JPH0891876A - Production of ultraviolet ray cut glass - Google Patents

Abstract

PURPOSE: To produce an ultraviolet ray cut glass excellent in thermal stability and chemical stability, made of an expensive material by a method safe and easy to handle by thermally decomposing the coating film after applying one or more kind of a solution of an organic acid metallic salt of a metal selected from among specific metals on a glass plate. CONSTITUTION: A metal oxide thin film is formed on the surface of the glass plate by dissolving the organic acid metallic salt composed of a metal selected from among Ti, Zn, Ce, Fe and V and an aliphatic monocarboxylic acid such as naphthenic acid, octylic acid, tall oil fatty acid or the like in an aliphatic hydrocarbon based solvent or an aromatic hydrocarbon based solvent such as mineral tarpen or xylene, applying alone or a mixture of >=2 kinds thereof on the glass plate by spray, dipping, spin coating or screen printing method or the like and thermally decomposing it at >=400 deg.C for >=5min after previously drying it at a room temp. to 200 deg.C for 5-300min.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a glass plate having excellent ultraviolet ray shielding properties for construction and various vehicles.

[0002]

2. Description of the Related Art In recent years, ultraviolet shielding glass has been widely used as glass for automobiles and construction. There are roughly two methods of producing the glass, a method of forming a glass composition of titanium oxide, cerium oxide, zinc oxide or the like having excellent ultraviolet absorption performance, and a method of forming a film of an ultraviolet absorber on the glass surface. . As a method for forming an ultraviolet absorbing film on the glass surface, a method such as an ion plating method, a sputtering method, a CVD method, a vapor deposition method, a method of applying a sol using a metal alkoxide as a raw material and then thermally decomposing it, a metal acetyl Spray the organic solvent solution of acetonate,
Then, a method of thermally decomposing and a method of attaching a transparent film containing an organic ultraviolet absorber are known.

[0003]

Among the methods described above, the method of using titanium oxide, cerium oxide, zinc oxide, etc., which have excellent ultraviolet absorption performance, as the glass composition is high in cost because it has a special glass composition. In addition, the ultraviolet absorption performance is also poor. A sputtering method for forming a thin film of titanium dioxide, cerium oxide, zinc oxide, vanadium oxide, iron oxide, etc., which has excellent ultraviolet absorption on the glass surface,
The methods such as the vapor deposition method have a drawback that expensive equipment is required and that only a small area can be processed on a plane. In addition, the coating pyrolysis method using a metal alkoxide sol can form the desired ultraviolet absorbing film, but the metal alkoxide is chemically unstable, and many of them are highly dangerous. There are many restrictions on the handling from generation to use. In addition, since metal acetylacetonate is in the form of solid powder, it must be dissolved in an organic solvent before use. In addition, there is a drawback that it is difficult to control during use, because once it dissolves it deteriorates. Furthermore, the method of attaching a transparent film in which an organic ultraviolet absorber is kneaded is not practical because the strength of the film is weak and the durability of the organic ultraviolet absorber is problematic.

Metal alkoxides have the general formula M (OR) _n
Compounds such as (M is a metal, n is a metal valence, and R is an alkyl group), often have a low boiling point, are chemically active, and are easily hydrolyzed by water. Therefore, when it is used as a metal oxide thin film precursor, it is used in a vapor deposition method or a method in which water, alcohol and an acid are hydrolyzed to be in a sol state, which is applied, gelled and thermally decomposed.

Metal acetylacetonate is M (O2
C5 H7) n (M is a metal, n is a valence of a metal) and is chemically active and easily hydrolyzed by water, but its tendency is weaker than that of metal alkoxide.
Since it is usually in a powder or crystalline state, when used for forming a metal oxide thin film on the glass surface, a solution prepared by dissolving an organic peroxide in an organic solvent such as xylene is added,
It is known to use by spraying on heated glass. (JP-A-5-195232) The method using metal alkoxide or metal acetylacetonate is the most widely known method, but all of them are expensive and chemically unstable, and their handling is limited. Further, there is a problem that many metal alkoxides are dangerous.

[0006]

DISCLOSURE OF THE INVENTION As a result of earnest research, the present invention has found that an organic acid metal salt solution is useful for forming a metal oxide thin film on a glass surface in the production of an ultraviolet shielding glass. Is. That is, the organic acid metal salt, compared to metal alkoxide and metal acetylacetonate,
Since it is chemically stable, highly safe, and has no restrictions on handling, it was found that a glass excellent in UV shielding can be easily manufactured by applying them to the glass surface and pyrolyzing them. It was done. That is, according to the present invention, a solution of an organic acid metal salt of a metal selected from Ti, Zn, Ce, Fe and V is applied alone or a mixture of two or more kinds is applied to a glass plate and then thermally decomposed to obtain a glass. It is a method for producing an ultraviolet-shielding glass in which a transparent metal oxide thin film is formed on a plate surface.

The organic acid metal salt used in the present invention is chemically,
A thermally stable compound represented by the general formula (RCOO) _n M (M is a metal, n is a metal valence, and R is an alkyl group), and has conventionally been used as a coating desiccant, a fuel additive, and a reaction catalyst. ,
It is used as a lubricant additive and waterproofing agent. However, the present invention is the first to be used as an ultraviolet shielding glass.

