JP2001354447A - Ceramic paste and windowpane with light shielding film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a windowpane with a light shielding film comprising a transparent colored film by using a ceramic paste. SOLUTION: The ceramic paste prepared by mixing a low melting point glass frit and a coloring pigment in a weight ratio of (50:50) to (98:2), adding 3-10 wt.% resin and 10-20 wt.% solvent to the mixture in such a way that the total amount is adjusted to 100 wt.% and carrying out kneading is applied to at least a part of the surface of plate glass and cured by heating to 620-670 deg.C to form the transparent colored film on the plate glass.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic paste which is applied to the surface of a glass sheet and cured by heating to form a light-shielding film on the surface of the glass sheet. Further, the present invention relates to a window glass with a light-shielding film for a vehicle or a building using a light-shielding film formed by applying a ceramic paste to a surface of a plate glass by screen printing or the like and heating and curing the same, and further relates to a method of manufacturing a window glass with a shade band for an automobile. About.

[0002]

2. Description of the Related Art In order to prevent glare of a driver and improve decorativeness, a certain amount of visible light transmission is secured on the upper part of a recent vehicle window glass, especially a vehicle front window glass, and the solar light is provided. A shade band is formed in which transmission of light is appropriately suppressed.

[0003] In addition, modern vehicle window glass and building window glass, particularly rear window glass and side window glass for automobiles, have reduced cooling and heating loads.
In order to prevent glare and fading of interior materials,
That is, window glasses colored in green or gray or the like that appropriately suppress transmission of infrared light, visible light, and ultraviolet light and maintain a comfortable indoor environment have been widely used. Further, when the colored glass is used for a window glass for an automobile, the interior of the automobile is difficult to see, which has an effect of protecting privacy and can impart decorativeness to the automobile.

The transparent colored glass includes a transparent colored glass having a color on the glass itself and a transparent colored glass having a colored thin film formed on the surface of a glass sheet.

[0005] Transparent colored glass having a color on the glass itself,
In the glass manufacturing process, for example, if the glass is manufactured by a float method, a metal and / or a metal compound which is a coloring source must be charged when the raw material is charged into the float bath, and the manufacturing apparatus becomes large-scale, and other It takes time for pre-setup and post-processing for switching the production with glass, which is expensive. In the float method, it is difficult to color only a part of the glass sheet.

There are a sputtering method and a sol-gel method as a method for coloring the glass by forming a colored film on the surface of the glass. In addition, a metal salt is sprayed on a high-temperature sheet glass to thermally decompose the metal salt on the surface of the sheet glass. There is a thermal spray method to color the glass by attaching the metal oxides generated by it, and in any case, it is possible to adjust the visible light transmittance of the colored film by controlling the thickness of the colored film It is.

[0007] The sputtering method is a method in which argon ions or the like are struck against a metal target in a vacuum, metal particles are beaten out, and a metal thin film is formed on the surface of a glass sheet facing the target. It is possible to form a film on only a part of the glass by partially masking the glass using a baffle or the like that blocks the film formation. Large and expensive vacuum equipment is required.

In the sol-gel method, after a metal alkoxide is applied to a glass surface, the glass surface is colored by dispersing a metal oxide or pigment, which is a coloring source, in a hard film dehydrated and condensed. As a coating method, a spin coating method, a dipping method, or the like can be considered. However, when coloring only a part of the glass plate, it is necessary to attach a masking sheet or the like to a portion of the glass plate where a colored film is not formed, so that a colored film is formed. There is also a large loss of coating liquid.

In the heat spraying method, a metal salt is dissolved or dispersed on the surface of a high-temperature band-shaped sheet glass which is continuously taken out from a float bath outlet and conveyed by a roller in a manufacturing process of a sheet glass by a float method. This is a method in which a coating liquid is sprayed by a spray gun, and a metal oxide generated by thermal decomposition of a metal salt is attached to the surface of the glass sheet to color the glass sheet. Even if the coating liquid is sprayed only on one end of the strip-shaped glass sheet that is continuously conveyed, it is difficult to color only a part of the strip-shaped glass sheet because the coating liquid evaporates and expands on the high-temperature glass sheet. It is.

