JPH05213630A - Heat ray reflecting glass - Google Patents

Abstract

PURPOSE:To provide low-cost heat ray reflecting glass having high electric resistance and low solar radiation transmissivity. CONSTITUTION:Glass is held at 650 deg.C and then sprayed with a stock soln. prepd. by dissolving acetylacetonatocobalt (III), dipropionylmethane of nickel (II) and acetylacetonatoiron (III). The resulting film is made of a spinel type oxide contg. cobalt, iron and nickel and has >=10<4>OMEGA.cm<2> surface resistivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-reflecting glass for buildings or automobiles and vehicles.

[0002]

2. Description of the Related Art In recent years, heat-reflecting glass having a low luminous transmittance has been used for window glass for buildings or automobiles / vehicles for the purpose of reducing the cooling load or reducing the heat sensation caused by direct sunlight. There is. Such a heat ray reflective glass having a low luminous transmittance has a high utility value from the viewpoint of protecting privacy. As a heat ray reflective glass that meets these requirements, a spinel type oxide film of cobalt containing a transition metal such as Cr or Fe and having strong absorption in the visible light region is formed on a normal soda lime glass. Was known.

By the way, when a heat ray reflective glass having a small luminous transmittance is used as a window glass for an automobile, it is necessary to block solar radiation energy while maintaining a certain luminous transmittance.

As a heat ray reflecting glass that meets this requirement, there is an article having a nickel cobaltite coating formed on the glass, which is described in Japanese Examined Patent Publication No. 63-32736. In this case, the nickel cobaltite coating is also used in the infrared region. By having the absorption, the solar energy-shielding effect can be enhanced without significantly lowering the luminous transmittance.

[0005]

However, Cr,
In the heat ray reflection glass in which the spinel type oxide film of cobalt containing a transition metal such as Fe and having strong absorption in the visible light region is formed on the ordinary soda lime glass, the effect of blocking solar radiation energy is There was a limit in terms of visible light transmittance. Generally, the solar radiation energy has an energy composition of about 4% of ultraviolet rays, about 50% of visible rays, and about 46% of near infrared rays.
%. Since such heat-ray reflective glass mainly shields solar radiant energy by absorbing and reflecting light rays in the visible region, the luminous transmittance becomes too small if the solar energy-shielding effect is sufficiently enhanced. There was a problem.

Further, in the case of an article in which a nickel cobaltite coating described in Japanese Patent Publication No. 63-32736 is formed on glass, the nickel cobaltite coating is described as a conductive metal oxide coating although the above problems can be solved. Since the electric resistance is low as described above, when the glass formed with such a coating is used for construction and vehicles, it reflects TV radio waves and the like, which hinders reception of radio waves and has become a particular problem in recent years. There is a problem of causing ghost failure.

As described above, as a heat ray reflective glass having a small luminous transmittance, an inexpensive glass having both a high solar energy-shielding effect (that is, a small solar radiation transmittance) and a low conductivity is required. However, such a glass has not been obtained. For example, as a means for producing such glass, it is conceivable to form a thin film having a multilayer structure composed of a metal film or a metal nitride film and a dielectric film on the glass, but the production cost of this glass is high. There's a problem.

The present invention has been made in order to solve the above problems, and an object thereof is to provide an inexpensive heat-reflecting glass having a large electric resistance and a small solar radiation transmittance.

[0009]

According to the heat ray reflective glass of claim 1, a spinel type oxide polycrystalline film in which all three elements of cobalt, iron and nickel are present is formed on the glass, and the surface resistance of the film is formed. The rate is greater than 10 ⁴ Ω / square.

The heat ray reflective glass of claim 2 is characterized in that, in the heat ray reflective glass of claim 1, the weight percentage of cobalt in the oxide film is larger than 25%.

The heat-reflecting glass according to claim 3 is characterized in that, in the heat-reflecting glass according to claim 1 or 2, the weight percentage of iron in the oxide film is in the range of 5 to 60%.

[0012]

The present invention is characterized in that a spinel type oxide containing all three elements of cobalt, iron and nickel is formed as a polycrystalline film on glass and has a surface resistivity of more than 10 ⁴ Ω / square. It is a heat ray reflective glass with low solar radiation transmittance.

