JPH10316885A - Composition for forming colored film and production of glass product coated with colored film thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for forming colored films, capable of controlling the formation of fine gold particles and separation of the fine gold particles in the film surface, and excellent in storage stability by including an organosilicon compound, gold chloride and compound having a maximum exothermic peak observed in the differential thermal analysis in a specific temperature range. SOLUTION: This composition contains at least an organosilicon compound (e.g. tetramethoxysilane), gold chloride, and at least one type of compound showing a maximum exothermic peak observed by the differential thermal analysis at 170 to 250 deg., selected from the group consisting of an organic compound having an ether bond and C-C double bond in the molecule and compound having 6 ethylene oxide units (e.g. trimethylol propane triacrylate), preferably at 0.5 to 5 wt.% based on the whole composition. It is preferable to heat and sinter the composition spread over a glassy base material, to produce the glass product coated with the colored film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a colored film, particularly a composition having excellent storage stability for forming a colored film used for vehicles such as automobiles and windows and mirrors of buildings. The present invention relates to a method for producing a colored film-coated glass article using a colored film forming composition.

[0002]

2. Description of the Related Art As a method of obtaining a colored glass, a silver inorganic salt or a copper inorganic salt is applied to a glass surface and then baked, whereby fine particles of silver or copper in the inorganic salt penetrate into a glass substrate. There is an ion-exchange method for colloidally developing glass. In addition, there is a method in which a metal salt such as gold or silver is dissolved in a solution of silicon alkoxide, and the solution is applied to a substrate and heat-treated to form a silicon oxide film containing fine metal particles.

[0003] In particular, glass colored with surface plasmons of fine particles of gold or silver has excellent heat resistance and light resistance, and has been used as a colored glass or a filter glass for some time. In recent years, the sol-gel method is often used. For example, J. Sol-Gel. Sci. Techn. 1, 305-312 (1994)
Is formed by applying a solution containing chloroauric acid and an alkoxide of silane onto a glass substrate and then heat-treating the solution so that gold fine particles are dispersed in a silica film serving as a matrix. It is stated that a board is obtained.

[0004]

However, when obtaining a glass coated with a fine gold particle-dispersed colored film by the sol-gel method,
What has been a problem so far is that, during the heat treatment of the coating film, the growth of the fine gold particles and the shrinkage of the matrix occur simultaneously, so that the fine gold particles are likely to be repelled out of the film. The flipped-out gold fine particles are easily peeled off by wiping with a hand, so that the ratio of chloroauric acid in the coating solution remaining as gold fine particles in the colored film is reduced and the coloring effect is reduced.

In an actual mass production process, the amount of fine particles repelled to the outside of the film fluctuates, which causes the quality of the colored glass to fluctuate, resulting in a decrease in yield and an increase in cost.

The present invention provides a colored film forming composition for preventing the above-mentioned deposition of gold fine particles on the film surface and stably producing gold fine particle-dispersed glass by a sol-gel method, and coloring using the same. It is an object to provide a method for producing a film-coated glass article.

[0007]

That is, the present invention provides a composition for forming a colored film containing at least an organosilicon compound and chloroauric acid, which has a maximum exothermic peak at 170 ° C. to 250 ° C. in differential thermal analysis. It is a composition for forming a colored film, characterized by adding a kind of compound.

[0008] In the present invention, the maximum exothermic peak in differential thermal analysis (temperature at which the maximum exothermic peak is observed among several exothermic peaks) is added to a composition for forming a colored film containing at least an organosilicon compound and chloroauric acid. ) At 170 ° C
As the compound having a temperature of up to 250 ° C., an organic compound or an inorganic compound can be used. As the organic compound, an organic substance having an ether bond and a carbon-carbon double bond in the molecule can be preferably used.

Examples of the organic substance include acrylates, methacrylates, and vinyl compounds having an ether bond in the molecule. Specific examples thereof include trimethylolpropane triacrylate having six ethylene oxide units in the molecule (maximum heat generation). Peak temperature = 23
4 ° C.) is a preferred example. The amount of the organic substance to be added is preferably 0.5 to 5% by weight, more preferably 0.7 to 4% by weight, based on the total amount of the colored film forming composition (including the total amount of the coating liquid and the solvent). By changing the addition amount within these ranges, it is presumed that the particle size or particle shape of the gold fine particles will probably change, but the transmission color tone of the colored film can be adjusted. If the addition amount is too small, the effect of preventing deposition on the film surface is thin, and if the addition amount is too large, the film becomes a color close to metal gold without obtaining a bright color, and the haze is undesirably large. . This is probably because the size of the gold fine particles became too large.

Inorganic compounds having a maximum exothermic peak at 170 ° C. to 250 ° C. in differential thermal analysis include, for example, cerium nitrate (maximum exothermic peak temperature = 200 ° C.), cobalt chloride (maximum exothermic peak temperature = 234 ° C.), Iron nitrate (maximum exothermic peak temperature = 225 ° C.) and iron chloride (maximum exothermic peak temperature = 249 ° C.).
The amount of the inorganic compound to be added is 0.3 to 0.3% based on the total solid content of the composition for forming a colored film (the total solid content when the composition for forming a colored film is dried and fired to form a solid film). 20% by weight is preferred. More preferably, it is 0.5 to 15% by weight.
Since these inorganic compounds remain in the colored film as oxides, when the amount used is large, cerium oxide absorbs ultraviolet light, and cobalt oxide and iron oxide absorb visible light to change the color tone of the colored film. .

