JP2007302547A - Glaze for kimachi-like ceramic, kimachi-like ceramic product, and method for producing the product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a glaze for a Kimachi-like ceramic, a Kimachi-like ceramic product, and a method for producing the product. <P>SOLUTION: The glaze for the Kimachi-like ceramic contains, in Seger expression, >0 to 0.6 mol of CaO, >0 to 0.5 mol of MgO, >0 to 0.5 mol of ZnO, 0.5-1.5 mol of Al<SB>2</SB>O<SB>3</SB>, 0.2-0.6 mol of P<SB>2</SB>O<SB>5</SB>, and 1.0-3.0 mol of SiO<SB>2</SB>. The Kimachi-like ceramic product (roof tile) is obtained by applying the glaze, and the method for producing the product comprises firing a glazed body at a temperature of ≤1,250°C. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a glaze for a traditional ceramic, a traditional ceramic product such as a traditional ceramic tile, and a method for manufacturing the product.

First, the natural waiting glaze targeted in the present invention is a unique glaze with a unique brightness that changes color depending on the angle seen by the vitreous surface after firing, and the tuff produced in Shimane Prefecture It is a traditional glaze that directly uses more than 70% of the powder of Kamaishi stone, a kind of rock. That is, the change in the color of the glaze is such that when the baked glassy surface is viewed from the front, it looks bright red from reddish brown to white when viewed from an oblique angle.
From the glaze classification, it can be said that it belongs to the agate with iron as a coloring component, but its unique shine itself is
1. An optical phenomenon caused by reddish-brown crystals deposited in the glaze layer, a kind of polarization phenomenon due to the difference in reflection depending on the angle of light hitting the crystals,
2. Or can it be said that the surface of the glaze is synergistic with the specular reflection effect due to the image like metallic luster?
In any case, the micrograph of the surface clearly shows the presence of bright flat crystals and dark wedge-shaped crystals.

  This natural comedy glaze is usually obtained by a method that mixes the kurumachi stone produced in Shinji-cho, Matsue city and Venus powder produced in Onsen-zu, Ota city at an appropriate ratio, and adds water to crush the mud. In general, a ratio of 70% visit stone and 30% Venus flour is often used, and this natural mud cocoon is applied to roof tiles and cocoons and is usually fired at 1300 ° C. or higher. Especially for firing, it is said that reduction firing produces a more beautiful color.

For example, the following glazes are described in detail in the following publications.
Shimane Prefectural Industrial Technology Center: Industrial Technology Shimane 35 (January 1982) Page 12 “Overview of Visitors and Basic Characteristics of Visitor Rust”
According to this, the material used as a glaze material is called "Kurumachi rust stone", and in the old days it was used by crushing product scraps such as stones, foundation stones, stone monuments, etc. Iwami pottery products, Ishishu red tile (commercial tile) are the main uses.
Furthermore, as the basic characteristics, the analytical value of this “coming rust stone” and its utilization example are also shown.

However, this natural acupuncture glaze has the following drawbacks, and today it is a serious and big problem in the world.
1. First of all, there is a problem of high cost because there is a depletion of raw stones and a decrease in the shortage of miners.
2. This glaze originally uses natural ore as it is, so it goes without saying that there is a certain difference in color development, and it is not possible to stably supply a certain quality, sorting in a poor labor force, etc. This complicated process is required, and quality control is extremely difficult.
3. Since it is necessary to increase the firing temperature to 1300 ° C. or higher, in addition to technical problems in the production of ceramics, it is no longer matched with the current state of energy saving as an environmental problem.
It is an object of the present invention to develop and provide a new glaze for a traditional Japanese porcelain ceramic that overcomes these drawbacks, a product such as a traditional glaze ceramic tile obtained by glazing and firing the glaze, and a method for producing the product. It is in.

Based on the above objectives, the present inventors have solved the shortcomings of traditional glazes, and as a result of intensive studies, created new glazes that can retain the original image of traditional glazes by synthesis and put them on an industrial base. By oxidizing and firing at around 1100-1200 ° C, we have succeeded in stably producing traditional ceramic products such as ceramic tiles, and at the same time energy saving by lowering the firing temperature to 1250 ° C or less It was achieved at the same time.
In addition, the present invention was developed for the first time by discovering a glaze for ceramics and a glazed product superior to natural products, and the present invention was developed. In particular, the use of the new glaze stabilizes quality. In particular, it enables mass production of ceramic tiles with excellent weather resistance and no penetration (cracking on the glaze surface).