In the present invention, when the surface resistivity is less than 10 ⁴ Ω / square, television radio waves are reflected, which hinders the reception of radio waves and is likely to cause a ghost failure which has become a particularly serious problem in recent years. Therefore, the surface resistivity is made larger than 10 ⁴ Ω / square.

In order for the coating film to exhibit strong absorption in the visible light region, it is necessary to form a spinel type oxide containing cobalt, but the weight percentage of cobalt in the oxide film is more than 25%. When it is small, the spinel structure is not shown and the luminous transmittance is large.

If the iron concentration in the coating is too low, the electrical resistance of the coating will be low, and as described above, it will reflect television radio waves and the like, which will interfere with the reception of radio waves and will cause ghosting. Prone to failure. On the other hand, if the iron concentration is too high, the transparent hue of the coating becomes red, impairing the high-class feeling and reducing the commercial value. Therefore, the weight percentage of iron in the coating is preferably in the range of 5 to 60%.

The method of forming the heat-reflecting film of the present invention on glass is not particularly limited, but the easiest method is to form the cobalt-iron-nickel composite oxide on the heated glass substrate by the thermal decomposition spray method. preferable. As the spraying raw material liquid, one in which cobalt, iron and nickel metal compounds are dissolved in a liquid solvent is generally used. Here, cobalt compounds include acetylacetone cobalt (both divalent and trivalent salts are acceptable), cobalt acetate, cobalt chloride, etc., iron compounds include acetylacetone iron, iron chloride, etc., and nickel compounds include acetylacetone nickel, dipropionyl. Examples include methane nickel, nickel acetate, and nickel chloride. As a solvent for dissolving these metal compounds, an organic solvent such as aromatic or ketone / alcohol is generally used. As an example, the thing which melt | dissolved nickel dipropionyl methane, trivalent cobalt acetylacetone, and trivalent acetylacetone iron in benzene is mentioned.

When such a spraying liquid is sprayed on the heated substrate in the atmosphere, a spinel type oxide film containing cobalt, iron and nickel is formed on the substrate. Ordinary soda lime glass is the most common substrate, but a colored soda lime substrate or other translucent substrate may be used. Substrate temperature during spraying is 350 ° C
It is necessary to carry out at about 800 ° C. If the temperature is 350 ° C or lower, an amorphous film is not formed and an oxide polycrystal film is not formed.
Above 0 ° C, a preferable combination of complex oxides cannot be obtained.

When producing the heat ray-reflecting glass in the present invention, the preferred content of the metal compound in the spray liquid is
It must be experimentally determined in advance according to the device used. This content has an optimum range depending on the substrate temperature at the time of spraying, the nozzle used for spraying, the gas exhaust mechanism, the film formation rate, and the like. That is, if the total amount of metal compounds in the spray liquid is too small, a sufficient film formation rate cannot be obtained, and conversely, if the total amount is too large, a good film thickness distribution cannot be obtained. By forming a spinel-type composite oxide film in which cobalt, iron, and nickel are present in appropriate amounts in the film, a heat-reflecting glass having high electrical resistance and low solar radiation transmittance can be obtained.

【Example】

Example 1 Soda-lime glass having a size of 150 mm × 150 mm and a thickness of 4 mm was washed and dried to obtain a substrate. This substrate was fixed by a suspending tool and kept in an electric furnace set at 650 ° C. for 5 minutes, then taken out and put in 200 cc of toluene, 3.56 g of trivalent cobalt acetylacetonate, and divalent nickel dichloride. 4.70 g of propionylmethane was dissolved in 1.77 g of trivalent iron acetylacetonate, and the raw material solution was put on a substrate using a commercially available spray gun for about 30 seconds, air pressure of 1.5 kg / cm ² , air. Volume 50 liters / mi
Spraying was performed at a spray rate of 120 ml / min.
The thickness of the obtained film was about 150 nm. For this sample, the luminous transmittance and the solar radiation transmittance were determined according to JIS-3106. The surface resistivity of the obtained film was 1.
It was 4 × 10 ⁶ Ω / square. These results are shown in Table 1.
Shown in. Comparative Example 1 Using the same soda lime glass as that used in Example 1 as a substrate, 3.56 g of trivalent cobalt acetylacetonate in 200 cc of toluene, and trivalent iron acetylacetonate 5 were used. .30 g, trivalent chromium acetylacetona
A film was formed in the same manner as in Example 1 by using a raw material liquid in which 1.75 g of the aluminum oxide was dissolved. The film thickness of the film thus obtained was about 150 nm. The luminous transmittance and the solar radiation transmittance of this sample were determined by the same method as in Example 1. The surface resistivity of the obtained film is the upper limit of measurement (300 × 10 ⁶ Ω
/ Square). The results are shown in Table 1.

