JP2002167236A - Colored membrane, glass with colored membrane and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass with colored membrane having high optical concentration and excellent scratch resistance and chemical resistance at a low cost, to be used for general purpose glass such as window glass of vehicles or construction, using precious metal colloids as the color source. SOLUTION: This colored membrane is formed on a glass substrate from a membrane composition comprising an oxide of at least one element selected from the group consisting of Si, Ti, Al and Zr, and gold and silver microparticles, where the membrane may be coated with a hard protecting membrane of a metal oxide to enhance scratch resistance, or the protecting membrane may contain an oxide of a transition metal to make a tint close to neutral gray color.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored film used for a window glass for a vehicle or a building and an edge light glass, a glass with the colored film, and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, window glass for vehicles and window glass for buildings are designed to reduce the load on cooling and heating, prevent glare, prevent fading of interior materials, and the like, so that sunlight, that is, infrared light and visible light are used. In addition, colored glass colored green or gray, which appropriately suppresses transmission of ultraviolet light and maintains a comfortable indoor environment, has been widely used. Further, when the colored glass is used for an automobile glass, the interior of the automobile is difficult to see, which has an effect of protecting privacy, and can impart decorativeness to the automobile.

[0003] In the production of the glass, for example, if the glass is colored by a float method, a metal and / or a metal compound as a coloring source must be supplied when the raw material is supplied to a float bath. In addition, the manufacturing process becomes large-scale, and it takes a long time for pre-setup and post-processing for switching the production to another type of glass, which is expensive.

On the other hand, methods for forming a colored film on the surface of a glass substrate include dry film forming methods such as vacuum evaporation, sputtering and CVD, and wet film forming methods such as a sol-gel method and a thermal spray method. Also, forming a colored film on the surface of the glass substrate has an advantage that a half mirror-shaped colored coated glass can be easily obtained, and it is easy to obtain an infrared reflection and / or ultraviolet absorption function, and to effectively block sunlight. It is possible to provide a comfortable internal environment and protect privacy.

According to the sol-gel method, in addition to various metal alkoxides, a coating solution for forming a colored film in which a metal nitrate or chloride salt or the like is dissolved in an appropriate solvent as a coloring source is applied to the glass surface and then fired. Thus, a glass with a colored film is obtained.

More specifically, in the sol-gel method, a small amount of water or a solvent such as an alcohol to which an acid or an alkali is added is used.
Dissolve or disperse the metal alkoxide, hydrolyze to generate OH groups to form a coating solution, immerse the plate glass in the coating solution, and then pull up, for example, a coating film on the surface of the plate glass by a wet coating method such as dipping. Is formed, the solvent in the coating film is volatilized, and the OH groups generated from the metal alkoxide and / or the OH groups generated from the metal alkoxide and the OH groups on the plate glass are hydrogen-bonded. By causing a dehydration condensation reaction to generate a bond represented by metal-O-metal,
A dense and hard thin film is obtained on the sheet glass.

In order to obtain a colored coating film by using the sol-gel method, usually, a transition metal compound is added as a coloring source to an alkoxide solution of Si or the like and dissolved to form a coating liquid for forming a colored film. After being hydrolyzed, it is applied to the surface of a glass sheet, and is further heated and dehydrated and condensed to obtain a hard colored film. The transition metal, which is a coloring source, is oxidized during heating to form a metal oxide and is dispersed in the coloring film.

However, when the transition metal oxide is used as a coloring source, the color tone obtained is limited, and only a dull color tone such as gray, bronze or green (dark green) can be obtained.

On the other hand, noble metal fine particles having a particle size that becomes a noble metal colloid in a matrix such as a silica film or a titanium oxide film can exhibit a vivid color tone by colloid resonance absorption (plasmon absorption) in the matrix. It has been known for a long time, and is disclosed in, for example, JP-A-43-25211, JP-A-47-4470, and JP-A-47-149.
No. 89 and JP-A-47-28885.

For example, when gold is present as colloidal particles in a matrix, gold has a wavelength of 5 due to colloidal resonance absorption.
It absorbs light from 00 nm to 680 nm and develops a color.
It has different colors of red, orange, blue and purple. When silver is present as colloidal particles in the matrix, it absorbs light having a wavelength of 350 nm to 500 nm by colloidal resonance absorption and develops a yellow color, and exhibits vivid green and the like when coexisting with colloidal gold particles.

Further, although the noble metal fine particles are conductive, they are dispersed as a noble metal colloid in a matrix that does not conduct electricity. Therefore, a colored film using the noble metal fine particles as a coloring source has a high film resistance and radio wave transmission. It has the characteristic of being sexual.

In recent years, there has been an increasing demand for vivid colors other than dull colors due to coloring of transition metal oxides with respect to glass with a colored film, and a coating solution for forming a colored film using a noble metal colloid as a coloring source, and a colored film. , A glass article with a colored film and a method for producing the same, are disclosed in JP-A-11-34935.
No. 1, JP-A-2000-103644, JP-A-2
000-169187.

