JP2003226555A - Glass base body with colored film, liquid composition for forming colored film and method for manufacturing glass base body with colored film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass base body with a colored film which can be recycled as a cullet raw material and which has moisture resistance and water resistance and a liquid composition for forming the colored film and further to provide a method for manufacturing the glass base body with the colored film. <P>SOLUTION: In the glass base body with the colored film which is constituted of the glass base body and an oxide film covering a base body surface, the oxide film comprises at least two kinds of alkali metal oxides, silicon oxide and a colorant. Further the liquid composition for forming the colored film comprises at least two kinds of alkali silicon oxides, silicon oxide and the colorant consisting essentially of carbon. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass substrate with a colored film, a liquid composition for forming a colored film, and a method for producing a glass substrate with a colored film. In particular, the present invention relates to a glass substrate with a colored film, which can be used as a cullet for a glass raw material and is provided with moisture resistance. The liquid composition for forming a colored film according to the present invention is suitable for a ceramic color formed around a window glass plate for an automobile.

[0002]

2. Description of the Related Art In automotive glass, a glass substrate with a colored film coated with a ceramic color on the peripheral portion thereof is used for the purpose of preventing the ultraviolet ray deterioration of an organic adhesive due to sunlight and providing a beautiful appearance.

Among the ceramic colors, Cr,
About 20 mass% of a pigment based on a transition metal ion such as Fe, Co, Ni or Cu is contained. In the case of ordinary clear float glass, the amount of transition metal is less than 1%, and even a few tens of ppm affects the color tone, enabling recognition. Therefore, it is not possible at present to remelt and recycle the portion coated with the ceramic color, and it is indirectly used as a recycled material for other materials, such as roadbed materials, or must be discarded. I didn't get it.

Conventionally, some ceramic color glass components contain lead, but in recent years, the use of lead has been restricted in order to protect the global environment.

New ceramic colors not containing lead are being proposed, for example, P ₂ O ₅ system, alkali metal oxide-ZnO-B ₂ O ₃ -SiO ₂ system, and the like.

A P ₂ O ₅ composition is disclosed in Japanese Patent Laid-Open No. 7-69.
672, JP-A-8-183632 and JP-A-9-20.
Japanese Patent No. 8259 discloses a glass composition and a frit composition.

Further, alkali metal oxide-ZnO-B
_{As a 2} O ₃ —SiO ₂ composition, there is disclosed in JP-A-8-1337.
Japanese Patent Publication No. 84 discloses a ceramic color composition.

[0008]

However, the above-mentioned respective compositions have problems such as a large difference in acid resistance and a large expansion coefficient. In the above P ₂ O ₅ based composition, P ₂ O ₅ ,
It is composed of alkali metal oxides and alkaline earth oxides. For this reason, the temperature dependence of the expansion coefficient becomes larger than that of the float glass that is often used as the substrate. Such a difference in the expansion coefficient causes distortion when the glass substrate is heated and cooled, which causes a reduction in the strength of the glass and, in some cases, deformation and cracks of the glass substrate.

The above-mentioned alkali metal oxide-ZnO
In the —B ₂ O ₃ —SiO ₂ -based composition, B ₂ O ₃ is contained in an amount of 10 to 20 without containing a component such as TiO ₂ that improves acid resistance.
%, ZnO is contained in an amount of 35 to 45%, which causes a decrease in acid resistance.

Further, since the glass coated with these ceramic colors contains about 20% of transition metal ions as a coloring component as described above, it is difficult to use it as a raw material for cullet in float glass. Therefore, they could not be recycled and had to be industrial waste.

In view of the above situation, the present invention provides a glass substrate with a colored film that can be recycled as a cullet raw material, a liquid composition for forming a colored film, and a method for producing a glass substrate with a colored film. To aim.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above problems, and as a result, two or more kinds of alkali metal oxides, silicon oxides, and a colorant containing carbon as a main component. By configuring the colored film with, it becomes possible to recycle as cullet, and it has moisture resistance, and also has a light-shielding property even if it does not substantially contain a transition metal or a transition metal compound, and it is hard and Acid resistance
It has been found that it is possible to obtain a colored film having alkali resistance.

That is, the glass substrate with a colored film according to the first embodiment of the present invention is a glass substrate and a glass with a colored film in which the surface of the substrate is coated with a colored film containing an oxide as a main component. Is characterized in that it comprises at least two kinds of alkali metal oxides and silicon oxide, and further contains a colorant containing carbon as a main component.