After the composition is applied to the surface of a substrate, in a heat treatment step, the organosilicon compound is hydrolyzed and polycondensed to form a silica matrix, and chloroauric acid is thermally decomposed to form gold fine particles. However, by adding a compound having a maximum exothermic peak at 170 ° C. to 250 ° C. to the composition, the gold fine particles are repelled out of the film and deposited on the surface of the film and do not contribute to coloring. And increase the coloring effect. Further, by adjusting the amount of the compound added, a subtle color tone can be changed.

The reason why the additive compound prevents the deposition of gold fine particles on the film surface is presumed as follows. That is, judging from the TG-DTA characteristic curve of the compound, the added compound shows a maximum exothermic peak at a certain temperature in the range of 170 to 250 ° C., and its weight is rapidly reduced. When the above-mentioned coating film is heat-treated, at a temperature near 200 ° C., the network structure of the silica matrix becomes smaller due to rapid shrinkage of the film. At that time, in the network structure, the gold fine particles in the growth process tend to be pushed out of the film as a result of being pushed out of the network, but at this time, the additive compound causes rapid shrinkage of the film. In order to secure the growth area of the gold fine particles, the gold fine particles are prevented from being pushed out of the film. In addition, after the gold microparticles have completely grown, the matrix does not extrude because the contraction of the matrix has progressed.

Further, the heat generation of the additive compound causes the growth of the fine gold particles and the contraction of the matrix around the fine gold particles to be performed simultaneously, and the growth and fixation of the fine gold particles are performed in a short time. Further, by adjusting the amount of the additive, that is, by adjusting the space region where the gold fine particles grow and the amount of generated heat, delicate control of the color tone becomes possible.

If a compound having a maximum exothermic peak of less than 170 ° C. or exceeding 250 ° C. is added, the temperature of the exotherm does not coincide with the temperature for forming and depositing the fine gold particles, so that the fine gold particles are extruded out of the film. Can not be prevented.

The components of the composition for forming a colored film according to the present invention will be described below. The organic silicon compound causes the film to have a silicon oxide component, and silicon oxide is necessary as a matrix material having a low refractive index in order to fix gold fine particles and make the color of the gold fine particles red-based. Further, it is necessary to keep the visible light reflectance of the film low. If the content is too low, the reflectance will be too high. In addition, if the amount is too large, the coloring becomes thin, and the commercial value of the colored glass decreases. Therefore, the content of the organic silicon compound relative to the total solid content of the composition for forming a colored film is 50 to 94% by weight in terms of SiO ₂ , and more preferably 70 to 94% by weight.
92%.

In the present invention, the organic silicon compound which is a raw material of silicon oxide for forming a colored film is a compound which can form a transparent and strong film by a sol-gel method and has excellent stability, that is, a compound which undergoes hydrolysis and polycondensation. Any compound can be used as long as it is a silicon compound that can be formed, and is specifically described below.

As the organic silicon compound which is a raw material of silicon oxide, an alkoxide of silicon is preferable, and examples thereof include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane. Condensates of these (n ≧ 2, where n represents the degree of condensation) or mixtures of the condensates are also conveniently used. For example, as a condensate, hexaethoxydisiloxane (n = 2), octaethoxytrisiloxane (n = 3), decaethoxytetrasiloxane (n = 2)
4), ethoxypolysiloxane (n ≧ 5) and the like can be used. “Ethyl silicate 40” (trade name, manufactured by Colcoat Co., Ltd.) consisting of a mixture of a monomer (n = 1) and a condensate (n ≧ 2) [composition: Colloids, Cihlar literature
and Surfaces A: Physicochem.Eng.Aspects 70 (1
993), pp. 253 to 268. Monomer (n = 1) by weight fraction: 12.8% by weight, 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]].

In addition, an alkyl trialkoxysilane in which the alkoxy group of the above compound is substituted with an alkyl group or other hydrocarbon group can also be used. For example, when the alkoxy group is a methyl group, an ethyl group, a propyl group, a butyl group,
-Ethylbutyl group, linear or branched alkyl group such as octyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, vinyl group, allyl group, γ-
Methacryloxypropyl group, alkenyl group such as γ-acryloxypropyl group, aryl group such as phenyl group, toluyl group, xylyl group, aralkyl group such as benzyl, phenethyl group or γ-mercaptopropyl group, γ-chloropropyl And those substituted with a γ-aminopropyl group.

The chloroauric acid in the composition for forming a colored film according to the present invention disperses and deposits fine gold particles in the film, and the fine gold particles in the film are necessary for coloring the film to a bright color. Yes, too much will not only reduce the durability of the membrane,
In production, since gold fine particles are formed after coating the film, the shape of the fine particles becomes large, and a desired coloring cannot be obtained. Therefore, the content of chloroauric acid based on the total solid content of the composition for forming a colored film is 5 to 20% by weight, and preferably 7 to 18% by weight in terms of Au.

The composition for forming a colored film of the present invention comprises
The maximum exothermic peak in the differential thermal analysis was 170 ° C. to 250
In addition to the compound having a temperature of ℃, the organic silicon compound contains 50 to 94% by weight in terms of SiO ₂ , and chloroauric acid in an amount of 5 to 20% by weight in terms of Au. , If necessary, other components, organic zirconium compound, organic aluminum compound, organic titanium compound, organic or inorganic manganese compound, organic or inorganic chromium compound, organic or inorganic nickel compound, organic or inorganic copper compound, organic Alternatively, a metal compound such as an inorganic zinc compound, an organic or inorganic vanadium compound, an organic or inorganic indium compound, an organic or inorganic bismuth compound, an organic or inorganic antimony compound, or an organic or inorganic tin compound can be contained. .