On the other hand, conventionally, a ceramic paste obtained by adding powder of a heat-resistant pigment (metal oxide), which is an inorganic component, and powder of a glass frit to a resin and a solvent and kneading the resin is screened around a window glass of an automobile. After being applied to the surface of the glass plate by printing and dried, a frame-shaped black frame portion made of a ceramic print heated and baked in a heating bending process or the like for shaping into a window glass is provided.

The purpose of providing the frame-shaped black frame portion on the window glass is to adhere the window glass to the window frame when the window glass is adhered.
Deterioration of urethane-based adhesive due to solar radiation from outside, and terminal of conductive thin-film electrode or heating wire formed on the inside surface of the window glass, or the peripheral portion of the interlayer film of the laminated glass. Hiding the separation or the like from the outside may be mentioned.

Normally, the ceramic color paste is prepared by kneading a powder of low melting glass frit (low melting point lead glass), a powder of pigment (metal oxide), a resin such as acryl, resin, ethyl cellulose and the like in a solvent such as terpineol. ,
For example, to prevent transmission of visible light and ultraviolet light,
Adjusted to black or gray.

For example, Japanese Patent Publication No. 2-22013 discloses a ceramic color composition containing a pearly luster pigment and capable of forming a pearly luster film.

Further, Japanese Patent Application Laid-Open No. 3-40397 discloses that
A ceramic color paste in which a pigment is wrapped in a glass frit in order to use a high viscosity, low expansion glass frit is disclosed.

Japanese Patent Application Laid-Open No. 6-256039 discloses a ceramic composition which does not impair the releasability from a press die during bending, suppresses the temperature dependence of color tone, and has excellent scratch resistance. It has been disclosed.

[0016]

The ceramic printed portion formed in a frame shape around the window glass of an automobile has a blindfold of an adhesive portion and an adhesive strength of the adhesive portion when the window glass is attached to a vehicle body. It is preferable that visible light and ultraviolet light are not transmitted in order to prevent deterioration due to ultraviolet light, and the color tone is limited to black or gray. Ceramic prints that can transmit visible light have not been studied yet.

On the other hand, since a windshield of an automobile is a laminated glass, a colored transparent shade band is produced by dyeing a laminated film of polyvinyl butyral, which is widely used.

However, the rear glass and side glass of automobiles, which are single-panel tempered glass, are manufactured by forming a light-shielding film that does not transmit visible light as a shade band in a dot pattern by screen printing or the like inside the window glass room. Shade bands such as windshields that transmit visible light are not widespread.

[0019]

Means for Solving the Problems The present inventors apply a ceramic print capable of transmitting visible light to the surface of a glass sheet by screen printing using a ceramic paste,
A method for manufacturing a glass substrate with a light-shielding film using a colored transparent film has been intensively studied.

Usually, the portion of the ceramic paste which is heated and hardened after being applied around the windshield of an automobile by screen printing is limited to black or gray, and has high light-shielding performance, that is, does not transmit light. .

For example, glass cups and the like have colorful ceramic prints of brilliant colors, but there are almost no brilliant colors as automotive glass, and a window glass with a light-shielding film made of a transparent coloring film made of ceramic paste. Is not used in the window glass of commercial vehicles.

The present inventors usually change the composition of the ceramic paste used to form a black frame in a frame shape with respect to the window glass, that is, by reducing the concentration of the pigment in the ceramic paste. By coating the ceramic paste on the sheet glass surface with a screen printing machine and adjusting the visible light transmittance of the colored film obtained by heating and curing, and forming a transparent colored film on the sheet glass surface, the appearance without color unevenness is excellent. It was found that a window glass with a light-shielding film was obtained.

Also, not only gray and brown,
By using a pigment with a vivid color tone such as blue or green as the composition of the ceramic paste, a vivid transparent colored film can be formed on the surface of the plate glass by screen printing, and a glass substrate with a light-shielding film made of a colorful transparent colored film is manufactured. I can do it.

