JP3088074B2 - Manufacturing method of paint for ceramics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an overpaint used for overglazing an object to be glazed in the manufacture of porcelain.

[0002]

2. Description of the Related Art In the manufacture of ceramics, overpaints used for overpainting are roughly classified into Japanese paints in which a colorant is ion-dissolved in glass and Western paints in which a colorant is suspended in glass. . In addition, there are colorless paints that do not contain a coloring agent. Of these, Japanese paint has a feature that it imparts high transparency and gloss because the colorant dissolves into the glass structure to form a color. On the other hand, Western paints are not excellent in transparency and gloss because the color is developed while the colorant remains undecomposed. Upper paints are classified into leaded paints and lead-free paints according to the composition of lead paint.

[0003] In general, the production of traditional ceramics is performed as follows. First, raw materials such as porcelain stone, clay, feldspar, etc. are crushed and mixed, and molded, and the molded product is unbaked at a temperature of 500 to 900 ° C. After applying a glaze (base glaze) on the sketch, 1,250-1300 ° C
Bake at a temperature of about. Thereafter, the surface of the base glaze of the fired product is painted with an upper paint, and refired at a temperature of about 750 to 800 ° C. The firing temperature at this time is affected by the base material and the base glaze, and varies considerably depending on the raw material used for the object to be glazed. In addition, as essential conditions for firing, defects such as sufficient coverage of the glaze with the melt of the upper paint, non-devitrification of the upper paint, and separation of the upper paint from the glaze are required. It is required that the colorant does not occur and that the coloring of the coloring agent in the upper paint is not hindered. In other words, the properties to be provided in the ceramic paints include those that do not lose transparency due to devitrification during firing, that the colorant can be sufficiently colored, and that the coefficient of thermal expansion with the substrate ( Difference in thermal shrinkage) is in the range where defects such as peeling do not occur, and are completely fused with the object to be glazed. Gloss does not change compared to currently used leaded paint Is required.

[0004] The traditional Japanese ceramic paint for ceramics uses a crushed glass commonly called "Shiratama". About 30% by weight of this shiratama is mixed with about 30% of Karatoku and about 10% of silica stone. Japanese color paints are prepared by mixing an appropriate amount of a coloring agent into the material. However, Japanese paints using white balls give top priority to improving the commercial value and aesthetic sensation of appearance, and do not scientifically consider the chemical durability and chemical stability of ceramics.

[0005]

In the over-painting by the conventional over-painting technique, the amount of white balls, coloring materials, etc. used in the over-paint is determined by the appearance of the product to be applied by painting. Is the highest priority, and is selected mechanically according to the method established since ancient times, exclusively based on the experience and intuition of workers. As described above, the chemical durability of the upper paint has not been considered in terms of its composition or the like from a scientific viewpoint. Therefore, ceramic tableware manufactured using conventional paints, among the requirements to be provided for tableware as a product, that there is no appearance defects such as peeling, color development and transparency, It has sufficient quality in terms of aesthetics such as gloss, but has insufficient chemical durability (acid resistance) and chemical stability.

However, in recent years, ceramic tableware has been required to have chemical durability from the aspect of public regulation, that is, the chemical durability that can completely clear the standard for the amount of eluted lead specified in the Food Sanitation Law. There is a strong demand for the use of lead-free paints, and lead-free paints tend to be avoided. However, in the current lead-free top paints, the melting, gloss, coloring and transparency are not fully developed as compared to the leaded top paints, and especially in the field of ceramic tableware as a traditional industry, melting, gloss, coloring and Because quality, such as transparency, is a major factor in determining the market value of products,
There is a practical situation that it is not possible to switch from using leaded paints to using lead-free paints. For this reason, there is a strong demand for a leaded top paint that sufficiently exhibits the excellent characteristics of the leaded top paint and has excellent chemical durability, safety, and chemical stability.

