare film)
Next, the glass plate was preheated to 95 ° C. in a preheating furnace (manufactured by ISUZU, VTR-115). Next, with the surface temperature of the glass plate kept at 90 ° C., the arithmetic average roughness Ra shown in Table 3 is applied on the glass plate using the coating solution (A) by the spray method under the following conditions. The coating liquid (A) was applied so that a chemically strengthened glass plate with an antiglare film was produced. Other conditions at the time of application are as shown in Table 3.
・ Spray pressure: 0.2 MPa
・ Nozzle moving speed: 750 mm / min,
-Spray pitch: 22 mm.
Then, it dried at 200 degreeC for 3 minute (s), and obtained the chemically strengthened glass plate with a glare-proof film.
For application by the spray method, a 6-axis coating robot (manufactured by Kawasaki Robotics, JF-5) was used. As the nozzle, a VAU nozzle (manufactured by Spraying System Japan) was used.
Table 3 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, the arithmetic average roughness Ra, and the wear resistance ΔG of the obtained chemically strengthened glass plate with an antiglare film.

[Example 13]
A chemically strengthened glass plate with an antiglare film was applied in the same manner as in Example 12 except that the coating liquid was applied so as to have the arithmetic average roughness Ra shown in Table 3 under the coating liquid, coating conditions, and drying conditions shown in Table 3. Obtained.
Table 3 shows the surface compressive stress, the thickness of the compressive stress layer, the glossiness, the arithmetic average roughness Ra, and the wear resistance ΔG of the obtained chemically strengthened glass plate with an antiglare film.

[Example 14]
(Production of glass plate with low reflection film)
As the glass plate, an aluminosilicate glass plate (manufactured by Asahi Glass Co., Ltd., product name: glass before strengthening of Leoflex. Size: 100 mm × 100 mm, thickness 0.85 mm, glass strain point temperature: 556 ° C.) was prepared.
The glass plate was preheated in a preheating furnace (manufactured by ISUZU, VTR-115). Coating the reverse roll coater (manufactured by Sanwa Seiki Co., Ltd.) on the glass plate with the coating solution (C) under the following conditions with the glass surface temperature kept at 30 ° C. The coating liquid (C) was applied with a predetermined film thickness using a roll to produce a glass plate with a low reflection film. The other conditions at the time of application are as shown in Table 2.
・ Conveying speed of glass plate: 8.5 m / min,
・ Gap between coating roll and conveyor belt: 2.9 mm,
・ Indentation thickness between coating roll and doctor roll: 0.6 mm.
As the coating roll, a rubber lining roll lined with rubber (ethylene propylene diene rubber) having a surface hardness (JIS-A) of 30 was used. As the doctor roll, a metal roll having lattice-like grooves formed on the surface thereof was used.
Then, it dried at 200 degreeC for 30 minutes, and obtained the glass plate with a low reflection film.

(Chemical strengthening treatment of glass plate with low reflection film)
Subsequently, the chemical strengthening process was performed like Example 1 except having used the said glass plate with a low reflection film as a glass plate, and the chemically strengthened glass plate with a low reflection film was obtained.
Table 2 shows the surface compressive stress, the thickness of the compressive stress layer, the transmittance difference Td, and the film thickness of the low reflective film of the obtained chemically strengthened glass plate with the low reflective film.

[Examples 15 to 16]
A chemically strengthened glass plate with a low reflection film was obtained in the same manner as in Example 14 except that the drying temperature was changed to the temperature shown in Table 2.
Table 2 shows the surface compressive stress, the thickness of the compressive stress layer, the transmittance difference Td, and the film thickness of the low reflective film of the obtained chemically strengthened glass plate with the low reflective film.

When Example 1 is compared with Examples 3 to 6 and 10 to 11, the chemically strengthened glass plates with antiglare films of Examples 3 to 6 and 10 to 11 are chemically strengthened after the formation of the functional film (antiglare film). However, the thickness of the compressive stress layer of the chemically strengthened glass plate was equal to or greater than that of the chemically strengthened glass plate of Example 1 in which chemical strengthening was performed without forming a functional film. In particular, in Examples 10 to 11 where the coating film was dried at 300 to 400 ° C., the surface compressive stress of the chemically strengthened glass plate was equal to or higher than that of the chemically strengthened glass plate of Example 1.

When Example 2 is compared with 7 to 9 and 14 to 16, the chemically strengthened glass plate with antiglare film of Examples 7 to 9 and the chemically strengthened glass plate with low reflection film of Examples 14 and 15 are functional films (antiglare). Example 2 in which chemical strengthening was performed after formation of the film, low-reflection film, and the surface compressive stress of the chemically strengthened glass plate and the thickness of the compressive stress layer were chemically strengthened without forming a functional film. It was equal to or better than the chemically strengthened glass plate.
On the other hand, the chemically tempered glass plate with a low reflection film of Example 16 in which the coating film was dried at 500 ° C. had the surface compressive stress of the chemically tempered glass plate and the thickness of the compressive stress layer of the chemically tempered glass plate of Example 2. Was inferior.
Further, compared to Examples 12 to 13 in which a functional film is formed on a chemically strengthened aluminosilicate glass plate, the glass plate of Example 8 that has been chemically strengthened after forming the functional film can only be chemically strengthened at least as much as Example 2. Rather, it had sufficient wear resistance. The process of forming the functional film is not only performed at a temperature of 450 ° C. or lower, but also by performing chemical strengthening after the functional film is formed, for example, densification is performed while maintaining a structure through which ions can pass. Abrasion is considered to improve.