According to the present invention, when a ceramic paste is prepared by kneading a low-melting glass frit, a coloring pigment, a resin and a solvent, the coloring of the coloring pigment, the combination thereof, and the concentration of the pigment are adjusted so that the ceramic paste is made of a glass plate. By adjusting the color tone and visible light transmittance of the light-shielding film when applied to the surface to form a light-shielding film, a window glass with a light-shielding film made of a transparent colored film made of a ceramic paste is obtained. An object of the present invention is to provide a highly decorative vehicle window glass and an architectural window glass by using a window glass with a light-shielding film.

The present invention provides a ceramic paste obtained by kneading a low-melting glass frit, a coloring pigment, a resin and a solvent, wherein the low-melting glass frit and the coloring pigment are mixed in a weight ratio of 5%.
The ratio is 0:50 to 98: 2, the resin is 3 wt% or more and 10 wt% or less, and the solvent is 10 wt% or more and 2 wt% or more.
A ceramic paste prepared by adding and blending 0 wt% or less and kneading to be 100 wt% and capable of forming a transparent colored film on the surface of a window glass.

Further, the present invention is a ceramic paste characterized in that, in addition to the above-mentioned ceramic paste, metal powder is kneaded to form a metallic-colored transparent colored film on the surface of the window glass.

Further, the present invention provides a transparent colored film formed by applying the above-mentioned ceramic paste on at least a part of the surface of a window glass, drying and then heating and curing at 620 ° C. or more and 670 ° C. or less. A window glass with a light-shielding film, comprising a light-shielding film made of a metallic transparent coloring film.

Further, according to the present invention, a black frame is applied to the periphery of a window glass with a ceramic paste and dried, and then the above-mentioned ceramic paste is applied to at least a part of the surface of the window glass and dried, and then the temperature is 620 ° C. or higher. 670 ° C. or lower to form a black frame, a transparent colored film, and / or a metallic transparent colored film.

The composition ratio of the low melting point glass frit, which is the composition of the ceramic paste used in the window glass with a light-shielding film of the present invention, to the coloring content is a weight ratio by weight percentage, and the low melting point glass frit: coloring pigment = 50: 50. To 98: 2
It is.

By adjusting the composition ratio of the coloring pigment to the glass frit within the above-mentioned weight ratio, that is, by adjusting the concentration of the coloring pigment with respect to the ceramic paste, the transparent coloring of the window glass with a light-shielding film of the present invention is performed. The visible light transmittance of the light shielding film by the film can be adjusted.

Although depending on the type of the coloring pigment, the composition of the coloring pigment is expressed by weight ratio of low melting glass frit: coloring content = 50:
Even if it is larger than 50, the color tone does not become dark, and the durability of the light shielding film deteriorates. Further, in the present invention, the transparent colored film is used as a light-shielding film. When the composition of the color pigment is larger than the low melting point glass frit: coloring content = 50: 50 by weight ratio, the thickness of the light-shielding film is not reduced much. limit,
Even if a pigment of any color is used, the color tone becomes too dark to form a transparent colored film.

The weight ratio of the coloring pigment to the low-melting glass frit is low-melting glass frit: coloring content = 98: 2.
If the coloring content is lower, the film formed on the surface of the glass sheet is visually colorless and transparent even if the film thickness is increased, and a transparent colored film serving as a light shielding film cannot be obtained.

For example, in the case where CoO which is a blue pigment is used, a preferable composition of a color pigment which can obtain a transparent colored film is a low melting glass frit: coloring content = 70: 30 in a weight ratio to a low melting glass frit. To 98: 2.

As the color pigment which is the composition of the ceramic paste used for the window glass with a light-shielding film of the present invention, a blue pigment is cobalt oxide, ie, CoO; a green pigment is chromium oxide (dichromium trioxide); That is, Cr ₂
O ₃ , titanium oxide as a white pigment, ie, TiO ₂ , as a red pigment, a mixed pigment of cadmium oxide and cerium oxide, ie, a mixed pigment of CdO and CeO ₂ , and as a black pigment, copper oxide, nichrome trioxide, and cobalt oxide Mixed pigments, that is, mixed pigments of CuO, Cr ₂ O ₃ and CoO, etc., as long as they are heat-resistant pigments that can withstand the temperature at which the ceramic paste is cured by heating. And the color tone of the light shielding film can be arbitrarily adjusted.