The above-mentioned compounds are used to form zirconium oxide, aluminum oxide, titanium oxide, manganese oxide, chromium oxide, nickel oxide, copper oxide, zinc oxide,
It contains vanadium oxide, indium oxide, bismuth oxide, antimony oxide, and tin oxide. These components can be contained for adjusting the color tone if necessary. If the amount is too large, the reflectance of the film becomes too high.

Further, a small amount of an organic or inorganic boron compound or an organic or inorganic phosphorus compound may be contained.
Therefore, the organic zirconium compound, the organic aluminum compound, the organic titanium compound, the organic or inorganic manganese compound, the organic or inorganic chromium compound, the organic or inorganic nickel compound, the organic or inorganic copper based on the total solid content of the colored film forming composition Compound, organic or inorganic zinc compound, organic or inorganic vanadium compound, organic or inorganic indium compound, organic or inorganic bismuth compound, organic or inorganic antimony compound, organic or inorganic tin compound, organic or inorganic boron compound , And the content of a metal compound such as an organic or inorganic phosphorus compound is ZrO ₂ , Al ₂ O ₃ , TiO ₂ ,
MnO ₂ , Cr ₂ O ₃ , NiO, CuO, ZnO, V
₂ O ₅ , In ₂ O ₃ , Bi ₂ O ₃ , Sb ₂ O ₅ , SnO ₂ , B ₂ O
₃ and P ₂ O ₅ , and their sum is 0 to 1
It is preferably 0% by weight, more preferably 0 to 8% by weight.

Examples of the organic zirconium compound which is a raw material of zirconium oxide include tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra n-propoxy zirconium, tetraisopropoxy zirconium isopropanol complex, tetraisobutoxy zirconium, and tetra n-zirconium. Butoxyzirconium, tetrasec-butoxyzirconium, tetrat-butoxyzirconium and the like can be conveniently used. Zirconium halide alkoxides such as zirconium monochloride trialkoxide and zirconium dichloride dialkoxide in which the alkoxy group is replaced by a halogen group can also be used. 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 COCH ₃ COOR, such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, and butyl acetoacetate, where R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ , or C _{3 The} acetoacetates represented by ₄ H ₉ ) can be listed, and among them, acetoacetate alkyl esters, particularly methyl acetoacetate and ethyl acetoacetate, are preferable because they can be obtained at relatively low cost.

The degree of chelation of the zirconium alkoxide may be part or all, but chelation at a molar ratio of (β-ketoester) / (zirconium alkoxide) = 2 is because the chelate compound is stable. preferable. 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 precipitates, making it impossible to prepare a coating solution. Further, at least one of the alkoxy groups of the zirconium alkoxide is acetic acid, propionic acid,
It is also possible to use alkoxyzirconium organic acid salts replaced by organic acids such as butanoic acid, acrylic acid, methacrylic acid and stearic acid.

As the organic aluminum compound which is a raw material of aluminum oxide, an aluminum alkoxide, an inorganic aluminum compound such as aluminum nitrate and aluminum chloride, an organic aluminum compound and the like are preferable.

As the organic titanium compound which is a raw material of titanium oxide, an organic compound of titanium such as titanium alkoxide, titanium acetylacetonate and titanium carboxylate is preferably used. The titanium alkoxide is generally represented by Ti (OR) ₄ (R is an alkyl group having up to 4 carbon atoms). Titanium isopropoxide and titanium butoxide are preferable in view of reactivity.

It has also been known that in the case of titanium, the use of acetylacetonate is preferred from the viewpoint of its stability. In this case, the general formula is Ti
(OR) _m L _n (m + n = 4, n ≠ 0)
L is acetylacetone. In this case, the titanium alkoxide may be acetylacetonated with acetylacetone, or commercially available titanium acetylacetonate may be used. Further, a carboxylate can be used.

The composition for forming a colored film of the present invention is obtained by dissolving each of the above-mentioned raw materials in a solvent and mixing them at a predetermined ratio. The usual use amount of the total solvent is 10 to 100 parts by weight based on 10 parts by weight of the total amount of the organometallic compound and the chloroauric acid. When a silicon alkoxide is used in the present invention, examples of the hydrolysis catalyst include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid, oxalic acid, formic acid, propionic acid and p-toluenesulfonic acid.

The 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 1 times that of butyl acetate.
It is generally evaluated using a relative evaporation rate index of 00. Solvents with a value of 40 or less are classified as solvents with very slow evaporation rates,
It is preferable as an organic solvent for the gravure coating method, flexographic printing method, and roll coating method.

Examples include ethyl cellosolve, butyl cellosolve, cellosolve acetate, diethylene glycol monoethyl ether, hexylene glycol, diethylene glycol, tripropylene glycol, diacetone alcohol, and tetrahydrofurfuryl alcohol. The solvent for the composition for forming a colored film (coating solution) used in the present invention desirably contains at least one such solvent. However, in order to adjust the viscosity, surface tension, etc. of the coating solution, the solvent may be used. May be used plurally. Further, a solvent having a high evaporation rate and a relative evaporation rate exceeding 100, for example, methanol (61
0), ethanol (340), n-propanol (30
A solvent such as 0) may be added to the above-mentioned solvent having a relative evaporation rate index of 40 or less.

The composition for forming a colored film of the present invention is applied on a substrate by a coating method described below, and then at a temperature of 200 to 300 ° C. for 5 to 200 minutes in an oxidizing atmosphere.
After heating to precipitate gold fine particles, baking is performed at a temperature of 500 to 800 ° C. for 10 seconds to 5 minutes, so that a thickness of 200
A thin film of nm or less is formed.

