JP3042957B2 - Glaze for Ibushi silver ceramic tile - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glaze for silver-colored porcelain tile.

[0002]

2. Description of the Related Art Conventionally, a method of forming a thin anodized silver-colored carbon film on the surface of a clay tile requires a reduction firing and a smoking process, and in particular, a smoking condition at a high temperature and a reducing atmosphere in a cooling process. Very careful attention has to be paid to the management of the product, which has the disadvantage that the product yield is low and it is not suitable for mass production. Also, depending on the smoking conditions and the composition of the base soil, discoloration called rust and show and peeling of the carbon film may occur, which is also a major defect in quality. In contrast, the present inventors have
JP-A-58-79838, JP-B-63-3141
No. 8 and Japanese Patent Application Laid-Open No. 2-243537 have provided a method for obtaining an anodized silver glaze tile by oxidizing and firing without requiring a smoking step, but these methods have the following disadvantages. Was.

The method exemplified in JP-A-58-79838 contains at most 0.22 mol of PbO and contains Mn
O, TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , NiO, Co
Although an anodized silver color is obtained by using the components of O, MoO, and WO ₄ , it is not sufficient in terms of an anisotropic silver color as compared with an anisotropic silver tile produced by a reduction firing and a smoking process.

[0004] The method exemplified in JP-B-63-31418 contains 0.3 mol or less of PbO and contains MnO.
And 0.9 to 1.0 mol of Zr, Ti, V, and Sn oxides, and optionally, Sb oxide in a total amount of 0.1%.
A glaze characterized by containing 2 to 1.5 moles is used to obtain a silver color. The silver-glazed tile in this method was excellent in color development, very similar to the silver-colored tile produced by the reduction firing and smoking processes, but (a) the fired product tile was mechanical. The glaze surface is easily damaged by impact. (B) The original aesthetic appearance of the glaze is impaired due to the influence of surface defects of the tile material such as uneven cracks. (C)
In the production process of the tile, there were major drawbacks such as being easily affected by the atmosphere (temperature conditions, gas composition, type of packing in the kiln, etc.) in the firing furnace, large variation in color development for each furnace, and low yield of the product tile.

[0005] The glaze and method disclosed in Japanese Patent Application Laid-Open No. 243535/1990 are an improved version of the glaze and method disclosed in Japanese Patent Publication No. 31418/1988, and the number of moles of SiO _{2 in} the glaze component. And Zr, Ti, V and Sn
The present invention is characterized by simultaneously increasing the total number of moles of the oxide and optionally the oxide of Sb, but has the following drawbacks in mass-producing anodized silver glaze tiles by this method. (B) Because of the production process of glaze tiles, it is common to fire glaze tiles of different colors at the same time. Therefore, depending on the type of glaze tile that is fired at the same time as the above-obtained silver glaze tile, fired silver glaze after firing The melting state and color development of the tile are affected. (B) Roof tiles are not only sunny days but also the appearance of being wetted by water during rainy weather is one of the great conditions after roofing. When wet with water, it looked brownish and the silver color after roofing was insufficient.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks, and is similar to an anisotropic silver tile produced by a reduction firing and smoking process. An object of the present invention is to provide a method of obtaining a covered silver glaze tile by oxidative firing.

[0007]

Means for Solving the Problems The inventor of the present invention has conducted intensive studies to solve the above-mentioned drawbacks, and as a result, the glaze is represented by a Zegel display.
MnO 0.3 to 0.7 mol, PbO 0.3 mol or more
0.7 moles, SiO ₂ 0.9 to 5.0 mol, Al ₂ O ₃
0.08 to 1.0 _{moles, SiO 2 / Al 2 O 3} 1.1~
16.5, total 0.5 of ZrO ₂ + TiO ₂ + V ₂ O ₅
The glaze having a composition of up to 3.5 mol and SnO _{2 of} 0.5 mol or less has good melting property and silver color development, has little color change due to simultaneous firing with different color glaze, and is suitable for mass production. I found it.

[0008] Solve the fluctuation of glaze melting and silver color development
In the present invention, the number of moles of MnO, PbO and
SiO_Two/ Al_TwoO_ThreeThe value of is particularly important. MnO is
It is an essential component for rusted silver color development, and its amount is 0.3 to
0.7 mol. If it is less than 0.3 mol, it is difficult to develop color. P
mol number of bO and SiO_Two/ Al_TwoO_ThreeThe value of the ratio is
It is a condition for determining the meltability, and its range is 1.1 to 1
6.5, and preferably 2.5 to 8.5. Si
O_Two/ Al_TwoO_ThreeThe ratio value is 1.1 or less or 16.5 or more
In case of PbO, even if PbO is 0.7 mol, it does not melt sufficiently.
No. The amount of PbO is greater than 0.3 mole to 0.7 mole.
You. ZrO_Two, TiO_Two, V_TwoO_FiveIs with MnO
It is an essential component for silver color development.
If it is less than 0.5 mol, it will not become silvery and 3.5 mol
Above で は, the glaze does not melt sufficiently. SnO _TwoSilver
It is an effective ingredient for coloring, but it is the same as a different color glaze.
0.5 mol or less to reduce the color change
It is necessary to be below.