For example, in JP-A-11-349351, 1 is selected from Si, Ti, Zr and Al.
A coating liquid for forming a colored film, a colored film, and a glass article with a colored film containing at least one kind of alkoxide and / or chelate and a gold compound are disclosed.

For example, in Japanese Patent Application Laid-Open No. 2000-103644, a colored film containing an oxide of an element other than gold and silver and gold fine particles is formed on a glass base material containing silver fine particles in the base material. Disclosed are a glass article with a colored film and a method for producing the same.

For example, Japanese Patent Application Laid-Open No. 2000-169187 discloses a colored film, a glass article provided with a colored film, and a method for producing the same, characterized by containing gold, bismuth oxide, and an oxide other than bismuth oxide. .

[0016]

However, the colored film described in JP-A-11-349351 is
When the content ratio of the gold fine particles in the colored film increases, that is, when the content ratio of the gold fine particles is 5% by weight or more, the binding of other components is inhibited, and as a result, the durability of the film is deteriorated.
There was a problem that a large amount of gold fine particles could not be contained and a dark-colored film could not be obtained.

Japanese Patent Application Laid-Open No. 2000-103644 discloses that
When the silver fine particles are present in the coloring film, the silver fine particles are thermodynamically unstable, migrate to the surface of the coloring film by irradiation of ultraviolet rays or the like, and are oxidized and discolored. Therefore, it is described that the silver fine particles need to be contained in a substrate capable of stably existing thermodynamically. For that purpose, it is said that after forming a film containing a silver compound on the glass surface, it is necessary to heat the film to 400 ° C. or higher.
If the temperature is lower than 400 ° C., the diffusion of silver into the interior of the glass does not proceed and remains in the coating, which is considered to be inappropriate. However, even if heated above 400 ° C,
When the content of silver in the coating is large, there is a problem that silver remains in the coating.

Japanese Patent Application Laid-Open No. 2000-169187 discloses that
Bismuth oxide has been added to the colored film in addition to the gold fine particles and the matrix silicon oxide or titanium oxide.By adding bismuth oxide, the colored film can be glossy and a clear transmission color can be obtained. With a single application that could not be achieved by the conventional wet method, a colored film and a glass article with a colored film exhibiting clear blue, bronze, green and gray colors, and having excellent abrasion resistance and chemical resistance. Although it is described that it can be provided, even if bismuth oxide is added, the total amount of the noble metal in the film is 20 atomic% or less, preferably 5 atomic% or less, based on all elements constituting the colored film, If the content exceeds 20 atomic%, there is a problem that the binding of other components is inhibited, and as a result, the durability of the film is deteriorated. Further, when the total amount of the noble metal in the film with respect to all the elements constituting the colored film exceeds 20 atomic%, the noble metal colloid precipitates on the surface of the film, so that the film has poor surface smoothness and is practically durable. There was a problem that a certain film could not be obtained.

[0019]

SUMMARY OF THE INVENTION The present invention is directed to a colored film comprising a noble metal fine particle as a coloring source and an oxide of at least one element selected from Si, Ti, Al and Zr as a matrix. Even if a high concentration of noble metal salt is added to the coating solution and applied to glass, and then baked to form a colored film containing a large amount of noble metal fine particles, by further coating a protective film on the colored film, it is resistant. It is intended to obtain a colored film having high scratch resistance and excellent durability.

In the present invention, the particle size of the fine noble metal particles present in the matrix is preferably a particle size capable of forming a color by colloid resonance absorption in the matrix.
If the particle size is not such that the color develops by the colloid resonance absorption in the matrix, it does not develop a vivid color tone.

According to the present invention, an oxide of at least one element selected from Si, Ti, Al and Zr, gold fine particles,
A colored film comprising silver fine particles in a film composition.

Further, according to the present invention, the number of moles of fine gold particles contained in the colored film is 46% of the total number of moles of the element forming the colored film.
Or less, and the mole number of the silver fine particles is 12% or less with respect to the total mole number of the coloring film forming element.

Further, the present invention is a glass with a colored film, wherein the above-mentioned colored film is formed on at least one glass surface of a glass plate.

Further, the present invention relates to Si, Ti, Al, Zr
A first colored film containing an oxide of at least one element selected from the group consisting of oxides of precious metal and Si, Ti, Al, Z
A glass with a colored film, characterized in that a second film containing an oxide of at least one element selected from r is laminated on the glass surface.

Further, the present invention relates to Si, Ti, Al, Zr
A first colored film containing an oxide of at least one element selected from the group consisting of oxides of precious metal and Si, Ti, Al, Z
an oxide of at least one element selected from the group consisting of
A glass with a colored film, wherein a second film containing an oxide of at least one element selected from u, Cr, Mn, Ni, Zn, and Co is laminated on the glass surface.

Further, the present invention is an edge light glass using the above-mentioned glass with a colored film.