The present invention has been made in view of the above circumstances, and does not cause defects such as peeling of ceramics from the glazed material, similarly to conventional leaded paints. In addition to imparting excellent luster, coloring and transparency to ceramic products, the ceramic products have chemical durability and chemical stability that fully comply with the regulations for the amount of eluted lead specified in the Food Sanitation Law. It is another object of the present invention to provide a method of manufacturing a ceramic paint for a ceramic tableware or the like, which can provide a high level of safety.

[0008]

The invention according to claim 1 is
Silica (SiO ₂₎ containing a 30.0 to 45.0% by weight of lead oxide (PbO) 45.0 to 60.0 wt%, the total amount of their SiO ₂ and PbO from 85.0 to 90. 0
% By weight and alumina (Al ₂ O ₃ )
The a 0.5 to 4.0% by weight boron oxide (B ₂ O ₃₎ 1.0
~ 4.0 wt% and calcium oxide (CaO) 0.5 ~
4.0 wt% and 1.0 to the lithium oxide (Li ₂ O)
3.0% by weight and zirconium oxide (ZrO ₂ )
To 3.5% by weight to prepare a glass composition in a total amount of 100% by weight, and the glass composition is subjected to 1,000 to 1,400 ° C in an oxidizing atmosphere.
After heating to a temperature of and rapidly aging and aging, the melt is quenched, and the resulting solid is crushed,
The gist is to manufacture paint for ceramics.

According to a second aspect of the present invention, there is provided the glass composition wherein a colorant comprising a transition metal oxide and / or a colored rare earth element oxide is mixed with the glass composition having the above composition, and the colorant is mixed. In an oxidizing atmosphere for 1,00
After heating to a temperature of 0 to 1,400 ° C. for rapid melting and aging, the melt is quenched, and the obtained solid is pulverized to produce a ceramic paint. .

[0010] The invention according to claim 4 is to provide a glass composition having the above composition in an oxidizing atmosphere at 1,000 to 1,
After heating to a temperature of 400 ° C. to rapidly melt and mature,
The melt is quenched, the obtained solid is pulverized to prepare a pulverized glass, and a colorant and / or a pigment made of a transition metal oxide is mixed with the pulverized glass to obtain a paint for ceramics. The gist is to manufacture.

The upper paint manufactured using the glass composition having the above composition contains SiO 2 as a main component in the glass composition.
₂ is contained in an amount of 30.0 to 45.0% by weight. Therefore, as in the case where SiO ₂ is 30% by weight or less, chemical durability is poor, or SiO ₂ is 45% by weight or more. , The firing temperature after overpainting is 850
There is no inconvenience such as higher than ° C.
PbO acts as a glass-forming component and works particularly well with regard to the transparency, melting, gloss and durability of paints,
When the amount of PbO in the glass composition is small, its action is not sufficiently exhibited. On the other hand, when the amount of PbO is excessively large, the acid resistance decreases and the thermal expansion coefficient increases. PbO is contained in an amount of 45.0 to 60.0% by weight, which is appropriate. Al ₂ O ₃ has a function of increasing the melting temperature of the paint and improving the chemical durability, but the appropriate amount of Al ₂ O ₃ in the glass composition is 0.5 to 4.0.
% By weight. When the content of Al ₂ O ₃ in the glass composition is less than 0.5 wt%, tend to cause phase separation, over significantly pair acid is degraded, will be also impaired transparency, whereas, Al ₂ O _If the content of ₃ is 4.0% by weight or more, devitrification occurs. B ₂ O ₃ is one that is contained as the purpose of reducing the viscosity of the glass, B ₂ in the glass composition
An appropriate amount of O ₃ is 1.0 to 4.0% by weight. When the content of B ₂ O ₃ is less than 1% by weight, the effect of lowering the viscosity of the glass becomes insufficient, while when the content of B ₂ O ₃ is 4% by weight or more, the chemical durability is reduced. Will do. Ca
O promotes the flow of the glass at high temperatures, promotes the clarification and homogenization of the glass melt, and is effective for improving the acid resistance when contained in a small amount, but 0.5 to 4.0. weight%
Is appropriate. Li ₂ O is mainly contained for the purpose of lowering the melting point, but the content in the glass composition is suitably 1.0 to 3.0% by weight, and the content of less than 1% by weight is not effective. On the other hand, when it is contained in an amount of 3% by weight or more, the acid resistance is reduced and devitrification tends to occur. In addition, in order to maintain chemical durability and chemical stability, it is necessary to minimize the mixing of Na ions and K ions having a large ionic radius, but lithium has the smallest ionic radius in alkali metals, The use of Li ₂ O as the alkali metal oxide is also significant in this regard. ZrO ₂ is known to contribute to improving the chemical durability of glass (Ceramic Industry Association Journal 83 [2] 8
1-86 (1975)), by the ZrO ₂ is contained 1.0 to 3.5 wt% in the glass composition, so that the chemical durability is greatly improved. If the content of ZrO ₂ is less than 1% by weight, the effect is insufficient, while if the content is 3.5% by weight or more, devitrification and chemical durability are rather lowered.

