JPH0873242A - Heat ray reflecting glass - Google Patents

Abstract

PURPOSE: To obtain a heat ray reflecting glass having high visible light transmissivity, low heat ray transmissivity and low radio wave reflectance and excellent in durability. CONSTITUTION: A coating film made essentially of Sn oxide or a coating film consisting essentially of a mixture of Sn oxide with Sb oxide is formed as, a 1st coating film 2 on a glass substrate 1 and a coating film consisting essentially of Ti oxide is formed as a 2nd coating film 3 on the 1st, coating film 2 to obtain the objective heat ray reflecting glass.

Description

Detailed Description of the Invention

[0001]

[Field of Industrial Application] The present invention is for building or automobile.
The present invention relates to a heat ray reflective glass for vehicles.

[0002]

2. Description of the Related Art In recent years, heat ray absorbing glass and heat ray reflecting glass have been widely used for buildings, automobiles, vehicles, etc. for the purpose of reducing the cooling load or reducing the heat sensation of sunlight. Here, the heat ray absorbing glass is a glass having a normal soda lime composition containing coloring components such as iron oxide, cobalt oxide, and selenium, and absorbs visible light and near infrared rays to build solar radiation energy. It suppresses the inflow to the inside of a thing or an automobile / vehicle. Further, the heat ray reflective glass is usually an oxide having a high optical refractive index on the surface of a glass plate, for example, a thin film of an oxide of iron, cobalt, chromium, titanium or the like is formed, and the surface reflectance is measured by using the optical interference effect. By reflecting high solar energy, it suppresses the inflow of solar radiant energy into buildings or automobiles / vehicles. Further, with the recent development of thin film forming technology by the sputtering method, heat ray reflective glass utilizing reflection / absorption of metal thin films of titanium, nickel, stainless steel, etc. or nitride thin films thereof has been widely used.

By the way, the solar radiant energy generally consists of about 4% of ultraviolet rays, about 50% of visible rays, and about 46% of near-infrared rays in energy composition. Therefore, the heat ray absorbing glass or the heat ray reflecting glass formed by forming an oxide thin film of iron, cobalt, chromium, etc. on the glass shields the solar radiation energy mainly by absorbing or reflecting in the visible light region. Considering this, the effect of these glasses to block solar radiation energy was limited in terms of visible light transmittance. That is, in the case of construction, there is a problem that the higher the solar energy blocking effect is, the darker the interior becomes and the comfort is impaired. Therefore, from the viewpoint of energy economy, there is a problem that lighting energy in the building is increased. was there. Further, it was clear that even for automobiles and vehicles, if the visible light transmittance is low, the product characteristics are significantly impaired in terms of see-through safety.

Therefore, a heat ray reflective glass having a high visible light transmittance is desired. As such a heat ray reflective glass having a high visible light transmittance, a glass to which a film of titanium oxide alone is attached has been used for a long time. Alternatively,
A laminate in which one or both surfaces of a gold / silver metal thin film layer proposed in Japanese Patent Publication No. 59-44993 is covered with a transparent high refractive index layer, for example, TiO ₂ / Ag / TiO ₂ , Bi ₂ O ₃ / Au /
A tin oxide thin film in which Bi ₂ O ₃ , ZnS / Ag / ZnS, or the like is further added with fluorine or antimony has been proposed.

[0005]

However, in recent years, when heat-reflecting glass having a high visible light reflectance is used for building construction, etc., the reflected light is reflected on surrounding buildings and houses due to glare due to the reflection of sunlight. Harm has become a problem.

Further, when the surface resistance value of the heat ray reflective glass is low, the radio wave reflectivity is high. Therefore, when such glass is used for building construction, the radio wave entering the room or the radio wave emitted from the indoor communication device is shielded. , For example, TV in the surrounding house
Problems such as causing a ghost phenomenon of an image have appeared (in order to avoid this ghost phenomenon, it is generally desirable that the surface resistance value is 10 ⁴ Ω / square or more).

From these viewpoints, in the case of the heat ray reflective glass using the above-mentioned titanium oxide film, since titanium oxide is an insulator, there is no problem of radio wave reflection, but to some extent it has a heat ray reflection function. When a titanium oxide film having a thickness of 1 is formed on glass, the refractive index of titanium oxide is high, and the visible light reflectance is high, which causes reflected light damage.

Also, in the laminated body using the metal thin film of gold or silver, not only the problem that the visible light reflectance is high and the reflected light damage is caused, but also heat, light, moisture, gas, etc. Since various elements cause deterioration of the laminated body, there is a problem in film durability that performance and life remain uncertain not only when using a single plate but also when using as a laminated glass or multi-layer glass.

[0009] In the past, Japanese Patent Publication Nos. 40-28772 and 40-28673 describe radiation-reflecting glass using a film made of an oxide of Sn-Sb. However, this tin oxide thin film to which Sb is added is generally used as a transparent conductive film and is not used as a heat ray reflective glass, and its surface resistance value is low, so that the above problems cannot be solved.

In view of the above circumstances, it is an object of the present invention to provide a heat ray reflective glass having high durability and low visible light reflectivity as well as high visible light transmittance.