The present invention further provides a noble metal compound which becomes noble metal fine particles by a reducing action by heating, and a Si,
Si, Ti, which provide an oxide of Ti, Al, or Zr;
A coating liquid for forming a colored film containing a compound of at least one element selected from Al and Zr is applied to the glass surface, and then Si, Ti,
Si, Ti, Al to give an oxide of Al or Zr,
The method for producing glass with a colored film as described above, wherein a film is obtained by applying a coating solution containing a compound of at least one element selected from Zr and heating and curing the coating solution.

Further, according to the present invention, a noble metal compound which becomes noble metal fine particles by a reducing action by heat treatment and an oxide of Si, Ti, Al or Zr are given to the surface of the plate glass as the bottom surface of the float glass by heat treatment. Si,
After applying a coating liquid for forming a colored film containing a compound of at least one element selected from Ti, Al, and Zr to a glass surface, a compound of a transition metal to be a metal oxide is formed on the surface of the colored film obtained by heat treatment. , And Si, Ti, A by heating
Si, Ti, Al, Z to give an oxide of l or Zr
r, a compound of at least one element selected from the group consisting of Cu, Cr, Mn, Ni, Zn, and C, which gives an oxide of Cu, Cr, Mn, Ni, Zn, or Co by heating.
The method for producing a glass with a colored film described above, wherein a film is obtained by applying a coating solution containing a compound of at least one element selected from the group consisting of o and heating and curing the coating solution.

According to the present invention, an oxide of at least one element selected from Si, Ti, Al and Zr, gold fine particles,
A colored film comprising silver fine particles and a film composition, wherein a matrix in which gold fine particles and silver fine particles are dispersed is transparent and hard when formed into a thin film.
It is preferably an oxide of at least one element selected from i, Ti, Al, and Zr.

In the present invention, the number of moles of the fine gold particles contained in the transparent colored film is 46% or less of the total number of moles of the elements forming the colored film, and the number of moles of the fine silver particles is
It is preferably 12% or less based on the total number of moles of the coloring film forming element.

When the number of moles of the fine gold particles contained in the colored film exceeds 46% of the total number of moles of the elements forming the colored film,
Aggregation of the gold fine particles is likely to occur, and if the aggregation occurs, the glass with the colored film becomes opaque, which is not preferable. Similarly,
When the number of moles of the silver fine particles contained in the colored film is more than 12% based on the total number of moles of the elements forming the colored film, the silver fine particles tend to aggregate, and when the aggregation occurs, the glass with the colored film becomes opaque, which is preferable. Absent.

Noble metals that exhibit vivid colors by colloid resonance absorption when dispersed as colloidal particles of noble metal in a matrix include gold, silver, platinum, palladium, etc., and exhibit various colors depending on the combination thereof. Although it is possible to use various combinations of noble metals, platinum, palladium or compounds thereof are extremely expensive, and the glass with a colored film of the present invention is used for general-purpose glass such as vehicle windows or architectural windows. It is difficult to use in terms of price if you consider it.

Among the noble metals, it is preferable to use inexpensive silver or a compound thereof. However, when only silver fine particles are used, the colored film becomes yellow. It is preferable to use a colored film having the same color. The colored film of the present invention, in which gold fine particles and silver fine particles coexist in a matrix and are colored by colloidal resonance absorption, can provide the glass substrate with a colored film of the present invention using noble metal fine particles at low cost. The color tone can be increased by increasing the concentration of the fine particles as a noble metal colloid in the colored film.

A film containing a large amount of gold fine particles and / or silver fine particles as a noble metal colloid, as it is, becomes a film having poor surface smoothness due to the deposition of the fine particles on the surface of the film. It does not give a durable colored film glass suitable for use in window glass, but it can give a colored film glass with excellent surface smoothness and durability by forming a hard protective film on it. .

The protective film is preferably a film made of an oxide of at least one element selected from Si, Ti, Al and Zr, and has Cu, Cr, Mn, Ni and Z as coloring components.
An oxide of at least one element selected from n and Co may be added to darken the color.

The method for obtaining a glass with a colored film having a protective film according to the present invention includes, for example, a method in which a noble metal compound that becomes noble metal fine particles by a reducing action by heating, Ti,
Si, Ti, Al to give an oxide of Al or Zr,
After applying a coating liquid for forming a colored film containing a compound of at least one element selected from Zr to the surface of glass, and heating and curing the surface of the colored film, Si, Ti, A are heated.
Si, Ti, Al, Z to give an oxide of l or Zr
A method of applying a coating liquid for forming a protective film containing a compound of at least one element selected from r, followed by heating and curing is applied.

