JPH09301743A - Colored film coated glass article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored film coated glass article capable of freely controlling its color tone, visible light transmissivity, reflectance and reflected color tone, especially having low saturation of reflected color and ensuring a reflected hue close to a transmitted hue. SOLUTION: This colored film coated glass article has a colored film contg. 0-7wt.% SiO2 , 25-95wt.% at least one selected from among TiO2 , ZrO2 , CeO2 , ZnO and Ta2 O5 and 5-30wt.% fine coloring particles of at least one selected from among Au, Ag and Pd as essential components and a middle layer interposed between the colored film and the glass substrate, contg. 20-100wt.% SiO2 , 0-80wt.% at least one selected from among TiO2 , ZrO2 , CeO2 , ZnO and Ta2 O5 and 0-30wt.% fine coloring particles of at least one selected from among Au, Ag and Pd and having a lower refractive index than the colored film by at least 0.08.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored film-coated glass article, and more particularly to a colored film-coated glass sheet used for vehicles such as automobiles and windows of buildings.

[0002]

2. Description of the Related Art As a method for obtaining colored glass, there is a method in which a metal oxidizer is dissolved in a solution of a metal alkoxide, which is applied to a base material and heat-treated to form ultrafine metal particles. In particular, the coloring of ultrafine metal particles by surface plasmons is excellent in heat resistance and light resistance, and has been used for coloring glass, pottery, etc. for a long time. For example J.Sol-Gel.Sci.Te
In chn.1, 305-312 (1994), an ultrafine gold particle is formed by applying an alkoxide solution of chloroauric acid and silane onto a glass substrate and then heat-treating to obtain a colored film.

Further, in Japanese Patent Laid-Open No. 6-191896, a colored film containing silicon oxide, titanium oxide and gold fine particles, for example, as a preferable composition, 85 to 3% by weight of TiO ₂ and S
Glass articles coated with a colored film in the range of 40-0 wt% iO _{2 and} 5-60 wt% Au are described.

[0004] As a material coated with a coating on vehicle glass or architectural glass, the reflectance is generally low, and the saturation of the reflected color is low, and the color is neutral gray (neutral).
Something close to is sometimes required. Further, conventionally, the hue of the reflected color on the glass surface tends to be a complementary color of the transmitted color, but a glass article with a colored film in which the hue of the reflected color is as close as possible to the hue of the transmitted color is sometimes required.

However, the reflection color tone of the conventional colored film-coated glass article described above is a complementary color of the transmission color and has a considerably high saturation, and it is difficult to control the hue and saturation of the reflection color.

[0006]

According to the present invention, the color tone, visible light transmittance, reflectance, and reflection color tone can be freely controlled, and particularly, the saturation of the reflection color is low and the reflection color is close to the transmission hue. An object of the present invention is to provide a colored film-coated glass article capable of obtaining a hue.

[0007]

The present inventors have developed a colored film-coated glass article having a new coloring function and capable of freely controlling the reflection color tone in order to solve such a problem.

That is, the present invention represents, in weight percent, at least one selected from the group consisting of 0 to 70 silicon oxide, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide. 95, at least one kind of coloring fine particles 5 to 30 selected from the group consisting of gold, silver, and palladium, as a main component, and a colored film provided between the colored film and the glass substrate. %, At least one selected from the group consisting of 20 to 100 of silicon oxide, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide, consisting of gold, silver, and palladium. The coloring film containing at least one kind of coloring fine particles 0 to 30 selected from the group is at least 0.
08 is a colored film coated glass article having an intermediate layer having a low refractive index.

Each component of the composition of the colored film in the present invention will be described below. Although silicon oxide is not an essential component, it is effective for adjusting the refractive index of the film, and when the content thereof is low, the refractive index of the colored film becomes high and the film exhibits a blue color. On the contrary, when the content is large, the refractive index of the colored film becomes low and the film exhibits reddish purple, and when the content is too large, the substrate is deformed due to the large shrinkage of the film in the heating process of the film. The content of silicon oxide is S
It is 0 to 70% by weight in terms of iO ₂ , and preferably 0.
-40% by weight, more preferably 10-40% by weight.

At least one high refractive index material selected from the group consisting of titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide is used for forming a film and for increasing the refractive index of the colored film. If the content is low, the refractive index of the colored film becomes low and the film exhibits reddish purple, and if it is too low, the film formability and transparency of the film deteriorate. When the content is large, the refractive index of the colored film becomes high, and the film exhibits blue. The total content of these high refractive materials is 25 to 95% by weight, preferably 45 to 95% by weight.
It is 85% by weight, more preferably 45 to 75% by weight.

At least one kind of fine particles for coloring selected from the group consisting of gold, silver and palladium is necessary for obtaining bright coloring, and if the content is too low, sufficient coloring cannot be obtained. On the contrary, if the amount is too large, the durability of the film is reduced. Therefore, the content of the coloring fine particles (the total amount when a plurality of types are used in combination) is 5 to 30% by weight, preferably 5 to 20% by weight, and more preferably 10 to
It is 20% by weight.

