JPH03279211A - Yellow transparent film-forming composition and transparent glass having yellow transparent film - Google Patents

Abstract

PURPOSE:To obtain an organic composition, capable of forming a yellow transparent colored film excellent in heat resistance on the surface of transparent glass used in high-temperature environment by mixing respective organometallic compounds of Zr Pr and Si with an organic solvent at a specific molar ratio, applying the resultant mixture to a substrate and thermally decomposing the applied mixture. CONSTITUTION:Respective organometallic compounds of Zr, Pr and Si (metal alkoxides are preferably used) are mixed with an organic solvent so as to provide (0.8-1):(0-0.2):1 molar ratio of the Zr, Pr and Si in the mixture solution. The resultant solution is then applied to a substrate and thermally decomposed to afford a composition capable of forming a yellow transparent film having the composition expressed by the formula (0<x<0.2). The above-mentioned composition is capable of forming a yellow transparent colored film excellent in heat resistance on the surface of transparent glass used in high-temperature environment or transparent glass used as illuminating lamps or alarm lamps, etc., of vehicles, ships, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides heat-resistant coatings on the surface of transparent glass used in high-temperature environments and for lighting lamps or warning lamps for vehicles, ships, etc. The present invention relates to an organic composition that forms a yellowish transparent colored film with excellent properties, and also relates to a heat-resistant yellowish colored transparent glass provided with a film made of the composition.

[Conventional technology and its issues]

Generally, methods for forming a colored film include electrostatic coating method,
Sputtering methods, vapor deposition methods or coating liquid coating methods are conventionally known. However, when producing a heat-resistant transparent yellow coating, there are the following problems. In the electrostatic coating method, it is difficult to control the particle size, and since the film formed is an aggregate of particles, light scattering tends to occur and transparency is poor. Furthermore, sputtering and vapor deposition require expensive equipment, low productivity, and compositional fluctuations. On the other hand, the coating method has the advantage of high productivity, the ability to easily form a homogeneous film, and the ease of controlling the composition, but the conventionally known yellowish film compositions have the problem of poor heat resistance. There is. For example, JP-A-61
No. 34185 and No. 63-103083 disclose a method of forming a cerium-containing titanium oxide film using a liquid mixture of a titanium organic compound such as titanium alkoxide and a cerium compound, but this method is generally known. As mentioned above, titanium dioxide is partially reduced at high temperatures and generates oxygen defects, which causes a change in light absorption characteristics and a disadvantage of impairing the yellow color. Similarly, 1 in JP-A-54-101821
A metal oxide coating is disclosed that is mainly composed of iron oxide and titanium oxide, and optionally contains cobalt, chromium, zirconium, and tin oxides.
It has poor heat resistance at high temperatures around 00°C.

[Means for solving the problem: Structure of the invention]

The present inventor attempted to improve the coating method and achieved superior heat resistance by replacing the conventional coating composition, which was mainly composed of titanium oxide, with a composition of a ternary compound of zirconium, silicon, and praseodymium. It has been found that a yellowish transparent film can be formed.

According to the present invention, metal organic compounds of zirconium, silicon, and praseodymium are mixed in an organic solvent, and the molar ratio of zirconium, silicon, and praseodymium in the mixed solution is 0.8 to 1:0 to 0.2: 1, which is coated on a substrate and thermally decomposed to form Zr(1-X)PrxS
A composition that forms a yellowish transparent film having a composition of i04 (0<x<0.2) is provided.

Further, according to the present invention, there is provided a heat-resistant colored transparent glass body having a coating made of the above composition.

Metal alkoxides can be suitably used as the metal organic compounds of zirconium, silicon, and praseodymium. Specifically, tetramethoxyzirconium,
Examples include tetraethoxyzirconium, tetrapropoxyzirconium, tetramethoxysilicon, tetraethoxysilicon, tetrapropoxysilicon, trimethoxypraseodymium, triethoxypraseodymium, tripropoxypraseodymium, and the like. In addition, carboxylic acid salts, β-diketone complexes, and the like are used as other metal organic compounds. Note that the above compounds are just examples, and the invention is not limited thereto.

