JP2000203882A - Coating solution for forming colored film, glass with colored film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating solution having a color tone of transmitted light of black, blackish blue or bluish gray by making the solution include one or more metal compounds of metals selected from Co, Cr, Mn, Fe and Ni and a Cu compound. SOLUTION: This coating solution for forming a film comprises one or more compounds of metals selected from Co, Cr, Mn, Fe and Ni and a Cu compound. If required, the coating solution comprises one or more compounds of elements selected from Si, Ti, Zr, Al, In, Sn, Sb and lanthanoid. The coating solution is applied to a glass substrate having >=300 deg.C surface temperature to give glass with a colored film having >=104 Ω/(square) surface resistivity in 10-300 nm film thickness. An oxide film containing Si, Ti, Zr, Ce, etc., is applied to the colored film as an overcoat to improve durability. The total amount of Cu and Mn based on the total metal amount in the oxide film is >=10 wt.% and the ratio of Mn to the total amount of Cu and Mn is preferably 10-90 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating solution for forming a colored film, a glass with a colored film, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the field of glass for vehicles (especially for automobiles) or architectural use, the demand for colored glass is increasing from the viewpoint of design. In addition, we block sunlight effectively,
There is also an increasing demand for low-permeability colored glass that is useful for protecting the interior environment such as the inside of a car and a room, and protecting privacy.

[0003] Colored glass can be roughly classified into 1) colored glass obtained by adding a coloring component to a glass base material, and 2) colored glass formed by forming a colored film on a glass surface or ion-exchanging the glass surface. There are two types. Surface treatment is more suitable for small-quantity multi-product production than glass substrate replacement.
There is an advantage that the adjustment of reflectance, which is difficult with a glass substrate, can be made relatively easily.

Heretofore, many techniques have been proposed for forming an oxide film on a glass surface to obtain a colored glass. Examples of the oxide film forming method include a dry method such as a vacuum evaporation method, a sputtering method, and a CVD method, and a wet method such as a sol-gel method and a spray pyrolysis method (hereinafter, simply referred to as a spray method). Among them, the wet method, particularly the spray method, is advantageous in industrial production because it is easy to operate and can form a film on a large area at low cost. Further, when the film is formed by the spray method when the ribbon-shaped glass manufactured by the float method or the like is in a high temperature state, the manufacturing cost can be further reduced.

As the oxide film, a transition metal oxide film is particularly preferable from the viewpoint of absorbance and film formability. When a transition metal oxide film is densely coated on a glass surface, the glass exhibits various colors due to ion absorption, and a low-permeability colored glass having a greatly reduced transmittance can be obtained. In addition, if a dense and uniform transition metal oxide film is formed, the reflectance may be increased and half-mirror-like reflection may be exhibited.

As a transition metal oxide film formed by a spray method, an oxide film containing each of cobalt, iron and chromium oxides is known (Japanese Patent Application Laid-Open No. Hei 8-059299).
The oxide film has a transmission color of brown and exhibits half-mirror reflection, and a glass with a colored film using the oxide film is:
Widely used for window glasses of automobiles and the like.

However, an oxide film containing a large amount of cobalt is
As a characteristic of the cobalt oxide film, the transmission color becomes brown,
There is a problem that a transmission color oxide film such as black, black-based gray or black-based blue-gray having high market needs cannot be obtained. An oxide film containing an oxide of Sn and an oxide of Sb has a gray color tone,
Since the absorbance is not high, it is difficult to reduce the transmittance even if the film is thickened.In addition, since the conductive oxide film has a low surface resistance and high electromagnetic wave reflection performance, the use of a mobile phone and the antenna function are reduced. There was a problem in the required recent urban environment.

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention provides a color film having a color tone such as black, black-based gray or black-blue-gray, and having electromagnetic wave transmittance. An object of the present invention is to provide a coating solution for forming a colored film capable of forming glass, a glass with a colored film using the coating solution, and a method for producing the same.