If the thickness of the colored film is too thin, the coloring effect will be reduced, and if it is too thick, cracks will occur and the film strength will decrease, so a thickness of 30 to 200 nm is preferred. More preferably 40-180
nm, and more preferably 80 to 120 nm. The refractive index of the colored film is preferably 1.80 to 2.25, more preferably 1.80 to 2.10.

In the present invention, in order to adjust the reflection color tone of the colored film, and particularly to reduce the saturation of the reflected color, silicon oxide is contained between the colored film and the glass article substrate, and It is at least 0.08 lower than the refractive index, more preferably 0.10 to 0.70 lower, and further preferably 0.1.
An intermediate layer having a low refractive index of 0 to 0.40 is formed.

This intermediate layer has 20 to 100% by weight, preferably 40 to 70% by weight, more preferably 55 to 65% by weight, of silicon oxide in terms of SiO ₂ , titanium oxide, zirconium oxide and cerium oxide. , At least one selected from the group consisting of zinc oxide, and tantalum oxide (the total amount when plural kinds are used in combination)
_{iO 2, ZrO 2, CeO 2} , ZnO, and in terms of Ta ₂ O _5, 0 to 80 wt%, more preferably 0-50 wt%, more preferably 35 to 45 wt%, gold, silver, palladium 0 to 3 at least one kind of fine particles for coloring selected from the group consisting of (the total amount when plural kinds are used in combination)
It contains 0% by weight, more preferably 0 to 20% by weight.

The refractive index of the intermediate layer is 1.45 to 2.05, more preferably 1.60 to 1.85, and further preferably 1.
The thickness is 65 to 1.75, and the thickness thereof is preferably 50 to 100 nm, more preferably 60 to 90 nm, and further preferably 65 to 85 nm.
The refractive index of the intermediate layer is adjusted by the content of at least one selected from the group consisting of silicon oxide and titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide. By adjusting the refractive index and the film thickness of the intermediate layer having a refractive index lower than that of the colored film by 0.08 or more,
The reflection color tone can be adjusted, and especially, the saturation of the reflection color can be reduced.

Since the fine particles for coloring in the colored film show different coloring depending on the value of the refractive index of the matrix,
When the intermediate layer also contains fine particles for coloring, particularly fine particles of the same type as the fine particles for coloring in the colored film, the fine particles for coloring in the intermediate layer have a different refractive index from the intermediate layer. Since the coloring is different from that of the fine particles for use, the entire film shows a composite transmitted light color tone.

When the glass plate having the above-mentioned two-layer structure is attached to an automobile window so that the coating surface of the glass plate faces the inside of the car, if the visible light reflectance seen from the inside of the car is too high, the inside of the car It is preferable that the reflectance of visible light when light is incident from the coating surface side of the glass plate is less than approximately 13%, which is as small as possible, because the luggage and the like may be reflected on the glass and interfere with the driver's view. . Also, if the visible light reflectance seen from the outside of the car is too high, it may cause glare and impair the aesthetics. Therefore, the reflectance of visible light when light is incident from the glass surface (uncoated surface) side of the glass plate is It is preferably as small as possible at about 14% or less. Further, the reflection color tone of the glass surface preferably has a low saturation close to neutral, and in the Lab color system, a is -7 to 5 and b is-.
It is preferable that it is 8 to 6, and more preferably, a is -5.
It is preferable that b is -6 to 4 in -3. If the value of a becomes too large, the reflection color tone becomes reddish, and if the value of b becomes too large, the reflection color tone becomes too yellowish and glares.

In the colored film-coated glass article of the present invention, the transmitted color is represented by the Lab color system, where a is -20 to 10 and b is -2.
It preferably has a color tone of 0 to 10. More preferably, a has a color tone of -18 to 5 and b has a color tone of -20 to -5.

In the present invention, the type and amount of the fine particles for coloring in the colored film and the intermediate layer are changed, or selected from the group consisting of silicon oxide and titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide. At least 1
By changing the ratio of the species and changing the refractive index of the film, various transmission colors from red purple to blue can be realized, and the visible light transmittance can be arbitrarily adjusted to about 30% to 80%. Furthermore, by using a two-layer structure in which a low refractive index layer is used as an undercoat, the reflectance can be lowered, and the saturation of the reflected color can be lowered by adjusting the reflection color tone, or the hue of the reflected color can be reduced. You can get closer to the hue of. Moreover, by including colored fine particles in the intermediate layer, the variation of the transmission color tone is widened, and the visible light transmittance can be controlled to be further low.

As a raw material for the fine particles of gold, silver and palladium which are fine particles for coloring used in the colored film and the intermediate layer of the present invention, chlorides or nitrates such as chloroauric acid, silver nitrate and palladium chloride are suitable. However, it is not particularly limited as long as it is stable and soluble.