The low melting point glass frit, which is a composition of the ceramic paste used in the window glass with a light-shielding film of the present invention, is necessary for hardening the film obtained by heating and curing the ceramic paste. That is, the coloring pigment is dispersed in the cured glass frit to form a colored film. Since the glass frit itself becomes a transparent cured product, in the present invention, when preparing the ceramic paste, the visible light transmittance can be changed even at the same film thickness by changing the weight ratio with the pigment, so that the light shielding film The visible light transmittance of the light-shielding film can be adjusted without changing the application conditions when manufacturing the window glass.

The low melting point glass frit may be a leaded glass frit or a lead-free glass frit. In addition, lead-free glass frit has recently been studied due to environmental problems.

When the composition of the ceramic paste used in the window glass with a light-shielding film of the present invention is 100% by weight of the ceramic paste, the composition ratio of the resin to the ceramic paste is 3% by weight or more and 10% by weight.
t% or less.

The resin is added in order to increase the strength of the light-shielding film obtained by applying a ceramic paste to the surface of the plate glass by screen printing and drying the resin, followed by heating and curing. If only the low melting point glass frit cures,
Cracks may occur in the light-shielding film, and the light-shielding film does not have elasticity and thus cannot have sufficient film strength. When the ceramic paste is 100 wt%, the amount of the resin added is 3
If it is less than wt%, sufficient light-shielding film strength cannot be obtained. When the ceramic paste is 100 wt%,
If the added amount of the resin is more than 10 wt%, the resin is thermally decomposed at the time of sintering and colored, and adverse effects such as deterioration of the transparency of the light shielding film are caused.

Examples of the resin that is the material of the ceramic paste used for the window glass with a light-shielding film of the present invention include acrylic resins, cellulose resins such as ethyl cellulose, and rosin.

The weight percentage of the solvent, which is the material of the ceramic paste used for the window glass with a light-shielding film of the present invention, relative to the ceramic paste is 10 wt% or more and 20 wt% or less when the ceramic paste is 100 wt%.

When preparing the ceramic paste, the solvent is used in addition to the low melting point glass frit, the coloring pigment, and the resin.
It is necessary to form a paste, and when the ceramic paste is 100 wt%, the weight% with respect to the ceramic paste is smaller than 10 wt% or 20 wt%.
If it is larger than wt%, a paste having a desired viscosity suitable for performing screen printing cannot be obtained.

Examples of the solvent which is the material of the ceramic paste used for the window glass with a light-shielding film of the present invention include terpineol, butyl carbitol, phthalate and the like.

Low melting point glass frit, heat resistant color pigment,
In addition to the resin and the solvent, as a material of the ceramic paste used for the window glass with the light-shielding film of the present invention, a metal powder such as an aluminum powder is used, and by mixing the respective compositions, the light-shielding film is transparently colored in a metallic tone. The film can be used to further provide decorativeness.

In the present invention, if screen printing is used for applying the ceramic paste, it is possible to form a light-shielding film in an arbitrary pattern on a part of the plate glass. For example, by forming the light-shielding film of the present invention, which is a transparent colored film made of a ceramic paste, only on the upper part of the window glass of an automobile, a window glass with a shade band for an automobile can be provided.

In the method for manufacturing a window glass with a light-shielding film according to the present invention, a ceramic paste is applied to the surface of a plate glass, dried, and the low-melting glass frit is heated and softened, and is heat-cured together with the resin, that is, fired. In addition, the strength of the transparent colored film formed on the surface of the glass sheet is obtained.

When manufacturing the window glass with a light-shielding film of the present invention as a window glass for automobiles, a preferable heating temperature range is from 620 ° C. to 670 ° C. 620 ° C
As described above, by heating to 670 ° C. or lower, the ceramic paste can be heat-cured at the same time as being bent by heating as an automotive window glass. Usually, the glass sheet manufactured by the float method is 620 ° C.
It does not soften at lower temperatures and becomes too soft at temperatures above 670 ° C., making bending difficult.

