WO2003095390A1 - Process for producing firing-denatured tenmoku tile, firing-denatured tenmoku tile and glaze - Google Patents

Abstract

A process for producing a firing-denatured Tenmoku tile, comprising filling a metal mold with a tile body material in powdery form and a firing-denaturable Tenmoku glaze in powdery form, effecting forming thereof under pressure and demolding, optionally conducting a double coating with glazes of different properties, drying the molded item and firing the dried molded item; glazes suitable for use in the process; and a firing-denatured Tenmoku tile.

Description

 Description: Method of manufacturing kiln-modified Tenmoku tile, kiln-modified Tenmoku tile and glaze

 The present invention relates to a method for manufacturing a glazed tile, a glaze, and a glazed tile. More particularly, the present invention relates to a method for manufacturing a kiln with a modified Tenmoku tile, a kiln with a modified Tenmoku glaze, and a kiln with a modified Tenmoku tile. Background art

 Tiles that emit metallic colours or irises (colors reminiscent of rich rainbows) include the so-called ras-yui tiles, which are raster-colored. Ras Yuichi tiles are tiles that are heated to 400 ° C to 450 ° C and a metal salt solution (for example, titanium chloride solution) is deposited on the surface to form an extremely thin metal film. Is generated. The metal film itself does not have adhesiveness, and is easily scratched and bald due to its micron-order thickness. Also, if used on the outer wall, it will fade in several years and will not shine. Therefore, it is difficult to use it as a building material. Also, since a large amount of chlorine gas is generated in the manufacturing process, metal equipment and equipment corrode, and there are many health problems.

 Another method for producing luminous tiles is to use glaze that contains a large amount of PbO. This method does not have a large problem because the amount of PbO used is small for products with relatively low production volume such as ceramics, but when applied to products such as ceramic tiles with large production volume, lead poisoning problem in glaze treatment There is a problem that it will occur, and there has been almost no demand for building materials since the 1970s.

As a method for producing glowing oil, a further method is to dissolve soluble oil in an oily solvent. There is also a method in which water gold containing 10 to 20% by mass of the compound is applied to the tile surface with a brush or by transfer and fired. However, this method is very expensive and difficult to apply as a method of manufacturing building materials except in special cases. Disclosure of the invention

 The present invention provides a method for producing a glazed tile, a glaze, and a glazed tile, in particular, a method for producing a kiln-modified Tenmoku tile, a kiln-modified Tenmoku glaze, and a kiln-modified Tenmoku tile glazed thereon.

 1. The mold is filled with a powdery tile body and a powdery kiln varnished glaze, molded under pressure, demolded, dried and fired to produce a kiln varnished tile. Law.

2. Fill the mold with the powdery tile body and the powdery kiln varnished glaze, press-mold, remove the mold, double-glaze the glaze with different properties, dry and fire. This is a method of manufacturing kiln-modified Tenmoku tiles.

 3. Fill the mold with the powdery tile body and the powdery kiln varnished glaze, press mold, remove the mold, and apply the glaze with different properties three times or more. After drying and firing, the method of manufacturing a kiln-modified Tenmoku tile. .

 4. Filling the mold with powdery tile body, press molding, demolding, then applying paste-like or mud-like kiln varnished glaze, drying and firing. A method of manufacturing a kiln-changed tile.

 5. Fill the mold with a powdery tile body, press-mold, remove the mold, apply a paste-like or mud-like kiln, and then apply a different quality A method for manufacturing a kiln-modified Tenmoku tile, characterized by double-glazing, drying and firing

6. Fill the mold with powdery tile body, press mold, remove the mold, then apply the paste or mud-like kiln varnished glaze on it, and then have different properties on it. Glaze A method of manufacturing a kiln with a multi-layered or multi-layered drug, followed by drying and firing.

 7. Fill the mold with the powdered tile body, then fill it with the powdered kiln varnished glaze, then fill it with the powdered tile body, press mold, and remove it. After molding, the nails are inserted from both sides into the kiln tentem glaze layer of the molded body, cracks are generated and divided into upper and lower parts, and the divided molded bodies are dried and fired. Manufacturing method.

 8. Fill the mold with the powdery tile body, then fill it with the powdery kiln, then fill it with the powdery tile body, press mold, and remove it. After the molding, the nails were inserted into both sides of the molded-body kiln Tenten-glaze layer and cracks were formed.Then, the upper and lower parts were divided into two parts. A method for manufacturing a kiln tentem tile, which comprises multiplying or multiplying, drying and firing.

9. A kiln characterized by kneading or stirring the raw material of the tile body, wet- or mold-molding it, drying it, and then glazing it with a plaster-like or mud-like kiln, and drying and firing. The method of manufacturing the phenomena tile.

 10. Knead or agitate the raw material of the tile body, wet or mold it, dry it, apply a paste-like or mud-like kiln, and then apply another glaze with different properties on it. A method of manufacturing a kiln with a multi-layered or multi-layered tile, followed by drying and firing.