[0019]

[Table 1]

Example 2 Soda-lime glass having a size of 150 mm × 150 mm and a thickness of 4 mm was washed and dried to obtain a substrate. This substrate was fixed by a suspending tool and kept in an electric furnace set at 650 ° C. for 5 minutes, and then taken out to 200 cc of toluene and acetylacetonate of trivalent cobalt (7.12 g) and divalent nickel divalent. A raw material solution in which 2.09 g of propionylmethane and 1.18 g of trivalent iron acetylacetonate were dissolved was placed on a substrate using a commercially available spray gun for about 30 seconds, air pressure of 1.5 kg / cm ² , air. Volume 50 liters / mi
The sample sprayed at a spray rate of 120 ml / min was used as a sample. The film obtained had a thickness of 150 nm and a surface resistivity of 90,000 Ω / square. This sample had a luminous transmittance of 11.4% and a solar radiation transmittance of 20.4%. The results are shown in Table 1. Comparative Example 2 Using the same soda lime glass as used in Example 2 as a substrate, 200 cc of toluene was added with trivalent cobalt acetylacetonate 7.12 g and divalent nickel dipropionylmethane 3.13 g. A film was formed in the same manner as in Example 2 by using the raw material liquid in which The film thus obtained had a film thickness of 150 nm and a surface resistivity of 1000 Ω / square. This sample had a luminous transmittance of 8.7% and a solar radiation transmittance of 12.4%. The results are shown in Table 1. Example 3 Soda lime glass having a size of 150 mm × 150 mm and a thickness of 4 mm was washed and dried to obtain a substrate. This substrate was fixed by a suspending tool and kept in an electric furnace set at 650 ° C. for 5 minutes, then taken out and put in 200 cc of toluene, 3.56 g of trivalent cobalt acetylacetonate and divalent nickel dichloride. A raw material solution in which 1.57 g of propionylmethane and 5.30 g of acetylacetonate of trivalent iron were dissolved was put on a substrate for about 30 seconds using a commercially available spray gun, air pressure of 1.5 kg / cm ² , air. Volume 50 liters / mi
The sample sprayed at n and a spray rate of 120 ml / min was used as a sample. The thickness of the film thus obtained is about 1
It was 50 nm. For this sample, the luminous transmittance obtained by the same method as in Example 1 is 25.1%, and the solar radiation transmittance is 37.4%. The results are shown in Table 1.
Table 2 shows the results of the weight percentages of cobalt and iron in the coatings of the samples of Examples 1 to 3 and Comparative Examples 1 and 2 determined by high-frequency plasma emission analysis. Further, when the X-ray diffraction analysis was performed on the samples of Examples 1 to 3, all showed a spinel structure.

[0021]

[Table 2]

[0022]

According to the present invention, as is apparent from the examples, the solar radiation transmittance is low, the electric resistance is high, the television radio waves are not reflected, the reception of radio waves is not disturbed, and the
It is possible to obtain a heat-reflecting glass that does not cause a strike failure.

Claims (3)

[Claims] 1. A spinel type oxide polycrystalline film in which all three elements of cobalt, iron and nickel are present on glass, and the surface resistivity of the film is larger than 10 ⁴ Ω / square. Heat ray reflective glass. 2. The heat ray reflective glass according to claim 1, wherein the weight percentage of cobalt in the oxide film is larger than 25%. 3. The heat ray reflective glass according to claim 1 or 2, wherein the weight percentage of iron in the oxide film is 5 to 60.
% Heat-reflecting glass.