The colored film and the intermediate layer of the present invention are at least one selected from the group consisting of a silicon oxide raw material, a compound forming colored fine particles, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide. It is obtained by coating a substrate with a solution containing a raw material and, if necessary, a catalyst, an additive and an organic solvent, drying and baking.

Further, as the raw material of the metal oxide for forming the colored film and the intermediate layer in the present invention, any material capable of forming a transparent film by the sol-gel method may be used, which will be specifically described below.

As a raw material of silicon oxide, a metal alkoxide is suitable, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. In addition, these condensates (n ≧
2) or a mixture of condensates is also conveniently used. For example, as the condensate, hexaethoxydisiloxane (n = 2), octaethoxytrisiloxane (n = 2)
3), decaethoxytetrasiloxane (n = 4), ethoxypolysiloxane (n ≧ 5) and the like can be used. Ethyl silicate 40 consisting of a mixture of a monomer (n = 1) and a condensate (n ≧ 2) [composition: Cihlar literature,
Colloids and Surfaces A: Physicochem.Eng.Aspects
70 (1993), pp. 253 to 268, and a monomer (n = 1): 12.8% by weight and a dimer (n
= 2): 10.2% by weight, trimer (n = 3): 12.0
% By weight, tetramer (n = 4): 7.0% by weight, multimer (n
≧ 5): 56.2% by weight, ethanol: 1.8% by weight)
Is preferably used.

It is also possible to use an alkyltrialkoxysilane in which the alkoxy group of the above compound is substituted with an alkyl group. For example, an alkoxy group is a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group,
Alkenyl such as a linear or branched alkyl group such as an octyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a vinyl group, an allyl group, a γ-methacryloxypropyl group, and a γ-acryloxypropyl group. Groups, phenyl groups, toluyl groups, aryl groups such as xylyl groups, aralkyl groups such as benzyl and phenethyl groups, or γ-mercaptopropyl groups, γ-chloropropyl groups, and γ-aminopropyl groups. .

As a raw material of titanium oxide, titanium organic compounds such as titanium alkoxide, titanium acetylacetonate and titanium carboxylate are preferably used. As the titanium alkoxide, generally, Ti (OR)
₄ (R is an alkyl group having up to 4 carbon atoms)
Considering the reactivity, titanium isopropoxide and titanium butoxide are preferable. It has also been known that in the case of titanium, the use of acetylacetonate is preferable in terms of its stability. In this case, the general formula is Ti (OR) _m L _n (m + n = 4, n ≠ 0), where L is acetylacetone. In this case,
The titanium alkoxide may be acetylacetonated with acetylacetone, or commercially available titanium acetylacetonate may be used. It is further conceivable to use a carboxylate.

The raw materials for zirconium oxide include tetramethoxyzirconium, tetraethoxyzirconium,
Tetraisopropoxy zirconium, tetra n-propoxy zirconium, tetraisopropoxy zirconium isopropanol complex, tetraisobutoxy zirconium, tetra n-butoxy zirconium, tetra sec-butoxy zirconium, tetra t-butoxy zirconium and the like can be conveniently used. It is also possible to use zirconium halide alkoxides such as zirconium monochloride trialkoxide and zirconium dichloride dialkoxide. A zirconium alkoxide obtained by chelating the above zirconium alkoxide with a β-ketoester compound is also preferably used. Examples of chelating agents include CH ₃ COC such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate and butyl acetoacetate.
H ₃ COOR, where R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , or C ₄ H ₉ can be listed, among which acetoacetic acid alkyl ester can be enumerated. , Especially methyl acetoacetate and ethyl acetoacetate, are preferred, as they are relatively inexpensively available. The degree of chelation of the zirconium alkoxide may be part or all, but it is preferable to chelate the zirconium alkoxide at a molar ratio of (β-keto ester) / (zirconium alkoxide) = 2 because the chelate compound is stable. A chelating agent other than the β-ketoester compound, for example, zirconium alkoxide chelated with acetylacetone is insoluble in a solvent such as alcohol and thus precipitates, so that the coating solution cannot be prepared. Furthermore, it is also possible to use alkoxyzirconium organic acid salts in which at least one of the alkoxy groups of the zirconium alkoxide is replaced with an organic acid such as acetic acid, propionic acid, butanoic acid, acrylic acid, methacrylic acid, stearic acid.

As the raw material for cerium oxide, cerium organic compounds such as cerium alkoxide, cerium acetylacetonate and cerium carboxylate can be preferably used. In addition, nitrates, chlorides,
Cerium inorganic compounds such as sulfates can also be used, but cerium nitrate and cerium acetylacetonate are preferred from the viewpoint of stability and availability.

The zinc oxide raw material is preferably zinc oxide fine particles dispersed in an organic solvent, organic acid zinc such as zinc acetylacetonate or zinc ethylhexanoate, or organic zinc modified with alkanolamines. .

As a raw material of tantalum oxide, a tantalum alkoxide, an organic tantalum compound or the like is preferable.