According to a third aspect of the present invention, in the method for producing a ceramic top paint according to the second aspect, the colorant mixed with the glass composition is 1.5 to 5 parts per 100 parts of the glass composition. 0.0 part of cupric oxide and 0 to 0.5 part of ferric oxide, 0.5 to 100 parts of the glass composition
1.5 parts of cobalt oxide and 0 to 1.6 parts of cupric oxide, 0.5 to 10.0 with respect to 100 parts of the glass composition
Parts of ferric oxide, or 0.5 to 2.0 parts of chromium oxide per 100 parts of the glass composition, or 1.0 to 15.0 parts of oxidation per 100 parts of the glass composition It is characterized by using one or more kinds of colored rare earth element oxides selected from the group consisting of cerium, praseodymium oxide, neodymium oxide and erbium oxide.

According to a fifth aspect of the present invention, in the method for producing a ceramic top paint according to any one of the first to fourth aspects, a high-purity alumina crucible is used when melting the glass composition. It is characterized by the following.

As described above, in order to maintain the chemical durability and chemical stability of a painted ceramic product, it is necessary to avoid mixing Na ions and K ions having a large ionic radius into the paint as much as possible. Desirably, the batch melting of the glass composition using a high-purity alumina crucible instead of a mullite crucible can prevent Na ions and K ions from being mixed into the paint.

According to a sixth aspect of the present invention, there is provided a method for producing a ceramic top paint according to any one of the first to fifth aspects, wherein B ₂ O ₃ is one of the components of the glass composition. Characterized in that colemanite is used as a feedstock for the above.

When colemanite is used as a raw material for B ₂ O _3, an extremely small amount of impurities are mixed in the glass composition.
The volatilization of ₂ O ₃ is extremely small, and most of B ₂ O ₃ is fixed in the glass structure, so that the stability and fluidity of the glass in a molten state are remarkably improved.

According to a seventh aspect of the present invention, there is provided a method for producing a ceramic overpaint according to any one of the first to sixth aspects, wherein Li ₂ O, which is one of the components of the glass composition, is used. It is characterized in that lithium nitrate is used as a feed material.

When lithium nitrate is used as a supply material of Li ₂ O, lithium nitrate is decomposed by firing and oxygen is released. Therefore, while the reduction of lead is prevented by the released oxygen, the oxide (Li ₂ O) is decomposed by decomposition. O) and the coloring of the glass by the reduced lead is prevented.

According to an eighth aspect of the present invention, there is provided a method of manufacturing a top paint for ceramics according to any one of the first to seventh aspects, wherein the supply of ZrO ₂ which is one of the components of the glass composition is provided. It is characterized in that zircon (zirconium silicate) is used as a raw material.