SiO ₂ and Al ₂ O ₃ are used for adjusting the fire resistance of the glaze;
That it is possible to select appropriately by setting the baking temperature of 980 ℃ ~1200 ℃, SiO ₂ 0.9
0-5.0 mol, preferably 2.0-4.5 mol, Al
₂ O ₃ is 0.08 to 1.0 mol, preferably 0.3 to
A range of 0.8 mol is suitable.

Further, in the present invention, B ₂ O ₃ , R
₂ O and RO ₂ can be added as long as they do not affect the properties of the glaze. 0.02 to 0.3 mol of B ₂ O _3, 0.0 to 0.1 mol of R ₂ O, and RO ₂ 0.0-0.2
Molar is preferred.

Further, metal oxides such as Sb, Co, Ni, Mo, and W can be appropriately selected within a range that does not hinder the development of silver. Next, the present invention will be specifically described with reference to examples.

The compositions of Examples 1 to 22 shown in Table 1 (see gel representation) using lead frit, silica powder, kaolin, alumina powder, titanium oxide, zirconium silicate, vanadium oxide, manganese dioxide, iron oxide and the like as raw materials ) Glaze is wet-ground with a pot mill, and the obtained slip is dried on a tiled body.
Japanese style tile tiles are glazed so as to have an adhesion amount of 60 to 90 g per JIS53A plate, and oxidized and fired at the temperature shown in Table 1,
A good silver-glazed roof tile was obtained. These anodized silver glaze tiles had no color change due to the type of other glaze tiles co-fired in the furnace, and the silver color development when wet with water was good. In addition, since the amount of adhesion was set to be as large as 60 to 90 g, the defects of the base soil were covered and the aesthetic appearance could be maintained. The yield as a product tile was 97% or more.

For comparison, oxidative firing was carried out in the same manner as in the examples, using glazes having the compositions (shown by Zegel) of Comparative Examples 1 to 7. Table 1 also shows the composition of each comparative example. In Comparative Examples 1 to 3, the glaze did not melt sufficiently and peeling occurred. Comparative Examples 4 and 7
With regard to, the calcined silver color after firing was insufficient, and a blackish color was exhibited. Comparative Examples 5 and 6 had a good sliver silver color after firing, but changed color to red purple when fired simultaneously with another glaze tile (for example, high silver), and became brownish when wet with water and developed silver color. Did not show. The yield as a product tile was about 85%. In Table 1,
The observation results were shown for (1) color development and melting state, (2) color development variation due to co-firing, and (3) color development variation due to temperature change. In the table, the symbol “〇” indicates “good”, “no change” and “no change” for the items (1), (2) and (3), respectively, and the X mark indicates “bad” and “change” respectively. "With" and "with fluctuation".

[0014]

[Table 1]

[Table 2]

[Table 3]

[0015]

Advantages of the Invention A glaze tile similar to an anisotropic silver tile produced through a reduction firing and smoking process can be obtained by oxidation firing. 2. Little variation in silver color development. 3. The yield of product tiles is improved and mass production is possible. 4. The melting property of the glaze is good, it is possible to increase the amount of adhesion, and it can cover the defects of the base earth.

Claims (5)

(57) [Claims] 1. MnO 0.3 to 0.7 in Zegel notation
Mol, more than 0.3 mol of PbO to 0.7 mol, SiO_Two
0.9-5.0 mol, Al_TwoO_Three0.08 to 1.0 m
, SiO_Two/ Al_TwoO_Three1.1-16.5, ZrO_Two
+ TiO_Two+ V _TwoO_Five0.5 to 3.5 mol, Sn
O_TwoCharacterized by having a composition of 0.5 mol or less,
Glaze for silver porcelain tile. 2. The composition according to claim 1, wherein the SiO ₂ content is 0.90 to 5.0 mol,
_{2. The} glaze for a silver-colored ceramic tile according to claim 1, wherein the ₂ O ₃ is 0.08 to 1.0 mol. ₃ . Wherein SiO ₂ is 2.0 to 4.5 mol, Al ₂
O ₃ is 0.3 to 0.8 mol, oxidized silver color pottery tile for glaze of claim 1. 4. A further B ₂ O ₃ 0.3 mol or less, R ₂ O
Is 0.1 mol or less and RO ₂ is 0.2 mol or less (where,
R is an alkali metal or an alkaline earth metal).
The glaze for an anisotropic silver ceramic tile according to claim 1. 5. The glaze for silver-colored ceramic tile according to claim 1, comprising a metal oxide of Sb, Co, Ni, Mo and / or W.