The colored film forming liquid composition according to the second embodiment of the present invention is characterized by containing at least two kinds of alkali silicon oxides, silicon oxides, and a coloring agent containing carbon as a main component. .

The method for producing a glass substrate with a colored film, which is the third embodiment of the present invention, comprises a step of applying the liquid composition for forming a colored film of the present invention onto the surface of a glass substrate, and a step of baking the glass substrate. It is characterized by

The glass substrate provided with a colored film, which is the first embodiment of the present invention, has a colored film containing two or more kinds of alkali metal oxides and silicon oxides, and is more preferable than a colored film having only one kind of alkali metal oxide. Excellent in moisture resistance and chemical durability. Generally, the phenomenon called the mixed alkali effect is that when a part of the alkali is replaced with another alkali, the property largely deviates from the additive rule even though the total amount of the alkali is constant. Properties that greatly change due to the mixed alkali effect include chemical durability represented by water resistance, acid resistance, and alkali resistance, electric conductivity, and diffusion coefficient. Since the colored film in the present invention is amorphous, the mixed alkali effect is exhibited, whereby the mobility of alkali is reduced and the alkali elution is suppressed, whereby it can be expected that the moisture resistance is improved.

The alkali metal oxide contained in the colored film of the glass substrate with a colored film of the present invention is preferably sodium oxide, potassium oxide and / or lithium oxide.

This colored film is expressed in terms of mass% and is expressed as Na ₂ O 1-18%, K ₂ O 0-18%, Li ₂ O 0-10%, K ₂ O + Li ₂ O 0.1 It is preferable to contain 19%, SiO ₂ 40 to 70%, and colorant 15 to 40%.

Hereinafter, the preferred embodiments of the colored film and the reasons for limiting the components will be described. The contents of the following components are shown by mass%.

If the content of Na ₂ O is less than 1%,
If the alkali resistance of the colored film is lowered and the thermal expansion coefficient is too small, the strength of the glass and the colored film is lowered, which is not preferable. A more preferable content is 5% or more. On the other hand, if the content of Na ₂ O exceeds 18%, the coefficient of thermal expansion becomes too large, the amount of shrinkage of the film during drying and baking becomes large, and cracks are likely to occur in the colored film, which is not preferable. It is more preferably 15% or less.

K ₂ O and / or Li ₂ O is Na ₂ O
By coexisting with, the coloring film is provided with moisture resistance and chemical durability. If the total amount of K ₂ O and Li ₂ O is less than 0.1%, water resistance and moisture resistance are reduced. Preferably 1
% Or more. If it exceeds 19%, the coefficient of thermal expansion becomes too large, and the shrinkage amount of the film during drying and firing becomes large, as in the case of Na ₂ O. As a result, cracks are likely to occur in the colored film. It is preferably 12% or less. Regarding the content of each component, the content of K ₂ O is preferably 18% or less, more preferably 11% or less, and the content of Li ₂ O is preferably 10% or less, more preferably 5% or less. is there.

SiO ₂ is an essential component and serves as a network former. If it is less than 40%, the strength of the colored film is lowered and further the alkali resistance is lowered, which is not preferable. More preferably, it is 50% or more. 7
If it exceeds 0%, the coefficient of thermal expansion tends to be small. Furthermore, the colored film, unlike glass, causes not only contraction due to thermal expansion but also contraction due to water evaporation. The contraction due to evaporation of water is suppressed by the presence of alkali, and the contraction due to thermal expansion becomes dominant, so it is preferably 70% or less.

The colorant containing carbon as a main component affects the film strength and the alkali resistance depending on the ratio to the alkali metal oxide and the silicon oxide. Therefore, the colorant, for alkali metal oxides and silicon oxides,
It is preferable to contain a predetermined amount. Specifically 15 to 4
It is preferably 0%, more preferably 35% or less.

Examples of the colorant containing carbon as a main component include carbon black and graphite composed of only carbon, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. The form of fine particles is particularly preferable. More preferably, it is carbon black fine particles.
Although various carbon blacks having different characteristics are manufactured depending on the manufacturing method, any carbon black may be used. As carbon black manufactured by different methods,
Examples include acetylene black, channel black, furnace black, and Ketjen black (trade name of Lion Corporation).