The kind and mixing ratio of at least one raw material of silicon oxide and titanium oxide, zirconium oxide, cerium oxide and tantalum oxide are such that the miscibility and stability with the solvent and the colored fine particles, the optical refractive index and the color. It is preferable to mechanically determine the reflection color tone in consideration of abrasion resistance and chemical durability.

When alkoxides are used as the raw material of the metal oxide used in the present invention, the hydrolysis catalysts include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, propionic acid and p-toluene. Organic acids such as sulfonic acid are used.

The coating liquid for coating the colored film and the intermediate layer can be obtained by dissolving each raw material in a solvent and mixing them at a predetermined ratio.

The organic solvent used in the present invention depends on the film forming method. For example, as the organic solvent for the gravure coating method, flexographic printing method, and roll coating method, a solvent having a low evaporation rate is suitable. This is because a solvent having a high evaporation rate evaporates before sufficient leveling is performed. The evaporation rate of the solvent is 100 times that of butyl acetate.
Is generally evaluated by the relative evaporation rate index. A solvent having a value of 40 or less is classified as a solvent having an "extremely slow" evaporation rate, and such a solvent is preferable as an organic solvent for the gravure coating method, the flexographic printing method, and the roll coating method. Examples include ethyl cellosolve, butyl cellosolve, cellosolve acetate, diethylene glycol monoethyl ether, hexylene glycol, diethylene glycol, tripropylene glycol, diacetone alcohol, tetrahydrofurfuryl alcohol and the like. It is desirable that the solvent of the coating liquid used in the present invention contains at least one kind of such a solvent. However, in order to adjust the viscosity, surface tension, etc. of the coating liquid, a plurality of the above solvents may be used. . Also, the solvent having a high evaporation rate and a relative evaporation rate of more than 100, for example, methanol (610), ethanol (34
0), n-propanol (110), isopropanol (30
A solvent such as 0) may be added to the solvent having a relative evaporation rate index of 40 or less.

The coating method used in the present invention is not particularly limited, but 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 above coating solution for colored film is applied on a glass substrate by the above coating method, and then 5 to 200 at a temperature of 100 to 400 ° C. in an oxidizing atmosphere.
Partial heat treatment is performed to precipitate fine particles for coloring in the film. Furthermore,
By firing at a temperature of 500 to 800 ° C. or higher for 10 seconds to 5 minutes, a colored film having a thickness of 30 to 200 nm is formed.

Since the present invention has the intermediate layer, the first layer is first applied and heat-dried, the second layer is applied again and heat-dried, and the above-mentioned operations are performed thereafter.

Further, as the glass substrate used in the present invention, in addition to the transparent glass plate of soda lime silicate glass composition, green glass, bronze glass and glass having an ultraviolet absorbing ability may be used. Since the colored film of the present invention itself does not have a very large ultraviolet ray shielding performance, the glass substrate has a transmittance of ultraviolet light having a wavelength of 370 nm of 20 to 70% and a visible light transmittance of 70 to 85.
%, The solar ray transmittance is 40 to 80%, and the transmitted light is
In the Lab color system, an automobile glass plate having a value of -9 to 4 and chromaticity of b of -5 to 8 and a thickness of 1.5 mm to 5.5 mm is preferably used. By coating the ultraviolet absorbing glass in this way, a colored glass having a high ultraviolet absorbing ability can be obtained.

In the present invention, the coloring by the metal fine particles and the two-layer coating can realize the reflectance control and the delicate color tone adjustment by utilizing the interference due to the film structure. Further, colored glass having various functions can be obtained by combining with a glass substrate.

[0039]

Next, the present invention will be described in more detail with reference to specific examples. Preparation of stock solution To 50 g of ethyl silicate (“Ethyl silicate 40” manufactured by Colcoat), 6 g of 0.1N hydrochloric acid and 44 g of ethyl cellosolve were added, and the mixture was stirred at room temperature for 2 hours. This solution was used as silicon oxide stock solution 1. It contains 20% SiO ₂ solids.

A chloroauric acid stock solution was prepared by dissolving chloroauric acid tetrahydrate in ethyl cellosolve so that the content of chloroauric acid tetrahydrate was 10% by weight when dissolved in a solvent.

2 mol of acetylacetone was added dropwise to 1 mol of stirring titanium isopropoxide with a dropping funnel. This solution was used as a titanium oxide stock solution. This is TiO ₂
It contains 16.5% solids.

Tetrabutoxy zirconium 388.6
Ethyl acetyl acetate 260.28 g was added to 8 g, and the mixture was stirred for 2 hours. This solution was used as a zirconium stock solution. It contains 17.8% ZrO ₂ solids.

Example 1 As a coating solution for the first layer, a silicon oxide stock solution was added in an amount of 0.
67 g and 7.27 g of ethyl cellosolve were added, and finally 2.06 g of zirconium stock solution was added and mixed and stirred to prepare coating solution 1. As the second layer coating liquid, take 3.03 g of titanium oxide stock solution, add 4.97 g of ethyl cellosolve, and finally add 2.0 g of chloroauric acid stock solution.
Coating solution 2 was prepared by adding g and mixing and stirring.