ADVANTAGE OF THE INVENTION According to this invention, after forming a functional film, the chemical strengthening glass plate with a functional film by which physical deterioration by the contact of an object was suppressed by chemically strengthening can be provided. Further, a method for producing a chemically tempered glass plate with a functional film capable of satisfactorily chemically strengthening the glass plate after forming the functional film, a chemically tempered glass plate with a functional film obtained by the production method, and a chemically tempered glass plate with the functional film Can be provided. In addition, physical deterioration due to contact with an object was suppressed by chemical strengthening after coating of the functional film. Note that the specification and claims of Japanese Patent Application No. 2014-117788 filed on June 6, 2014 The entire contents of the drawings and abstract are hereby incorporated by reference into the present disclosure.

1 Chemically strengthened glass plate with functional membrane 3 Chemically strengthened glass plate 5 Functional membrane

Claims (13)

1. A chemically tempered glass plate having a functional film containing a silica-based matrix on at least one surface, wherein the portion having the functional film containing a silica-based matrix has a 60 ° specular gloss and abrasion resistance before an abrasion resistance test. A chemically strengthened glass plate with a functional film having a wear resistance of 20 or less as a difference from the 60 ° specular gloss after the test.
2. The chemically strengthened glass plate with a functional film according to claim 1, wherein the silica-based matrix contains 50% or more of silica in the matrix.
3. The functional film-attached portion according to claim 1 or 2, wherein the portion having the functional film has an abrasion resistance of 10 or less as a difference in 60 ° specular gloss before and after the abrasion resistance test. Chemically strengthened glass plate.
4. The chemically strengthened glass plate with a functional film according to any one of claims 1 to 3, wherein the surface compressive stress is 400 MPa or more and the compressive stress thickness is 5 µm or more.
5. The chemically tempered glass plate is expressed in terms of mole percentage based on oxide, SiO ₂ is 56 to 75%, Al ₂ O ₃ is 1 to 20%, Na ₂ O is 8 to 22%, and K ₂ O is 0 to 10%. 5. The chemically strengthened glass plate with a functional film according to claim 1, comprising: 1%, MgO 0 to 14%, ZrO ₂ 0 to 5%, and CaO 0 to 10%.
6. The chemically strengthened glass plate with a functional film according to any one of claims 1 to 5, wherein the functional film is an antiglare film.
7. The chemically strengthened glass plate with a functional film according to any one of claims 1 to 6, wherein the functional film further contains solid inorganic particles.
8. A functional film is formed on the glass plate, and a chemical tempered glass plate with a functional film is produced by the chemical tempering treatment on the glass plate,
   Applying the following coating solution on a glass plate and drying to form a functional film;
   Chemically strengthening the glass plate on which the functional film is formed to obtain a chemically strengthened glass plate with a functional film, and
   A method for producing a chemically strengthened glass plate with a functional film, wherein the step of forming the functional film is performed at a temperature of 450 ° C. or lower.
   Coating solution: at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, and the content of the silica precursor However, it is 15 mass% or more with respect to the oxide conversion solid content in the said coating liquid.
9. A functional film is formed on the glass plate, and a chemical tempered glass plate with a functional film is produced by the chemical tempering treatment on the glass plate,
   A functional film is formed from the following coating solution at a temperature of 450 ° C. or lower, and then a glass plate that has not been heat-treated at a temperature higher than 450 ° C. is chemically strengthened to obtain a chemically strengthened glass plate with a functional film. A method for producing a chemically strengthened glass plate with a functional film, which is characterized.
   Coating solution: at least one silica precursor selected from the group consisting of a silane compound having a hydrolyzable group bonded to a silicon atom and a hydrolysis condensate thereof, and a liquid medium, and the content of the silica precursor However, it is 15 mass% or more with respect to the oxide conversion solid content in the said coating liquid.
10. The manufacturing method of the chemically strengthened glass plate with a functional film of Claim 8 or 9 with which the said glass plate has the following compositions.
    Glass composition: expressed in terms of mole percentage on oxide basis, SiO ₂ 56-75%, Al ₂ O ₃ 1-20%, Na ₂ O 8-22%, K ₂ O 0-10%, MgO 0-14%, ZrO ₂ 0-5% and CaO 0-10%.
11. 11. The coating liquid according to claim 8, wherein the coating liquid further contains solid inorganic particles, and the content of the solid inorganic particles is 10 to 85% by mass with respect to the oxide-converted solid content in the coating liquid. The manufacturing method of the chemically strengthened glass plate with a functional film as described in any one of Claims.
12. A chemically strengthened glass plate with a functional film obtained by the method for producing a chemically strengthened glass plate with a functional film according to any one of claims 8 to 11.
13. An article comprising the chemically strengthened glass plate with a functional film according to any one of claims 1 to 7 and 12.

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