 11. The method for producing a kiln varnished tile according to 9 or 10 above, wherein the paste is glazed at 600 to 800 ° C after wet or cold molding, and then a paste-like or mud-like varnished kiln is glazed. .

12. Kiln varying tenmoku glaze raw materials, (1) 5-25% by weight of Fe ₂ 0 _3, (2) 5 to 45% by weight of feldspathic material, (3) 5-45% by weight of siliceous material, (4) 5 to 25% by mass of a coloring agent and Z or a coloring auxiliary material, (5) 5 to 30% by mass of a clay material, and (6) 20 to 65% by mass of a solvent-soluble material. ~: Any one of L1 Manufacturing method of kiln-modified Tenmoku tile.

13. Kiln varying tenmoku glaze raw materials, (1) 5 to 15 wt% of Fe ₂ 0 _3, (2) 5 to 40% by weight of feldspathic material, (3) 5-45% by weight of siliceous material, (4) 5 to 20% by mass of a coloring agent and / or a coloring auxiliary material, (5) 5 to 30% by mass of a clay material, and (6) 25 to 65% by mass of a solvent-soluble material. 12. The method for producing a kiln-modified Tenmoku tile according to any one of items 1 to 11.

14. (1) Fe ₂ 0 ₃ material is Benigara, demon plate, an iron compound, selected from the group consisting of iron-containing raw material, and these mixtures of two or more, (2) feldspathic raw materials, Heizu feldspar, Selected from the group consisting of Kamado feldspar, Ohira feldspar, and a mixture of two or more of them; (3) the siliceous raw material is silica stone and Z or silica sand; (4) a coloring agent and / or a coloring auxiliary material Is selected from the group consisting of copper oxide, copper carbonate, cobalt oxide, manganese oxide, tin oxide, bone ash, rutile, manganese dioxide, titanium oxide, antimony oxide, and a mixture of two or more of these. The clay raw material is selected from the group consisting of frog eye clay, kaolin, kibushi clay, ceramic waste soil, and a mixture of two or more of these. (6) The solvent-soluble raw materials are limestone, limestone, and fluorite. , Talc, magnesite, zinc white, barium carbonate The above 12 selected from the group consisting of strontium carbonate, lithium carbonate, waste glass, sewage sludge incineration ash, sewage sludge melting slag, municipal waste incineration ash, municipal waste melting slag, earth ash, and a mixture of two or more of these Or The method for producing a kiln tentacle tile according to 13.

 15. Tile body raw materials are sewage sludge incineration ash, sewage sludge melting slag, Tokyo garbage incineration ash, Tokyo garbage melting slag, crushed stone, ceramic waste material, inorganic silica sand, mineral sand, ceramic chamotte, recycled material 15. The method for producing a kiln tentacle tile according to any one of the above items 1 to 14, comprising a material selected from the group consisting of a mixture of two or more of these.

16. If the tile is fired, use Laura-Heskirn (RHK), tunnel kiln, or 16. The method for producing a kiln-modified Tenmoku tile according to any one of the above items 1 to 15, which is performed in a kittle kiln.

 17. The method for producing a kiln tentacle tile according to any one of the above items 1 to 16, wherein the firing of the tile is performed for 1 to 15 hours.

 18. The method for producing a kiln tile according to any one of the above items 1 to 17, wherein the firing of the tile is performed by oxidizing, neutralizing, or reducing.

 1 9. Kiln transformation Tensume glaze represented by the following Zegel formula.

0.04-0.12 KNaO

0.59~ (.85 CaO -! 0.47 ~ 1.29 A1 2 0 3 · 0.76~4.10 Si0 2

0.11 ~ 0.30 MgO 0.21 ~; 1.10 P ₂ 0 ₅

5.5 ~; 15.0% Fe ₂ 0 ₃

2 0. Further B ₂ 0 _3, Ti0 kiln variable tenmoku glaze of the 1 9, further comprising at least one selected from ₂ the group consisting of CuO.

 21. A kiln metaten tile made by glazing the tile body base with the kiln metaten glaze described in 19 or 20 above.

2 2. Tile body raw materials are sewer sludge incineration ash, sewer sludge melting slag, Tokyo garbage incineration ash, Tokyo garbage melting slag, crushed stone, ceramic waste material, inorganic silica sand, mineral sand, ceramic chamotte, and these. 21. The kiln-modified tile according to 21 above, comprising a material selected from the group consisting of a mixture of two or more types. By the way, an electromagnetic wave with a wavelength of 4.0 to 14.0 zm is also called a growing light ray, and has the strongest energy as a weak energy that has a good effect on the cells of an object or a moving plant. A photoelectric effect, which is a materialization phenomenon of light, is provided to atoms or molecules as units. As will be described later, the kiln Tenten-y 夕 which is glazed with the kiln-tenten glaze of the present invention efficiently emits far-infrared rays even at a low temperature such as room temperature. Therefore, in addition to the beauty of the Tenten tiles, it also functions as a far-infrared radiator. Therefore, the kiln-modified tile of the present invention can also be used as a far-infrared radiator. BRIEF DESCRIPTION OF THE FIGURES

 Fig. 1 shows the far-infrared emissivity curves of the kiln tentacle tiles obtained in Example 1 and Example 3. In each case, the high-efficiency emissivity characteristics approximated to a flat blackbody in the far-infrared region. Is shown. Note that Examples 1 and 3 were both samples that were fired after double application, and the far-infrared emissivity was measured by the spectral emissivity measurement method of JIS, R1801, FTII (see Fig. The same applies to the measurements of 2 to 4).