The coating liquid 1 prepared above was spin-coated on an uncolored transparent glass substrate having a thickness of 3.4 mm and a size of 10 cm × 10 cm for 15 seconds at a rotation speed of 1000 rpm. After air-drying, it was heat-treated at 250 ° C. for 2 hours, then the coating liquid 2 prepared above was spin-coated in the same manner, and after air-drying, it was heat-treated at 250 ° C. for 2 hours to deposit fine gold particles. Further, it was baked at 720 ° C. for 105 seconds to obtain a glass plate having a colored film. Visible light transmittance of the colored film, visible light reflectance (light is made incident from the glass surface side and the film surface side not covered by the colored film),
Properties such as color (transmitted light) are shown in Tables 1 to 3. The colored film obtained showed good results in chemical resistance and abrasion resistance.

Example 2 0.33 g of a silicon oxide stock solution was added, 5.04 g of cellosolve acetate was added thereto, and finally a titanium oxide stock solution of 2.6 was added.
3 g was taken, and finally, 2 g of chloroauric acid stock solution was added and mixed and stirred to prepare coating solution 3.

A glass plate having a colored film was obtained in the same manner as in Example 1 except that the coating liquid 3 was used in place of the coating liquid 2 described in Example 1. Then, the optical characteristics were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 3. The colored film obtained showed good results in chemical resistance and abrasion resistance.

Example 3 0.501 g of a silicon oxide stock solution was added, 5.08 g of cellosolve acetate was added thereto, and a titanium oxide stock solution of 2.01 was added.
42 g was taken, and finally 2 g of a chloroauric acid stock solution was added and mixed and stirred to prepare a coating solution 4.

The coating solution 1 described in Example 1 was spin-coated on a transparent glass substrate having a thickness of 3.4 mm and a size of 20 cm × 40 cm at a rotation speed of 1000 rpm for 15 seconds. After air-drying, it was heat-treated at 250 ° C. for 2 hours, then the coating liquid 4 prepared above was similarly spin-coated, and after air-drying, it was heat-treated at 250 ° C. for 2 hours to precipitate fine gold particles. Further, after holding it in an electric furnace at 720 ° C. for 120 seconds, it was pulled up and press-molded, and immediately thereafter, it was tempered by air cooling to obtain a bending-strengthened glass plate for automobile having a colored film. The bent shape was as designed and no perspective distortion was observed. Characteristics such as visible light transmittance, visible light reflectance (light enters from the glass surface side and film surface side not covered by the colored film), color (transmitted light), etc. of the colored film are shown in Table 1.
3 are shown. The colored film obtained showed good results in chemical resistance and abrasion resistance.

Examples 4 to 5 0.68 g of silicon oxide stock solution was added, 5.11 g of cellosolve acetate was added, and titanium oxide stock solution was added to 2.2.
g, finally add 2 g of chloroauric acid stock solution, mix and stir,
A coating liquid 5 (Example 4) was prepared. Further, 1.07 g of a silicon oxide stock solution was added, 5.20 g of cellosolve acetate was added thereto, 1.73 g of a titanium oxide stock solution was further collected, and finally 2 g of a chloroauric acid stock solution was added and mixed and stirred to obtain a coating solution 6 (Example 5). ) Was produced.

A colored film was prepared in the same manner as in Example 1 except that the coating liquid 5 (Example 4) or the coating liquid 6 (Example 5) was used in place of the coating liquid 2 described in Example 1. I got a glass plate. Then, the optical characteristics were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 3. Both the obtained colored films showed good results in chemical resistance and abrasion resistance.

Example 6 Instead of the uncolored transparent glass substrate used in Example 2, a green glass substrate of the same size (visual transmittance Ya = 81.
2%, solar radiation transmittance Tg = 60.9%, visible light reflectance =
7.1%, T370 nm = 62.5%, transmitted color tone; light green, transmitted light chromaticity represented by chromaticity of Lab color system a = -4.
7, b = 0.9, L = 91, reflected light chromaticity a = -1.3,
A glass plate having a colored film was obtained in the same manner as in Example 2 except that b = -0.2) was used. Then, the optical characteristics were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 3. The colored film obtained showed good results in chemical resistance and abrasion resistance.

Example 7 As a coating solution for the first layer, 1.3 parts of silica stock solution was used.
3 g, ethyl cellosolve 5.25 g, titanium oxide stock solution 1.42 g, and finally chloroauric acid stock solution 2.0 g.
In addition, mixing and stirring were performed to prepare coating liquid 7. The coating liquid 3 described in Example 2 was used as the coating liquid for the second layer.