In the manufacture of the window glass with a light-shielding film for an automobile according to the present invention, the shade band portion made of a transparent colored film and the frame-shaped black frame portion made of an opaque film are both formed of a ceramic paste. In the bending step, heat curing can be performed at the same time. That is, after a black frame is screen-printed in a frame shape with a ceramic paste on the periphery of the window glass,
After drying and further applying the ceramic paste according to the present invention to the shade band portion and drying, the window glass is bent and heat-hardened at 620 ° C. or more and 670 ° C. or less. As shown in the plan view of the rear glass for use, a window glass having a black frame 2 in a frame shape and a shade band portion made of a transparent coloring film 1 is obtained.

The window glass with a light-shielding film having a transparent colored film obtained by applying the ceramic paste on the glass surface as a light-shielding film according to the present invention can be used as a vehicle window glass or an architectural window glass, and has a desired color tone. Can be selected, so that it is possible to provide a window glass with a light-shielding film having high decorativeness.

The window glass with a light-shielding film of the present invention can select a light-shielding film of an arbitrary color tone, and furthermore, is a colored transparent colored film that transmits visible light in the same manner as when an interlayer film of a laminated glass is dyed. Can be provided to a single-pane glass such as a rear window and a side window of an automobile glass.

When the window glass with a light-shielding film of the present invention is applied to a single-pane glass such as a rear window and a side window of an automobile glass, a light-shielding film having an arbitrary color tone can be selected. By using a window glass with a shade band formed of a colored film and a metal powder such as an aluminum powder, it is possible to provide a highly decorative automotive wind glass such as a window glass with a shade band formed of a metallic transparent colored film. .

Further, the window glass with a light-shielding film made of a transparent coloring film according to the present invention can be arbitrarily set by screen printing, for example, when screen printing is performed. For example, as shown in the plan view of the rear glass in FIG. 2 in which a logo mark such as a car name made of the transparent colored film 1 is used as a light-shielding film, a window glass with a highly decorative logo mark is produced. can do.

The window glass with a shade band of an automobile is preferably blurred, that is, has a gradation so that the boundary between the light-shielding portion and the transparent portion, which is a shade band, is not conspicuous. Is a gradation by gradually thinning the dyeing from the upper part to the lower part of the shade band when mounted on an automobile.

In the present invention, since the shade band is produced by applying a ceramic paste to the surface of a glass sheet by screen printing, a dot pattern such as a dot or a line is formed on the light shielding film when the paste is applied by screen printing. By continuously changing the size and / or shape of the dots, that is, by continuously changing the ratio of the area of the light-shielding film portion to the area of the transparent portion having no film, the light-shielding film portion which is a shade band is formed. It is possible to make the boundary between the transparent part and the transparent part inconspicuous.

Recently, even in the frame 2 of the frame of the windshield of the automobile, in order to make the boundary inconspicuous,
As shown in FIGS. 3A and 3B, which are partially enlarged views of the boundary between the black frame portion 2 and the transparent portion, the boundary portion is often processed so as to be inconspicuous by a dot pattern.

For example, FIG. 4A is a partially enlarged view of a boundary between the transparent portion of the black frame portion 3 and the transparent portion of the black frame portion 2 in which the transparent colored film 1 according to the present invention further makes the transparent portion less noticeable.
(B). If the dot processing by the transparent colored film 1 of the present invention is performed twice with the frame-shaped black frame portion 2, the boundary portion becomes further inconspicuous.

The plate glass with a light-shielding film formed of a transparent colored film formed by applying the ceramic paste of the present invention may be used as a laminated glass, a double glazing or the like. When a laminated glass or a multi-layer glass is used, at least one sheet of a window glass with a light-shielding film made of the transparent colored film of the present invention is used.

Further, as the glass to which the ceramic paste is applied and which is used as the plate glass having a light-shielding film of the present invention which is formed of a transparent colored film, various plate glasses such as soda-lime glass, aluminosilicate glass and borosilicate glass can be used. .
The glass sheet may be colored or uncolored as long as it has transparency.
Further, the glass may be air-cooled tempered glass that has been cooled after heating, or may be raw glass that has not been tempered.