 FIG. 2 is a far-infrared radiation divergence curve at 400 ° C. of the kiln-modified tiles obtained in Example 1 and Example 3. Each shows a high divergence curve close to a black body. FIG. 3 is a far-infrared radiation divergence curve at 100 ° C. of the kiln Tenten tiles obtained in Examples 1 and 3. It encompasses the 4.0 to 14.0 micron region, which is generally called far-infrared, and has a gentle curve close to the ideal blackbody. Various applications can be expected in this region in the future.

 FIG. 4 shows far-infrared radiation divergence curves at 3 ° C. of the kiln-modified Tenmoku tiles obtained in Example 1 and Example 3. Although the radiant emittance has been reduced, it has an indispensable attractiveness at room temperature. BEST MODE FOR CARRYING OUT THE INVENTION

Tenmoku is the name of a mountain on the border of Anhui Province in the northern part of Zhejiang Province in China. Kiln Transformation Tiles are tiles that exhibit unexpected glaze color and glaze phase during firing due to the temperature of the kiln and the components of the glaze. Say. In particular, iron glaze is mainly applied since there are many changes due to iron and iron-containing dangling products. Means a tile that has been used.

 The present invention provides a method for producing a glazed evening file that retains a very beautiful pattern and luminosity over many years without any fading of the kiln color even when used on the inner and outer walls. Is in the following points.

 First, the glass is fired at a high temperature of 1300 ° C or higher, so that the glaze melts and even if it contains a small amount of harmful substances such as heavy metals, it is sealed in the glaze, and the It does not elute.

 Second, the surface layer (glaze layer) is thick, for example, 1.0 to 2.0, and has a composition that is resistant to air pollution.

 Thirdly, in the present invention, the glaze surface has a beautiful and attractive pattern color, and a silver-colored spot appears in a drip-like manner on the glaze surface. It is reminiscent of oil droplets, moss, characters, shukko, and akiha, produced in the Southern Song Dynasty in the 12th and 13th centuries of China. Even today, with the advancement of science, the principle of formation of these glazes has not been clearly elucidated. Therefore, these pottery works are designated as national treasures and rebuns, and are very precious and expensive.

The present invention challenges these unknown worlds, and as a result of scientifically investigating the origins, provides a method for stably mass-producing kiln-mounted tentacle tiles with a surface finish comparable to Chinese products 900 years ago. Is what you do. Further, as shown in the representative examples 1 and 3 described later, the composition contains a high-efficiency far-infrared radiator. The raw material for the tile body used in the present invention is not particularly limited, and sewage sludge incineration ash, sewage sludge melting slag, Tokyo garbage incineration ash, Tokyo garbage melting slag, crushed stone, ceramics waste raw material, inorganic silica sand, and mineral sand , Pottery chamotte, recycled materials, and mixtures of two or more of these. In the present invention, Recycling raw materials such as waste ceramic waste, silica sand gira, ceramic waste, ceramic waste, etc., which were previously discarded, are mainly used, and the use of virgin materials is kept to a minimum. It is possible. The above-mentioned kiln meta-temporary glaze is applied to the kiln meta-temple tile used in the present invention.

 As the kiln varieties glaze used in the present invention, those represented by the above-mentioned Zegel type are preferred. This glaze is characterized in that it contains a predetermined amount of iron oxide and phosphorus. The amount of glaze is in the range of 0.5 to 2.5 bandages, preferably 1.0 to 2.0 Ornrn in terms of thickness after firing. The reason why the thickness of the glaze layer is made thicker than usual (for example, 1.0 to 2.0 mm after firing) is to promote the active movement of the glaze melted during firing and the generation of kiln phenomena. In addition, far-infrared emissivity is also highly developed.

 In the present invention, after the above-mentioned first kiln phenomena glaze, further, glazes having properties different from those of the first kiln phenomena glaze are double-coated, triple-coated, or multiply-coated, and It can be dried and fired. In this way, by performing double coating or multiple coating more than that, the first kiln variant Tenten glaze forming the glaze surface layer and the double haze glaze having different properties are melted and mixed, This has the advantage that the surface layer becomes more rigid and covered, making it less prone to scratches. In addition, it is possible to prevent wind danger due to air pollutants such as carbon dioxide gas and sulfur dioxide gas.

 Also, depending on the composition of the glaze, the double coating may cause a chemical reaction between the glaze and the glaze during firing, forming a certain beautiful pattern.