The same operation as in Example 1 was carried out except that the above coating liquid 7 and coating liquid 3 were used in place of the coating liquid 1 for the first layer and the coating liquid 2 for the second layer described in Example 1, respectively. A glass plate having a colored film was obtained. Then, the optical characteristics were measured in the same manner as in Example 1, and the results are shown in Tables 1 to 3. The colored film obtained showed good results in chemical resistance and abrasion resistance.

[0054]

[Table 1] ================================= Example Examples Intermediate layer composition (% by weight) Refractive index Film thickness Number SiO ₂ ZrO ₂ TiO ₂ Au (nm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 60.6 39.4 0 0 1.71 73 2 60.6 39.4 0 0 1.71 73 3 60.6 39.4 0 0 1.71 73 4 60.6 39.4 0 0 1.71 73 5 60.6 39.4 0 0 1.71 73 6 60.6 39.4 0 0 1.71 73 7 44.5 0 39.5 16.0 1.76 71 ========== =======================

[0055]

[Table 2] ================================ Example Examples Colored film composition (% by weight) Refractive index Film thickness Number SiO ₂ TiO ₂ Au (nm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 0 84.0 16.0 2.20 97 2 11.0 73.0 16.0 2.08 90 3 16.8 67.2 16.0 2.02 93 4 23.0 61.0 16.0 1.95 95 5 36.1 47.9 16.0 1.83 95 6 11.0 73.0 16.0 2.08 90 7 11.0 73.0 16.0 2.08 90 =================== ===============

[0056]

Table 3 ================================= Example Ya Tg Transmission color tone Transmission chromaticity Glass surface reflectance Number (%) (%) (a / b / L) (%) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 55.7 61.6 Green Blue -11.4 /-10.4/76.9 14.1 2 53.8 64.5 Green Blue -12.0 /-12.0/75.7 12.0 3 53.3 65.4 Blue -10.7 /-13.0/75.3 11.0 4 54.4 67.0 Blue -9.29 / -12.0 / 75.8 10.9 5 58.2 71.1 Blue Purple 0.47 / -12.0 / 77.2 8.33 6 47.9 44.2 Blue Green -17.3 /-11.4/72.3 9.91 7 39.2 58.0 Deep Blue -11.3 /-18.9/65.5 6.53 ================= ==================

[0057]

[Table 4] ================================= glass surface film surface example reflection chromaticity film surface reflectance Reflection chromaticity Reflection color tone number (a / b / L) (%) (a / b / L) (glass surface) ----------------------------- −−−−−−−−−− 1 -6.67 / 5.6 /38.0 13.0 -5.19 / -1.62 / 36.9 White Yellow 2 -2.66 / 1.02 / 34.9 12.3 -2.22 / -2.99 / 35.6 Neutral 3 -1.22 / 0.66 / 33.3 12.0 -0.64 / -2.90 / 34.9 Neutral 4 -1.21 / -0.93 / 33.3 10.5 -2.56 / -6.10 / 33.2 Neutral 5 1.34 / -1.16 / 28.8 8.77 3.45 / -3.21 / 29.5 Neutral 6 -2.30 / 1.96 / 31.6 12.9- 0.49 / -0.49 / 35.9 Neutral 7 -5.44 / 1.52 / 40.0 12.8 -3.50 / -5.39 / 26.4 Pale white =========================== =======

Comparative Examples 1 to 6 Coating of the first layer of Examples 1 to 6 was not carried out, and only the coating liquid of the second layer was applied, air-dried and heat treated in the same manner as in Examples 1 to 6. Examples 1 to 6
Comparative Examples 1 to 6 are provided corresponding to The characteristics of the obtained glass plate are shown in Tables 4 to 6.

Comparative Example 2 The characteristics of the glass plate obtained by coating, air-drying and heat-treating the coating solution 3 used in Example 2 alone as the coating solution in the same manner as in Example 1 are shown in Tables 4 to 6. The obtained colored film was colored blue and the reflection color tone of the glass surface was yellowish white.

Comparative Example 3 As in Example 1, only the coating liquid 4 used in Example 3 as a coating liquid was applied, air-dried and heat-treated, and the characteristics of the glass plate are shown in Tables 4 to 6. The obtained colored film was colored blue and the reflection color tone of the glass surface was yellow.

Comparative Example 4 The characteristics of the glass plate obtained by coating, air-drying and heat-treating only the coating liquid 5 used in Example 4 as the coating liquid in the same manner as in Example 1 are shown in Tables 4 to 6. The obtained colored film was colored blue and the reflection color tone of the glass surface was yellow red.

Comparative Example 5 The characteristics of the glass plate obtained by coating, air-drying and heat treating the coating liquid 6 used in Example 5 alone as the coating liquid in the same manner as in Example 1 are shown in Tables 4 to 6. The obtained colored film was colored blue, and the reflection color tone of the glass surface was red yellow.

