JP3234264B2 - Heat-resistant transparent yellow film and composition for forming the film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to the surface of transparent glass equipment as a coating for preventing deterioration due to ultraviolet rays, or as a transparent colored film for halogen lamps or alarm lamps for lighting vehicles and ships. The present invention relates to a highly heat-resistant transparent yellow film, and further to a composition for forming the film.

[0002]

2. Description of the Related Art As a method of forming a colored film, there are conventionally known an electrostatic coating method, a sputtering method, a CVD method, a coating liquid coating method and the like. Have their own problems. In the electrostatic coating method, it is difficult to control to optimize the particle size of the coating material, and the particles are easily aggregated, so that light scattering is likely to occur and transparency is poor.
In addition, the sputtering method and the CVD method require expensive equipment and have poor productivity. On the other hand, the coating method has good productivity, can easily form a uniform film, and can easily control the composition. However, the conventionally known yellow film-forming composition has a problem of poor heat resistance. For example, conventionally, cerium-containing titanium oxide (JP-A-61-34185, JP-A-63-103083), cobalt, chromium, zirconium, tin and the like are optionally contained in a system of iron oxide and titanium oxide. (JP-A-54-
No. 101821), those in which 0.1 μm or less of zinc oxide or the like is dispersed in a solvent or a binder (Japanese Patent Application Laid-Open Nos.
No. 6) is known, but these films have poor heat resistance at high temperatures of about 500 ° C. The present inventor, various materials for heat-resistant glass used in a high-temperature environment, for surface coating for the purpose of blocking or coloring ultraviolet rays, for example,
Pb-Zr-Cr-O, Zr-Si-Pr-O, Ti-Sb-Ni-Nb-O, Ti-Fe-Zn-O
And so on. However, each of them has a small extinction coefficient and is not effective as a colored thin film, or has a disadvantage that it deteriorates immediately in a high-temperature environment, and is insufficient as a heat-resistant colored film.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly heat-resistant transparent yellow film which solves the above-mentioned problems and a composition for forming the film. The present inventor has continued to study a high heat-resistant yellow transparent film and a composition for forming the film, and as a result, the silicon-vanadium-based oxide forms a yellow-based transparent film having more excellent heat resistance than the conventional film. I found something to do.

[0004]

According to the present invention: A solution means the configuration of the invention], in the silica, uniformly dispersed heat resistance yellow transparent in the range of 1.5 to 3.5 with a fine vanadium pentoxide SiO ₂ / V ₂ O ₅ weight ratio A membrane is provided. Furthermore, according to the present invention, a composition for forming a yellow film in which vanadium pentoxide powder having a particle size of 0.2 μm or less is uniformly dispersed in a solution of an alkyl silicate or a silica sol, and the content of the vanadium pentoxide powder is: A composition for forming a heat-resistant transparent yellow film, wherein the weight ratio of SiO ₂ / V ₂ O ₅ in the formed film is in the range of 1.5 to 3.5.

[0005] Coatings of the present invention, in the glass-like SiO _2, fine vanadium pentoxide is homogeneously dispersed in the range of a 1.5 to 3.5 at a SiO ₂ / V ₂ O ₅ weight ratio heat resistance of the transparent yellow film It is. If the weight ratio of SiO ₂ / V ₂ O ₅ is less than 1.5, vanadium pentoxide grain growth occurs in a high temperature environment and transparency is lost. In addition, heat resistance cannot be obtained. On the other hand, if the weight ratio of SiO ₂ / V ₂ O ₅ exceeds 3.5, the amount of vanadium pentoxide is relatively small, and the coloring power is undesirably reduced. Vanadium pentoxide is preferably fine particles having a particle size of 0.2 μm or less. When the particle size is larger than 0.2 μm, the transparency of the coating film is reduced. On the other hand, when the particle diameter of vanadium pentoxide is 0.2 μm or less, a wavelength of about 500 nm or less can be efficiently absorbed, and at a wavelength longer than that, a film having excellent transparency can be obtained.

The coating of the present invention can be prepared by a solution method (sol-gel method), CV
It can be formed by a usual method such as a D method or a sputtering method. As an example of the CVD method, tetraethoxyorthosilane is placed in a sealed container containing a heat-resistant transparent substrate.
(TEOS) and triethoxyvanadyl raw material gas
The coating is prepared in a weight ratio of iO ₂ / V ₂ O _{5 in} the range of 1.5 to 3.5, and the above-mentioned coating is grown on the surface of the transparent substrate by vapor phase. When the sputtering method is used, the weight ratio of SiO ₂ / V ₂ O ₅ is 1.5 to
The sputtering target described in 3.5 is prepared, and the coating can be formed on the surface of the heat-resistant transparent substrate using the sputtering target.
The composition used in the solution method is a composition in which vanadium pentoxide powder having a particle size of 0.2 μm or less is uniformly dispersed in a solution of an alkyl silicate or a silica sol, and the content of the vanadium pentoxide powder is formed. SiO ₂ /
A composition for forming a heat-resistant transparent yellow film, wherein the weight ratio of V ₂ O ₅ is 1.5 to 3.5, is preferably used.

[0007] As a silicon dioxide source of the composition solution used in the solution method, an alkyl silicate or a silica sol is used for the purpose of use in a high temperature environment. The alkyl silicate can be arbitrarily selected. In particular,
For example, tetraethoxyorthosilane (TEOS), tetramethylorthosilane (TMOS), tetrapropylorthosilane
(TPOS), tetrabutylorthosilane (TBOS), methylethoxysilane (MTES), dimethyldiethoxysilane, or a simple substance or a mixture thereof is used. When an alkyl silicate is used, for example, the alkyl silicate is dissolved in a solvent such as an alcohol and then partially hydrolyzed by adding dilute hydrochloric acid, and the concentration of the solid (SiO ₂ ) formed is adjusted with an alcohol or the like so as to have an appropriate concentration. It is preferable to use after adjusting.

