JPH11228184A - Plate glass coated with heat ray shielding colored film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plate glass coated with a heat ray shielding color film capable of controlling color tone, solar ray transmission, visible ray transmission and ultraviolet ray transmission. SOLUTION: A 1st metal oxide film consisting essentially of cobalt oxide of 61-98, iron oxide of 2-26 and chromium oxide of 0-37 by wt.% and having 10-70 nm film thickness is coated on the surface of a glass substrate and a 2nd metal oxide film containing a metal fine particle of 5-30, silicon oxide of 5-40, titanium oxide of 10-62 and cerium oxide of 10-50 by wt.% and having 40-150 nm film thickness is coated on the 1st metal oxide film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass sheet coated with a heat ray-shielding colored film, and more particularly to a glass sheet coated with a colored metal oxide film having heat ray-shielding performance and suitable for use in vehicles such as automobiles and windows for construction. Related to a glass plate.

[0002]

2. Description of the Related Art A method for coating a glass plate surface with a metal oxide thin film having a function such as color tone control is widely used. Among the thin film coating methods, there are a thermal decomposition method and a chemical vapor deposition method (CVD). Then, for example, by applying a pyrolysis method or a chemical vapor deposition method to a high-temperature glass plate formed into a plate shape and progressing in a band shape by a float method, a metal oxide thin film-coated glass plate can be continuously manufactured. Are known.

Japanese Patent Application Laid-Open No. 54-31417 discloses Fe-C
A glass with an r-Co-based oxide film is disclosed. Such a metal oxide thin film is colored mainly by utilizing the absorption of electrons of the metal oxide or the composite metal oxide by the band gap. For this reason, since the width of the absorption wavelength is relatively wide, a glass with a colored film having a low saturation and a dull color can be obtained.

On the other hand, a method of coloring using a fine particle-dispersed oxide thin film is also widely known. JP-A-7-53239
Discloses a glass with an oxide colored film containing fine metal particles such as fine gold particles. Such a fine particle-dispersed oxide thin film mainly utilizes absorption by surface plasmons, so that a glass plate with a colored film having a relatively narrow absorption wavelength and thus a high saturation and a vivid color can be obtained. Since the absorption wavelength of this film changes by changing the refractive index value of the metal oxide matrix, the hue of the transmitted light can be adjusted.

The former Fe—Cr—Co-based oxide film has coloring performance, heat ray shielding performance and ultraviolet absorption performance, but has a high visible light reflectance and a glaring appearance, and has a transmitted light hue of yellow to yellow. Limited to brown. In addition, the latter fine-particle-dispersed oxide colored film-coated glass article, the color tone of the transmitted light is limited to the hue by the absorption wavelength of the fine gold particles,
Further, the ultraviolet transmittance and the visible light transmittance cannot be freely controlled.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a transmitted light color tone,
Solar light transmittance (also called solar transmittance) and visible light transmittance (also called luminous transmittance) can be controlled,
It is another object of the present invention to provide a heat-shielding colored film-coated glass article having low ultraviolet transmittance and low visible light reflectance.

[0007]

According to the present invention, cobalt oxide: 61 to 98, iron oxide: 2 to 26, and chromium oxide: 0 to 37 are expressed in terms of% by weight on the surface of a glass substrate. A first metal oxide film having a film thickness of 10 to 70 nm, which is contained as a component, is coated, and on the first metal oxide film, expressed as% by weight, gold fine particles: 5 to 30, oxidation A heat-shielding colored film-coated glass plate containing silicon: 5 to 40, titanium oxide: 10 to 62, and cerium oxide: 10 to 50, and coated with a second metal oxide film having a thickness of 40 to 150 nm. is there.

[0008] The first metal oxide film (hereinafter sometimes simply referred to as a first film) in the present invention will be described. In the composition of the first film, the cobalt oxide reduces visible light transmittance, and is an essential component for brown coloring.If the content is too small, the visible light transmittance decreases and the brown color decreases. Since the effect of coloring cannot be obtained, and conversely, if it is too much, fogging tends to occur, which is inconvenient,
The cobalt oxide content is 61 to 61 in terms of Co ₃ O _4.
98% by weight.