As the organic solvent for dissolving the metal organic compound, general organic solvents such as alcohols, ketonic acids, and β-diketones can be used.

The film-forming composition of the present invention can be applied to a film-forming substrate and thermally decomposed to produce Zr(1-X)Pr.
, SiO4 (0<x<0.2), the molar ratio of zirconium, silicon, and praseodymium is 0.8 to 0.8 to
The metal organic compound is mixed with an organic solvent in a ratio of l:0 to 0.2:1. The mixing method is not limited.

A solution of the above composition was applied to a transparent glass surface and heated to 200°C.
By heating to ~700°C, Zr(1-X)Pr
A yellowish transparent film having a composition of xSiO* (0<x<0.2) is formed. The thickness of the coating film, the coating method, and the heating method are not limited.

The formed film is a transparent film with a yellow color tone, and the color tone and transparency do not change even at high temperatures of around 500°C.

〔Effect of the invention〕

According to the film-forming composition of the present invention, a yellowish transparent film with excellent heat resistance can be obtained. Therefore, the film-forming composition of the present invention can be suitably used when forming a yellowish transparent film on transparent glass used in a high-temperature environment. It is also suitable for producing yellow-colored lighting lamps and warning lamps for vehicles, ships, etc.

Further, the film-forming composition of the present invention has the advantage that the film can be easily formed by simply applying it to a substrate and heating it.

〔Example〕

Example 1 19.61 g of tetrabutoxyzirconium, 0.86 g of triisopropoxy praseodymium, and 11.21 g of tetraethoxy silicon were added to 68.32 g of a solution containing equal amounts of 2-methoxyethanol and toluene, and 2
The reaction was carried out for a period of time to obtain a coating solution with a concentration of 10% in terms of oxide.

This coating liquid was applied dropwise onto the surface of a transparent glass substrate using a spin coater, and after being spun at 2000 rpm for 15 seconds to coat it evenly, it was placed in an electric furnace and kept at a temperature of 150°C for 15 minutes to dry. This was further baked at 500° C. for 30 minutes to obtain a yellow transparent film. This yellow transparent film obtained a deeper yellow color as the number of coatings increased.

Next, the transparent glass substrate with the yellow transparent film formed by repeating coating and firing 10 times was placed in the electric furnace again, and the temperature was raised from room temperature to 600°C over 1 hour, and then heated at 600°C for 1 hour. After holding the film for an extended period of time, we conducted a heat cycle test of 5 to 50 times to bring it back to room temperature over a period of 3 hours, and examined changes in the state and color of the film.We found that the transparency and yellow color of the film did not change, and no cracks occurred. There wasn't.

Examples 2 to 9 The same procedure as in Example 1 was carried out, except that zirconium, praseodymium, and silicon were prepared using the raw materials shown in the vestments, and mixed with a solvent at the molar ratio shown in the same table to prepare a coating solution of 10% in terms of oxide. A transparent glass substrate with a yellow transparent film was manufactured using a similar method, and a similar heat cycle test was conducted to examine the state of the film and changes in color. As a result, the transparency and yellow color of the film did not change and there were no cracks in any of the samples. It did not occur.

Comparative Example A transparent glass substrate with a yellow film was produced in the same manner as in Example 1 except that a conventional coating solution consisting of a mixed solution of cerium chloride and titanium alkoxide was used, and the same heat cycle test was conducted. The film became slightly cloudy at the 30th and 40th time, and as it was repeated 30 and 40 times, the cloudiness increased.
At the 50th time, in addition to cloudiness, a blackish tinge appeared.

table

Claims (3)

[Claims] (1) Each metal organic compound of zirconium, praseodymium, and silicon is mixed in an organic solvent, and the molar ratio of zirconium, praseodymium, and silicon in the mixed solution is 0.8 to
1:0 to 0.2:1, and by applying it to the substrate and thermally decomposing it, Zr_(_1_-_X_)Pr_xSiO_4(0<x
<0.2) A composition that forms a yellowish transparent film. (2) The composition according to claim 1, wherein the metal organic compound is a metal alkoxide. (3) A heat-resistant transparent glass body having a coating made of the composition of claim 1.