Furthermore, glazes with different properties are multiplied three times or more, so that the glaze and the glaze melt and mix with each other to make the surface layer thicker and stronger, but also unexpected glows, patterns, oil spots It is possible to form texts and produce literal kiln tiles. The multiply or more multiply technique of the present invention can be used in the past. This is a unique method. By applying triple or multiple glazing with a variety of glazes with different properties and applying them in multiple layers, patterns and kiln phenomena that suddenly surpass the expectation are suddenly deposited. This rare chemical reaction is very complex and hard to explain, but it is the result of the excellence of modern science in a controlled atmosphere. As the glaze used for double coating, triple coating, or more multiple coating, a transparent glaze represented by the following Zegel formula is preferable.

0.20-0,27 KNaO

_{0.65~0.71 CaO · 0.13~0.42 Α1 2 0 3} · 1.20-4.50 Si0 2

_{0.01~0.15 MgO 0, 00~0.10 B 2 0} 3 0.00~0.55 P 2 0 5

0.00~0.14 ZnO 0.06~3.16 Ti0 ₂ double hung, glazed amount in triple seat, or more multi-threading is 0 in thickness after firing. 1 to 0. 5 mm, preferably 0.1 5 ~ 0.4 is recommended. If the amount of glaze is less than this range, the desired effect will not be sufficiently exhibited, and if it is too large, the glaze will flow too much in the kiln and the kiln and the kiln tools may be damaged.

 In the present invention, the mold is filled with a powdery tile body or a powdery evening body and a powdery kiln varnished glaze, molded under pressure, demolded, and dried. , Firing.

The pressure at the time of pressure molding is preferably 150 to 300 kg / cm ² , and more preferably 180 to 250 kg / cm ² . Drying must be performed sufficiently at 80 to 120 ° C for about 8 to 20 hours.

After the pressure molding, glazes of different properties may be doubled or multiplied if necessary, dried, and fired. Firing should be performed at 1280 ~ 1; 330 ° C for 1 hour to 3 hours for Laura-Haaskirn, and for 5 hours to 15 hours for tunnel kiln and ト ル shtor kiln. Is preferred.

 In the present invention, it is more desirable to perform baking at, for example, 130 ° C. for a short time, for example, for 70 to 180 minutes by using a roller-hearth kiln (R H K). The calcination can be carried out in an oxidized, neutral or reduced state. By baking for a short time using a roller and hearth kiln, it is possible to manufacture kiln-modified tiles that are sufficiently beautiful and practical. This firing method can save a great deal of energy for firing and has a low environmental impact.

 Conventionally, in the firing of crystal glaze or tiles that deposit surface patterns as in the case of a kiln, the use of a mouth-to-heart kiln will result in a lack of aging time for the glaze, making the kiln sufficiently beautiful and practical. A roof tile could not be manufactured.

 However, the present invention breaks the conventional wisdom by properly mixing glaze, baking time and temperature, atmosphere, cooling, and synergistic effect of melting the glaze and the glaze having different properties by twice or three times. It has become possible to produce tiles that are sufficiently beautiful and practical for short time firing for 70 to 180 minutes. Hereinafter, the present invention will be described more specifically with reference to examples. In addition, iron oxides and the like expressed in% are mass percentages of 100% by mass of the main component of the glaze. (Example 1)

No. 1 glaze type

 0.12 KNaO

_{0.59 CaO · 0.87 A1 2 0 3} 1.97 Si0 2

0.28 MgO 0.54 P ₂ 0 ₅

10.5% Fe ₂ 0 ₃

Double gel type of transparent hanging glaze (A)

0 0.27 KNaO

0.71 CaO 0.42 A1 ₂ 0 ₃ 4.52 SiO,

0.01 MgO 0.05 B ₂ 0 ₃

0.25% Fe ₂ 0 ₃ 0.06% Ti0 ₂

(1) The mold (length: 157.5 thigh x width: 157.5 鹏, height: 26 咖) has tile body material (30% by mass of silica sand, elutriation clay: 15% by mass, applied mass: 15% by mass, ceramic waste soil) Powder (20 mesh) of 15 mass%, 15 mass% of feldspar and 10 mass% of crushed cerben) was filled with 56 Og, and the thickness was averaged so as to average. On top of this, 84 g of the above No. 1 glaze powder (100 mesh) was filled and molded under a pressure of 230 kg / cm ² . Remove the molded body (length 157.5 recommended X width 157.5 brain X height 14) from the mold, RHK (length 50m width 1.5m, height 0.3m), maximum temperature 1300 ° Oxidation and baking for 160 minutes at C.

 The temperature change and the glaze change in the firing step will be described.

 ① Completely dried green tiles advance 1 Om in 32 minutes in the pre-tropics to reach 720 ° C.

 (2) In the next 32 minutes, advance by 1 Om and reach 1100 ° C, and the glaze gradually begins to melt.