Iron oxide is also an essential component for orange coloring. If its content is too small, the effect of orange coloring cannot be obtained. Since the light absorption efficiency of iron oxide is lower than that of cobalt oxide, if the amount of iron oxide is too large, the content of cobalt oxide relatively decreases, so that the visible light transmittance cannot be sufficiently reduced. Therefore, the iron oxide content is ₂ to 26% by weight in terms of Fe ₂ O _3.
It is. Chromium oxide is not an essential component, but can be included because it can be colored green. But because the content is disadvantageous becomes insufficient when film formability it is too large, the chromium oxide content, Cr ₂
In terms of O _3, it is 0 to 37 wt%.

One of the embodiments of the composition of the first metal oxide film is expressed in terms of weight% in terms of the above, cobalt oxide: 70 to 98, iron oxide: 3 to 26, chromium oxide: 0 ~ 14 (however, the iron oxide content is larger than the chromium oxide content) as a main component.

Further, in another embodiment of the composition of the first metal oxide film, expressed in terms of% by weight in terms of the above, cobalt oxide: 61 to 80, iron oxide: 2 to 19, chromium oxide: 14 To 35 (however, the chromium oxide content is larger than the iron oxide content).

In addition to cobalt oxide, iron oxide, and chromium oxide, which are the main components of the first film, copper oxide, manganese oxide, nickel oxide, and the like may be used as a color tone adjusting component if necessary. , MnO _{2, and} NiO can be added in a total amount of 5% by weight or less.

If the thickness of the first film is too small, the required coloring cannot be obtained. On the other hand, if the thickness is too large, the film is liable to be cracked and the substrate glass is liable to be deformed during firing, such as warpage. The thickness is 10 to 70 nm. 2
More preferably, the thickness is from 0 to 60 nm. The refractive index of the first film usually has a value of 2.0 to 2.9. The value of the refractive index depends on the firing temperature, and the higher the firing temperature, the higher the refractive index.

The first film can be formed by a method such as a thermal decomposition method, a sol-gel method, a chemical vapor deposition method, a sputter deposition method, and a vacuum deposition method. Among them, for example, the glass sheet is continuously formed by a float plate manufacturing method and is continuously cooled by a thermal decomposition method by spraying or a chemical vapor deposition method (CVD) on a surface of a high-temperature band-shaped glass sheet before being gradually cooled. Is preferably used.

The raw material of the first film in the case of the sol-gel method, the vapor deposition method and the thermal decomposition method will be described. As a raw material of cobalt oxide, a cobalt organic compound such as cobalt (dipropionylmethane complex), cobalt oxide alkoxide, cobalt acetylacetonate, and cobalt carboxylate can be suitably used. Other,
Cerium inorganic compounds such as nitrates, chlorides and sulfates can also be used, but cobalt chlorides and nitrates are preferred from the viewpoint of stability and availability.

As a raw material of iron oxide, iron organic compounds such as iron acetylacetonate, iron carboxylate, iron acetate and iron diethanolamine complex can be suitably used. In addition, iron inorganic compounds such as nitrates, chlorides and sulfates can also be used.

As a raw material of chromium oxide, chromium organic compounds such as chromium alkoxide, chromium acetylacetonate, and chromium carboxylate can be suitably used. In addition, chromium inorganic compounds such as nitrates, chlorides and sulfates can also be used.
Chromium chlorides and nitrates, and chromium acetylacetonate are preferred because of their availability.

For example, when the first film is coated by the thermal decomposition method in the above-mentioned float method, cobalt (dipropionylmethane complex), iron acetylacetonate and, if necessary, chromium acetylacetonate can be coated with, for example, toluene. The solvent has a solid content of 3 to 30% by weight,
By spraying the dissolved solution on a glass plate surface at, for example, 500 to 700 ° C., cobalt oxide, iron oxide,
And a first film containing chromium oxide.

Next, a second metal oxide film (hereinafter, sometimes simply referred to as a second film) in the present invention will be described. The second film is made of silicon oxide, titanium oxide, cerium oxide,
And gold coloring fine particles. Silicon oxide is necessary as a low-refractive-index material for maintaining the strength of the film and for causing the film to develop a reddish color with gold fine particles. If the content is too small, the strength of the film becomes insufficient, and The color of the gold fine particles shifts to bluish, and a desired color tone cannot be obtained. Conversely, if the content is too large, the color tone of the film will be too red. Therefore, the content of silicon oxide is SiO 2
_In terms of ₂ , it is 5 to 40% by weight, preferably 8 to 38% by weight.