[0009]

SUMMARY OF THE INVENTION The present invention is a coating solution for forming a colored film formed on a glass substrate to form a colored film comprising an oxide, comprising Co, Cr, Mn, Fe and Ni.
A compound of at least one metal selected from the group consisting of
The present invention provides a coating liquid for forming a colored film containing a compound of formula (1). In the present invention, a colored film made of an oxide is simply referred to as a colored film, and Co, Cr, Mn, Fe and N
a compound of at least one metal selected from the group consisting of i.
The coating liquid for forming a colored film containing a compound of Cu is simply referred to as a coating liquid.

In the case of obtaining a black colored film, it is preferable to form a colored film containing an oxide of Cu and an oxide of Mn.
Therefore, the coating liquid of the present invention preferably contains a compound of Mn. This is because Cu and Mn form a black spinel crystal oxide film.

The main component is an oxide of Co, Fe, Cr,
A black spinel crystal oxide film containing an oxide such as Cu or Ni can be formed at a high temperature (for example, 800 ° C.) for a long time (for example, 1 ° C.).
For more than 2 hours).
, Mn, and spinel crystal oxide are easily produced at a relatively low temperature, and are extremely effective when the upper limit of the heating temperature is limited.

Particularly, the present invention is effective in the case of an online spray method in which a coating liquid is sprayed on a ribbon-shaped glass in a high temperature state on a glass production line by a float method. On the glass production line, the upper limit of the heating temperature is about 600 ° C., and the heating time is very short.
Is formed even under such conditions, and a black oxide film is obtained.

The composition of Cu and Mn in the coating liquid does not always match the composition in the colored film after film formation. Rather, a spinel crystal oxide film having a sufficient absorbance may not be obtained with a liquid composition having the same ratio as the film composition. The reason is that even if a metal source that is stabilized in the coating solution by using a chelate or the like is used as the raw material, it partially sublimates during spraying to reduce the metal source, or the metal ionizes and migrates into the glass. As a result, Cu or Mn in the colored film
May be reduced.

[0014] In the coating liquid of the present invention, relative to the total amount of elements corresponding to M of the oxide precursor to be the oxide MO _x after the heat treatment, the total amount of Cu and Mn to the total amount of total metal is obtained From the viewpoint of making the transmission color of the colored film black,
It is preferably at least 10% by weight. If the amount is less than 10% by weight, the degree of coloring is too low and it is difficult to see black. From the viewpoint of efficiently obtaining a spinel crystal oxide film, the ratio of Mn to the total amount of Cu and Mn is 10%.
It is preferably about 90% by weight.

According to the ratio of Cu and Mn, or C
The temperature for spinel crystallization, the durability of the film, the transmission color tone, and the like can be adjusted by the metal species and the ratio of other metal components added in addition to u and Mn. For example, when a Cr oxide is added, spinel crystallizes at a lower temperature and develops a blackish gray color. In the Cr oxide-added system, the Cr oxide, which easily crystallizes at low temperature, becomes the nucleus, and the spinel crystallization of Cu and Mn oxides is promoted, and a spinel crystal composite oxide in which part of Mn is substituted by Cr is formed. It is thought to be formed. As the amount of added Cr oxide increases, crystallization is promoted and crystallization is easily performed at a low temperature, and the transmission color tone becomes bluish gray. However, if it is too large, the hardness of the film decreases.

On the other hand, by adding an oxide such as Fe, Co, or Ni, the durability of the film can be increased or the transmission color can be made closer to brown. The spinel crystallization temperature is C
In contrast to the case of adding the r oxide, the temperature rises, and a larger amount of heat (for example, long-time heating, high temperature) may be required. Further, in order to increase the absorbance of the oxide film, a noble metal compound such as ruthenium chloride, chloroauric acid, or chloroplatinic acid can be added.

Further, since the durability of the oxide film, such as abrasion resistance and chemical resistance, can be improved, the refractive index can be adjusted, and various functions can be imparted, Si, Ti, Zr, Al, I
The composition may further include a compound of at least one element selected from the group consisting of n, Sn, Sb, and lanthanoids (La to Lu). Conventionally, it is known that a silicon oxide film is difficult to form by a spray method. However, when an oxide of Si is added in the present invention, a composite oxide with an oxide containing Cu and Mn as main components is used. As a result, an oxide film containing Si is easily formed.