As the substrate on which the composition for forming a colored film of the present invention is applied, a glass substrate is suitably used. In addition to a glass plate having a transparent soda lime silicate glass composition, a green substrate is used as the glass substrate. Glass, bronze-colored glass, and glass having an ultraviolet absorbing ability. Since the colored film itself obtained by the present invention does not have a very large ultraviolet shielding performance, the transmittance (T) of ultraviolet light having a wavelength of 370 nm as a glass substrate is used.
370 nm) is 10% to 50%, and the visible light transmittance is 70%.
A glass sheet for automobiles having a thickness of 1.5 to 5.5 mm and a thickness of 1.5 to 5.5 mm is preferably used. Thus, by coating the composition for forming a colored film of the present invention on an ultraviolet absorbing glass plate, a colored glass plate having high ultraviolet absorbing ability can be obtained.

The coating method used in the present invention is not particularly limited, and examples thereof include a spin coating method, a dip coating method, a spray coating method, and a printing method. 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 high use efficiency of the coating liquid composition.

The surface plasmon absorption, which causes coloring of the gold fine particles, shifts in the absorption range depending on the value of the refractive index of the matrix. The maximum exothermic peak is 170 ° C to 25
The absorption peak can also be adjusted by changing the concentration of the compound additive having a temperature of 0 ° C., whereby the transmission color tone can be adjusted.

Accordingly, a colored glass article obtained by applying and heating the composition for forming a colored film of the present invention, particularly a glass plate coated with a colored film used for automobile windows, architectural windows, etc.
A represents −4 to 20, and b represents −15 to 5 in the Lab color system.
It is preferable to have a transmission color tone having a chromaticity in the range of
More preferably, the chromaticity of transmitted light is such that a is −2 to 15 and b is −1
It is in the range of 2-3. Also, this colored glass article has 60
It preferably has a lightness (L) of transmitted light of 90.

If the thickness of the colored film obtained by applying and heating the composition for forming a colored film of the present invention is too small, sufficient coloring cannot be obtained. Conversely, if the thickness is too large, the film strength may decrease. 30 ~ 200nm
And more preferably 40 to 180 nm.
More preferably, it is 50 to 160 nm. The colored film has a refractive index of 1.40 to 1.70.

[0037]

Next, the present invention will be described in more detail with reference to specific examples. In the optical evaluation in the present invention, in order to clarify the effect of the present invention, before wiping the film surface after sintering with a wiping cloth, and after wiping, the surface deposition state of the gold fine particles was evaluated by optical measurement. . ΔYa in the table is the value of the visible light transmittance (Ya) after wiping the film surface (thereby removing gold fine particles that may precipitate on the surface) and the visible light before wiping the film surface. The value of the difference (Ya-Y1) between the transmittance values (Y1) indicates that the smaller the value of ΔYa, the smaller the amount of gold fine particles deposited on the surface, and the greater the effect of the present invention.

[Example 1] 0.1N was added to 50 g of ethyl silicate ("Ethyl silicate 40" manufactured by Colcoat).
6 g of 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.

Chloroauric acid tetrahydrate was dissolved in ethyl cellosolve to a concentration of 10% by weight to obtain a chloroauric acid stock solution.

2.5 g of the silicon oxide stock solution 1 prepared as described above was taken, and 5.9 g of ethyl cellosolve and trimethylolpropane acrylate ethylene oxide 6 were added thereto.
After adding 0.1 g of the adduct, the chloroauric acid stock solution was finally added to 1.
5 g was added and mixed and stirred to prepare a coating liquid 1.

The coating solution 1 prepared above was spin-coated on a transparent glass substrate (non-colored) having a thickness of 3.4 mm and a size of 10 cm × 10 cm at a rotation speed of 1,000 rpm for 15 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. 105 ° C at 720 ° C
The firing was performed for 2 seconds to obtain a colored film-coated glass plate.

For the glass plate coated with the colored film, the refractive index and thickness of the colored film, the visible light transmittance (Ya), the difference between the visible light transmittance before and after wiping the film surface (ΔYa), the transmission color tone, Transmission chromaticity (a, b) / brightness (L), visible light reflectance (“glass surface reflectance”) and reflection chromaticity / brightness (“glass surface reflection color” when light is projected from the glass surface side) Every time·
Brightness ") and the characteristics of visible light reflectance (film surface reflectance) and reflected chromaticity / brightness (" film surface reflected chromaticity / brightness ") when light is projected from the film surface side. 1 to 3.

Examples 2 and 3 and Examples 12 and 1
3 (Table 7) is applied in the same manner, but “film composition” in Table 1
“EO6” in the column indicates the trimethylolpropane acrylate ethylene oxide 6 adduct, and its value (1.0
% By weight) is the ratio to the weight of the total amount of the coating liquid (including the solvent). The calcined film no longer contains trimethylolpropane acrylate ethylene oxide 6 adduct. In Table 1, the refractive index indicates the value of the film composition excluding the fine gold particles (the same applies to Tables 4 and 7).

The obtained colored film showed good results in chemical resistance and abrasion resistance. Further, ΔYa in the table is as small as 0.3, and it can be seen that the addition of trimethylolpropane acrylate ethylene oxide 6 adduct as an additive prevents the deposition of gold fine particles on the surface. Further, the surface precipitation of the fine gold particles could not be detected by visual inspection.

[Example 2] Coating liquid 1 of Example 1
5.85 g of ethyl cellosolve used in the preparation of
, And the amount of the trimethylolpropane acrylate ethylene oxide 6 adduct was changed to 0.15 g, respectively, except that the coating liquid 2 was prepared.