Titanium oxide acts as a color tone regulator that adjusts the delicate color tone by changing the plasmon absorption of the fine gold particles by adjusting the refractive index of the second film.
If the content of titanium oxide is too small, the refractive index required to adjust the color tone of the second film cannot be obtained.If the content is too large, the refractive index of the second film increases and the color film-coated glass plate becomes The reflectance of visible light cannot be reduced. Therefore the titanium oxide content of 10 to 62% by weight in terms of TiO _2, more preferably 12 to 50 wt%, more preferably from 16 to 34 wt%.

Cerium oxide changes the plasmon absorption of the fine gold particles by adjusting the refractive index of the second film, and acts not only as a color tone adjusting agent for adjusting a subtle color tone, but also as a fine particle in the film. It also has the effect of uniformly dispersing and supporting. If the content of cerium oxide is too small, the fine gold particles are not taken into the film at the time of film formation and are likely to precipitate on the film surface, so that coloring by the fine gold particles cannot be obtained. Gets worse. Therefore, the cerium oxide content is 1 in terms of CeO _2.
It is 0 to 50% by weight, preferably 13 to 45% by weight, and more preferably 15 to 40% by weight.

The fine gold particles are necessary for imparting a red color to the second film as described above, are chemically stable, and can be produced relatively easily. If the content is too low, sufficient coloring cannot be obtained, and if it is too high, the durability of the film decreases. Therefore, the content of the gold fine particles for coloring is 5 to 30% by weight, preferably 10 to 3% by weight.
0% by weight, more preferably 16 to 28% by weight.

If the refractive index of the second film is too high, the visible light reflectance cannot be lowered as described below, so that it is 1.80 to 2.10 and higher than the refractive index of the first film. The amounts of titanium oxide and cerium oxide added to the silicon oxide are adjusted so that the value is at least 0.10, more preferably at least 0.2 or less. The more preferable value of the refractive index of the second film is 1.80 to 1.97.

If the thickness of the second film is too small, the ability to retain the gold fine particles for coloring is lowered. On the other hand, if the thickness is too large, the film may be cracked or the substrate glass may be deformed during warping. 40 ~ 15
The thickness is preferably 0 nm, and more preferably 65 to 140 nm so that the reflected color of visible light projected from the glass surface side (non-film surface side) is as close as possible to neutral gray. By providing a second film having a lower refractive index than the first film on the first film,
The reflectance of visible light can be reduced, and the reflection tone of light projected from the glass surface side can be adjusted so as to be a color close to neutral gray.

In addition to the fine gold particles, silicon oxide, titanium oxide and cerium oxide which are the main components of the second film, copper oxide, manganese oxide,
Cobalt oxide, iron oxide, chromium oxide, etc.
In terms of uO, MnO _2, Co ₃ O _4, Fe ₂ O _{3 and} Cr ₂ O ₃ , they can be added in a total amount of 5% by weight or less.

Next, the raw material of the second film will be described. As the gold fine particle raw material, for example, a gold fine particle carrier polymer, chloroauric acid, sodium chloroaurate, or the like that can form gold fine particles at the stage of film formation can be used.

An alkoxide of silicon is preferable as a raw material of silicon oxide. Examples include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and the like. In addition, a mixture of these condensates or condensates can be used. Examples of the condensate include hexaethoxydisiloxane, octaethoxytrisiloxane, decaethoxytetrasiloxane, and ethoxypolysiloxane. In addition, a mixture of these can be used, and for example, ethyl silicate 40 (manufactured by Colcoat) can be used.

As a raw material for titanium oxide, titanium organic compounds such as titanium alkoxide, titanium acetyl acetate, and titanium carboxylate are preferable. As the titanium alkoxide, titanium isopropoxide, titanium butoxide and the like are preferable. However, it is also possible to substitute a part of this alkoxide with β-diketones such as acetylacetone to increase the liquid stability.

As a raw material of cerium oxide, cerium inorganic compounds such as cerium nitrate, cerium chloride and cerium sulfide are suitable.

As a method for forming the second film on the first film coated on the glass substrate, the second film can be formed by a sol-gel method, a CVD method or the like which can be processed at room temperature. However, considering the reheating of the substrate and the liquid use efficiency, it is most preferable to use the coating technique by the sol-gel method.

The sol-gel method will be described below. Raw materials of gold fine particles as described above, for example, chloroauric acid, a raw material of silicon oxide, for example, an alkoxide of silicon, a raw material of titanium oxide, for example, a raw material of titanium alkoxide, and a raw material of cerium oxide,
For example, cerium nitrate and, if necessary, a catalyst and additives are dissolved in a solvent to obtain a coating solution for a second film.