(3) The glaze is completely melted during the next 32 minutes while traveling 10 m and kept at 1300 ° C for 25 minutes. This glaze has a large amount of clay and is hard to flow, but it reacts with CaO and MgO as a solvent to promote melting. On the other _{hand, P 2 0 5, Sb 2} 0 3 coloring adjuvant also, contaminants traces contained and therein F e ₂ 0 ₃ of釉中also narrowing melted in the glaze, creating bubbles, saturation state The activated Fe ₂ O ₃ behaves vigorously and exerts various glaze effects, and crystals of metal spots precipitate on the glaze surface.

冷却 In the cooling zone during the next 32 minutes while moving 1 Om, cool rapidly from 1300 ° C to 600 ° C in the first 17 minutes and gradually cool to 500 ° C in the next 15 minutes. 徐 Continue slow cooling for the last 32 minutes, and remove the kiln from the kiln at 100 ° C ~; I 30 ° C.

 The baked tiles have a shiny rat-silver-colored kiln-denten glaze deposited on the entire surface of the glaze.

In the production of conventional Tenten tiles, firing takes at least 10 to 15 hours and then naturally cools. Nevertheless, it was often difficult to control during firing, and products of uniform quality could not be obtained. The method of manufacturing the Tenten tiles in the kiln by the extremely short-time firing by the RHK of the present invention is a kiln with uniform quality by adopting a glaze mix suitable for the kiln, firing time, firing temperature, firing atmosphere and appropriate cooling. It is a baking method that can stably produce metamorphic tiles and breaks the conventional belief. (2) The above-mentioned transparent glaze is slightly double-coated on the molded body prepared in the above (1) so as to have a thickness of 0.1 to 0.2 after firing, and then the same as in the above (1). When fired under the firing conditions, large silvery crystals and oil droplets were deposited without gaps on the black fine underglaze. This is to create a bubble glaze that is sticky is melted at high temperature, it can flow into the crystal spots of iron in it and kiln strange Tianmu glaze of T i 0 ₂ and the lower layer of this flow easy transparent釉中reacts It is thought that it was.

(Example 2)

No.2 glaze type

 0.11 KNaO

0.60 CaO0.88 A1 ₂ 0 ₃ 1.98 Si0 ₂

0.29 MgO 0.55 P ₂ 0 ₅

二重掛透明釉 (A) 重接卜透明釉 （B) のゼーゲル式

Double hanging transparent glaze (A) Seedling type of transparent glaze (B)

 0.20 KnaO

_{0.65 CaO · 0.36 A1 2 0 3} ■ 3.89 Si0 2

 0.01 MgO

 0.14 ZnO

0.26% Fe ₂ 0 ₃ 3.16% Ti0 ₂

(1) In the same manner as in Example 1, the powder of the tile body raw material was added to the mold (20 mesh).

2700 g were filled, and 490 g of the powder of No. 2 glaze (100 mesh) was filled thereon. The No.2 glaze, A1 ₂ 0 medium solvent than in ₃ (alkali metal oxides and alkaline earth metal oxides) is a glaze with a sticky less flow in small amounts. The glaze used in the powder so as to have a thickness of glaze becomes nonuniform, consciously evening with the unevenness with Irubode one matrix material in釉表layer, integrally molded by applying a pressure of 25 Okg / cm ² Was.

 Remove the molded body (320 vertical x 320 horizontal thigh x convex height: 18.5, concave height: 16.5 mm) from the mold and lightly apply a low-viscosity transparent glaze (A) on it (after firing). Approximately 0.15 brains in thickness) Double hang and dry at 100 ° C for 10 hours, then RHK 1

It was baked at 300 ° C for 80 minutes by oxidation.

 The temperature change and the glaze change in the firing step will be described.

 ① The first pre-tropical zone will go 10m in 15 minutes and reach 800 ° C.

 (2) In the next 15 minutes, the temperature will advance 1 Om and reach 1200 ° C, and the glaze will begin to melt rapidly.

③ During the next 15 minutes, the glaze will melt completely during 10m, and keep at 1300 ° C for 12 minutes. This glaze is a sticky and hard glaze, but moves slightly from the convex part to the concave part of the glaze layer. In addition, the double-glazed transparent glaze has low viscosity and is easy to flow, so it starts to work first, and iron flows into bubbles to promote the deposition of vivid silver raster. 急 During the next 15 minutes, cool rapidly from 1250 ° C to 600 ° C while traveling 10m. During this time, the bubbles subside.

 徐 Slowly cool for the last 15 minutes and take out the tile from the kiln at 120-140. As a result, the silver raster floats evenly on the surface, and in some places the surface of the surface cracks reveals a blackish brown underglaze, making it look as if the sunset shines on the surface of the sea. ,

(2) The triple-glazed transparent glaze (B) was glazed (approximately 0.2 strokes after firing) on the double-glazed molded product, and dried at 100 ° C for 10 hours. Oxidized and calcined at 1300 ° C for 160 minutes with RHK, as in 1. As a result, an even deeper mottle pattern was deposited on the entire surface. This phenomenon is Fe ₂ 0 ₃ and Ti_〇 ₂ contained in different glaze compositions further actively moved from the time of the double-seat, presumably because the crystal with a large grain oil droplets tenmoku have emerged.