Further, the method of coloring the protective film with a transition metal oxide to obtain the glass with a colored film of the present invention, which has been made deeper, can be performed, for example, by reducing the surface of a plate glass as the bottom surface of a float glass by heating. Coating for forming a colored film containing a compound of a noble metal that becomes noble metal fine particles by action and a compound of at least one element selected from Si, Ti, Al, and Zr that gives an oxide of Si, Ti, Al, or Zr by heating After applying the liquid to the glass surface, the surface of the colored film formed by heating and curing is heated to form Si, Ti, Al, or Z by heating.
a compound of at least one element selected from Si, Ti, Al and Zr to give an oxide of
u, Cr, Mn, Ni, Zn, or after applying a protective film forming coating solution containing a compound of at least one element selected from Cu, Cr, Mn, Ni, Zn, and Co to give an oxide of Co, A method of curing by heating may be used.

In this case, the transition metal oxide (Cu,
Neutral gray (neutral gray) by adjusting the composition ratio of oxides of Cr, Mn, Ni, Zn, and Co), that is, by adjusting the amount of the transition metal element compound in the coating liquid for forming a protective film. A film having a color tone close to that of the noble metal can be obtained, the visible light transmittance can be reduced without changing the vivid color tone due to the colloidal resonance absorption of the noble metal fine particles, and the color tone of the image due to the transmitted light is not changed.

Therefore, when the protective film is colored, it is preferable to color the protective film so as to have a color tone close to neutral gray, which absorbs visible light at a constant absorptivity in the visible light region. For example, some sunglasses, lens filters, and the like are colored neutral gray using a vacuum deposition method so as to reduce the transmittance of visible light without changing the color tone of the image due to transmitted light. Neutral density) filters and the like are known.

In the glass with a colored film of the present invention, a film having a color tone close to neutral gray may be provided below the colored film due to the colloidal resonance absorption of the noble metal fine particles.

In the production of the glass with a colored film of the present invention, as a method of dispersing fine particles of a noble metal as a noble metal colloid in a matrix, a noble metal is added to an alkoxide of Si, Ti, Al or Zr which gives a matrix by dehydration condensation by heating. After a coating liquid for forming a colored film to which a compound is added is applied to the glass surface, a matrix is formed by heating and the noble metal compound is reduced to obtain a colored film in which noble metal fine particles are dispersed in the matrix.

Therefore, it is preferable to form a colored film on the bottom surface side (contact surface side with molten tin) of the float glass so that the noble metal compound is easily reduced. A small amount of tin remains on the bottom surface side of the float glass, and the tin activates the reduction of the noble metal compound. When the coating liquid for forming a color is applied to the top surface (the surface that does not come into contact with the molten tin), the noble metal compound is not reduced, and a film in which the noble metal fine particles are dispersed in the matrix cannot be obtained. In particular, when a silver compound is used, only a blue color tone can be obtained.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION In the glass with a colored film of the present invention, a colored film in which fine particles of a noble metal as a coloring source are dispersed as a noble metal colloid in a hard matrix is formed on the surface of a glass substrate.

A noble metal compound which is dissolved in a coating solution for forming a colored film to give the glass with a colored film of the present invention as a coloring source and reduced by heating to become noble metal fine particles as a noble metal colloid in the colored film includes, for example, Examples thereof include chloroauric acid that gives gold fine particles, silver nitrate, silver chloride, silver perchlorate, and silver acetate that give silver fine particles.

Further, noble metal fine particles having a particle diameter capable of absorbing colloidal resonance as noble metal colloid particles in the colored film may be used.

In the present invention, the matrix in which the noble metal fine particles are dispersed is preferably an oxide of Si alkoxide, Ti alkoxide, Al alkoxide, or Zr alkoxide.
After a coating liquid for forming a colored film containing l-alkoxide or Zr-alkoxide is applied to the glass surface, it is heated and subjected to dehydration condensation to form a hard matrix.

Si alkoxide, Ti alkoxide, Al alkoxide, or Zr in the coating solution for forming a colored film
If the concentration of the alkoxide is low, the colored film cannot be formed, and if the concentration of the Si alkoxide, Ti alkoxide, Al alkoxide, or Zr alkoxide is high, the Si alkoxide, Ti alkoxide, Al alkoxide, or Zr The stability of the alkoxide deteriorates, and solids are generated with the passage of time. Furthermore,
The coating solution itself may be gelled.

Therefore, the total concentration of the Si alkoxide, Ti alkoxide, Al alkoxide or Zr alkoxide in the coating solution for forming a colored film is 0.01 mol / kg or more for forming the colored film. In order to stabilize the Si alkoxide, Ti alkoxide, Al alkoxide, or Zr alkoxide in the coating liquid for forming a colored film, the content is preferably 5.0 mol / kg or less, more preferably 1.5 mol / kg or less.

Examples of the Si alkoxide which can be used in the coating solution for forming the colored film and the glass with the colored film of the present invention, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. Si alkoxides usually used in the sol-gel method, such as monomers and condensates, as well as monomers and condensates such as alkylalkoxysilanes in which some of the alkoxy groups have been substituted by alkyl groups, can be used.