The use of zircon as a feedstock for ZrO ₂ improves the chemical durability of the painted paint.
The effect of ZrO ₂ is most effectively exerted.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the method of manufacturing an upper color (colorless color) according to the present invention, a glass composition having a predetermined composition is prepared, and the glass composition is prepared in an oxidizing atmosphere at 1,000 to 1,1. After heating to a temperature of 400 ° C. for rapid melting and aging, the melt is quenched and the resulting solid is ground to about 10 μm. In the case of manufacturing a Japanese paint, after preparing a glass composition having a predetermined composition, the glass composition is mixed with a colorant comprising a transition metal oxide or a colored rare earth element oxide or both. After heating the glass composition mixed with the colorant to a temperature of 1,000 to 1,400 ° C. in an oxidizing atmosphere to rapidly melt and ripen, the melt is quenched to obtain a solid product. Is ground to about 10 μm. On the other hand, when manufacturing Western paints, a colorant and / or a pigment composed of a transition metal oxide is mixed with the colorless paint (glass crushed material) obtained as described above.

The composition of the glass composition, SiO ₂ is 3
0.0-45.0% by weight, PbO 45.0-60.0
Contained by weight%, their total amount of SiO ₂ and PbO is a 85.0 to 90.0 wt%, Other Al ₂ O ₃ is 0.5 to 4.0 wt%, B ₂ O ₃ is 1 .0～4.0 wt%, CaO is 0.5 to 4.0 wt%, Li ₂ O 1.0
3.0 wt%, ZrO ₂ is 1.0 to 3.5 wt%, are contained respectively, in total is 100 wt%.
As the supply source of each component, for example, silica sand (purified product) for SiO ₂ , leadtan, Al for PbO, Al
Aluminum hydroxide is about ₂ O _3, colemanite for B ₂ O _3, colemanite or calcium hydroxide for CaO, Li ₂ O, lithium nitrate for, Zr
The O ₂ is a zircon. When colemanite is used as a supply source of B ₂ O ₃ , MgO, K ₂ O, Na ₂
O and the like are mixed into the glass composition in an extremely small amount as a sub-component of colemanite, but the amount is usually 0.1% by weight or less.

As a colorant to be mixed with the glass composition when manufacturing a Japanese color paint, for example, the glass composition 10
A mixture of Fe ₂ O ₃ of CuO and 0 to 0.5 parts of 1.5 to 5.0 parts by 0 parts, and CoO of 0.5 to 1.5 parts per glass composition 100 parts A mixture with 0 to 1.6 parts of CuO, and 0.5 to 1 with respect to 100 parts of the glass composition.
0.0 part of Fe ₂ O ₃ , 0.5 to 2.0 parts of Cr ₂ O ₃ per 100 parts of glass composition, 1.0 to 15.0 parts of color per 100 parts of glass composition Any of the rare earth element oxides is used. Examples of the colored rare earth element oxides include cerium oxide, praseodymium oxide, neodymium oxide, and erbium oxide. One of these oxides is used, or two or more oxides are used in combination. As these colored rare earth element oxides, those commercially available as reagents are used. The content of the colored rare earth element oxide varies depending on the type of the additive component. However, if the content exceeds 5 parts with respect to 100 parts of the glass composition, the transparency is reduced. In this case, the colored rare earth element oxide is used. It is advisable to dilute with a colorant-free top paint.

The glass composition or the glass composition containing the colorant is mixed in an oxidizing atmosphere at 1,000 to 1,4.
When the batch is melted by heating to a temperature of 00 ° C., a high-purity alumina crucible (containing 96% or more of Al ₂ O ₃ ) or a platinum crucible may be used instead of a mullite crucible generally used. preferable. When a high-purity alumina crucible is used, it is possible to prevent Na ions and K ions from being mixed into the glass composition when the glass composition is melted.