The compounds (compounds of Cu and other metals) used in the coating solution include alkoxides, carboxylate salts (for example, stearic acid, benzoic acid, naphthenic acid, 2-
Salts, such as ethylhexanoic acid and acetic acid), chelates (eg, acetylacetonate complexes), chlorides, borates, sulfates, nitrates, bromides, fluorides, iodides, oxalates, phosphates, and phosphorous acid One or more selected from the group consisting of acid salts are exemplified.

Examples of the Cu compound include copper alkoxides, copper carboxylate (eg, copper stearate, copper benzoate, copper naphthenate, copper 2-ethylhexanoate, copper acetate), and copper chelates (eg, acetyl) Copper acetonate), copper chloride, copper borate, copper sulfate, copper nitrate, copper bromide, copper oxalate, copper phosphate and copper phosphite.

For example, manganese alkoxides, manganese carboxylate (for example, manganese stearate, manganese benzoate, manganese naphthenate,
Manganese 2-ethylhexanoate, manganese acetate, etc.),
Manganese chelates (eg manganese acetylacetonate), manganese chloride, manganese borate, manganese sulfate, manganese nitrate, manganese bromide, manganese oxalate,
At least one selected from the group consisting of manganese phosphate and manganese phosphite is included. Co, Fe, Ni, C
As the r compound, various compounds can be used similarly to the Cu compound.

As the compound of Si, an organosilicon compound is preferable. Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Examples include monomers such as tetrabutoxysilane. Further, there may be mentioned hexaethoxydisiloxane, octaethoxytrisiloxane, decaethoxytetrasiloxane, ethoxypolysiloxane and the like, which are condensates of the above-mentioned monomers. Ethyl silicate 40, which is a mixture of a monomer and a condensate, may also be used.

Further, an alkoxysilane in which a part of the alkoxy group is substituted by various organic groups, or a silicone having a high degree of polymerization may be used. Examples of the organic group include a linear or branched alkyl group such as methyl, ethyl, propyl, butyl, 2-ethylbutyl and octyl; a cycloalkyl group such as cyclopentyl and cyclohexyl; a vinyl group; an allyl group; and γ-methacryloyl. An oxypropyl group,
γ-acryloyloxypropyl group, phenyl group, toluyl group, xylyl group, benzyl group, phenethyl group, γ-
Examples include a mercaptopropyl group, a γ-chloropropyl group, and a γ-aminopropyl group.

Ti, V, Zr, Al, In, Sn, S
b, compounds such as lanthanoids (La to Lu) include chelates (for example, acetylacetonato complex),
An acetate, an inorganic compound (for example, chloride), or the like can be used. Further, Si, Ti, V, Zr, Al, In, S
Mixing fine particles of oxides such as n, Sb, and lanthanoids (La to Lu) with the coating solution is also effective for improving the film quality.

The solvent for dissolving the compound used in the coating solution is not particularly limited, and organic solvents such as esters, ketones, alcohols, ethers and aromatics are used. In addition, some of them not only serve as a solvent but also coordinate with a metal in a coating solution to form a chelate and contribute to stabilization of a metal source. For example, ether alcohol-based solvents, diol-based solvents and the like can be mentioned.

The present invention also provides a glass with a colored film formed by applying the coating solution on a glass substrate to form a colored film made of an oxide.

In the present invention, the measurement of the thickness of the colored film
X combined with sputter etching by r ion beam
The analysis was performed by using a line photoelectron spectroscopy (XPS) in the depth direction from the surface. In this measurement, the sputter etching time by the Ar ion beam corresponds to the depth from the surface, that is, the film thickness. The sputter etching time was defined as the difference between the sputter etching time at which the XPS peak intensity in the profile in the depth direction became 50% of the maximum intensity at the rise and fall.

The conversion from the sputter etching time to the film thickness was determined by a calibration curve prepared using a standard sample having a known film thickness and the same film configuration. The XPS spectrometer used was
A 15 kV, 20 W Al Kα ray monochromated by an X-ray monochromator was used as the X-ray source. The X-ray beam was perpendicularly incident on the sample surface, and the beam diameter was 100 μm.