Examples of the solvent include cellosolves such as ethyl cellosolve and butyl cellosolve; alcohols such as ethanol, isopropyl alcohol and butanol;
Glycols such as ethylene glycol, propylene glycol and hexylene glycol can be used, and chelating agents such as acetylacetone and ethyl acetoacetate can be added to adjust viscosity, solvent evaporation rate, liquid stability, etc. it can. In addition, light drying property is improved,
To prevent whitening, acrylates such as trimethylolpropane acrylate, methacrylates, and vinyl compounds can be mixed.

The method for applying the second film coating liquid is not particularly limited, and examples thereof include a spin coating method, a dip coating method, a spray coating method, and a printing method. In particular, printing methods such as a gravure coating method, a flexographic printing method, a roll coating method, and a screen printing method are preferable because of high productivity and good use efficiency of the coating liquid composition.

The coating solution for the second film is applied on the first film coated on the surface of the glass substrate by the above-mentioned coating method, and then heated in an oxidizing atmosphere by hot air heating, ultraviolet irradiation, infrared irradiation, electromagnetic wave 100-400 ° C depending on irradiation etc.
At 200 ° C. for 5 to 200 minutes to precipitate gold fine particles in the film. Further, the film surface temperature is 450 ° C. or more, preferably 550 ° C. or more and 720 ° C. or less for 10 seconds to
By baking for 5 minutes, a second film having a thickness of 40 to 150 nm is formed.

As the glass substrate in the present invention, in addition to a transparent glass plate having a soda lime silicate glass composition, a glass plate having a glass composition colored green or a glass having a glass composition colored bronze A plate and a glass plate having a glass composition capable of absorbing ultraviolet light may be used. Since the first film and the second film do not have very large ultraviolet shielding performance, as a glass substrate,
The transmittance of ultraviolet light having a wavelength of 370 nm (T370) is 20.
-70%, visible light transmittance (Ya) is 70-85%,
Sunlight transmittance is 40-80% and thickness is 1.5m
An automotive glass plate having a diameter of m to 5.5 mm is preferably used. Further, in the glass substrate, the transmitted light has a value of a of -9.0 to -4.0 and a chromaticity of b of -1.0 to 4.0 in a Lab color system based on a thickness of 3.4 mm. And is colored light green, and has an ultraviolet light transmittance (Tuv) of 5 to 7 according to ISO.
A glass plate having a composition of 0% is preferred. By forming the first film and the second film on the surface of the ultraviolet absorbing glass plate in this way, a colored glass plate having high heat ray blocking performance and ultraviolet absorbing performance can be obtained, and in particular, visible light transmittance of 15 to 30%. (Ya), 10-30
%, A glass sheet coated with a heat-shielding colored film having a solar light transmittance (Tg) of 10%, a visible light reflectance of 18% or less, and an ultraviolet transmittance (Tuv) of 10% or less.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not limited to these embodiments. Example 1 A glass plate having a size of 100 mm × 100 mm, a thickness of 3.5 mm, and having the composition and optical characteristics shown in Table 1 was washed and dried. The chromaticities of the transmitted light and the reflected light in Table 1 are values expressed in the Lab color system (the same applies to the following Examples and Comparative Examples). The substrate was held by a hanger and held in an electric furnace set at 650 ° C. for 5 minutes. Then, immediately after being taken out of the electric furnace, a coating solution for a first film having a composition shown in Table 2 was commercially available by spraying. An air pressure of 3.0 kg / cm ² and an air volume of 9 kg were applied to one surface of the substrate using a gun.
Spraying was performed for about 10 seconds under the conditions of 0 liter / minute and a spray amount of 20 ml / minute to obtain a glass plate with a first film.
Table 3 shows the composition of the first film and the optical characteristics of the glass plate with the first film.
Shown in

[0037]

Table 1 ================ Glass substrate composition, optical characteristics, etc. --------------------- Glass composition (% by weight) SiO ₂ 70.4 Al ₂ O ₃ 1.5 Fe ₂ O ₃ 0.62 (FeO in) 0.185 CeO ₂ 1.67 TiO ₂ 0.14 CaO 8.0 MgO 4.0 Na ₂ O 13.0 K ₂ O 0.70 Refractive index 1.51 Plate thickness (mm) 3.5 Ya (%) 81.0 Tg (%) 60.9 T370 (2O 0.70 −−−−−−−−−−−−−−) %) 62.5 Tuv (%) 52.6 Visible light reflectance Rg (%) 7.2 Transmissive | Transmissive color tone Green Over | Chromaticity a = -4.7, b = 0.3 Light | Principal wavelength λd (nm) 522 | Stimulation purity Pe (%) 2.29 Reflected light chromaticity a = -1.3, b = -0.8 ================