On the other hand, in the case of manufacturing Western paints, a colorant and / or a pigment composed of a transition metal oxide is directly mixed into a colorless paint (glass crushed material). Reagents such as Fe ₂ O ₃ , CoO and Cr ₂ O ₃ and various commercially available pigments for ceramics are used. Further, a carbonate such as copper carbonate can also be used as a coloring agent.
It should be noted that copper carbonate and cobalt oxide can be mixed and used in a small amount. However, if an amount of 0.3% or more is mixed with the pulverized glass, the foam is remarkably foamed, the appearance is deteriorated, and the surface area is increased. The chemical durability is remarkably reduced, and the lead elution amount is increased, so that copper carbonate or cobalt oxide may not be used in some cases. In this case, for defoaming, a colored glass may be once prepared, crushed, and used as an upper paint. The coloring density can be freely controlled by changing the content of the colorant or pigment.

In addition, an alkaline earth metal oxide such as barium oxide is added to the above glass composition to impart chemical durability and gloss to the upper paint, and the chemical stability of the upper paint is enhanced. Therefore, zinc oxide may be contained, and in that case, the content is 0.1 to 10
Weight percent.

Next, the manufacturing process of the ceramic paint will be described. First, a natural material such as quartzite or colemanite and a colorant are sufficiently mixed, and the mixture is made into a fine powder having a size of 60 mesh or less, and the mixture is put into a high-purity alumina crucible. Then, while maintaining an oxidizing atmosphere to prevent lead reduction, at a temperature of 1,000 to 1,400 ° C, preferably 1,250 to 1,350 ° C for 1.5 to 3 hours,
The formulation is heated to melt and mature. Thereafter, the melt is dropped into water to be quenched, and the obtained solid is pulverized by a mill into fine particles having a diameter of about 10 μm. Thereby, a ceramic paint (Japanese paint) is obtained.

As described above, a glass pulverized material is prepared through the same steps as described above without adding a coloring agent, and an appropriate amount of a coloring agent or a pigment is mixed with the glass pulverized material. By doing so, it is possible to obtain a ceramic paint (Western paint).

When a ceramic paint is applied to a ceramic object, water or an appropriate amount of a cloth or an aqueous solution of several percent CMC is added to obtain a paint having an appropriate viscosity, and the base formed on the ceramic substrate After applying the paint for application on the glaze (object to be painted) and drying it sufficiently, the painted object is heated to 700 ° C. to 850 ° C.
C., preferably at about 780.degree.

The coefficient of thermal expansion of the ceramic paint according to the present invention is 5.5 × 10 _{−6 to} 6.5 × 10 ₋₆ (100 to 35).
0 ° C), and the thermal expansion coefficient of the conventional top paint is 6 × 10 _-6 to
Compared to 10 × 10 ₋₆ (100 to 350 ° C.), this upper paint can be set to a firing temperature range of 700 ° C. to 800 ° C., which has good coloring properties of the colorant. . Furthermore, regarding the acid resistance, the appearance does not change at all even if the painted material is immersed in a 4% acetic acid aqueous solution for 24 hours in accordance with the inspection method of the safety inspection procedure specified by the Ceramics Safety Management Committee of the Japan Ceramic Industry Federation. Regarding the alkali resistance, even if the painted matter is immersed in a 0.5% anhydrous sodium carbonate aqueous solution for 6 hours and boiled in accordance with the method according to ASTMC 556, the appearance does not change at all, and the acid resistance test is performed. lead elution amount in a regulatory value of the food sanitation Law 17μg / cm ₂ against 1 [mu] g / cm ₂ or less (paint coverage 50%).

[0031]

Next, a more specific embodiment of the present invention will be described.

Flatary silica sand and lead tan are used as natural raw materials, and are mixed with colemanite, zircon and lithium nitrate. SiO ₂ : 34.0% by weight, PbO: 5
6.1% by weight, Al ₂ O ₃ : 2.1% by weight, B ₂ O ₃ : 3.
1 wt%, CaO: 1.6 wt%, Li ₂ O: 1.5 wt%, ZrO _2: 1.5 wt%, impurities: 0.1 wt%
After mixing and thoroughly mixing the glass composition having the composition described above, the mixture was passed through a 60-mesh sieve. Next, this mixture was put into a high-purity alumina crucible and melted and aged at 1,250 ° C. for 1 hour in a gas burner melting furnace. Then, the molten material is dropped into water and quenched,
Next, the obtained solid was pulverized into fine particles having a diameter of about 10 μm using a pot mill to prepare a colorless upper paint. As a result of measuring the characteristics of the obtained upper paint, the transition point was 387 ° C,
The yield point is 504 ° C, the coefficient of thermal expansion is 5.9 × 10 _-6 ,
In the acid resistance test results, there was no change in the appearance, and the amount of lead eluted was 0.
It was 5 μg / cm ₂ (50% paint coverage area).