The detection angle of X-ray photoelectrons was 45 °, and in order to avoid the influence of charging, charging correction was performed using both an electron shower and an Ar ion shower. Ar ion beam for sputter etching has an acceleration voltage of 1.0 ke
V, the current density was 37 nA / mm ² , the beam was refracted by 5 ° to make the energy distribution uniform and neutral particles were removed, and the sample surface was irradiated at an incident angle of 45 °. The depth resolution under this condition is 4.6 when expressed by the steepness of the interface between the SiO ₂ film having a thickness of 100 nm and the Si wafer substrate (16 to 84%).
nm.

The thickness (geometric thickness) of the colored film in the present invention is 10 to 3 from the viewpoints of design and practical durability.
It is preferably 00 nm. By adjusting the film thickness, a glass with a colored film having a desired visible light transmittance can be obtained. Further, an overcoat may be provided on the colored film for improving durability. Although the film composition and thickness of the overcoat are not particularly limited, it is preferable to use an oxide film containing Si, Ti, Zr, Ce, or the like as the overcoat because durability can be significantly improved.

Further, an undercoat may be provided between the glass substrate and the colored film in order to prevent the elution of the glass component and to improve the adhesion to the glass substrate. For example, in the case where a colored film is formed by an on-line spray method at a place exiting a tin bath of a glass production line, an undercoat is formed by a CVD method before the on-line spray film formation, that is, in a tin bath. By giving the overcoat or the undercoat various functions (for example, heat ray absorbing ability, heat ray reflecting ability, ultraviolet absorbing ability, etc.), a glass with a colored film of higher added value can be obtained.

Various functions may be imparted to the colored film itself.
For example, by forming a colored film containing an oxide of Sn and an oxide of Sb or an oxide of In and an oxide of Sn, heat ray reflectivity can be exhibited, and oxidation of Ti and / or Ce can be performed. By forming a colored film containing a substance, an ultraviolet absorbing ability can be exhibited. In the case of the above-described multilayer film, the total thickness of the entire multilayer film is 10% from the viewpoint of practical durability.
It is preferably from 500 to 500 nm.

The glass with a colored film of the present invention preferably has a surface resistivity of 10 ⁴ Ω / □ or more from the viewpoint of electromagnetic wave transmission. If it is 10 ⁴ Ω / □ or more, it can be used for a part requiring electromagnetic wave transmission, such as an automobile door glass.

The present invention also provides a method for producing a glass with a colored film, wherein the coating liquid is applied to the surface of a glass substrate having a surface temperature of 300 ° C. or higher.

At a temperature of less than 300 ° C., thermal decomposition does not easily proceed, so that it is difficult to obtain a dense colored film. On the other hand, there is no particular upper limit on the temperature, and the substrate can be heated to a heat-resistant temperature (for example, about 650 to 700 ° C. in the case of ordinary soda lime glass), and the higher the temperature, the denser the colored film. Therefore, for example, it is also effective to heat the colored film obtained by the online spray method again. However, since Cu ions easily migrate, heating in a high temperature range changes the film composition, film physical properties, and film quality, so care must be taken.

As a method of applying the coating solution, spin coating, dip coating, spray coating, meniscus coating, flow coating, transfer printing, screen printing, and the like are used. In particular, a so-called online spray method of applying a coating solution on the surface of a high-temperature glass substrate is preferable from the viewpoint of manufacturing cost.

In the glass with a colored film of the present invention, the visible light transmittance can be arbitrarily selected and can be adjusted by the thickness and composition of the film. The glass with a colored film of the present invention is suitable for a window glass with a colored film for automobiles and buildings.