The organic solvent solution of the organic acid metal salt used in the present invention is Ti. Zn. Ce. Fe. V. With a metal selected from organic acids such as naphthenic acid, octylic acid, tall oil fatty acid, versatic acid, hexanoic acid, organic acid metal salts of aliphatic monocarboxylic acids such as heptanoic acid, an aliphatic hydrocarbon solvent or aromatic It is a solution dissolved in a group hydrocarbon solvent such as mineral terpene or xylene. The type of metal is limited depending on the ultraviolet absorbing ability of the metal oxide, but the type of organic acid is not particularly limited as long as the produced organic acid metal salt is soluble in an organic solvent. The organic acid metal salt of the present invention has good thermal stability and storage stability, and is stable as long as it does not come into contact with a large amount of water, acid or alkali, and these points are greatly different from alkoxide and acetylacetonate.

There is no limitation on the method of coating the glass plate, and any method such as spraying, dipping, spin coating, or screen printing can be used. At the time of coating, these organic acid metal salt solutions can be used alone or in advance. The above can be mixed and used. After coating at room temperature to 200 ℃ 5 ~
After preliminary drying for 30 minutes, the target metal oxide thin film can be formed on the surface of the glass plate by thermally decomposing at a temperature of about 400 ° C. or more for 5 minutes or more. Further, the organic acid metal salt solution is sprayed on a glass plate heated to 40 ° C. or higher,
A method of heating to 400 ° C. or higher is also possible.

The film thickness of the metal oxide thin film of the present invention can be easily adjusted by changing the concentration of the organic acid metal salt, but it is also possible to use a method in which coating, drying and thermal decomposition are performed a plurality of times. . Furthermore, although not limited to these,
Zr, Al, Co, Mn, and C for the purpose of coloring the metal oxide thin film, improving the hardness of the thin film, and improving the ultraviolet shielding performance.
It is also possible to disperse and use organic acid metal salts such as r and Ni, or ultrafine particles of these metal oxides, or to coat different metal salt solutions to form different metal oxides in layers. Further, for the purpose of improving the film quality of the metal oxide thin film or shortening the thermal decomposition time, it is possible to perform firing in an oxygen atmosphere.

[0011]

【Example】

Example 1 Ti naphthenate 5% by weight solution, Ce octylate 8% by weight
Solution, Versatic acid Zn 8% by weight solution, Naphthenic acid V
A 2 wt% solution was prepared as shown in Table 1. Quartz glass of 5 cm square and 2 mm thickness was spin-coated with the solution at 2000 rpm for 20 seconds and dried at 100 ° C. for 5 minutes.
Then, it was put in an electric furnace and pyrolyzed in air at 600 ° C. for 15 minutes. As a result, a transparent thin film having a thickness of 0.18 to 2.2 μm was obtained. As for the visible light and ultraviolet ray transmittance of the film, as shown in Table 2, an ultraviolet ray shielding effect was recognized.

Example 2 5 wt% Ti naphthenate solution and 8 wt% Ce octylate
The solution was mixed in a weight ratio of 1: 1 and diluted with xylene to a weight of 2 times, and applied in the same manner as in Example 1,
It was dried and further pyrolyzed. As a result, a 0.2 μm transparent thin film was obtained. As for the visible light and ultraviolet ray transmittance of the film, an ultraviolet ray shielding effect was confirmed as shown in Table 2.

Example 3 A solution of 8 wt% Zn versatic acid and 2 wt% naphthenic acid V solution was mixed at a weight ratio of 1: 1 and diluted with xylene to a weight of 2 times, and the same method as in Example 1 was performed. Was applied, dried, and fired and decomposed at 800 ° C. As a result, a 0.21 μm transparent thin film was obtained. As for the visible light and ultraviolet ray transmittance of the film, as shown in Table 2, an ultraviolet ray shielding effect was recognized.

Example 4 A 5% by weight solution of Ti naphthenate diluted with xylene at a ratio of 2 (weight ratio) was applied in the same manner as in Example 1, dried, and calcined and pyrolyzed to a glass plate. A 2% (weight ratio) solution of the weight% solution was diluted with xylene, applied and dried in the same manner as in Example 1, and then pyrolyzed to give a 0.5 μm thin film. As for the visible light and ultraviolet ray transmittance of the film, as shown in Table 2, an ultraviolet ray shielding effect was recognized.

COMPARATIVE EXAMPLE 1 A 12% by weight solution of Zr octylate was diluted with xylene by a factor of 2 (weight ratio), applied in the same manner as in Example 1, dried, and pyrolyzed to give 0.2 μm of transparent material. A thin film was obtained. As for the visible light and ultraviolet ray transmittance of the film, as shown in Table 2, no ultraviolet ray shielding effect was observed.

Comparative Example 2 A 6 wt% Co naphthenate solution diluted with xylene to 2 times (weight ratio) was applied by the same method as in Example 1, dried, and pyrolyzed to give a darkness of 0.2 μm. A colored film was obtained. Regarding the transmittance of visible light and ultraviolet rays of the film, as shown in Table 2, the effect of blocking ultraviolet rays was recognized, but the transmittance of visible light was inferior.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

Industrial Applicability Since the organic acid metal salt is chemically stable, its organic solvent solution is easy to handle. As a result, it has become possible to economically form a single metal oxide thin film or a composite oxide thin film of dissimilar metals excellent in ultraviolet light shielding property on the glass surface regardless of the size of the area.

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Claims (1)

[Claims] 1. A glass plate is coated with an organic acid metal salt solution of a metal selected from Ti, Zn, Ce, Fe and V, or a mixture of two or more of them is applied to a glass plate and then thermally decomposed. A method for producing an ultraviolet shielding glass, which comprises forming a transparent metal oxide thin film on the surface of a glass plate.