Comparative Example 6 As in Example 6, only the coating liquid 3 used in Example 2 as a coating liquid was applied, air-dried, and heat-treated, and the characteristics of the glass plate are shown in Tables 4 to 6. The obtained colored film was colored blue, and the reflection color tone of the glass surface was yellowish green. Comparative Example 1 A glass obtained by coating, air-drying, and heat-treating the coating solution 2 used in Example 1 alone as the coating solution without coating the first layer of Example 1 in the same manner as in Example 1. The properties of the plates are shown in Tables 4-6. The obtained colored film was colored blue and the reflection color tone of the glass surface was yellow.

Comparative Example 2 The characteristics of the glass plate obtained by coating, air-drying and heat-treating the coating solution 3 used in Example 2 alone as the coating solution in the same manner as in Example 1 are shown in Tables 4 to 6. The obtained colored film was colored blue and the reflection color tone of the glass surface was yellowish white.

Comparative Example 3 The characteristics of the glass plate obtained by coating, air-drying, and heat-treating only the coating liquid 4 used in Example 3 as the coating liquid in the same manner as in Example 1 are shown in Tables 4 to 6. The obtained colored film was colored blue and the reflection color tone of the glass surface was yellow.

Comparative Example 4 The characteristics of the glass plate obtained by coating, air-drying and heat-treating the coating solution 5 used in Example 4 alone as the coating solution in the same manner as in Example 1 are shown in Tables 4 to 6. The obtained colored film was colored blue and the reflection color tone of the glass surface was yellow red.

Comparative Example 5 The characteristics of the glass plate obtained by coating, air-drying and heat-treating the coating solution 6 used in Example 5 alone as the coating solution in the same manner as in Example 1 are shown in Tables 4 to 6. The obtained colored film was colored blue, and the reflection color tone of the glass surface was red yellow.

Comparative Example 6 In the same manner as in Example 6, only the coating liquid 3 used in Example 2 as a coating liquid was applied, air-dried, and heat-treated, and the characteristics of the glass plate are shown in Tables 4 to 6. The obtained colored film was colored blue, and the reflection color tone of the glass surface was yellowish green.

[0069]

[Table 5] ================================= Comparative Example Film Composition (% by Weight) Refractive Index Film Thickness Number SiO ₂ TiO ₂ Au (nm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 10.0 84.0 16.0 2.2 97 2 11.0 73.0 16.0 2.08 90 3 16.8 67.2 16.0 2.02 93 4 23.0 61.0 16.0 1.95 95 5 36.1 47.9 16.0 1.83 95 6 11.0 73.0 16.0 2.08 90 ======================== ===========

[0070]

[Table 6] ================================= Comparative Example Ya Tg Transmission color tone Transmission chromaticity Glass surface reflectance Number (%) (%) (a / b / L) (%) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 54.1 58.6 Green Blue -15.1 /-13.4/76.5 14.5 2 50.7 61.4 Green Blue -14.5 /-16.3/74.3 10.7 3 51.0 63.3 Blue -11.4 /-16.9/74.1 9.0 4 51.9 74.6 Blue -9.56 / -17.0 / 74.6 10.5 5 56.2 68.8 Purple -0.62 / -15.5 / 76.3 10.2 6 48.5 43.5 Blue-green -17.5 /-13.4/72.9 11.6 ============================ ======

[0071]

[Table 7] ================================= glass surface film surface comparative example reflection chromaticity film surface reflectance Reflection chromaticity Reflection color tone number (a / b / L) (%) (a / b / L) (glass surface) ----------------------------- −−−−−−−−−− 1 -1.54 / 12.3 / 37.3 14.5 -1.84 / 8.9 /37.6 Yellow 2 2.26 / 7.38 / 31.8 12.8 1.46 / 7.09 / 35.0 Yellow White 3 3.49 / 4.32 / 29.2 13.3 2.23 / 7.7 /35.5 Yellow 4 4.44 / 6.32 / 31.4 13.4 0.08 / 8.07 / 36.0 Yellow Red 5 6.28 / 4.88 / 30.8 12.1 1.94 / 6.34 / 34.1 Red Yellow 6 -1.91 / 8.60 / 33.0 14.8 -2.44 / 10.5 /37.9 Yellow Green ===== ============================

The above-mentioned Examples 1 to 6 and Comparative Examples 1 to 6 differ from each other only in the presence or absence of the first layer by the same reference numbers. The Comparative Example does not include the first layer of the Example, and the same second example as the Example. It has only layers.

As shown in Table 8, the saturation (value of (a ² + b ² ) ^{1/2 in} the Lab color system) of the reflection color of the glass surface is as follows. In the example, the saturation of reflected color is 3.7 to 6.2 lower than that in the comparative example. In the present invention, it can be seen that by providing the intermediate layer, the saturation of the reflected color is lowered and the reflected color is close to neutral gray (neutral).