Examples of the Ti alkoxide which can be used in the coating solution for forming the colored film and the glass having the colored film of the present invention include titanium tetraethoxide, titanium tetrabutoxide, titanium isopropoxide, titanium methoxide and the like. No. Al alkoxides and Zr alkoxides include the same alkoxides.

Further, Ti alkoxide is a very unstable substance and easily gels. Therefore, by coexisting with acetylacetone and a solvent, Ti alkoxide forms a complex with Ti, that is, acetylacetonate which is a chelate compound. The hydrolysis reaction is less likely to occur, and the gelation is suppressed. Therefore, when using a Ti alkoxide, it is preferable to add acetylacetone to the colored film of the present invention and the coating solution for forming a colored film that gives the glass with the colored film.

The organic solvent used for the coating solution for forming the colored film and the glass having the colored film of the present invention is a solution of Si alkoxide, Ti alkoxide, Al alkoxide, or Zr alkoxide and a noble metal compound as a coloring source. It may be kept in a stable state in the liquid, and lower alcohols such as methanol, ethanol, normal propanol and isopropanol; diols such as ethylene glycol, propylene glycol and butanediol; and cellosolves such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether. Or cellosolve acetates, a mixed solvent thereof and the like.

A noble metal compound is used as a coloring source, and Si alkoxide, Ti alkoxide,
A coating liquid for forming a colored film using an Al alkoxide or a Zr alkoxide is applied to the surface of a glass sheet by a wet coating method to form a coating film, and then the coating film is cured. The reaction proceeds rapidly, and a dense and hard colored film is obtained.
The coating film is heated and cured at a temperature of not less than ℃ to obtain a colored film on the surface of the glass sheet. The upper limit of the temperature can be raised to the heat-resistant temperature of the glass, and can be heated up to about 800 ° C. with ordinary soda-lime glass.

When the concentration of the noble metal fine particles in the coating film thus formed is high and used for a vehicle window or a building window glass, there is a problem in the smoothness and scratch resistance of the surface, or If the coloring film contains silver fine particles that are thermodynamically unstable and migrate to the surface of the coloring film due to irradiation with ultraviolet rays or the like and are oxidized and discolored, a hard protective film is coated as described above. As a result, a glass with a colored film having a high coloring density and having excellent surface smoothness and scratch resistance can be obtained. The protective film is obtained by dissolving a Si alkoxide, Ti alkoxide, Al alkoxide, or Zr alkoxide in an organic solvent, and heat-curing the same protective film forming coating liquid as the above-described colored film forming coating liquid except that it does not contain a noble metal compound. It is obtained by doing.

The coating method of the coating liquid for forming a colored film on the surface of the glass sheet may be a flow coating method, a spray coating method, a roll coating method, a spin coating method, a dip coating method, or a printing method such as screen printing or flexographic printing. It is conceivable that the coating liquid for forming a colored film is expensive because the coloring source is a noble metal compound, and therefore a coating method with high use efficiency of the coating liquid is preferable. Examples of the wet coating method with high use efficiency of the coating liquid include a screen printing method and a flexographic printing method.

In the screen printing, the use efficiency of the coating solution is high, but since the resin is used to increase the viscosity of the coating solution,
There is a problem that the obtained colored film is difficult to be dense and is inferior in abrasion resistance and the like and lacks in durability. Further, there is a problem that streaks parallel to the printing direction are easily generated in the colored film.

Therefore, the most preferable method for applying the coating liquid for forming a colored film to give the colored film and the glass with the colored film of the present invention to the surface of the glass sheet is flexographic printing.

The glass with a colored film using the noble metal fine particles obtained in the present invention as a coloring source does not fade even when heated and maintains a sufficient coloration near the softening point of the glass. It is possible to strengthen by heating and / or cooling.

A coating liquid for forming a colored film or a coating liquid for forming a protective film is applied to the surface of a glass sheet to form a coating film.
The sheet glass can be bent and / or strengthened at the same time as the Si alkoxide, Ti alkoxide, Al alkoxide, or Zr alkoxide is heated and cured by dehydration condensation.

As the plate glass used in the present invention, various plate glasses such as soda-lime glass, aluminosilicate glass, and borosilicate glass can be used. The glass sheet may be colored or non-colored as long as it has transparency, but it is preferable to use a colorless and transparent glass sheet in order to obtain a desired color tone in the produced colored coating glass.

The colored glass of the present invention using noble metal fine particles as a coloring source can be used in an edge light device by using a colorless and transparent plate glass and forming a colored film on at least one surface. The endlight device is used to secure the safety of a window glass such as a side window glass or a back window glass of a vehicle with the aim of ensuring nighttime safety by illuminating the upper free end of the window glass that is attached to the vehicle so that it can move up and down. Device. The inside of the colorless and transparent plate glass is used as an optical waveguide, and the light incident from the lower end of the wind glass is carried to the upper end of the wind glass by being internally reflected by a colored film using a noble metal as a color source,
The glass with a colored film of the present invention can be an edge light glass.