[0011]

The heat ray reflective glass according to the present invention is the heat ray reflective glass in which a first layer coating and a second layer coating are formed on a glass substrate in this order from the glass substrate side. The coating is a coating consisting essentially of Sn oxide or a coating consisting essentially of a mixture of Sn oxide and Sb oxide, and the second layer coating is a coating consisting essentially of Ti oxide. It is a heat ray reflective glass characterized by being present.

Here, the film thickness of the first layer coating is 10 to
The thickness is preferably 100 nm, more preferably 20 to 50 nm, and similarly, the film thickness of the second layer coating is preferably 10 to 100 nm, and further 20 to 20 nm.
It is preferably 50 nm.

The first layer coating and the second layer coating can be formed by a sputtering method, a vacuum vapor deposition method, a coating method, or the like, but a chemical vapor deposition method (CVD
Method) or a spray method such as a solution spray method, a dispersion spray method or a powder spray method is preferable from the viewpoint of productivity and film durability.

Among the above-mentioned methods, in the solution spray method, a first layer forming solution containing Sn or a compound of Sn and Sb and a second layer forming solution containing a compound of Ti are sprayed on a high temperature glass substrate. In the dispersion spray method or the powder spray method, the first layer forming dispersion liquid in which fine particles of Sn or a compound of Sn and Sb are dispersed in a solution or a solvent and fine particles of Ti compound are used in place of the above respective solutions. A second layer-forming dispersion liquid in which is dispersed in a solution or a solvent, or a first layer containing Sn or a compound of Sn and Sb.
The layer forming powder and the second layer forming powder containing the compound of Ti may be used respectively. As these spraying methods, a liquid in which each component is mixed in advance may be sprayed as fine droplets / powder, or each component may be separately sprayed / reacted as droplets / powder simultaneously. Further, in the chemical vapor deposition method, vapor for forming each layer containing the above compound may be used.

Raw materials that can be used for such a so-called thermal decomposition method are exemplified below. Examples of the Sn raw material include tin tetrachloride, dibutyltin dichloride, tetrabutyltin, dioctyltin dichloride, tetraoctyltin, dibutyltin oxide, dibutyltin dilaurate, monobutyltin trichloride, dibutyltin diacetate, dioctyltin diacetate, dioctyltin dilaurate, Monobutyltin fatty acid salt, dimethyltin dichloride, tetramethyltin, monobutyltin triacetate, monobutyltin tripropionate, monobutyltin triisopropoxide, dibutyltin dimethoxide, dioctyltin oxide, tetrabutoxytin, etc. Antimony chloride, antimony pentachloride, triphenylantimony, antimony methoxide, antimony ethoxide, antimony butoxide, antimony acetate, ammonium oxychloride Mon, antimony fatty acid salts, and the like triphenyl antimony fatty acid salts. The Sb raw material may be a combination of solvents containing Sb ₂ O ₅ and HCl. As the Ti raw material, titanium tetrachloride, titanium tetraethoxide, acetylacetone titanyl, titanium sulphate,
Titanium sulfate, titanium tetrabutoxide, titanium isopropoxide, titanium methoxide, titanium diisopropoxy bis octylene glycol oxide, titanium dinormal propoxy bis octylene glycol oxide, titanium diisopropoxy monooctylene glycol oxy acetonate , Titanium dinormal butoxymonooctylene glycoloxyacetylacetonate, titanium tetraoctyleneglycoxide, titanium dinormalpropoxybisacetylacetonate, and the like.

In the present invention, cobalt, iron, manganese, nickel, chromium, titanium, vanadium, bismuth, copper, zirconium, zinc, in order to adjust the color tone, optical properties or coating durability of the heat ray reflective glass obtained,
A metal salt such as aluminum, silicon or indium, or a halogen element such as fluorine, chlorine or bromine may be contained in the coating film as long as the object of the present invention is not impaired.

As a glass substrate for forming the above oxide film, ordinary soda lime glass is generally used, and it is easy to obtain a high visible light transmittance. However, soda lime colored in gray, bronze, blue, green or the like is used. By using glass, it is possible to obtain heat ray reflective glass having various transmitted colors and visible light transmittance and having excellent heat ray shielding properties.

[0018]

In the heat ray reflective glass according to the present invention, the near-infrared absorbing performance is mainly exerted by the first layer coating, and the second layer coating has the function of improving the durability and adjusting the appearance color tone.

In the present invention, when the film thickness of the first layer coating is too thick, the surface resistance value becomes low and the radio wave reflectivity becomes high, and when the film thickness of the second layer coating is too thick, the visible light reflectance is high. Is too high, the film thickness of each layer is preferably within a certain range as described above.

[0020]

EXAMPLES Specific examples will be described below. A schematic sectional view of the glass obtained in the examples is shown in FIG.