Next, transmission hue and reflection color (glass reflection surface)
The difference from the hue will be compared. The hue is defined by the polar coordinate angle (θ) where a and b are represented in Cartesian coordinates in the Lab color system. Red is 0 degrees, yellow is 90 degrees, and green is 1
80 degrees and blue are displayed as 270 degrees. The transmission hue and the reflection hue are defined by the transmission hue angle (θt) and the reflection hue angle (θr), respectively. As shown in Table 9, the difference between the transmission hue angle (θt) and the reflection hue angle (θr) (| θt-θr |, but if this difference exceeds 180 degrees, it is shown as a value subtracted from 360 degrees). Is 115 to 176 degrees in the comparative example. On the other hand, in the embodiment, 1
It is as small as 5 to 83 degrees, which indicates that the transmitted color tone and the reflected color tone are relatively close to each other in the present invention.

[0075]

[Table 8] ===================== Reflected color (glass reflective surface) Saturation --------------- --- Example 1 8.7 Comparative Example 1 12.4 --------------------------- Example 2 2.8 Comparative Example 2 7.7 ------------ --------------- Example 3 1.4 Comparative Example 3 5.6 ----------------------- Example 4 1.5 Comparative Example 4 7.7 ----- −−−−−−−−−−−−−−−− Example 5 1.8 Comparative Example 5 8.0 −−−−−−−−−−−−−−−−−−−− Example 6 3.0 Comparative Example 6 8.8 =====================

[0076]

[Table 9] =============================== Hue Angle (degree) Example Comparative Example -------- −−−−−−−−−−−−−−−−−−−−−−−−−− Transmission reflection difference Transmission reflection difference θt θr ｜ θt-θr ｜ θt θr ｜ θt-θr ｜ --- −−−−−−−−−−−−−−−−−−−−−−−−−− Example 1 222 139 83 Comparative Example 1 221 97 124 −−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Example 2 224 159 65 Comparative Example 2 228 72 156 −−−−−−−−−−−−−−−−−−− −−−−−−−−−−−− Example 3 230 151 79 Comparative Example 3 235 51 176 −−−−−−−−−−−−−−−−−−−−−−−−−−− ----- Example 4 232 217 15 Comparative Example 4 240 54 174 ------------------------------------------ 5 27 2 319 47 Comparative Example 5 264 37 133 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 6 213 139 74 Comparative Example 6 217 102 115 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 7 239 164 75 =========== ====================

[0077]

As described above, according to the present invention, with the coloring film having the reflection color of the glass surface, the saturation of the reflection color becomes small, the reflection color tone is close to neutral, and the hue of the reflection color is close to the hue of the transmission color. A glass article is obtained. The glass article with a colored film of the present invention can be used for windows, mirrors and the like for vehicles and construction.

Claims (7)

[Claims] 1. At least one element selected from the group consisting of 0 to 70 silicon oxide, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide, expressed as% by weight, gold, gold and gold. A coloring film containing as a main component at least one kind of coloring fine particles 5 to 30 selected from the group consisting of silver, silver, and palladium, and provided between the coloring film and the glass substrate and expressed in% by weight. A silicon oxide 20-100, at least one selected from the group consisting of titanium oxide, zirconium oxide, cerium oxide, zinc oxide, and tantalum oxide, and a group consisting of gold, silver, and palladium. The refractive index of the colored film containing at least one kind of selected coloring fine particles 0 to 30 is at least 0.
08 A colored film-coated glass article having an intermediate layer having a low refractive index. 2. The colored film-covered glass article according to claim 1, wherein the transmitted color has a color tone of Lab -20, where a is -20 to 10 and b is -20 to 10. 3. The transmitted color has a color tone of Lab color system, wherein a has a color tone of −20 to 5 and b has a color tone of −20 to −5.
The colored film-covered glass article according to claim 2. 4. The reflection color on the glass surface side is represented by Lab color system, a is −7 to 5 and b is −8 to 6, and the reflectance on the film surface side is 13% or less. The colored film-covered glass article according to any one of claims 1 to 3. 5. The colored film-covered glass article according to claim 1, wherein the reflection color of the glass surface is represented by the Lab color system, where a is −6 to 2 and b is −3 to 2. . 6. The colored film, expressed in weight%, comprises silicon oxide 10-40, titanium oxide 45-75, and gold 10-20, and has a thickness of 80-120 nm and 1.80-2.1.
It has a refractive index of 0, and the intermediate layer is represented by weight% and comprises silicon oxide 55-65, zirconium oxide 35-45, and a thickness of 65-85 nm and 1.65-1.75.
The refractive index of the colored film is 0.10 to 0.10.
The colored film-coated glass article according to any one of claims 1 to 5, which has a refractive index lower than 0.40. 7. The glass substrate has a thickness of 1.5 to 5.5 mm, and the transmitted light thereof has a value of −9.0 to 4 and a color of b of −5 to 8 in the Lab color system. A glass plate for an automobile window, which has a transmittance of ultraviolet light having a wavelength of 370 nm of 20 to 70%, a visible light transmittance of 70 to 85%, and a solar light transmittance of 40 to 80%. Item 7. A colored film-coated glass article according to any one of items 1 to 6.