Carbon black reacts with oxygen to volatilize into carbon dioxide at temperatures not lower than 1000 ° C and lower than 1000 ° C. Float plate glass is usually manufactured by heating raw materials to 1000 ° C. or higher, melting and shaping, and thus carbon black is a preferable colorant in consideration of recyclability. Further, since it has a black color and is in the form of fine particles, it is a preferable substance as a colorant.

The colored film of the glass substrate with a colored film of the present invention preferably contains substantially no transition metal or transition metal compound. According to the present invention, a colored film having sufficient coloring can be obtained without containing a transition metal and a transition metal compound. As transition metals involved in coloring, Ti, V, Cr, Mn, Fe, Co, Ni, C
u, Mo, etc. are mentioned. These oxides, such as C
A glass substrate with a colored film containing a few% of oO, Cr ₂ O ₃ , CuO, NiO, MnO, etc., when mixed as recycled cullet when producing transparent glass or glass with different coloring components, has a target optical property (transparency). It is difficult to obtain glass having (or colored).

Cadmium sulfide and antimony sulfide may become colloids in the glass and may color the glass. Therefore, it is preferable that the colored film does not substantially contain these elements and compounds.

The term "substantially free of" means that it is not intentionally included, and inclusion of an impurity level unintentionally mixed in from raw materials or the like is allowed.

The colored film of the glass substrate with a colored film of the present invention preferably contains substantially no lead (Pb) and / or a lead compound.

Further, as described above, since the colored film contains the alkali metal oxide and the coloring agent, the shrinkage amount can be suppressed to be lower than that of the film composed only of silicon oxide, and the film strength is improved. Can be made. Therefore, it is possible to form a thick film without overcoating. The preferred thickness of the colored film in the invention is 1 to 20 μm.

The above-mentioned preferred form is suitable for recycling as a cullet raw material for general soda lime silica glass, and particularly suitable for recycling as a cullet raw material for float glass. Further, since it has moisture resistance and light-shielding property, and is hard and has acid and alkali resistance, it can be preferably applied to window glass plates for automobiles.

The colored film forming liquid composition of the second aspect of the present invention is characterized by containing at least two kinds of alkali silicon oxides, silicon oxides, and a coloring agent containing carbon as a main component. . In addition, (A) sodium silicate and
It is preferable that (B) potassium silicate and / or lithium silicate and two or more kinds of alkali silicates.

The component ratio of the solid content of the liquid composition is expressed in terms of mass% and the content of the component (A) is 1 to 18% of the oxide-converted sodium (Na ₂ O) and the component (B) is oxidized. Physical conversion of potassium (K ₂ O) and / or lithium (Li ₂
O) is 0.1 to 19%, and the silicon oxide (SiO ₂ ) of the components (A), (B) and (C) is 40 to 7%.
0%, and the colorant as the component (D) is 15 to 40%.
Is preferred.

When the content of the alkali silicon oxide and the silicon oxide is small, the strength of the colored film obtained by this liquid composition is lowered and the alkali resistance is also lowered. On the other hand, if the content of these components is too large, the content of the colorant becomes small, and desired coloring cannot be obtained. Furthermore, when the ratio of silicon oxide to alkali silicon oxide increases, the amount of shrinkage of the film during dry baking increases. As a result, cracks are likely to occur in the colored film. Therefore, it is preferable that the ratio of the alkali silicon oxide, the silicon oxide and the colorant containing carbon as the main component be such that the component ratio of the solid content thereof is within the above range.

Further, it is preferable to include a surfactant having a compound having an amino group, and it is more preferable to include it in a silicon oxide solution. The silicon oxide may be obtained by using, for example, colloidal silica as a starting material. Colloidal silica containing a compound having an amino group has an effect of improving dispersibility and an effect of suppressing phase separation of a liquid composition. Examples of the compound having an amino group include monomethyltriethanolammonium hydroxide.

The colored film forming liquid composition according to the present invention preferably contains a small amount of water in order to uniformly disperse it when applied to the surface of the glass substrate. When the components of the colored film forming liquid composition are provided as solids, it is preferable to add water. In addition, when the colorant containing the above-mentioned alkali silicon oxide, silicon oxide and carbon as a main component is provided in the form of an aqueous solution, it is not necessary to add water.

Further, the component (D) of the liquid composition is preferably carbon black fine particles, and the liquid composition preferably contains substantially no organic solvent.