[0037]

EXAMPLES The present invention will now be described in detail with reference to Examples (Examples 1 to 14).
And a comparative example (Example 15), but the present invention is not limited thereto. All of the glass substrates used in the following examples were manufactured by the float method and had a size of 15 mm.
It is a green heat ray absorbing glass (visible light transmittance 79%, solar radiation transmittance 60%, visible light reflectance 8%) having a thickness of 0 mm x 150 mm and a thickness of 4 mm. This glass was washed and dried, fixed with a hanging tool, kept in an electric furnace set at 650 ° C. for 5 minutes, taken out, and applied with various coating solutions shown in Table 1 on a glass substrate using a commercially available spray gun. Air pressure 1.5 kg / cm ² , air volume 50 liter / mi for about 5 seconds
n, spraying at a spray rate of 100 ml / min.
Then, it baked at 650 degreeC for 4 minutes in air | atmosphere.

Table 1 shows the type and amount (unit: g) of the metal source as the oxide precursor, the solvent, and the ratio of the charged metals.
The charged metal ratio, in the meaning of the weight ratio of Cu, Mn, and other elements, the total amount of the elements the total amount of Cu, Mn, and other elements, corresponding to M of the oxide precursor to be the oxide MO _x after heat treatment Becomes The abbreviations used in Table 1 are shown in Table 3. “Acac” in Table 3 means acetylacetonato ligand.

In Example 12, an undercoat-forming liquid was applied to the washed and dried substrate using a spin coater, and baked at 400 ° C. for 5 minutes to obtain a substrate with an undercoat. The coating solution was sprayed. Example 1
In Nos. 3 and 14, after the coating solution was sprayed as described above, an overcoat forming solution was applied using a spin coater, and baked at 650 ° C. for 5 minutes in the air to form an overcoat.

The total thickness, visible light transmittance,
Solar transmittance and visible light reflectance (according to JIS-R3106), transmission color, weight percentage of copper to all metals in the colored film (Cu / all metals), weight percentage of manganese to all metals in the colored film (Mn / Table 2 shows the weight ratio (Cu / Mn) of copper and manganese in the colored film. The “all metals” means “all of the elements M” of the oxide MO _x in the colored film. In the transmission colors in Table 2, “B” indicates black, “BG” indicates a black gray color, and “BBG” indicates a black blue gray color.

The film thickness was measured by the method described in the text. Also, cut out the sample into 5 cm × 4 cm, and an electrode painting silver paste in the width across the 0.5cm of the long side (5 cm), was measured surface resistance with a digital multimeter, both samples 10 ⁴ Ω / □ or more. In addition, all of the samples showed good adhesion without rubbing with a finger.

In Examples 1 to 14, the transmission colors were black-based gray, black, and black-based blue-gray. In Example 15, the color was brown.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

According to the present invention, it is possible to obtain a colored film exhibiting a transmission color such as black, gray or blue-gray and transmitting electromagnetic waves. Further, according to the present invention, a glass with a colored film suitable for an automobile door glass or the like can be obtained by an inexpensive and highly productive manufacturing method.

Claims (8)

[Claims] 1. A coating solution for forming a colored film which is applied on a glass substrate to form a colored film, comprising Co, Cr, Mn, Fe
And a coating liquid for forming a colored film, comprising a compound of one or more metals selected from the group consisting of Ni and Ni, and a compound of Cu. 2. The coating liquid for forming a colored film according to claim 1, wherein the metal compound includes a Mn compound. Wherein the total amount of elements corresponding to M of the oxide precursor to be the oxide MO _x after the heat treatment, the total amount of Cu and Mn, the coloring of claim 2 is 10 wt% or more Coating solution for film formation. 4. The coating liquid for forming a colored film according to claim 2, wherein the ratio of Mn to the total amount of Cu and Mn is 10 to 90% by weight. 5. Si, Ti, Zr, Al, In, Sn, S
b. and a compound of at least one element selected from the group consisting of lanthanoids (La to Lu).
5. The coating liquid for forming a colored film according to any one of items 4 to 4. 6. A glass with a colored film, wherein the coating liquid for forming a colored film according to any one of claims 1 to 5 is applied on a glass substrate to form a colored film made of an oxide. 7. The glass with a colored film according to claim 6, wherein the glass has a thickness of 10 to 300 nm and a surface resistivity of 10 ⁴ Ω / □ or more. 8. A method for producing a glass with a colored film, wherein the coating liquid for forming a colored film according to claim 1 is applied to the surface of a glass substrate having a surface temperature of 300 ° C. or higher.