(Example 3)

No.3 glaze type

 0.11 KNaO

0.59 CaO1.29 ΑΙ ₂ 3: 3 2.04 Si02

0.30 MgO 0.57 P, 0 ₅

9.7% Fe ₂ 0 ₃

 0.37% CuO

Double hanging transparent glaze (B)

(1) In the same manner as in Example 1, a mold (length: 157.5 thigh x width: 157.5 wisteria x height: 26 mm) was filled with 510 g of powder (20 mesh) of a raw material for tile body, and the thickness was reduced. Averaged to average. This was molded under a pressure of 23 Okg cm ² . Remove the molded body (length 157.5, X 157.5 删, height 12.5 flat) from the mold and put 84 g of the above No. 3 glaze powder (100 mesh) on 210 ml of water. The mixture was thickly applied (approximately 1.3 thighs after baking), dried, kept at 1300 ° C. for 12 minutes at RHK, and baked for 70 minutes with oxidized water. As a result, a beautiful metallic luster appeared on the entire surface of the surface. Ordinary lath Yuichisai is made by adding silver and copper to the glaze and firing at 1000C with lead glaze. However, firing at 1000 ° C loses its luster and makes it unusable when used on the outer walls of buildings. Since the raster color of the present invention is fired at 1300 ° C., gloss can be maintained for a long period of time even when used on the outer wall of a building.

 (2) The highly viscous transparent glaze (B) was coated on the tile body above with the No. 3 glaze and double-glazed, and baked under the same conditions as in (1) above. In addition to the glaze that does not flow, the upper and lower glazes do not move much because of the short baking time. In some places, the transparent glaze (B) flows in a crack-like manner, and the black glaze of the lower glaze appears from some places. The surface glaze (B) was doubled and kept thick, hardened, and the kiln-changed tiles that can withstand air pollution sufficiently were obtained. (Example 4)

No.4 glaze type

 0.04 KNaO

0.85 CaO0.55 A1 ₂ 0 ₃ 0.76 Si0 ₂

0.11 MgO 0.21 P ₂ 0 ₅

7.5% Fe ₂ 0 ₃ 0.46% Ti0 ₂

Double hanging transparent glaze (A)

(1) In the same manner as in Example 1, the mold was filled with 56 Og of powder (20 mesh) of the tile body raw material, and the thickness was equalized so as to average. 84 g of the above No.4 glaze powder (100 mesh) is filled on top of this, and a pressure of 230 kg / cm ² is applied to this. And molded. The molded body (157.5 in length X 157.5 in thigh X height 14.0 recommended) was removed from the mold and baked with RHK at 1300 ° C for 80 minutes with oxidized water. As a result, fine dots glistened on the upper layer, and glazes comparable to the mosquitoes appeared on the surface. This formulation is a hard glaze and hard to flow, but it is considered that the iron was precipitated in a short period of time by combining with a metallic substance containing various trace impurities.

 (2) The above molded product was lightly double-coated with low-viscosity transparent glaze (A) (about 0.15 in thickness after firing) under the same firing conditions as above, ie, at 1300 ° C for 80 minutes. Fired with oxide. As a result, large and small splendid oil-dropped crystals were heavily precipitated on the surface. It seemed as if I had a view of the countless Andromeda Galaxy in the night sky.

(Example 5)

No.5 glaze type

 0.04 KNaO

0.84 CaO0.47 A1 ₂ 0 ₃ 0.78 Si0 ₂

0.11 MgO 0.01 B ₂ 0 ₃ 0.21 P ₂ 0 ₅

8.0% Fe ₂ 0 ₃ 0.35% Ti0 ₂

Double hanging transparent glaze (B)

Triple glazed transparent glaze (A)

(1) In the same manner as in Example 1, the mold was filled with 560 g of the powder of the tile body raw material, and the thickness was averaged so as to average. On top of this, 84 g of the above No. 5 glaze powder (100 mesh) was filled and molded under a pressure of 230 kg / cm ² . Remove the molded body (length 157.5mm x width 157.5 thigh x height 14. Omni) from the mold and disperse the above transparent glaze (B) powder (100 mesh) 24. Og in 95ml water The resulting product was double hung so that the thickness after firing became 0.2 to 0.4 thigh, and oxidized and fired at 1300 ° C for 160 minutes at RHK. As a result, a spider's web-like pattern with oil all over the surface emerged clearly on the glaze surface dulling in reddish copper. The composition of the No. 5 glaze A1 ₂ 0 ₃ is small, on the easily flows glaze, double hung with transparent glaze (B) also for easily flows glaze, P ₂ 0 ₅ to Fe ₂ 0 ₃ of glaze, Ti0 melted ₂ in the early to reaction step, further each other and easily flows glaze be likewise melted flow above reaction glaze, is also considered to and to form an attractive reptile pattern.