[0038]

[Table 2] =========================== Coating Liquid Composition for First Film --------------- --------------------- Trivalent cobalt dipropionylmethane 12.5 g Ferric acetylacetonate 0.62 g Chromium acetylacetonate 1.83 g Toluene (solvent) 100 ml ==== =======================

[0039]

[Table 3] =========================== First Film Composition, Optical Properties of Glass Plate with First Film, etc. ------------------------ film composition Co ₃ O ₄ 78.6 wt% Fe ₂ O ₃ 4.1 wt% Cr ₂ O ₃ 17. 3% by weight Film thickness 50 nm Refractive index 2.64 (at light wavelength of 550 nm) Ya (%) 31.4 Tg (%) 30.9 T370 (%) 18.0 Tuv (%) 8.4 Visible light reflectance ( %) 37.4 (Film side) 23.9 (Glass side) Transmission color tone Yellow Transmission | Color a 0.2 Over | Degree b 10.0 Light | Principal wavelength λd (nm) 577.3 | Stimulation purity Pe (%) 17.82 Reflected light Chromaticity a -4.5 (film side) -8.2 (glass side) b 2.5 (film side) 4.3 (glass side) =================== =======

Preparation of coating solution for second film (1) As a silicon oxide raw material, 50 g of ethyl silicate ("Ethyl silicate 40", manufactured by Colcoat Co., Ltd.), 44 g of ethyl cellosolve, and a 0.1N aqueous hydrogen chloride solution were added. What was stirred for 2 hours was used. (Silicon Oxide Raw Material Liquid) (2) As a titanium oxide raw material, one obtained by dropping and reacting 2 mol of acetylacetone with a dropping funnel with respect to 1 mol of titaniisopropoxide was used. (Titanium oxide raw material liquid) (3) A cerium oxide raw material obtained by adding ethyl cellosolve to cerium nitrate hexahydrate and dissolving it so that CeO ₂ / (Ce raw material liquid) = 23.2% was used. .
(Cerium oxide raw material liquid) (4) As a gold raw material, a solution prepared by dissolving 5 g of chloroauric acid tetrahydrate in 20 g of ethyl cellosolve was used. (Gold raw material liquid)

Using these, the raw material liquids were mixed so as to have the composition ratio shown in Table 4 after the formation of the film, diluted with ethyl cellosolve, and stirred to obtain a second film coating liquid 1. In Table 4, the solid content ratio (%) is
The ratio of (weight after firing / weight of coating solution) when the coating solution 1 was fired at 600 ° C. is shown in percentage.

The substrate was spin-coated at 650 rpm.
In, coating liquid 1 was applied. After air drying,
After drying in an oven at 250 ° C. for 2 hours, the substrate was fixed by a hanger and baked at a maximum substrate temperature of 670 ° C., whereby a dark green colored glass plate was obtained. The thickness and refractive index of the second layer were as shown in Table 4. The refractive index of the second film is a value of a silicon oxide-titanium oxide-cerium oxide film containing no fine gold particles.

With respect to this sample, JIS R 3106
Luminous transmittance (Ya), solar transmittance (Tg), ultraviolet transmittance (Tuv), reflectance of visible light projected from the glass surface side (coating surface side), chromaticity (a, b), and film according to The reflectance and chromaticity (a, b) of the visible light projected from the surface side were obtained. Table 5 shows the results.

As can be seen from the table, the luminous transmittance is 21.1%, which is a good privacy performance of 30% or less.
The solar radiation transmittance was 27.0%, indicating a good heat ray shielding performance of 30% or less, and the ultraviolet transmittance Tuv was 4.
It shows good UV shielding performance of 5% or less and 10% or less, and has a visible light reflectance of 12.4 on a glass surface.
%, And 13.7% in film surface reflection, indicating that the film has low visible light reflectivity of 15% or less. The composition of the film coincided with the calculated value as shown in Table 4. Also their mechanical strength,
In order to evaluate the chemical strength, the surface strength, acid resistance, alkali resistance, and boil resistance by Taber test were measured, and good results were obtained in all cases.