First, the structural features of the glaze for a traditional ceramics according to the first aspect of the present invention are expressed in Zegel, CaO is more than 0 mol, maximum 0.6 mol, MgO is more than 0 mol, maximum 0.5 mol, ZnO Is greater than 0 mole, up to 0.5 mole, Al ₂ O ₃ is minimum 0.5 mole, maximum 1.5 mole, P ₂ O ₅ is minimum 0.2 mole, maximum 0.6 mole, SiO ₂ is minimum It is in the point which has a composition containing 1.0 mol and a maximum of 3.0 mol.

Next, the second aspect of the invention is characterized in that R ¹ ₂ O (R ¹ : Na, K and / or Li) and R ² O (R ² : Sr, Ba and / or Pb) are limited.

  A feature of the third invention is that, in the composition of the glaze of the first invention or the second invention, B, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sn, Sb and Bi are further included as components. The present invention is limited in that it contains an appropriate amount of at least one of these oxide groups and / or a trace amount of at least one of the oxide groups of Mo, W, Ta, Nb, and Y and lanthanoid rare earth elements.

The fourth invention is characterized in that, in the second invention, the CaO is 0.3 to 0.5 mol, the MgO is 0.3 to 0.5 mol, and the ZnO is 0.1 to 0.3 mol. Yes, Al ₂ O ₃ is 0.8-1.0 mol, P ₂ O ₅ is 0.3-0.5 mol, SiO ₂ is 1.8-2.2 mol, R ¹ ₂ O is included at a maximum of 0.2 mol and R ² O is included at 0.1 to 0.3 mol.

  The fifth aspect of the invention is characterized in a long-awaited ceramic product that is made by applying and baking a glaze for a traditional ceramics having the composition of the first invention. Of course, the products of the present invention include not only the following ceramic tiles (sixth invention), but also vase, camellia and other traditional ceramic products that are required in terms of design and aesthetics.

  The feature of the sixth invention that follows is that the case of a ceramic tile with a high demand is actually limited as the ceramic ceramic product according to the fifth invention.

Further, the seventh invention is characterized by the Zegel display referred to in the first invention, wherein CaO is more than 0 mol, a maximum of 0.6 mol, MgO is more than 0 mol, a maximum of 0.5 mol, and ZnO is 0 mol. More, maximum 0.5 mol, Al ₂ O ₃ minimum 0.5 mol, maximum 1.5 mol, P ₂ O ₅ minimum 0.2 mol, maximum 0.6 mol, SiO ₂ minimum 1.0 The glaze for ceramics, which has a composition containing up to 3.0 moles and has a particle size of + 75μ and less than 10%, is applied to white background for ceramic products. And baked at a firing temperature of 1250 ° C. or lower to produce a traditional ceramic product.

Further, an eighth invention is a method of manufacturing a Kimachi style ceramic product of the seventh invention, the composition of Kimachi wind ceramics for glazes used as component further _{^{includes, R 1 2 O (R 1}} : Na , K and / or Li) and R ² O (R ² : Sr, Ba and / or Pb).

  A feature of the ninth invention is that, in the composition of the glaze of the seventh invention or the eighth invention, B, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sn, Sb and Bi are further included as components. It is limited in that it contains an appropriate amount of at least one kind of the oxide group and / or a trace amount of at least one kind of oxides of Mo, W, Ta, Nb, and Y and lanthanoid rare earth elements.

  The tenth aspect of the present invention is that the firing temperature range is limited in the method for manufacturing a traditional ceramic product according to the seventh, eighth or ninth aspect.

  First, the peculiarity of the glaze of the present invention is that it produces a unique color by forming crystals in the fired layer of the glaze. Therefore, this glaze particularly requires the condition that a crystal is formed in the glaze (glass) melted sufficiently at a predetermined temperature and melted at the time of cooling. In addition, this glaze is a kind of so-called crystal habit in which the color development is influenced by the degree of growth.