Next, a pigment [Pigment No. VG-8] manufactured by Iwasaki Co., Ltd.
5 parts (Example 1), 3 parts of Iwasaki pigment [pigment number ZT-50 Turkish blue] (Example 2), 3 parts of Iwasaki pigment [pigment number ECB dark blue] (Example 3), Three kinds of various pigments were mixed with 3 parts of Iwasaki's pigment [semi-porcelain light yellow] (Example 4) and 3 parts of Iwasaki's gold-containing pigment [Lilac] (Example 5), and 5 types of upper paint (Western paint) were mixed. ) Was prepared.

In addition, copper parts 3 parts (Example 6), cobalt oxide 1 part (Example 7), and chromium oxide 0.5 parts (Example 8) were divided into 100 parts of the glass composition having the above composition. ),
5 parts of iron oxide (Example 9) and 10 parts of neodymium oxide (Example 10) were mixed with various reagent-grade colorants, and the other steps were performed in exactly the same manner as described above to obtain 5 types of upper paints ( Japanese paint) was prepared.

The paint was applied by melting each upper paint to a suitable viscosity, applying the paint on a glaze layer of ceramic, and firing the paint at a temperature of 780 ° C.
As a result, Example 1 was yellow-green, Example 2 was sky blue, Example 3 was dark blue, Example 4 was pale yellow, Example 5 was purple, Example 6 was green, Example 7 was dark blue, and Example 8 was yellow. Indicates yellow-green, Example 9 exhibits red-brown, and Example 10 exhibits blue-white (indicating polychromaticity).

The firing temperature and the acid resistance test (after 24 hours of 4% acetic acid treatment) of each ceramic paint were changed, and the appearance was observed without any change, and the lead elution amount (paint coverage 50%) ) Are shown in Table 1.

[0037]

[Table 1]

[0038]

According to the method for producing a ceramic overpaint according to each of the first, second and fourth aspects of the present invention, it is possible to perform baking at a baking temperature similar to the baking temperature in the conventional ceramic production. As with the conventional leaded paint, it does not cause defects such as peeling of the ceramic from the glazed material, and is superior to the ceramic appearance when using the traditional ceramic paint. A ceramic product with high gloss, coloration and transparency, chemical durability and quality stability that fully conforms to the regulations for the amount of eluted lead stipulated by the Food Sanitation Law, and high safety. Can be obtained.

According to the method of manufacturing an upper paint for ceramics according to the fifth aspect of the present invention, it is possible to prevent Na ions and K ions from being mixed into the paint, and to thereby achieve chemical durability of the painted ceramic product. And quality stability can be maintained.

According to the method for manufacturing a ceramic paint according to the sixth aspect of the present invention, most of the boron oxide in the raw material is fixed in the glass structure, and the stability and the flow of the glass in the molten state are improved. Sex can be significantly improved.

According to the method for manufacturing a ceramic paint of the invention according to claim 7, reduction of lead during firing is prevented,
Coloring of the frit by the reduced lead can be prevented.