The coating solution 2 prepared above was spin-coated on a transparent glass substrate (non-colored) having a thickness of 3.4 mm and a size of 20 cm × 40 cm at a rotation speed of 1000 rpm for 10 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. Further, after holding in an electric furnace at 720 ° C. for 120 seconds, it was pulled up and press-formed, and immediately thereafter, it was air-cooled to obtain a bent glass sheet for automobiles having a colored film. The bent shape was as designed, and no perspective distortion was observed.

Tables 1 to 3 show the properties of the colored film, such as visible light transmittance, visible light reflectance, and transmission color tone. The obtained colored film showed good results in chemical resistance and abrasion resistance.

Further, ΔYa in the table is as small as 0.13, and it can be seen that the addition of trimethylolpropane acrylate ethylene oxide 6 adduct as an additive prevents the deposition of gold fine particles on the surface. Further, the surface precipitation of the fine gold particles could not be detected by visual inspection. In this embodiment, the transmission color tone is shifted to blue as compared with the first embodiment, but it is considered that the particle diameter or the particle shape of the gold fine particles has changed.

Example 3 Coating Liquid 1 of Example 1
Was performed in the same manner as in Example 1, except that 0.20 g of trimethylolpropane acrylate ethylene oxide 6 adduct and 5.80 g of ethyl cellosolve were used to prepare the coating liquid 3.

Using the coating liquid 3 prepared above,
A glass plate having a colored film was obtained by using the same type of substrate as in Example 1 and treating it under the same application conditions and heating and firing conditions as in Example 1. Then, the optical properties measured under the same conditions as in Example 1 were measured, and the results were shown in Tables 1 to 1.
3 is shown.

The obtained colored film showed good results in chemical resistance and abrasion resistance. The addition of the additive prevented the surface precipitation of the gold fine particles, and the surface precipitation of the gold fine particles could not be detected by visual inspection or the like. In this embodiment, the transmission color tone is shifted to blue as compared with the first embodiment, but it is considered that the particle diameter or the particle shape of the gold fine particles has changed.

[Examples 4 to 6] <Preparation of coating liquids 4 to 6> 2 mol of acetylacetone was added dropwise to 1 mol of titanium isopropoxide under stirring using a dropping funnel. This solution was used as a titanium oxide stock solution. It contains 16.5% TiO ₂ solids.

1.99 g of silicon oxide stock solution 1, 0.25 g of titanium oxide stock solution, and 0.26 g of cerium oxide stock solution were mixed, and 5.50 g of ethyl cellosolve was added, and finally 2.0 g of chloroauric acid stock solution was added. These were mixed and stirred to prepare a coating liquid 4 (Example 4).

Ethyl solosolve was added at 90 ° C. so that the cerium nitrate hexahydrate had a solid content of 23.2% of CeO _2.
To obtain a cerium oxide stock solution.

2.15 g of silicon oxide stock solution 1, 0.17 g of titanium oxide stock solution, and 0.18 g of cerium oxide stock solution were mixed, and 5.50 g of ethyl cellosolve was added. Finally, 2.0 g of chloroauric acid stock solution was added. The mixture was mixed and stirred to prepare a coating liquid 5 (Example 5).

2.25 g of silicon oxide stock solution 1, 0.12 g of titanium oxide stock solution, and 0.13 g of cerium oxide stock solution were mixed, and 5.50 g of ethyl cellosolve was added. Finally, 2.0 g of chloroauric acid stock solution was added. The mixture was mixed and stirred to prepare a coating liquid 6 (Example 6).

Each of the coating solutions 4 to 6 prepared above was placed on a transparent glass substrate having a thickness of 3.4 mm and a size of 10 cm × 10 cm at a rotation speed of 1000 rpm for 15 seconds.
Each was spin-coated. Each of them was air-dried and then heat-treated at 250 ° C. for 2 hours to precipitate gold fine particles, and further baked at 720 ° C. for 120 seconds.
A variety of colored film-coated glass plates were obtained. Coating liquid 4,
The colored film-coated glass sheets obtained by using Examples 5 and 6 are referred to as Examples 4, 5 and 6, respectively. Tables 1 to 3 show properties of each colored film-coated glass plate such as visible light transmittance, visible light reflectance, and transmission color tone.

The obtained colored film showed good results in chemical resistance and abrasion resistance. Also, in any of the examples, the addition of cerium nitrate as an additive prevented the surface deposition of the fine gold particles, and the surface precipitation of the fine gold particles could not be detected by visual inspection or the like. It is shown that the addition of cerium nitrate leaves cerium oxide in the film in the amount shown in Table 1 in terms of CeO2.

Example 7 100 g of iron chloride hexahydrate was added to 1
A solution dissolved in 95.7 g of ethyl cellosolve was used as a 10 wt% iron oxide stock solution.

2.38 g of the silicon oxide stock solution 1 and 0.23 g of the iron oxide stock solution were mixed, and 5.39 g of ethyl cellosolve was added. Finally, 2.0 g of the chloroauric acid stock solution was taken and mixed and stirred. Produced.

The coating solution 7 prepared above was spin-coated on a transparent glass substrate having a thickness of 3.4 mm and a size of 10 cm × 10 cm at a rotation speed of 1000 rpm for 15 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. Further, baking was performed at 720 ° C. for 120 seconds to obtain a glass plate having a colored film. Tables 1 to 3 show properties of the colored film such as visible light transmittance, visible light reflectance, and transmission color tone.