[0045]

[Table 4] ================================= Percentage of Weight in Second Film (%) Second Film Coating II Second film Solids ratio −−−−−−−−−−− −−−−−−− Thickness Refractive index (%) Au SiO ₂ TiO ₂ CeO ₂ Method Rotational speed (nm) −−−−−− Example 1 6.05 17.4 19.1 25.3 38.2 Spine 650 rpm 120 1.87 2 6.91 27.7 9.4 25.1 39.9 Spine 1500 rpm 70 1.97 3 6.05 17.4 25.6 22.7 34.3 Spine 650rpm 120 1.81 4 6.05 17.4 31.0 20.6 31.1 Spine 700rpm 110 1.76 5 6.34 21.1 37.4 16.6 25.0 Spine 1000rpm 120 1.70 6 9.53 16.1 31.8 33.9 18.2 Qualifier-120 1.81-------------- −−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 − − − − − − − − − − − 2 6.05 17.4 31.0 20.6 31.1 Spine 700rpm 110 1.76 ======= === ========================

[0046]

================================================================================================================================================================================== V = V = = = = = = = = = = = == (%) (%) (%) a / b Rg (%) a / b Rf (%) a / b --- --- --- --- --- --- --- --- ------ −−−−−−−−−−− Example 1 21.1 27.0 4.5 -2.8 / 4.8 12.4 -6.7 / -8.5 13.7 -3.4 / -19.7 2 27.7 28.4 4.8 -10.0 / 10.0 11.3 -6.7 / -1.1 4.0 28.8 /- 27.3 3 18.7 26.8 4.6 -3.3 / 2.3 14.3 -9.4 / -7.5 12.0 -3.3 / -21.6 4 22.5 27.1 5.5 3.1 / 5.0 14.2 -8.0 / -6.6 13.1 -1.1 / -20.0 5 27.3 28.3 6.2 3.9 / 7.6 10.5 6.3 / -7.5 6.3 8.0 / -37.8 6 23.4 27.3 5.6 -1.5 / 6.1 14.0 -8.8 / -7.0 14.9 -8.4 / -20.3 −−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−− Comparative Example 1 31.4 30.9 8.4 0.2 / 10.0 23.9 -8.2 / 4.3 37.4 -4.5 / 2.5 2 53.5 60.1 31.2 5.1 / -9.7 12.2 3.2 / -7.2 15.6 3.7 / -8.9 3 34.3 30.3 2.3 -8.3 / -7.0 5.4 5.8 / -12.1 7.1 13.0 / -21.0 4 36.3 34.8 10.1 -9.7 / -1.0 9.5 -7.3 / 7.8 10 .2 -2.2 / 3.9 ==================================

[Examples 2 to 6] After the film formation, the raw material liquids were mixed so that the liquid composition ratio and the solid content ratio calculated as shown in Table 4 were obtained, diluted with ethyl cellosolve, and then stirred. Liquid. Second membrane coating liquids 2 to 6 correspond to Examples 2 to 6, respectively. At this time, with respect to the second film coating liquids 2 and 3, trimethylolpropane acrylate was added as a whitening inhibitor in an amount equivalent to 1.5% by weight of the total liquid. In addition, coating liquid 6
As for (2), ethylene glycol was added as a solvent additive in an amount equivalent to 1.5% by weight of the whole liquid. Then, following the same procedure as in Example 1 except that the above-mentioned coating liquids 2 to 6 are used instead of the coating liquid 1 for the second film in Example 1,
A colored glass plate was obtained. However, in Example 6, coating was performed using a gravure coater. Table 5 shows these optical characteristics.

From the table, the luminous transmittance is 18.7 to 27.3.
% And good privacy performance of 30% or less, and the solar radiation transmittance is 26.8 to 28.4% and 30%
Good UV shielding performance of 4.5 to 6.2% and good UV shielding performance of 10% or less, and a visible light reflectance of 10. 5-14.3%, 4.0-14.9 by film surface reflection
% And 15% or less of visible light low reflectivity. It also has various transmission colors. The composition of the film coincided with the calculated value as shown in Table 4. In order to evaluate the mechanical strength and the chemical strength, the surface strength, acid resistance, alkali resistance, and boil resistance were measured by Taber test, and all the examples obtained good results.