The above conditions are generally applicable to crystalline glazes, but in the case of the present invention, very special conditions are required for the glaze components, which are added.
In particular, the amount of Al ₂ O ₃ is abnormally large as compared with general brownish-brown luster glaze, and such Al ₂ O ₃ is usually difficult to melt, but P ₂ O ₅ The discovery of the fact that a certain amount of addition provides a long-lasting glaze in a special composition range that could not be imagined in the past has led to the present invention. This is the core of the technical features of the present invention.

Hereinafter, the amount of each component necessary for the present invention and the mutual relationship thereof will be described.
First, CaO and MgO in the present invention are essential components that help to melt the glaze, and the glaze can be easily melted by adding a certain amount. However, if it exceeds a certain level, it will hinder melting. Therefore, the range is
0 <CaO ≦ 0.6 mol,
0 <MgO ≦ 0.5 mol,
That is, CaO is required to be more than 0 mol and a maximum of 0.6 mol, and MgO is required to be more than 0 mol and a maximum of 0.5 mol. In particular, the preferred range for CaO is 0.3 to 0.5 mol. It is.

In addition, ZnO is a component that generally serves to assist melting of the glaze, but in the present invention, it is also an essential component for adjusting the color tone of the traditional glaze. Without addition, the glaze becomes difficult to melt, and as the addition amount increases, the glaze melts well and the color changes from red to yellow. This makes it possible to deal with various variations of the original glaze. However, if it is too much, not only the original glaze will not develop, but the glaze itself will also lose its gloss and become matt. The range is
0 <ZnO ≦ 0.5 mol,
That is, it is more than 0 and a maximum of 0.5 mol, but a range of 0.1 to 0.3 mol is particularly preferable.

Al ₂ O ₃ , SiO ₂ and P ₂ O ₅ are repeated as described above, but are the most fundamental components of the present invention. The present invention is characterized in that the amount of Al ₂ O ₃ is extremely higher than normal glaze, which is determined in relation to P ₂ O ₅ . There is a characteristic about each component, and when Al ₂ O ₃ is small, it will not develop the original color of the traditional glaze, but it will be a simple brown luster, and if it is too much, the glaze will not melt.
The range is
0.5 mol ≦ Al ₂ O ₃ ≦ 1.5 mol,
That is, a minimum of 0.5 mol and a maximum of 1.5 mol are necessary, and a preferable range is 0.8 to 1.0 mol.

SiO ₂ is a basic component that controls the properties of the glaze together with the Al ₂ O ₃ component. If it is too little, it will be matt, if too much, it will be a mere brown luster.
The range is
1.0 mol ≦ SiO ₂ ≦ 3.0 mol,
That is, the minimum is 1.0 mol, the maximum is 3.0 mol, and preferably is in the range of 1.8 to 2.2 mol, but in the present invention, further about Al ₂ O ₃ and SiO ₂ , SiO ₂ = (0. 67-6) There is a relationship of Al ₂ O ₃ .
Thus, in the case of a general glossy glaze, since SiO ₂ = 10Al ₂ O ₃ , it can be seen how the present invention has a special glaze composition.

P ₂ O ₅ is another basic component that supports the large amount of Al ₂ O ₃ which is also a feature of the present invention. It is impossible to achieve a glossy glaze in the composition range where only a matte glaze can be obtained without melting, without the presence of P ₂ O ₅ . Indeed, the present invention has been completed by finding the relationship between P ₂ O ₅ and Al ₂ O ₃ . The appropriate range of P ₂ O _{5 in} the present invention is as follows:
0.2 mol ≦ P ₂ O ₅ ≦ 0.6 mol,
That is, the minimum is 0.2 mol and the maximum is 0.6 mol, preferably in the range of 0.3 to 0.5.

R ¹ ₂ O (R ¹ represents Li, K and / or Na) is not particularly limited. When SiO ₂ and Al ₂ O ₃ components, for example, feldspar, petalite and the like are used as the raw material for the glaze, Li ₂ O, K ₂ O and / or Na ₂ O are inevitably contained to such an extent. . In the present invention, it can be added up to 0.2 mol.
Similarly, it is not always necessary to add R ² O (R ² represents Sr, Ba and / or Pb), but when it is added, it is limited to a range that does not interfere with the function of the essential essential component, and at most. From 0.1 to 0.3 mol is suitable.
However, PbO can be added in an amount that does not cause harm to the environment or the like for the purpose of lowering the melting point.