In the present invention, any method may be used as long as the ceramic paste can be uniformly applied to the glass substrate, but a transparent colored film having a uniform thickness is formed on the glass substrate without unevenness in color. It is preferable to use screen printing.

[0059]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. Hereinafter, the present invention is not limited to the examples.

[0060]

EXAMPLE 1 A low-melting glass frit and cobalt oxide, which is a blue pigment, were prepared at a composition ratio of 98: 2 by weight, such as low-melting glass frit: cobalt oxide, and an acrylic resin as a resin component, 5 wt% , Terpineol as solvent, 15wt
% And kneaded to prepare a ceramic paste with 100% by weight.

The produced ceramic paste was 3.5 mm
After coating on a transparent float glass with a screen printer and drying in a drying furnace at 120 ° C. for 5 minutes, the light-shielding film obtained by heating and curing at 650 ° C. in a firing furnace for 3 minutes is It was a bright blue color visually, and the visible light transmittance was 58% at a film thickness of 15 μm.

The visible light transmittance of the obtained glass plate with a colored film was measured with a spectrophotometer (Model 340, manufactured by Hitachi, Ltd.) at a wavelength between 340 and 1800 nm, according to JIS.
Z8722 and JIS R 3106 or JIS
It was determined according to Z8701. The thickness of the thin film on the glass surface can be measured using a surface profiler (DEKTA, manufactured by Sloan).
K3030), scraping off a part of the film with a cutter,
The measurement was carried out by scanning the stylus in contact with the stairs. Example 2 A low-melting glass frit and cobalt oxide as a blue pigment were prepared in a weight ratio of low-melting glass frit: cobalt oxide = 95: 5, acrylic resin as a resin component, 5 wt%, and terpineol as a solvent. , 15wt
% And kneaded to prepare a ceramic paste with 100% by weight.

The prepared ceramic paste was 3.5 mm
After coating on a transparent float glass with a screen printer and drying in a drying furnace at 120 ° C. for 5 minutes, the light-shielding film obtained by heating and curing at 650 ° C. in a firing furnace for 3 minutes is It was a bright blue color visually, and the visible light transmittance was 42% at a film thickness of 15 μm. Example 3 A low melting point glass frit and a blue pigment, cobalt oxide, were prepared in a weight ratio of low melting point glass frit: cobalt oxide = 92: 8, acrylic resin as a resin component, 5 wt%, and terpineol as a solvent. , 15wt
% And kneaded to prepare a ceramic paste with 100% by weight.

The prepared ceramic paste was 3.5 mm
After coating on a transparent float glass with a screen printer and drying in a drying furnace at 120 ° C. for 5 minutes, the light-shielding film obtained by heating and curing at 650 ° C. in a firing furnace for 3 minutes is It was a bright blue color visually, and the visible light transmittance was 33% at a film thickness of 15 μm. Example 4 A low-melting glass frit and a blue pigment, cobalt oxide, were prepared in a weight ratio of low-melting glass frit: cobalt oxide = 85: 15, acrylic resin as a resin component, 5 wt%, and terpineol as a solvent. , 15w
t% was added and kneaded to prepare a ceramic paste with 100% by weight.

The prepared ceramic paste was 3.5 mm
After coating on a transparent float glass with a screen printer and drying in a drying furnace at 120 ° C. for 5 minutes, the light-shielding film obtained by heating and curing at 650 ° C. in a firing furnace for 3 minutes is It was a bright blue color visually, and the visible light transmittance was 19% at a film thickness of 15 μm. Comparative Example 1 A low-melting glass frit and cobalt oxide as a blue pigment were prepared in a weight ratio of low-melting glass frit: cobalt oxide = 99: 1, an acrylic resin as a resin component, 5 wt%, and a terpineol as a solvent. , 15wt
% And kneaded to prepare a ceramic paste with 100% by weight.