The obtained colored film showed good results in chemical resistance and abrasion resistance. The additive iron chloride 6
The addition of the hydrate prevented the deposition of the gold fine particles on the surface and could not be identified by visual inspection or the like. The same applies to Examples 8 and 9, except that the addition of iron chloride converts the iron oxide into Fe ₂ O ₃ ,
This indicates that the amount shown in Table 1 remains.

Example 8 The silicon oxide stock solution 1 was used at 2.43.
g, and 0.13 g of an iron oxide stock solution, and 5.44 g of ethyl cellosolve. Finally, 2.0 g of a chloroauric acid stock solution was taken and mixed and stirred to prepare a coating solution 8.

Using the coating liquid 8 prepared above,
Using the same type of substrate as in Example 7, a glass plate having a colored film was obtained under the same application conditions and heating and firing conditions as in Example 7. Tables 1 to 3 show properties of the colored film such as visible light transmittance, visible light reflectance, and transmission color tone.

The obtained colored film showed good results in chemical resistance and abrasion resistance. The additive iron chloride 6
By adding the hydrate, the surface deposition of the fine gold particles was prevented, and the surface precipitation of the fine gold particles could not be detected by visual inspection or the like.

Example 9 A coating liquid 8 used in Example 8 was applied to a UV cut green glass substrate having a thickness of 3.4 mm and a size of 10 cm × 10 cm (visible transmittance Ya =
73.1%, solar radiation transmittance Tg = 48.9%, visible light reflectance rg = 6.6%, transmission color tone: green, expressed by chromaticity of Lab color system, transmitted light chromaticity a = − 7.1, b = 2.8, L
= 86, chromaticity of reflected light a = -1.7, b = -0.1), spin coating was performed at 1000 rpm for 10 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. Further, baking was performed at 720 ° C. for 120 seconds to obtain a glass plate having a colored film. Tables 1 to 3 show properties of the colored film such as visible light transmittance, visible light reflectance, and transmission color tone.

The obtained colored film showed good results in chemical resistance and abrasion resistance. The additive iron chloride 6
By adding the hydrate, the surface deposition of the fine gold particles was prevented, and the surface precipitation of the fine gold particles could not be detected by visual inspection or the like.

[0068]

Table 1 ================================= Actual Membrane Composition (% by Weight) Application Matrix Additive Amount Refractive index Thickness Example −−−−−−−−−−−−−−−−−−−− No (cerium nitrate) (iron chloride) SiO ₂ TiO ₂ Au CeO ₂ Fe ₂ O ₃ EO6 −−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 87.5 0.0 12.5 −− −− 1.0wt% 1.46 125nm 2 87.5 0.0 12.5 −− − − 1.5wt% 1.46 125nm 3 87.5 0.0 12.5 −− −− 2.0wt% 1.46 127nm 4 67.0 6.85 16.0 10.2 −− −− 1.54 110nm 5 72.1 4.79 16.0 7.1 −− −− 1.51 105nm 6 75.7 3.35 16.0 5.0 −− −− 1.50 108nm 7 80.1 0.0 16.1 −− 3.9 −− 1.49 85nm 8 81.7 0.0 16.1 −− 2.2 −− 1.47 90nm 9 81.7 0.0 16.1 −− 2.2 −− 1.47 87nm ================ ===================

[0069]

TABLE 2 ================================= Example Ya ΔYa Transmission Color Tone Transmission Chromaticity / Brightness Glass Surface reflectivity number (%) (a / b / L) (%) --------------------------------------------------- − 1 79.9 0.3 Winelet ゛ 6.4 / -1.6 / 88.8 7.98 2 78.0 0.13 Pink 7.4 / -3.3 / 87.7 8.08 3 76.9 0.24 Pink 6.3 / -4.1 / 87.3 7.96 4 74.2 -0.02 Pink 6.1 / -4.6 / 85.8 10.44 5 77.4 0.03 Pink 5.7 / -3.9 / 87.6 9.39 6 76.7 0.06 Pink 6.9 / -4.7 / 87.1 9.23 7 74.1 0.3 Pink 8.9 / -4.3 / 85.4 8.8 8 74.0 0.3 Pink 9.3 / -4.0 / 85.2 8.6 9 64.3 0.2 Neutral gray 0.1 / 0.5 /80.2 6.7 =================================

[0070]

[Table 3] =========================== Glass Surface Reflection Film Surface Reflection Example Chromaticity / Lightness Film Surface Reflectivity Lightness number (a / b / L) (%) (a / b / L) --- --- --- --- --- --- --- --- --- --- --- 10.2 / 0.3 /28.2 6.88 3.7 / -0.7 / 25.8 2 -0.4 / 0.5 / 28.4 5.95 5.5 / -2.6 / 23.9 3 -0.5 / 0.5 / 28.2 5.49 4.9 / -4.2 / 23.2 4 3.6 / 1.5 / 30.7 10.4 2.5 / 3.4 / 31.8 5 3.1 / 1.2 / 29.4 9.39 2.6 / 2.6 / 30.1 6 3.7 / 1.6 / 28.6 9.23 2.3 / 3.3 / 29.8 7 1.5 / 1.5 / 29.3 7.9 4.7 / 1.8 / 27.3 8 1.7 / 1.3 / 29.0 7.8 4.4 / 1.5 / 27.3 9 -0.8 /1.0/26.0 6.2 1.9 / 1.7 / 24.6 ===========================

[Comparative Example 1] 2.5 g of the silicon oxide stock solution 1 used in Example 1 was taken, and ethyl cellosolve 5.5 was added thereto.
g, and finally, 2 g of chloroauric acid stock solution was added and mixed and stirred to prepare a coating solution 9. Thereafter, coating, drying and baking were carried out in the same manner as in Example 1 to obtain a glass plate coated with a colored film. Visible light transmittance of the colored film-coated glass plate,
Tables 4 to 6 show properties such as visible light reflectance and transmission color tone.
In Table 4, the refractive index indicates the value of the film composition excluding the fine gold particles.