 (2) Further, the above-mentioned triple hung transparent glaze (A) is consciously shaded and glazed on the double hung molded body, and oxidized at 1300 ° C for 160 minutes as in (1) above. Fired. As a result, a spider web-like mottling of a large net with a darker blackish brown color, which was darker than the double hanger, appeared. This phenomenon is thought to be due to the fact that the glaze applied with triple glazing (A) moves and mixes more actively at high temperatures than in the case of double glazing. A kiln-changed tile with a surface pattern reminiscent of the earth of the burning Africa was obtained.

(Example 6)

 o. 6-glaze Zegel type

 0.11 KNaO

0.60 CaO0.88 ΑΙ 2, Ο ": 3 1.98 Si0 ₂

0.29 MgO 0.55 P ₂ 0 ₅

Similar to 10.7% Fe ₂ 0 ₃ Example 1, the mold filled with powder (2 0 mesh) 2 9 O g of Tairubode one matrix material and leveled to a thickness to average. On top of this, 280 g of the powder of No. 6 glaze (100 mesh) was filled, and on top of this, The powder was filled with 290 g, and the thickness was averaged so as to average. This was molded under a pressure of ²⁰⁰ kg // cm ² . The molded body (length 2 48 8 x width 66 6 x height 31 fiber) was removed from the mold, and nails were inserted into the glaze layer from both sides to split the glaze layer into two. This was fired at 1300 ° C for 80 minutes with an oxide at RHK. As a result, copper-brown tiles shining in rainbow colors have emerged on the surface with natural irregularities. The surface of the tile molded by this molding method had a pattern and shape similar to the surface obtained when a nail was put into natural stone and peeled off. What this formulation glaze A1 ₂ 0 ₃ is is a glaze with less motion in a large amount, which slightly motion as any irregularities in the surface it becomes hot during firing, it flows to the lower portion, to form a pattern and shape of the surface it is conceivable that. Industrial applicability

 In the southern dynasty of China in the 13th to 13th centuries, the varieties of sun and oil droplets glow with a metallic luster. Not elucidated.

 The present invention thoroughly investigates these unknown reasons scientifically, and provides a kiln-adapted tile that does not lose its beauty as a building material that can withstand aging over many years. Usually, most of the glaze raw materials used in the tile manufacturing process use purified raw materials from which impurities and contaminants have been removed to improve productivity. Unfortunately, however, if the glazes for kiln Tenten tiles are manufactured using such high-purity raw materials, only extremely ordinary or disappointing standardized products can be obtained.

On the other hand, the present invention uses glaze containing natural raw materials and recycled raw materials produced from the natural world. The dagger contains trace amounts of copper, tungsten, manganese, titanium, and the like as impurities, and these impurities are considered to have contributed to the formation of subtle surface patterns on the kiln-deformed tiles. The present invention uses raw materials produced in various states as much as possible, adjusts to a sticky glaze or a free-flowing glaze according to the purpose, and, if necessary, doubles or triples or more multiples The variety of metal glazes and kiln varieties of glaze that precipitates from them is sought to stabilize. In addition, unstable raw materials for stabilization, especially recycled raw materials, are secured in large quantities as much as possible, and by uniformly mixing these materials, high-efficiency far-infrared radiators close to black bodies can be obtained. This enables stable production of kiln-modified tiles with surface patterns, with less variation. In addition, short-time firing with RHK facilitates control of oxidation, reduction, and neutralization, and can automate temperature control, and contributes to the global environment and resource utilization, and has significant economic effects.