A third aspect of the present invention comprises a glass substrate with a colored film, which comprises a step of applying the above-mentioned colored film forming liquid composition to the surface of the glass substrate and a step of baking the glass substrate. Is a manufacturing method.

The method for applying the liquid composition for forming a colored film is not particularly limited, but for example, dip coating, flow coating, curtain coating, spin coating, spray coating, bar coating, roll coating, brush coating, Examples of the method include screen printing and inkjet.

The method for producing a glass substrate with a colored film, which is the third embodiment of the present invention, preferably includes a pre-drying step prior to the firing step. By performing the pre-drying, an effect of suppressing foaming of the colored film and generation of cracks due to foaming can be expected. In this pre-drying step, it is preferable to carry out the drying at a temperature of room temperature to 250 ° C., and the drying time may be set within 24 hours, if necessary.

Drying at 250 ° C. or higher in an air atmosphere
It is not preferable because it causes the colorant containing carbon as a main component to burn. In the case of only room temperature drying, long drying is required. At this time, when the atmosphere is high in humidity, the colored film easily adsorbs water, and therefore drying for a short time is preferable.

Furthermore, when the dispersion of the colorant containing carbon as the main component is made to be sufficient, phase separation of the film due to long-time drying is less likely to occur, and the colorant containing carbon as the main component is burned. Is suppressed, which is preferable in terms of light shielding characteristics.

The pre-drying step comprises a first drying step at room temperature and a second drying step while heating in order to suppress irregularities on the surface of the colored film and to obtain smoothness of the applied composition. It is preferable.

In the step of firing the glass substrate, 7
When the temperature exceeds 30 ° C., the deformation of the glass substrate becomes remarkable, so it is preferable to perform firing at the firing temperature.

If the firing temperature is 500 ° C. or higher,
Preferred for firing at the same time as heating processes such as bending and strengthening of glass substrates

The firing time is preferably 80 seconds to 20 minutes when the temperature is 500 ° C. or higher, and more preferably 600 ° C. or higher in order to improve the combustion of the coloring agent containing carbon as a main component and the strength of the film. In this case, it is preferable to carry out for about 80 seconds to 10 minutes.

When the glass substrate is manufactured without forming such as bending and strengthening of the glass substrate, 5
It is also possible to use glass with a colored film obtained by baking at 00 ° C. or lower or drying.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below with reference to examples. The following composition ratio is mass%
It is what was displayed in.

Example 1 23 g of sodium silicate solution (water glass No. 3, manufactured by Kishida Chemical), 8 g of potassium silicate solution (Snowtex K, manufactured by Nissan Chemical Industry), colloidal silica (PC500, manufactured by Nissan Chemical Industry). 29g, carbon black (Lion paste W-311N LI
(Manufactured by ON) 40 g was weighed and stirred to obtain a colored film forming liquid composition. Table 1 shows the component ratio of the solid content of the liquid composition.

This liquid composition was applied to a glass substrate (150 × 150 × 2.1) of a cleaned soda lime silicate glass composition.
(mm) surface was coated with a bar coater, dried at room temperature for 5 minutes, and then dried at 190 ° C. for 10 minutes in a drying furnace. Then, it baked for 90 seconds in the baking furnace heated to 720 degreeC. The thickness of the obtained colored film was about 7 μm. Table 1 shows the composition of the colored film and the film forming conditions.

The visible light transmittance and the ultraviolet light transmittance of the obtained glass substrate with a colored film were measured by a spectrophotometer (UVPC-3100 manufactured by Shimadzu Corporation). as a result,
It was found that the transmittance was 0.1% or less in all wavelength regions from visible light to ultraviolet light, and the colored film had a light-shielding function (see Table 1).

Further, the following tests were conducted to examine the acid resistance and alkali (base) resistance of the colored film according to the present invention. That is, 0.1N sulfuric acid (acid resistance test) and 0.
Using a spectroscopic colorimeter (SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.), the change in brightness of the glass surface and the film surface when the glass substrate with the colored film was immersed in a 1N sodium hydroxide (alkali resistance test) solution for 24 hours was measured. It was measured.

As a result, it was found that in the acid resistance test and the alkali resistance test, there was no change in the brightness of the colored film surface and the uncoated glass surface. That is, it was found that the colored film according to the present invention has good resistance to acidity and alkalinity.