In the obtained colored film, ΔYa was as large as 1.41 and the deposition of gold fine particles on the surface was clearly increased as compared with the system to which the additives and the like of the present example were added. Also, it was possible to identify that the gold fine particles were floating on the film surface.

Comparative Example 2 The same procedure as in Comparative Example 1 was carried out except that 1-ethoxy-2-propanol was used instead of ethyl cellosolve as a solvent. In the obtained colored film, the surface precipitation of the fine gold particles was clearly increased as compared with the system to which the additives and the like of this example were added, and the fine gold particles were floating on the film surface even when observed with the naked eye. Could be identified.

Comparative Example 3 The same operation was performed as in Comparative Example 1, except that methyl cellosolve acetate was used instead of ethylcellosolv. In the obtained colored film, the surface precipitation of the fine gold particles was clearly increased as compared with the system to which the additives and the like of this example were added, and the fine gold particles were floating on the film surface even when observed with the naked eye. Could be identified.

[0075]

Table 4 =========================== Comparative Example Film Composition (% by Weight) No. SiO ₂ Au Refractive Index Thickness ------ −−−−−−−−−−−−−−−−−−−−−−−−−− 1 84 16 1.46 115 nm 2 84 16 1.46 130 nm 3 84 16 1.46 120 nm ============ ================

[0076]

Table 5 =============================== Comparative Example Ya ΔYa Transmission Color Tone Transmission Chromaticity / Lightness Glass Surface Reflectivity No. (%) (a / b / L) (%) ---------------------------------------- 76.2 1.41 Pink 8.2 / -2.5 / 86.5 7.3 2 75.2 0.93 Pink 8.9 / -2.3 / 85.9 7.5 3 77.7 1.13 Pink 7.0 / -1.9 / 87.5 7.8 ================== ===============

[0077]

[Table 6] ============================ Glass Surface Reflection Film Surface Reflection Comparative Example Chromaticity / Brightness Film Surface Reflectance Chromaticity・ Brightness number (a / b / L) (%) (a / b / L) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 1.2 /0.9/26.9 6.8 2.7 / 0.1 / 26.8 2 1.5 / 1.2 / 27.3 6.9 2.5 / 0.5 / 25.9 3 1.0 / 1.3 / 28.5 7.2 2.2 / 0.8 / 26.5 ================ ============

Examples 10 to 11 <Preparation of Coating Solutions 10 and 11> A solution of 10 g of cobalt chloride hexahydrate dissolved in 40 g of ethyl cellosolve was used as a stock solution of cobalt oxide. 25 g of ethyl silicate
Then, 4.5 g of 1N hydrochloric acid and 20.5 g of ethyl cellosolve were added, and the mixture was stirred at room temperature for 2 hours. Further, 5.85 g of methyltriethoxysilane and 5.50 g of ethyl cellosolve were added to this solution.
14 g and 0.70 g of 0.1 N hydrochloric acid were added and stirred for 2 hours. This solution was used as a silicon oxide stock solution 2. This is SiO ₂
Contains 19.4% solids.

The silicon oxide stock solution 2 prepared as described above was
After taking 5.8 g, 3.5 g of a cobalt oxide stock solution and 12.1 g of ethyl cellosolve were added thereto, and finally 10 g of a chloroauric acid stock solution was added, followed by mixing and stirring to prepare a coating solution 10 (Example 10).

15.5 g of the above silicon oxide stock solution 2 was taken, and 3.0 g of cobalt oxide stock solution and ethyl cellosolve 1 were added thereto.
After adding 1.5 g, finally 10 g of chloroauric acid stock solution was added and mixed and stirred to prepare a coating solution 11 (Example 11).

<Coating, Heating and Measurement> The coating liquids 10 and 11 prepared above were coated with a thickness of 3.4 mm and a thickness of 10 cm.
Each coating was performed on a transparent glass substrate having a size of 10 cm using a gravure coating apparatus. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. Further, baking was performed at 720 ° C. for 130 seconds to obtain a glass plate having a colored film. The colored film-coated glass plates obtained using the coating liquids 10 and 11 were each prepared in Example 1.
0 and 11 are assumed. Tables 7 to 9 show properties of the glass plate coated with the colored film, such as visible light transmittance, visible light reflectance, and transmission color tone.

The obtained colored films were obtained in Examples 10 and 11.
In both cases, good results were obtained for chemical resistance and abrasion resistance. Further, the addition of cobalt chloride hexahydrate as an additive prevented the surface precipitation of the fine gold particles, and the surface precipitation of the fine gold particles could not be detected by visual inspection or the like. Further, by adding cobalt chloride hexahydrate, a bluish tone could be added to the color tone. By adding cobalt chloride, the oxide of cobalt is converted into CoO, and
This indicates that the amount shown in Table 7 remains.

Examples 12 and 13 As glass substrates,
A transparent glass substrate having a thickness of 2.1 mm and a size of 10 cm × 10 cm is prepared. <Preparation of coating liquids 12 and 13> Coating liquid 1 used in Example 1 is used as coating liquid 12 (Example 12). 1. The silicon oxide stock solution 2 prepared in Example 10 was
After taking 58 g of this solution, 0.1 g of diacetone alcohol and trimethylolpropane acrylate ethylene oxide 6 adduct were added thereto, and finally 1.5 g of chloroauric acid stock solution was added, followed by mixing and stirring to prepare a coating solution 13 (implementation). Example 13).