[Example 1] Size 100 x 100 mm
A soda lime glass having a thickness of 4 mm was washed and dried to obtain a substrate. A mixed gas of water vapor, oxygen gas, tin tetrachloride (anhydrous) vapor, and nitrogen gas was used for this substrate, and a mixture of Sn oxides was formed on a glass substrate heated to a predetermined temperature by a CVD method. Was formed. Then, this glass was heated to a predetermined temperature, and a Ti oxide film was formed by a CVD method using titanium tetrachloride as a raw material. The surface resistance of the obtained coating was 100 MΩ or more. Table 1 shows the optical characteristics and film thickness of the obtained glass.

[0022]

[Table 1]

[Embodiment 2] The size is 100 × 100 mm.
A soda lime glass having a thickness of 4 mm was washed and dried to obtain a substrate. For this substrate, a mixed gas of monobutyltin trichloride vapor, water vapor, oxygen gas, antimony pentachloride vapor and nitrogen gas was used, and Sn and Sb were deposited on a glass substrate heated to a predetermined temperature by the CVD method.
A film made of a mixture of oxides of Then, this glass was heated to a predetermined temperature, and a Ti oxide film was formed by a CVD method using titanium tetrachloride as a raw material. The surface resistance of the obtained coating was 100 MΩ or more. Table 1 shows the optical characteristics and film thickness of the obtained glass.

[Embodiment 3] The size is 150 × 150 mm.
A soda lime glass having a thickness of 4 mm was washed and dried to obtain a substrate. This substrate was fixed with a suspending tool and kept in an electric furnace set to a predetermined temperature for 5 minutes, then taken out and a raw material solution prepared by mixing monobutyltin trichloride, methanol, water and antimony trichloride with a commercially available spray gun. It was used to spray onto a substrate to form a coating of a mixture of oxides of Sn and Sb. Then, after heating this glass again in an electric furnace, it was taken out and sprayed with a raw material liquid in which titanium dinormal propoxybisacetylacetonate and xylene were mixed to form a film made of an oxide of Ti. The surface resistance of the obtained coating was 100 MΩ or more. Table 1 shows the optical characteristics and film thickness of the obtained glass.

[Embodiment 4] The size is 150 × 150 mm.
A soda lime glass having a thickness of 4 mm was washed and dried to obtain a substrate. This substrate was fixed with a suspending tool, held in an electric furnace set to a predetermined temperature for 5 minutes, then taken out and a raw material solution containing dioctyltin diacetate, toluene, xylene, and triphenylantimony was mixed with a commercially available spray gun. It was used to spray onto a substrate to form a coating of a mixture of oxides of Sn and Sb. Then, after heating this glass again in an electric furnace, it was taken out and sprayed with a raw material liquid in which titanium dinormal propoxybisacetylacetonate and xylene were mixed to form a film made of an oxide of Ti. The surface resistance of the obtained coating is 100M
It was more than Ω. Table 1 shows the optical characteristics and film thickness of the obtained glass.

[Embodiment 5] The size is 150 × 150 mm.
A soda lime glass having a thickness of 4 mm was washed and dried to obtain a substrate. This substrate was fixed with a suspending tool, kept in an electric furnace set to a predetermined temperature for 5 minutes, and then taken out and a raw material solution containing dioctyltin diacetate, toluene, xylene and antimony butoxide was mixed using a commercially available spray gun. And sprayed onto the substrate to form a film made of a mixture of oxides of Sn and Sb. Then, after heating this glass again in an electric furnace, it was taken out and sprayed with a raw material liquid in which titanium dinormal propoxybisacetylacetonate and xylene were mixed to form a film made of an oxide of Ti. The surface resistance of the obtained coating is 100 MΩ
That was all. Table 1 shows the optical characteristics and film thickness of the obtained glass.

As shown in Table 1, the heat ray reflective glass according to this example has a visible light transmittance of 65% or more and a visible light reflectance of 30% or less. Here, the visible light reflectance is a measured value on the film formation side.

Comparative Example Soda lime glass having a size of 150 × 150 mm and a thickness of 4 mm was washed and dried to obtain a substrate. This substrate was fixed with a suspending tool, held in an electric furnace set to a predetermined temperature for 5 minutes, taken out, and a raw material solution obtained by mixing titanium dinormal propoxybisacetylacetonate and xylene was used with a commercially available spray gun. The film was sprayed on the substrate to form a film made of an oxide of Ti. The surface resistance value of the obtained coating was 1000 MΩ or more. Table 1 shows the optical characteristics and film thickness of the obtained glass.

[0029]

According to the present invention, a heat ray reflective glass having a high visible light transmittance, a low visible light reflectance, a low radio wave low reflection performance and a high durability can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a heat ray reflective glass according to the present invention.

[Explanation of symbols]

 1: Glass, 2: First layer coating, 3: Second layer coating

Claims (2)

[Claims] 1. A heat ray reflective glass having a first layer coating and a second layer coating formed on a glass substrate in this order from the glass substrate side, wherein the first layer coating essentially consists of an oxide of Sn or A heat-reflecting glass, which is a film consisting essentially of a mixture of an oxide of Sn and an oxide of Sb, wherein the second layer film is a film consisting essentially of an oxide of Ti. 2. The heat ray reflective glass according to claim 1, wherein both the first layer coating and the second layer coating have a thickness of 10 to 100 nm.