Hereinafter, the glass with a colored film of the present invention will be described in detail with reference to Examples, but the glass with a colored film of the present invention is not limited to the following Examples.

[0063]

Example (Preparation of Colored Film Forming Coating Solution Using Noble Metal Fine Particles as Coloring Source) In 1 kg of the prepared colored film forming coating solution, silver nitrate was measured to have the concentration shown in Table 1, and then water was added. Was weighed and added. Further, Table 1 shows an industrial alcohol which is a mixture of ethyl alcohol and isopropyl alcohol at a weight ratio of 9: 1, acetylacetone which is a chelating agent for isopropyl titanate, tetraethoxysilane, isopropyl titanate, and chloroauric acid in this order. The coating liquids for forming the colored films of the types shown in Table 1 were prepared in addition to each other so as to obtain the concentrations.

[0064]

[Table 1]

(Preparation of Coating Solution for Protective Film Formation) Manganese nitrate, copper nitrate, chromium nitrate, and cobalt nitrate were weighed so as to have the concentrations shown in Table 2 in 1 kg of the adjusted coating solution for forming a protective film. Thereafter, industrial alcohol, which is a mixture of ethyl alcohol and isopropyl alcohol at a weight ratio of 9: 1, was added as a solvent, and 1,4-butanediol was further added so as to have a concentration shown in Table 2, and then heated to 80 ° C. 3
The mixture was heated for 0 minutes to dissolve the metal nitrate. Thereafter, tetraethoxysilane was added so as to have a concentration shown in Table 2 to prepare a coating solution for forming a protective film.

When forming a protective film on a colored film using a noble metal as a coloring source, the protective film is close to neutral gray so that only the visible light transmittance is reduced without affecting the vivid color tone of the noble metal fine particles. The composition of the metal nitrate in the coating solution for forming a protective film was adjusted to be as follows.

[0067]

[Table 2]

(Method of Forming Colored Film and Protective Film) A coating solution for forming a colored film was applied to the bottom surface side of a 3.5 mm thick, 20 cm square, colorless and transparent float glass substrate with a spin coater at 2,600 RPM. Applied. The glass substrate to which the coating liquid for forming a colored film was applied was heated to 350 ° C. and dried for 7 minutes, then further heated to 750 ° C. and baked for 3 minutes to obtain a glass with a colored film.

With respect to the protective film, a coating liquid for forming a protective film was applied on the colored film side of the glass with the colored film using a spin coater at a rotation speed of 2600 RPM. The glass substrate to which the coating liquid for forming a protective film was applied was heated to 350 ° C. and dried for 7 minutes, and then heated to 750 ° C. and baked for 3 minutes to form a protective film. (Evaluation of colored film) For the obtained glass substrate with the colored film, visible light transmittance, solar light transmittance, ultraviolet light transmittance, film thickness of the colored film, haze, abrasion, chemical resistance and radio wave transmittance Was measured and tested.

With respect to the visible light transmittance of the obtained glass substrate with a colored film, a spectrophotometer (U4000, manufactured by Hitachi, Ltd.) was used by using a D65 light source and irradiating light from the glass surface side.
(Type) wave, the transmittance between 340 and 1800 nm was measured and determined in accordance with JIS Z8701.

The solar light transmittance was measured by using a C light source and irradiating light from the glass surface side with a spectrophotometer (Hitachi, U.S.A.).
4000 type), the transmittance between wavelengths of 300 to 2500 nm was measured, and determined in accordance with JIS Z8701. The ultraviolet light transmittance was determined based on ISO9050.

The thickness of the colored film on the glass surface was measured by using a surface shape measuring device (DEKTAK3030 manufactured by Sloan) to scrape off a part of the film with a cutter, and scan the stepped portion with a needle to scan.

The haze was measured by a digital haze meter (NDH-20D, manufactured by Nippon Denshoku Industries Co., Ltd.), and the haze (degree of haze) was determined according to JIS K6714.

The wear resistance was measured using a flannel cloth under a load of 500 g.
A 1000 reciprocal traverse test was performed on the film surface side, and the presence or absence of defects such as cloudiness and peeling was visually evaluated.

The chemical resistance was evaluated by immersing in a 0.1 N sulfuric acid solution or a 0.1 N sodium hydroxide solution for 24 hours, and then visually checking the colored film for the presence of defects such as cloudiness and peeling. evaluated.