<Coating, Heating, Processing, and Measurement> The coating solutions 12 and 13 prepared above were separately spin-coated on the transparent glass substrate at 1500 rpm for 15 seconds. After air drying, heat treatment was performed at 250 ° C. for 2 hours to precipitate gold fine particles. These were further placed in a heating furnace, heated to 610 ° C. in 2 hours, and kept for 10 minutes, and then naturally cooled to obtain two types of glass plates having a colored film.

The colored glass plate and the transparent glass plate were heated and pressed at 250 ° C. for 15 minutes in an autoclave with a 0.8 mm thick polyvinyl butyral intermediate film interposed therebetween so that the colored film was on the inside. Two types of laminated glass plates having a colored film in between were obtained. The laminated glass plates coated with the colored films obtained using the coating liquids 12 and 13 are referred to as Examples 12 and 13, respectively. Tables 7 to 9 show properties of the colored film-coated laminated glass plate such as visible light transmittance, visible light reflectance, and transmission color tone.

The obtained colored films showed good results in chemical resistance and abrasion resistance in both Examples 12 and 13.
In Tables 8 and 9, the columns of "reflectance of glass surface" and "reflection chromaticity" show the total surface when light is incident from the outer glass surface of the glass plate with the colored film on both surfaces of the laminated glass. It represents the measured value of the reflected light, and the column of the reflectance of the `` film surface '' and the column of the reflected chromaticity allow light to enter from the other surface of the laminated glass plate, that is, from the outer surface side of the glass plate without a colored film. Represents a measured value of light reflected from the entire surface when the light is reflected.

[0087]

[Table 7] ================================= Example Film Composition (% by Weight) No. Matrix Additive Amount Refractive index Thickness--------------(Cobalt chloride) SiO2 Au CoO EO6 (nm)-------------------------- −−−−−−−−−−−− 10 83.6 12.9 3.5 − 1.48 120 11 81.9 12.9 5.1 − 1.49 120 12 87.5 12.5 − 0.1wt% 1.46 100 13 87.5 12.5 −0.1wt% 1.46 110 ======== ==========================

[0088]

TABLE 8 ================================ Example Ya ΔYa Transmission Tone Transmission Chromaticity / Lightness Glass Surface Reflectivity No. (%) (a / b / L) (%) ----------------- 68.4 0.1 Magenta 7.6 / -7.6 / 82.4 8.7 11 67.0 0.05 Magenta 8.2 / -8.4 / 81.5 9.0 12 76.9 0.01 Winelet ゛ 4.5 / -1.5 / 87.9 7.8 13 74.2 -0.03 Winelet ゛ 3.8 / -0.8 / 88.5 7.5 == ==============================

[0089]

Table 9 =========================== Glass Surface Reflection Film Surface Reflection Example Chromaticity / Lightness Film Surface Reflectance Lightness number (a / b / L) (%) (a / b / L) −−−−−−−−−−−−−−−−−−−−−−−−−−−− 10 3.5 / 1.3 /26.2 8.6 3.7 / 1.4 / 25.8 11 4.1 / 1.3 / 25.4 7.6 7.5 / 1.0 / 23.9 12 0.8 / 0.6 / 28.2 7.9 0.9 / 0.3 / 28.2 13 0.7 / 0.5 / 30.7 7.5 1.2 / 0.5 / 31.8 ====== =====================

[0090]

As described above, according to the present invention, 170 ° C.
Between 250 ° C. and the maximum exothermic peak, by adding a small amount of an organic or inorganic additive to the composition for forming a colored film, it is possible to control the production of the fine gold particles and to prevent the fine gold particles from being deposited on the film surface. Can be prevented. By further adjusting the amount of addition, fine color tone control became possible.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Koichi Maeda 3-5-11 Doshomachi, Chuo-ku, Osaka City Japan Sheet Glass Co., Ltd.

Claims (7)

[Claims] 1. A composition for forming a colored film containing at least an organic silicon compound and chloroauric acid, wherein at least one compound having a maximum exothermic peak in a differential thermal analysis at 170 ° C. to 250 ° C. is added. For forming a colored film. 2. The composition for forming a colored film according to claim 1, wherein the additive compound is an organic compound having an ether bond and a carbon-carbon double bond in a molecule. 3. The composition for forming a colored film according to claim 2, wherein the additive compound is contained in an amount of 0.5 to 5% by weight based on the total amount of the composition for forming a colored film. 4. The composition for forming a colored film according to claim 2, wherein the additive compound is trimethylolpropane triacrylate having six ethylene oxide units in a molecule. 5. The composition for forming a colored film according to claim 1, wherein the additive compound is at least one inorganic compound selected from the group consisting of cerium nitrate, cobalt chloride, iron nitrate and iron chloride. 6. The colored film forming composition according to claim 5, wherein the additive compound is contained in an amount of 0.3 to 20% by weight based on the total solid content of the colored film forming composition. 7. A method for producing a colored film-coated glass article in which a composition for forming a colored film containing at least an organosilicon compound and chloroauric acid is applied to a glass substrate, and heated and fired, the maximum heat generation in differential thermal analysis is obtained. 17 peaks
A method for producing a colored film-coated glass article, comprising adding at least one compound having a temperature of 0 ° C to 250 ° C to the composition for forming a colored film.