[Comparative Example 1] As shown in Table 5, the glass plate coated with only the first film without coating the second film in Example 1 had a visible light reflectance on the glass surface side (non-film surface side) as shown in Table 5. ) In 2
3.9% and 37.4% on the film surface side exceeded 20% on both the glass surface side and the film surface side. Also, the visible light transmittance (Y
a) was 31.4% and exceeded 30%.

[Comparative Example 2] After the film was formed, the raw material liquids were mixed according to the ratio shown in Table 4, diluted with ethyl cellosolve, and stirred to obtain a coating liquid. A transparent, uncolored soda-lime silicate glass plate having a size of 100 mm × 100 mm and a thickness of 3.5 mm by a float method (visible light transmittance (Ya) = 90.0%, sunlight transmittance (Tg) ) = 84.7%, UV transmittance (T
uv) = 76.2%, chromaticity of transmitted light a = −0.9, b =
0.3, visible light reflectance 8.0%, reflected light chromaticity a = −0.0.
2, b = 0.2) as a coating substrate, and without coating the first film in Example 1, and using the above coating solution instead of the coating solution 1 in Example 1 to form only the second film. A colored glass plate was obtained according to the same procedure as in Example 1 except for coating. Table 5 shows the optical characteristics. This glass plate has visible light reflectance on the glass surface side (non-film surface side).
Although it is as low as 12.2% and 15.6% on the film surface side, the visible light transmittance (Ya) is as high as 53.5%, privacy performance is low, and the sunlight transmittance is 60.1%. The heat ray shielding performance was also insufficient.

Comparative Example 3 As a glass substrate, a green glass substrate having dimensions of 100 mm × 100 mm having the same glass composition (% by weight), plate thickness and optical characteristics as shown in Table 1 was prepared.

The cerium nitrate stock solution, titanium oxide stock solution, and silicon oxide stock solution prepared in Example 1 were obtained so that the film compositions shown in Table 6 below were obtained, and ethyl cellosolve was added thereto. Ethyl cellosolve solution of chloroauric acid tetrahydrate prepared in Example 1 was added and mixed and stirred to prepare an upper layer and lower layer coating solution. The green glass substrate shown in Table 1 was used to carry out spin coating. The steps of coating, air-drying, drying and baking of the second film in Example 1 were repeated for the upper layer and lower layer coating liquids to obtain a colored glass plate. Table 5 shows these optical characteristics.

As can be seen from the table, the solar radiation transmittance was 30.3%, indicating good heat ray shielding performance, and the UV transmittance was 2.30%.
A good ultraviolet shielding performance is exhibited at 3%, and a visible light reflectance at a glass surface side and a film surface side is also less than 18%, which indicates a low visible light reflection performance, but the luminous transmittance is 34.3%, which is 30%.
%, Which means that it cannot be said to have good privacy performance. The composition of the film coincided with the calculated value as shown in Table 6.

Comparative Example 4 Preparation of Coating Solution Ti Raw Material Liquid A mixture of tetraisopropoxytitanium and acetylacetone at a molar ratio of 1: 2 was used as a Ti raw material liquid. Au raw material solution The above Ti raw material solution 10.0 g and 0.66 g of chloroauric acid dissolved in 23.0 g of ethyl cellosolve were used as the Au raw material solution. Co raw material liquid 40 g of cobalt acetate and 33.75 g of diethanolamine as a stabilizer were added to ethyl cellosolve 18.
The Co raw material liquid was prepared by stirring and mixing in 4 g. Ni raw material liquid 40 g of nickel nitrate and 28.90 g of diethanolamine as a stabilizer were added to ethyl cellosolve 137.
The resulting mixture was stirred and mixed in the same amount to prepare a Ni raw material liquid. Coating liquid A 100 g of Co raw material liquid E and 46.4 g of Ni raw material liquid were mixed and stirred to obtain coating liquid A. -Coating liquid B 2.1 g of Ti raw material liquid and 7.9 g of Au raw material liquid are mixed and stirred to obtain a coating liquid B.

A green glass plate having a size of 100 mm × 100 mm and a thickness of 3.4 mm (luminous transmittance Ya = 8)
1.2%, solar radiation transmittance Tg = 60.9%, visible light reflectance Rg = 7.1%, T370 = 62.5%, transmission color tone: light green, transmitted in chromaticity of Lab color system Light chromaticity a = -4.
5, b = 1.9, chromaticity of reflected light a = −1.3, b = −0.
After 2) was washed and dried, it was used as a coated substrate. The coating solution A was applied to the substrate under the spin coating condition of 2000 rpm. After air drying, it was dried in an oven at 250 ° C. for 2 hours. Then, further apply the coating solution B on the dried substrate,
The coating was performed under a spin coating condition of 2000 rpm. After air drying, it was dried in an oven at 250 ° C. for 2 hours.