The hardness of the colored film was evaluated by using a Taber abrasion tester (TABER INDUSTRIES 5150 ABRASER) with a glass substrate having a colored film at a load of 500 g.
The abrasion wheel was rotated and the change in permeability was measured before and after the test. As a result, it was found that the colored film according to the present invention did not change in permeability both before and after the test, had a very high hardness, and had good wear resistance (Table 1).
reference).

Further, a high temperature melting test was carried out in order to investigate the influence of the liquid composition for forming a colored film according to the present invention, which was remelted during the production of glass as a cullet raw material. The test was conducted using a TG-DTA analyzer (Rigaku thermal analyzer
TAS-100) was used to heat the liquid composition to 1300 ° C. at a heating rate of 10 ° C./min.

When the liquid composition after melting was visually observed, carbon as a coloring agent was burnt and disappeared.
It was confirmed that the liquid composition was transparent. As a result, it was found that the colored film according to the present invention does not affect the coloring of the glass even if it is contained in the cullet raw material during the glass production.

Furthermore, in order to confirm the moisture resistance, 5
A temperature / humidity tester (JLH-300 manufactured by ETAC Engineering) held at 0 ° C and 95% RH was used to measure the change in lightness of the glass surface and the film surface when the glass substrate with a colored film was held for 400 hours. (SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.) and the film state was visually observed. As a result, the brightness did not change on either the glass surface or the film surface, and peeling of the colored film did not occur.

(Example 2) Sodium silicate solution 10
g, potassium silicate 17 g, colloidal silica 33
g and 40 g of carbon black were weighed and stirred to obtain a dispersion liquid. This dispersion was applied on the surface of a washed glass substrate of a soda lime silicate glass composition with a spin coater, dried at room temperature for 5 minutes, and then at 190 ° C. for 30 minutes.
It was dried in a drying oven for one minute. Then, it baked for 120 seconds in the baking furnace heated to 720 degreeC. The thickness of the obtained colored film was about 5 μm (see Table 1).

(Example 3) Sodium silicate solution 23
g, potassium silicate 8 g, colloidal silica 29 g,
Carbon black (Lion paste W-310A,
40 g (manufactured by LION) was weighed and stirred to obtain a dispersion liquid. This dispersion is applied with a bar coater on the surface of a glass substrate of a washed soda lime silicate glass composition,
After drying at room temperature for 5 minutes, it was dried at 190 ° C. for 10 minutes in a drying furnace. Then, it baked for 600 seconds in the baking furnace which heated up to 620 degreeC. The thickness of the obtained colored film was about 4 μm (see Table 1).

(Example 4) Sodium silicate solution 29
g, lithium silicate (LSS35, Nissan Chemical Industries)
7 g, colloidal silica 24 g, carbon black (Lion paste W-311N, manufactured by LION) 40 g
Was weighed and stirred to obtain a dispersion liquid. This dispersion was applied on the surface of a washed glass substrate of soda lime silicate glass composition with a bar coater, dried at room temperature for 10 minutes, and then dried at 190 ° C. for 15 minutes in a drying furnace. Then, it baked for 90 seconds in the baking furnace heated to 720 degreeC. The thickness of the obtained colored film was about 8 μm (see Table 1).

The visible light transmittance and the ultraviolet light transmittance of the obtained glass substrate provided with a colored film are 0.1% or less in each of these wavelength ranges and have a light-shielding function. I understood.

An acid resistance test and an alkali resistance test were conducted in the same manner as in Example 1. As a result, both the acid resistance test and the alkali resistance test, both the colored film surface and the uncoated glass surface,
It turned out that there was no change in brightness.

Further, the hardness of the film was evaluated in the same manner as in Example 1. As a result, it was found that there was no change in permeability both before and after the test, and the film had a very high hardness.

Further, the liquid composition for forming a colored film was melted at a high temperature, and a high temperature melting test of a colorant was conducted. As a result, it was confirmed that in the liquid composition after melting, carbon was burnt and disappeared, and the liquid composition was transparent.

Further, a moisture resistance test was conducted in the same manner as in Example 1. As a result, there was no change in brightness on either the glass surface or the film surface, and peeling did not occur.

(Examples 5 to 7) Glass substrates with colored films having various film compositions shown in Table 1 were produced, and Examples 1 to 4 were manufactured.
Its properties were evaluated as well. The results are also shown in Table 1.