According to the method for manufacturing an upper paint for ceramics of the invention according to claim 8, the chemical durability of the painted paint can be further improved.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshihiko Asai 2-10-11, Oeda Minamifukunishi-cho, Nishikyo-ku, Kyoto (72) Inventor Shuji Mori 6-13-13, Gakuen Higashi-cho, Nishi-ku, Kobe-shi (58) (Int.Cl. ⁷ , DB name) C04B 41/86 C03C 8/00-8/24

Claims (8)

(57) [Claims] 1. Silica contains 30.0 to 45.0% by weight and 45.0 to 60.0% by weight of lead oxide, and the total amount of silica and lead oxide is 85.0 to 90.0% by weight. % Of alumina, 0.5 to 4.0% by weight of alumina, 1.0 to 4.0% by weight of boron oxide, 0.5 to 4.0% by weight of calcium oxide, and 1% of lithium oxide. 0.0-3.
A glass composition containing 0% by weight and zirconium oxide in an amount of 1.0 to 3.5% by weight so that the total amount of the glass composition becomes 100% by weight is reduced to 1,000 to 1,000% in an oxidizing atmosphere.
A method for producing a ceramic top paint, comprising heating to a temperature of 1,400 ° C., rapidly melting and ripening, rapidly cooling the melt, and pulverizing the obtained solid. 2. The composition contains 30.0 to 45.0% by weight of silica and 45.0 to 60.0% by weight of lead oxide, and the total amount of silica and lead oxide is 85.0 to 90.0% by weight. % Of alumina, 0.5 to 4.0% by weight of alumina, 1.0 to 4.0% by weight of boron oxide, 0.5 to 4.0% by weight of calcium oxide, and 1% of lithium oxide. 0.0-3.
A transition metal oxide and / or a colored rare earth element oxide are added to a glass composition containing 0% by weight and 1.0 to 3.5% by weight of zirconium oxide so as to be 100% by weight in total. And mixing the glass composition mixed with the colorant in an oxidizing atmosphere for 1,00.
A method for producing a ceramic top paint, comprising heating to a temperature of 0 to 1,400 ° C., rapidly melting and ripening, rapidly cooling the melt, and pulverizing the obtained solid. 3. The coloring agent is used in an amount of 1.5 to 5.0 parts of cupric oxide and 0 to 0.5 part of ferric oxide, based on 100 parts of the glass composition, based on 100 parts of the glass composition. 0.5-1.
5 parts of cobalt oxide and 0 to 1.6 parts of cupric oxide, 0.5 to 10.0 parts of ferric oxide for 100 parts of glass composition, or 100 parts of glass composition 0.
5 to 2.0 parts of chromium oxide or glass composition 100
3. A color rare earth element oxide selected from the group consisting of cerium oxide, praseodymium oxide, neodymium oxide and erbium oxide in an amount of 1.0 to 15.0 parts per part by weight. Production method of ceramic paint. 4. A silica containing 30.0 to 45.0% by weight of silica and 45.0 to 60.0% by weight of lead oxide, and the total amount of silica and lead oxide is 85.0 to 90.0% by weight. % Of alumina, 0.5 to 4.0% by weight of alumina, 1.0 to 4.0% by weight of boron oxide, 0.5 to 4.0% by weight of calcium oxide, and 1% of lithium oxide. 0.0-3.
A glass composition containing 0% by weight and zirconium oxide in an amount of 1.0 to 3.5% by weight so that the total amount of the glass composition becomes 100% by weight is reduced to 1,000 to 1,000% in an oxidizing atmosphere.
After heating to a temperature of 1,400 ° C. for rapid melting and aging, the melt is quenched, and the obtained solid is pulverized to prepare a pulverized glass. A method for producing a ceramic top paint, comprising mixing a coloring agent and / or a pigment comprising: 5. The method according to claim 1, wherein a high-purity alumina crucible is used when melting the glass composition.
The method for producing a ceramic top paint according to any one of the above. 6. The method for producing an overpaint for ceramics according to claim 1, wherein colemanite is used as a raw material for supplying boron oxide. 7. The method for producing a ceramic overpaint according to claim 1, wherein lithium nitrate is used as a raw material for supplying lithium oxide. 8. The method for producing an overpaint for ceramics according to claim 1, wherein zircon is used as a feed material for the zirconium oxide.