Claims

The scope of the claims 1. The mold is filled with a powdery tile body and a powdery kiln varnished glaze, molded under pressure, demolded, dried and fired to produce a kiln varnished tile. Law. 2. Fill the mold with the powdery tile body and the powdery kiln varnished glaze, press-mold, remove the mold, double-glaze the glaze with different properties, dry and fire. This method is characterized by the fact that this method is used to produce kiln-modified Tenmoku tiles.  3. Fill the mold with the powdery tile body and the powdery kiln varnished glaze, press mold, remove the mold, and apply the glaze with different properties three times or more. After drying and firing, the method of manufacturing a kiln-modified Tenmoku tile.  4. Filling the mold with powdery tile body, press molding, demolding, then applying paste-like or mud-like kiln varnished glaze, drying and firing. A method of manufacturing a kiln-changed tile.  5. Fill the mold with a powdery tile body, press-mold, remove the mold, apply a paste-like or mud-like kiln, and then apply a different quality A method of manufacturing a kiln-modified Tenmoku tile, which comprises drying and firing the glaze after double-glazing. 6. Fill the mold with powdery tile body, press mold, remove the mold, then apply the paste or mud-like kiln varnished glaze on it, and then have different properties on it. A method of manufacturing a kiln zenten tile, characterized in that glaze is applied three times or more, then dried and fired. 7. Fill the mold with the powdery tile body, then fill it with the powdery kiln, then fill it with the powdery tile body, press mold, and remove it. After molding, the nails are inserted from both sides into the kiln tentem glaze layer of the molded body, cracks are generated and divided into upper and lower parts, and the divided molded bodies are dried and fired. Manufacturing method. 8. Fill the mold with the powdery tile body, then fill it with the powdery kiln, then fill it with the powdery tile body, press mold, and remove After the molding, the nails were inserted into both sides of the molded-body kiln Tenten-glaze layer and cracks were formed.Then, the upper and lower parts were divided into two parts. A method for producing a kiln with a multi-layered or multi-layered, dried, and fired tile. 9. Mixing or agitating the raw material of the tile body, wet- or mold-molding it, drying it, applying a paste-like or slurry-like kiln-like glazing, drying and firing. Tile manufacturing method.  10. Knead or agitate the raw material of the tile body, wet or mold it, dry it, apply a paste-like or mud-like kiln, and then apply another glaze with different properties on it. A method of manufacturing a kiln with a multi-layered or multi-layered tile, followed by drying and firing.  11. The method according to claim 9 or 10, wherein the paste is glazed at 600 to 800 ° C after wet or cold molding, and then is glazed with a paste-like or slurry-like kiln. Manufacturing method. 12. Kiln varying tenmoku glaze raw materials, (1) 5 to 25 wt% of Fe ₂ 0 _3, (2) 5-45% by weight of feldspathic material, (3) 5-45% by weight of siliceous material, (4) 5 to 25% by mass of a colorant and Z or a coloring auxiliary material, (5) 5 to 30% by mass of a clay material, and (6) 20 to 65% by mass of a solvent-soluble material. 12. The method for producing a kiln-changed tile according to any one of 1 to 11. 13. The raw materials for the kiln-changed glaze are (1) 5-: L 5 mass% Fe ₂ 〇 ₃ , (2) 5-40 mass% feldspar material, (3) 5-45 mass% siliceous material Raw material, (4) 5 to 20% by mass of colorant and / or coloring auxiliary material, (5) 5 to 30% by mass of clay material, and (6) 25 to 65% by mass of solvent-soluble material A method for producing a kiln-transformed tile according to any one of claims 1 to 11. 1 4. (1) F e 2 0 3 material is Benigara, demon plate, an iron compound, selected from the group consisting of iron-containing raw material, and these a mixture of two or more, (2) feldspathic material, Heizu Selected from the group consisting of feldspar, kamado feldspar, ohira feldspar, and a mixture of two or more of them; (3) the siliceous material is silica stone and Z or silica sand; and (4) a coloring agent and / or a coloring aid. The raw material is selected from the group consisting of copper oxide, copper carbonate, cobalt oxide, manganese oxide, tin oxide, bone ash, rutile, manganese dioxide, titanium oxide, antimony oxide, and a mixture of two or more of these. (5) The clay raw material is selected from the group consisting of frog eye clay, kaolin, kibushi clay, ceramic waste soil, and a mixture of two or more of these. (6) The solvent-soluble raw material is limestone, Takayuki light. , Fluorite, talc, magnesite, zinc white, charcoal Selected from the group consisting of barium, strontium carbonate, lithium carbonate, waste glass, sewage sludge incineration ash, sewage sludge molten slag, municipal waste incineration ash, municipal waste molten slag, earth ash, and a mixture of two or more of these A method for producing a kiln with a tile according to claim 12 or 13.  1 5. Tile body raw material is sewer sludge incineration ash, sewer sludge molten slag, Tokyo garbage incineration ash, Tokyo garbage molten slag, crushed stone, ceramic waste, inorganic silica sand, mineral sand, ceramic chamotte, recycled raw material 15. The method for producing a kiln tile according to any one of claims 1 to 14, comprising a material selected from the group consisting of a mixture of two or more of these.  16. The firing of the tile according to any one of claims 1 to 15, wherein the firing of the tile is performed in a mouth-lah kiln (RHK), a tunnel kiln, or a shuttle kiln. 17. The method for producing a kiln tentacle tile according to any one of claims 1 to 16, wherein the firing of the tile is performed for 1 to 15 hours. 18. The method for producing a kiln tentacle tile according to any one of claims 1 to 17, wherein the firing of the tile is performed by oxidizing, neutralizing, or reducing. 19. A kiln with a zenten glaze represented by the following Zegel formula. 0.04-0.12 KNaO _{0.59~0.85 CaO · 0.47~1.29 A1 2 0 3} , 0.76~4.10 Si0 2 0.11 ~ 0.30 MgO 0.21 ~: 1.10 P ₂ 0 ₅ 5.5 to 15.0% Fe ₂ 0 ₃ 20. Further B ₂ 0 _3, Ti0 ₂ and kiln varying tenmoku glaze of claim 19 further comprising at least one selected from the group consisting of CuO.  21. A kiln metaten tile obtained by glazing a tile body base with the kiln metaten glaze according to claim 19 or 20.  22. Tile body raw materials are sewer sludge incineration ash, sewer sludge molten slag, Tokyo garbage incineration ash, Tokyo garbage molten slag, crushed stone, ceramic waste material, inorganic silica sand, coagulated sand, ceramic chamotte, 22. The kiln tile according to claim 21, comprising a material selected from the group consisting of a mixture of two or more kinds.