[0067]

[Table 1] ──────────────────────────────────── Example 1 2 3 4 5 6 7 ─ ─────────────────────────────────── (Film composition) Na ₂ O (mass%) 11 7 14 15 11 6 8 K ₂ O (mass%) 4 10 5 5 14 6 Li ₂ O (mass%) 2 2 SiO ₂ (mass%) 60 54 63 65 65 60 60 63 C (mass%) 25 29 18 18 18 30 20 21 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− (Film characteristics) Film thickness (nm) 7 5 4 8 10 12 10 UV / Visible rays <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Transmittance (%) Acid-base resistance Good Good Good Good Good Good Good Abrasion resistance Good Good Good Good Good Good Good High temperature melting test Good Good Good Good Good Good Good Good Moisture resistance Good Good Good Good Good Good Good Good ──────────────────────────────────── (Ratio of solid content of liquid composition) Na ₂ O (mass%) 10 5 10 12 9 3 6 K ₂ O (mass%) 3 8 3 3 12 4 Li ₂ O (mass%) 11 SiO ₂ (mass) %) 57 51 56 60 49 49 56 59 Colorant (% by mass) 30 36 31 27 39 39 29 30 ----------------------------- −−−−−−−− (Film forming conditions) Coating method Bar Spin Bar Spin Bar Bar Bar Coater Coater Coater Coater Coater Coater First drying temperature (° C) Room temperature Room temperature Room temperature Room temperature Room temperature Room temperature First drying time (minutes) 5 5 5 10 20 20 5 2nd drying temperature (℃) 190 190 19 190 190 190 190 230 Second drying time (min) 10 30 10 10 15 20 20 10 Firing temperature (° C.) 720 720 620 720 720 720 720 720 Firing time (sec) 90 120 120 600 90 100 80 80 90 ---------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−

Summarizing the above results, the ceramic color formed by the colored film forming liquid composition according to the present invention has a visible light transmittance and an ultraviolet transmittance of 0.1% or less in the entire wavelength region. Therefore, it was found that it has a sufficient light shielding function.

Further, in the acid resistance and alkali resistance tests, it was found that there was no change in the glass surface and the film surface before and after the test, and peeling did not occur.

In the abrasion resistance test, it was confirmed that the film had a shielding property even after the test, no permeation part was observed, and the coloring film had high hardness.

Further, in a high temperature melting test of a colorant after high temperature melting, it was confirmed that the liquid composition after melting was transparent. Therefore, the glass substrate with a colored film according to the present invention was
It was revealed that it can be reused as a raw material for cullet in the production of glass.

Furthermore, in the moisture resistance test, it was found that neither the glass surface nor the film surface changed before and after the test, and peeling did not occur, and the moisture resistance and water resistance can be improved by the mixed alkali effect. I understood it.

(Comparative Examples 1 to 3) As a comparative example, a colored film-forming liquid composition containing no silicic acid alkali salt and composed only of silicon oxide and a coloring agent and only silicic acid alkali salt and a coloring agent were used. A glass substrate with a colored film was produced using the constituted liquid composition for forming a colored film. The composition and production conditions are shown in Table 2.

[0074]

[Table 2] ─────────────────────────────── Comparative Example 1 Comparative Example 2 Comparative Example 3 ─────── ───────────────────────── (Ratio of solid content of liquid composition) Na ₂ O (mass%) 24 SiO ₂ (mass%) 83 74 74 C (mass%) 17 26 2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−− (Film forming conditions) Coating method Bar coater Bar coater Bar coater No. 1 Drying temperature (° C) Room temperature Room temperature Room temperature First drying time (min) 5 5 5 First drying temperature (° C) 190 190 190 190 Second drying time (min) 30 30 10 Firing temperature (° C) 720 720 720 Firing time (second) ) 90 90 90 −−−−−−−−−−−−−−−−−−−−−−−−−−−−− (Film characteristics) Abrasion resistance Defects Defects Defects ─────────────────────────────

In Comparative Examples 1 to 3, cracks were innumerably generated in the colored film after firing, and the glass substrate with the colored film could not be formed. Furthermore, in Comparative Example 3, the moisture resistance was poor, and peeling of the film occurred when the moisture resistance test was performed.

[0076]

According to the present invention, the coloring film of the glass substrate provided with the coloring film is constituted by two or more kinds of the alkali metal oxide, the silicon oxide, and the coloring agent containing carbon as a main component, so that the coloring film is colored. The film-coated glass substrate can be reused as a cullet raw material and has an excellent effect of imparting moisture resistance and water resistance.