The prepared ceramic paste was 3.5 mm
Is coated on a transparent float glass by a screen printer, dried in a drying furnace at 120 ° C. for 5 minutes, and then heat-cured in a firing furnace at 650 ° C. for 3 minutes to obtain a light-shielding film. It was 15 μm thick, had a visible light transmittance of 82%, and was visually colorless and transparent. Comparative Example 2 A low-melting glass frit and a blue pigment, cobalt oxide, were prepared in a weight ratio of low-melting glass frit: cobalt oxide = 45: 55, an acrylic resin as a resin component, 5 wt%, and a terpineol as a solvent. , 15w
t% was added and kneaded to prepare a ceramic paste with 100% by weight.

The prepared ceramic paste was 3.5 mm
Is coated on a transparent float glass by a screen printer, dried in a drying furnace at 120 ° C. for 5 minutes, and then heat-cured in a firing furnace at 650 ° C. for 3 minutes to obtain a light-shielding film. It was 15 μm thick and was not transparent, and did not transmit visible light.

[0068]

According to the present invention, the visible light transmittance of a film made of a ceramic paste is increased by reducing the concentration of the pigment in the ceramic paste conventionally used for a black frame around an automobile glass or the like. A transparent colored film is provided as a window glass with a light shielding film made of a transparent colored film made of a ceramic paste.

Furthermore, according to the present invention, for example, in the manufacture of window glass for automobiles, a black frame is applied to the periphery of the window glass with a ceramic paste and dried, and further, the ceramic paste is applied to a shade band portion and dried. While bending the wind glass, 620
By heating and curing at a temperature of not less than 670 ° C. and not less than 670 ° C., a window glass with a black band and a shade band is obtained.

According to the present invention, not only a shade band of a window glass of an automobile is formed with a ceramic paste, but also a shade band of the same color as an automobile, a metallic shade band, a window glass with a logo mark, etc., having a high decorative property. Give window glass with film.

[Brief description of the drawings]

FIG. 1 is a plan view of a rear window glass with a shade band of an automobile, which is an example of a window glass with a light-shielding film according to the present invention.

FIG. 2 is a plan view of a rear window glass with a logo mark of an automobile, which is an example of a window glass with a light-shielding film according to the present invention.

FIG. 3A is a partially enlarged view showing an example of a boundary between a frame-shaped black frame portion made of a ceramic print of a window glass of an automobile and a transparent portion. (B) It is the elements on larger scale which show the example of the boundary of the frame-shaped black frame part and transparent part which consist of a ceramics print of the window glass of a motor vehicle.

FIG. 4 (a) is a partially enlarged view showing an example of a boundary between a frame-shaped black frame portion made of a ceramic print of a window glass of an automobile using a transparent coloring film according to the present invention and a transparent portion. FIG. 3B is a partially enlarged view showing an example of a boundary between a frame-shaped black frame portion made of a ceramic print of a window glass of an automobile using the transparent coloring film according to the present invention and a transparent portion.

[Explanation of symbols]

 1 transparent colored film 2 black frame

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Claims (4)

[Claims] 1. A ceramic paste obtained by kneading a low-melting glass frit, a coloring pigment, a resin and a solvent, wherein the low-melting glass frit and the coloring pigment are in a weight ratio of 50:50 to 98: 2, and the resin is 3 wt. % Or more, 10wt%
A ceramic paste characterized in that a transparent colored film can be formed on the surface of a window glass prepared by adding and mixing a solvent in an amount of not less than 10 wt% and not more than 20 wt% to be 100 wt%. 2. A ceramic paste characterized by being capable of forming a metallic-colored transparent colored film on the surface of a window glass by kneading a metal powder in addition to the ceramic paste according to claim 1. 3. A transparent coloring formed by applying the ceramic paste according to claim 1 or 2 on at least a part of the surface of a window glass, drying and heating and hardening at 620 ° C. or more and 670 ° C. or less. A window glass with a light-shielding film, comprising a light-shielding film made of a film and / or a transparent colored film having a metallic tone. 4. A black frame is applied to the periphery of a window glass with a ceramic paste and dried, and the ceramic paste according to claim 1 or 2 is applied to at least a part of the surface of the window glass and dried. , 620 ° C or higher, 670 ° C
A method for producing a window glass with a light-shielding film, characterized by forming a black frame, a transparent colored film and / or a metallic transparent colored film by heating and curing below.