As for the radio wave transmission, a surface resistance measuring instrument was used.
(Made by Shisido Electrostatec, trade name, Megaless
The surface resistance of the colored film was measured and evaluated using
did. Example 1 Prepare a coating solution for forming a colored film with the composition shown in Example 1 of Table 1.
After applying on a glass substrate under the above conditions,
And an evaluation sample was obtained. Shown in Example 1 of Table 3
Like, film thickness, 200nm, color tone, emerald green
And a haze of 0.9 was obtained. Optical characteristics
As shown in Example 1 of Table 4, the visible light transmittance, 1
0.5%, solar light transmittance, 12.6%, ultraviolet light transmittance,
It was 15.3%, which was a satisfactory value. Colored film type
The amount of chloroauric acid charged to the coating solution for coating was large.
In this way, a film with low visible light transmittance and low solar light transmittance can be obtained.
Was. Visually inspect samples after abrasion and chemical resistance tests
Upon observation, no abnormality was found in the appearance. Also,
When the surface resistance was measured with a megaresta, 100 MΩ
Thus, the radio wave transmission was satisfied.Example 2 A coating liquid for forming a colored film was prepared with the composition shown in Example 2 of Table 1.
After applying on a glass substrate under the above conditions,
And an evaluation sample was obtained. Shown in Example 2 of Table 3
Film thickness, 215 nm, color tone, orange film
The haze was 0.4. For the optical characteristics, see the table
As shown in Example 2 of Example 4, the visible light transmittance was 54.4.
%, Solar light transmittance, 66.9%, ultraviolet light transmittance, 29.
4%, which was a satisfactory value. Abrasion resistance, chemical resistance
Visual observation of the sample after the
No abnormalities were seen in the view. In addition, the surface resistance
When measured with a star, there is more than 100MΩ
Was satisfied.Example 3 A coating liquid for forming a colored film was prepared with the composition shown in Example 3 of Table 1.
After applying on a glass substrate under the above conditions,
And an evaluation sample was obtained. Shown in Example 3 of Table 3
As a result, a film having a thickness of 240 nm, a color tone and a pink color is obtained.
Haze was 0.1. For the optical characteristics, see Table 4
As shown in Example 3, visible light transmittance, 47.5%, day
In the light transmittance, 65.4%, ultraviolet light transmittance, 27.5%
There was a satisfactory number. Abrasion and chemical resistance test
Visual observation of the sample after performing
Was not seen. Also, measure the surface resistance with a megaresta.
It was over 100MΩ and satisfied
I wasExample 4 A coating liquid for forming a colored film was prepared with the composition shown in Example 4 of Table 1.
After applying on a glass substrate under the above conditions,
And an evaluation sample was obtained. Shown in Example 4 of Table 3
Film thickness, 260nm, color tone, orange film is obtained
And the haze was 0.5. For the optical characteristics, see the table
As shown in Example 4 of Example 4, the visible light transmittance was 55.2.
%, Solar light transmittance, 63.9%, ultraviolet light transmittance, 11.
9%, which was a satisfactory value. Abrasion resistance, chemical resistance
Visual observation of the sample after the
No abnormalities were seen in the view. In addition, the surface resistance
When measured with a star, there is more than 100MΩ
Was satisfied.Example 5 A coating liquid for forming a colored film was prepared with the composition shown in Example 5 of Table 1.
After applying on a glass substrate under the above conditions,
And an evaluation sample was obtained. Shown in Example 5 of Table 3
Thus, a film having a thickness of 280 nm, a color tone, and a green film was obtained.
And the haze was 0.5. For the optical characteristics, see the table
As shown in Example 5 of Example 4, the visible light transmittance was 45.3.
%, Solar light transmittance, 57.9%, ultraviolet light transmittance, 21.
3%, which was a satisfactory value. Abrasion resistance, chemical resistance
Visual observation of the sample after the
No abnormalities were seen in the view. In addition, the surface resistance
When measured with a star, there is more than 100MΩ
Was satisfied.Example 6 On the colored film side of the substrate with a colored film obtained in Example 5,
After preparing a coating liquid for forming a protective film with the composition shown in Example 6,
After applying on a glass substrate under the above conditions, heat and cure
Thus, an evaluation sample was obtained. As shown in Example 6 of Table 3
In addition, the total thickness of the colored film and the protective film on the glass surface is 465.
nm, color tone and green film with haze of 0.8
there were. The optical characteristics are shown in Example 6 of Table 4.
, Visible light transmittance, 30.8%, solar light transmittance, 4
7.6%, UV light transmittance, 9.8%, satisfactory
It was a numerical value. Apply protective film so that it is close to neutral gray
Vivid green color due to adjustment of liquid composition
Visible light transmittance and solar light transmittance decrease
Was. Visually inspect samples after abrasion and chemical resistance tests
Upon observation, no abnormality was found in the appearance. Also,
When the surface resistance was measured with a megaresta, 100 MΩ
Thus, the radio wave transmission was satisfied.Example 7 On the colored film side of the substrate with a colored film obtained in Example 5,
After preparing a coating solution for forming a protective film with the composition shown in Example 7,
After applying on a glass substrate under the above conditions, heat and cure
Thus, an evaluation sample was obtained. As shown in Example 6 of Table 3
In addition, the combined thickness of the colored film and the protective film on the glass surface is 650.
nm, color tone and green film with a haze of 0.7
Was. The optical characteristics are as shown in Example 7 of Table 4.
, Visible light transmittance, 25.6%, solar light transmittance, 41.
0%, UV light transmittance, 6.6%, satisfactory value
Met. Apply the coating solution so that the protective film is close to neutral gray.
By adjusting the composition, the color tone is vivid green
As it was, the visible light transmittance and the solar light transmittance decreased.
Visual observation of samples after abrasion and chemical resistance tests
As a result, no abnormality was found in the appearance. Also the surface
When the resistance value is measured with a Megaresta, it is 100MΩ or more
There was satisfactory radio wave transmission.Comparative example A coating liquid for forming a colored film was prepared with the composition shown in Comparative Example in Table 1.
After applying on the glass substrate under the above conditions, heat curing
Then, an evaluation sample was obtained. As shown in the comparative example of Table 3
Thickness, 250nm, color tone, emerald green coloring
A film was obtained, but the haze was 2.6 and it was cloudy
Condition. Concentration of chloroauric acid in coating solution for forming colored film
Was too high, the amount of gold particles in the colored film increased,
This is the result of the aggregation of the fine gold particles.