After this treatment, the substrate coated with the two layers was fixed by a hanging tool and held at an atmosphere temperature of 760 ° C. for 2 minutes to perform firing. At this time, the maximum substrate temperature was 670 ° C., and a dark green colored glass plate was obtained. Table 7 shows the composition, refractive index, and film thickness of these films, and Table 5 shows the optical characteristics. From the table, the UV transmittance is 10.1%, which indicates good UV shielding performance, and the visible light reflectance on the glass surface side and the film surface side is about 15% or less, and the visible light low reflection performance is exhibited. 34.8%, which exceeds 30%, and cannot be said to show good heat ray shielding performance, and the luminous transmittance is 36.3%, which exceeds 30%. It turns out that it cannot be said that it has.

[0057]

[Table 6]

[0058]

[Table 7]

[0059]

According to the present invention, by combining a thin film of a vivid color and a thin film of a dull color and controlling the thickness of each thin film, a desired transmitted light chromaticity and a low visible light can be obtained. It has a transmittance (especially 30% or less), a visible light reflectance of 18% or less, an ultraviolet ray shielding performance (especially an ultraviolet ray transmittance Tuv of 10% or less), and a heat ray shielding performance (especially a sunlight ray transmittance of 30% or less). % Or less).

Further, as compared with the case where the color tone is realized with a single layer, the control of the reflectance using the interference by the film configuration and the fine adjustment of the color tone can be realized.

Further, in terms of the process, the glass film coated with the first film by on-line coating during the plate making process can be used, so that a glass plate with a two-layer film can be manufactured at a relatively low cost. .

Claims (6)

[Claims] 1. A glass substrate containing, as a main component, cobalt oxide: 61 to 98, iron oxide: 2 to 26, and chromium oxide: 0 to 37 expressed as a percentage by weight on the surface of a glass substrate, and 10 to 70 nm. A first metal oxide film having a thickness of 3 nm is coated, and gold fine particles: 5 to 30, silicon oxide: 5 to 40, and titanium oxide are expressed by weight% on the first metal oxide film. : A heat-shielding colored film-coated glass plate containing: 10 to 62, cerium oxide: 10 to 50, and coated with a second metal oxide film having a thickness of 40 to 150 nm. 2. The method according to claim 1, wherein the first metal oxide film is expressed in terms of% by weight: cobalt oxide: 70 to 98; iron oxide: 3 to 26; chromium oxide: 0 to 14; The glass sheet coated with a heat ray-shielding colored film according to claim 1, which contains, as a main component, an amount larger than the chromium oxide content. 3. The first metal oxide film is represented by weight%, cobalt oxide: 61 to 80, iron oxide: 2 to 19, chromium oxide: 14 to 35, but containing chromium oxide. The heat-shielding colored film-coated glass sheet according to claim 1, which contains, as a main component, an amount larger than the iron oxide content. 4. The method according to claim 1, wherein the glass substrate has a thickness of 1.5 to 5.5 mm and the transmitted light has a thickness of 3.4 mm.
In the color system, a value of -9.0 to -4.0 and -1.0 to
It has a b chromaticity of 4.0, is colored light green, has an ultraviolet light transmittance (Tuv) of 5 to 70%, and has a visible light transmittance (Y
a) is 70 to 85%, and the sunlight transmittance (Tg) is 40 to
The heat-shielding colored coated glass sheet according to any one of claims 1 to 3, which is a glass sheet for an automobile window having a composition of 80%. 5. The method according to claim 1, wherein the heat-shielding colored coated glass plate is 15 to
The glass substrate having a visible light transmittance (Ya) of 30%, a solar light transmittance (Tg) of 10 to 30%, a visible light reflectance of 18% or less, and an ultraviolet transmittance (Tuv) of 10% or less. Is a glass sheet for an automotive window having a thickness of 1.5 to 5.5 mm. The glass sheet coated with a heat ray-shielding colored film according to any one of claims 1 to 4. 6. The method according to claim 1, wherein the first metal oxide film is coated by a thermal decomposition method or a chemical vapor deposition method, and the second metal oxide film is coated by a sol-gel method.
The heat-shielding colored film-coated glass plate according to any one of Items 1 to 5.