The colored film of the glass substrate provided with the colored film according to the first embodiment of the present invention has a sufficient light-shielding function that the visible light transmittance and the ultraviolet light transmittance are 0.1% or less in the entire wavelength range. There is. Further, this colored film is a colored film which is hard and has acid / alkali resistance even if it does not substantially contain a transition metal or a transition metal compound.

The colored film of the glass substrate with a colored film according to the first aspect of the present invention can be formed by the colored film forming liquid composition of the second aspect.

Further, in the high temperature melting test, since the liquid composition for forming a colored film is transparent in the high temperature melting test, the glass substrate with a colored film coated therewith is reused as a cullet raw material in the production of glass. it can.

Further, since the colored film forming liquid composition can be formed without including an organic solvent, it is preferable from the viewpoint of environmental problems that the environmental load is small at the time of manufacturing the colored film.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshifumi Tsujino             7-28 Kitahama 4-28, Chuo-ku, Osaka City, Osaka Prefecture             Within Nippon Sheet Glass Co., Ltd. F-term (reference) 4G059 AA01 AC08 EA01 EA05 EA11                       EA18 EB05                 4J038 AA011 HA026 HA036 HA171                       HA441 HA451 JB11 KA08                       KA09 NA27 PC03

Claims (15)

[Claims] 1. A glass substrate and a glass with a colored film, the surface of which is coated with a colored film containing an oxide as a main component, wherein the colored film is at least two kinds of alkali metal oxides,
A glass substrate with a colored film, comprising: and a silicon oxide, and further containing a colorant containing carbon as a main component. 2. The glass substrate with a colored film according to claim 1, wherein the alkali metal oxide of the colored film is sodium oxide and potassium oxide and / or lithium oxide. 3. The colored film, expressed in terms of mass%, is Na ₂ O 1-18%, K ₂ O 0-18%, Li ₂ O 0-10%, K ₂ O + Li ₂ O 0.1-. The colored film-coated glass substrate according to claim 1, which comprises 19%, SiO ₂ 40 to 70%, and a colorant 15 to 40%. Wherein said colored film, expressed in mass% in _{terms, Na 2 O 5~15%, K} 2 O 0~11%, Li 2 O 0~5%, K 2 O + Li 2 O 1~12% The glass substrate with a colored film according to any one of claims 1 to 3, further comprising: SiO ₂ 50 to 70% and a colorant 15 to 35%. 5. The glass substrate with a colored film according to claim 1, wherein the colored film is substantially free of a transition metal and a transition metal compound. 6. The glass substrate with a colored film according to claim 1, wherein the colored film is substantially free of lead (Pb) and a lead compound. 7. The glass substrate with a colored film according to claim 1, wherein the colored film is a thick film having a thickness of 1 to 20 μm. 8. The glass substrate with a colored film according to claim 1, wherein the colorant containing carbon as a main component is carbon black fine particles. 9. A liquid composition for forming a colored film, comprising at least two kinds of alkali silicon oxides, silicon oxides, and a coloring agent containing carbon as a main component. 10. A method comprising: (A) sodium silicate, (B) potassium silicate and / or lithium silicate (C) silicon oxide, and (D) a colorant containing carbon as a main component. The colored film forming liquid composition according to claim 9. 11. The component ratio of the solid content of the liquid composition, expressed in mass%, is 1 to 18% of the oxide-equivalent sodium (Na ₂ O) of the component (A), and the component (B). Oxide equivalent potassium (K ₂ O) and / or lithium (L
i ₂ O) is 0.1 to 19%, and the silicon oxide (SiO ₂ ) of the components (A), (B) and (C) is 40.
~ 70%, and the colorant of the component (D) is 15 to 4%.
It is 0%, The liquid composition for colored film formation of Claim 10. 12. The colored film forming liquid composition according to claim 9, further comprising a surfactant having a compound having an amino group. 13. The colored film forming liquid composition according to claim 9, wherein the colorant containing carbon as a main component is carbon black fine particles. 14. The liquid composition for forming a colored film according to claim 9, wherein the liquid composition contains substantially no organic solvent. 15. A method comprising: a step of applying the liquid composition for forming a colored film according to claim 9 to a surface of a glass substrate; and a step of firing the glass substrate. A method for manufacturing a glass substrate with a colored film.