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

The colored film in which the fine gold particles and the fine silver particles coexist and are dispersed in the matrix exhibits a bright green color due to the colloidal resonance absorption of each fine particle. Silver fine particles are easily oxidized and discolored compared to other noble metal fine particles, but the present invention in which a protective film is laminated on a film containing silver fine particles does not oxidize and discolor the silver fine particles to obtain a highly durable colored film. It is also possible to add an oxide of a transition metal to the protective film to make it darker, and according to the present invention, a vivid color tone film suitable for use as a vehicle window glass or an architectural window glass is provided. It is possible to provide sheet glass.

When the concentration of the noble metal fine particles in the colored film is increased, the color can be darkened, but the noble metal fine particles precipitate on the surface of the colored film and the surface smoothness is disturbed. However, by applying the protective film on the colored film, the colored film has a smooth surface and the durability of the colored film is improved.

Further, by coloring the protective film to a color tone close to neutral gray, it is possible to make the color film darker without changing the color tone.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yukihiro Ogiya 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Glass Research Laboratory F-term (reference) 4G059 AA01 AB11 AC08 EA01 EA04 EA05 EA18 GA01 GA04 GA12

Claims (8)

[Claims] 1. A colored film comprising an oxide of at least one element selected from Si, Ti, Al and Zr, gold fine particles and silver fine particles in a film composition. 2. The mole number of the fine gold particles contained in the colored film is 46% or less based on the total mole number of the element forming the colored film, and the molar number of the silver fine particles is based on the total mole number of the element forming the colored film. 1
The colored film according to claim 1, wherein the content is 2% or less. 3. A glass with a colored film, wherein the colored film according to claim 1 is formed on at least one glass surface of a glass plate. 4. A first colored film containing an oxide of at least one element selected from Si, Ti, Al, and Zr and fine particles of noble metal, and at least one element selected from Si, Ti, Al, and Zr. A glass with a colored film, wherein a second film containing an oxide of the above is laminated on the glass surface. 5. A first colored film containing an oxide of at least one element selected from Si, Ti, Al and Zr and fine particles of noble metal, and at least one element selected from Si, Ti, Al and Zr. Oxides and Cu, Cr, Mn,
A glass with a colored film, wherein a second film containing an oxide of at least one element selected from Ni, Zn, and Co is laminated on a glass surface. 6. An edge light glass using the glass with a colored film according to claim 3. 7. A compound of a noble metal which becomes noble metal fine particles by a reducing action by heating and an oxide of Si, Ti, Al or Zr which is heated to give a noble metal fine particle to a surface of a plate glass as a bottom surface of the float glass. , A coating solution for forming a colored film containing a compound of at least one element selected from the group consisting of Zr, Si, Ti, Al, or Zr by heating on the surface of the colored film obtained by heating and curing.
5. A film is obtained by applying a coating liquid containing a compound of at least one element selected from Si, Ti, Al, and Zr that gives an oxide of the above, followed by heating and curing.
3. The method for producing a glass with a colored film according to item 1. 8. A compound of a noble metal which becomes a noble metal fine particle by a reducing action by heating and an oxide of Si, Ti, Al or Zr which is heated to provide a noble metal fine particle on a surface of a plate glass as a bottom surface of the float glass. , A coating solution for forming a colored film containing a compound of at least one element selected from the group consisting of a transition metal compound which becomes a metal oxide, and a heating agent. A compound of at least one element selected from Si, Ti, Al, and Zr to give an oxide of Si, Ti, Al, or Zr, and Cu, Cr, M by heating
Cu, C to give an oxide of n, Ni, Zn or Co
6. A glass with a colored film according to claim 5, wherein a coating liquid containing a compound of at least one element selected from the group consisting of r, Mn, Ni, Zn, and Co is applied, and then heated and cured to obtain a film. Production method.