[0008] The amount of the fine vanadium pentoxide powder mixed with the composition solution is in the range where the weight ratio of SiO ₂ / V ₂ O _{5 in} the formed film is 1.5 to 3.5. The method for uniformly dispersing the vanadium pentoxide fine powder in the composition solution is not limited. For example, a usual mixing device such as a ball mill can be used. In addition, when mixing, it is preferable to sufficiently disperse the vanadium pentoxide powder in the composition solution over a sufficient time. If the dispersion is insufficient, the vanadium pentoxide grains easily grow in a high-temperature environment of 500 ° C. or more, causing clouding and devitrification of the film in a short time, failing to obtain a heat-resistant effect. The composition solution of the present invention is applied to one or both sides of a transparent substrate such as heat-resistant glass, heated, and thermally decomposed to obtain a highly heat-resistant yellow transparent body. The thickness of the coating film, the coating method and the heating method may be performed according to a conventional method. The formed film is a transparent film having a yellow color tone, and its color tone and transparency do not change even in a high temperature environment of 500 ° C. or higher.

[0009]

The SiO ₂ / V ₂ O ₅ -based coating of the present invention is a yellow film having high heat resistance and excellent transparency. It has high heat resistance and is suitable for use at high temperatures. Further, the composition for forming a film can be easily applied to a transparent substrate such as a halogen lamp for lighting or an alarm lamp and heated to easily form a transparent yellow film having high heat resistance.

Example 1 5.00 g of tetraethoxyorthosilane (TEOS) was dissolved in isopropanol, and diluted hydrochloric acid was added for partial hydrolysis.
The concentration was adjusted with isopropanol so that the weight of the solid (SiO ₂ ) became 10% to obtain a binder solution. 10 g of this solution
0.4 g of vanadium pentoxide fine powder having a particle size of 0.05 μm or less was added therein, mixed well, and stirred with a ball mill for 100 hours to uniformly disperse the vanadium pentoxide fine powder to obtain a film-forming composition. This composition was applied to Vycor glass by a dipping method, dried by heating, and the chromaticity (x, y) of the XYZ color system =
(0.498, 0.448), Y = 85.1, a yellow colored transparent body was obtained. As shown in FIG. 1, the Y value of this colored product when kept at a high temperature of 700 ° C. did not substantially change, and the film was excellent in high temperature heat resistance without clouding or devitrification.

Example 2 After dissolving 5.00 g of tetraethoxyorthosilane (TEOS) in isopropanol and adding dilute hydrochloric acid to partially hydrolyze,
The concentration was adjusted with isopropanol so that the weight of the solid (SiO ₂ ) became 10% to obtain a composition solution. 10 g of this solution
0.5 g of vanadium pentoxide fine powder having a particle size of 0.05 μm or less was added therein, mixed well, and stirred for 100 hours with a ball mill to uniformly disperse the vanadium pentoxide fine powder to obtain a film-forming composition. This composition was applied to Vycor glass by a dipping method, dried by heating, and the chromaticity (x, y) of the XYZ color system =
(0.504, 0.449), Y = 84.8, a yellow colored transparent body was obtained. The heat resistance when this colored body was held at a high temperature of 700 ° C. was the same as in Example 1.

Comparative Example 1 A film-forming composition was prepared in the same manner as in Example 1. However, the uniform dispersion time by a ball mill was only 10 minutes. This composition was applied to Vycor glass in the same manner as in Example 1, and the chromaticity (x, y) of the XYZ color system was (0.496,
0.4538), Y = 79.4 to obtain a yellow colored transparent body. FIG. 2 shows a change in Y value when the colored body is held at a high temperature of 700 ° C. As shown in the figure, the colored body of this example has a film turbidity in a short time,
Devitrification occurred and heat resistance was poor. This is considered to be because the dispersibility of vanadium pentoxide was lower than that in Example 1 and grain growth easily occurred.

[Brief description of the drawings]

FIG. 1 is a graph showing a change over time of a Y value when the colored body of the present invention obtained in Example 1 is maintained at 700 ° C.

FIG. 2 is a diagram showing a change over time of a Y value when the colored body obtained in Comparative Example 1 is kept at 700 ° C.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Isamu Sato 2-9-13 Nakameguro, Meguro-ku, Tokyo Inside Stanley Electric Co., Ltd. (56) References JP-A-63-48358 (JP, A) JP-A-63-48358 Hei 2-265976 (JP, A) JP-A-56-78445 (JP, A) JP-A 2-157137 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 1 / 00-23/00 C01B 33/12-33/44

Claims (2)

(57) [Claims] 1. A heat-resistant yellow transparent film in which fine vanadium pentoxide is uniformly dispersed in silica in a weight ratio of 1.5 to 3.5 in a SiO ₂ / V ₂ O ₅ weight ratio. 2. A composition for forming a yellow film in which a vanadium pentoxide powder having a particle size of 0.2 μm or less is uniformly dispersed in a solution of an alkyl silicate or silica sol, wherein the content of the vanadium pentoxide powder is formed. SiO ₂ / V _{2 in} the film
A composition for forming a heat-resistant transparent yellow film, wherein the weight ratio of O ₅ is in the range of 1.5 to 3.5.