In addition, it is also possible to add B, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sn, Sb, Zr, Bi, etc. that are generally used as glaze components. That is, the glaze for a traditional ceramics according to the present invention further includes an appropriate amount of at least one of oxides of B, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sn, Sb and Bi. It is possible.
For example, in the case of V ₂ O ₅ , when V ₂ O ₅ is added in a large amount, the color becomes too dark, but if it is up to about 4%, it can be used for fine adjustment of the color, and in the case of B ₂ O ₃ , the surface of the glaze can be used. Although it can be used in terms of giving softness, the maximum is 5%. Too much foam will form on the glaze surface.
In the case of Fe ₂ O ₃ , it is the most essential pigment and colorant that influences the color development for the brown glaze. In general, the addition amount is set in the sense of adjusting the darkness of color development, but in the present invention, in addition to this, it is also related to crystals formed in the glaze, so the minimum addition amount is 3%. Is preferred.
In the case of Ti, Cr, and Sn, it is used to adjust the color of the glaze surface, particularly the brightness. Ti can be added to about 10%, preferably up to about 5%, Cr can be added up to about 5%, preferably about 3%, and Sn can be added up to about 10%, preferably about 5%.
Natural coming glazes are affected by the raw materials, and the color may naturally differ to some extent depending on the place of production. In order to adjust these subtle shades, heavy metal components such as Ni, Co and Mn, and emulsion components such as Sb and Zr can be used as long as the characteristics of the traditional glaze are not impaired. About 3% is preferable for Ni, Co, and Mn, and about 6% is preferable for Sb and Zr. Similarly, it is possible to bring out a more subtle natural hue by including a trace amount of at least one of Mo, W, Ta, Nb, and an oxide group of Y and lanthanoid rare earth elements. In addition, an appropriate amount of Bi, which is frequently used as a substitute for lead recently, can be used.

Next, regarding the relationship between the firing temperature in the case of applying the glaze for ceramics according to the present invention and the color of the glaze, as described above, a unique color is formed by the formation of crystals on the surface of the glaze. In particular, it is necessary to have a condition that a crystal is formed in the molten glaze (glass) layer when it is sufficiently melted at the time of firing, and the color development is influenced by the degree of crystal growth. It is. According to the new knowledge of the present invention, when a clear crystal is seen, the most anticipated color is obtained, followed by a crystal that is not clear but appears to some extent. The temperature control is extremely important because the goal and purpose of this invention cannot be fully achieved.
Therefore, in order to cause the product to have a natural long-lasting glaze-like color on the product, it is particularly necessary to calcinate in the vicinity of 1100 to 1200 ° C., that is, 1050 to 1250 ° C., more preferably 1180 to 1200 ° C. This is because even if a similar product can be obtained near 1000 ° C., which is a lower temperature, and 1300 ° C., which is a higher temperature, it is not possible to obtain a complete product for the purpose of coming.

［注］来待釉薬は結晶が出ていることが特徴で、明瞭になるほど発色が良好。
この表から、焼成温度としては１０５０〜１２５０℃が必要であり、特に１１８０〜１２００℃が最も好ましいことがわかる。

この表から、粒度は細かいほうがより好ましい（◎）が、＋７５μで１０％以下なら使用することが可能である（○）ことがわかる。

この表から、付着量は７０ｇ以上が好ましい（◎）が、３０ｇ程度の付着量のものでも使用可能である（○）ことがわかる。 In addition, regarding the relationship between the firing temperature, particle size, adhesion amount, and the color of the incoming wind, ◎ when the product is observed (visually) and a clear crystal is seen, and ◎ when the crystal is not clear but is visible to some extent, The results are as follows.

[Note] Long-acting glazes are characterized by crystals, and the clearer the color, the better.
From this table, it can be seen that a firing temperature of 1050 to 1250 ° C. is necessary, and 1180 to 1200 ° C. is particularly preferable.

From this table, it can be seen that finer particle size is more preferable (）), but it is possible to use (）) if it is 10% or less at + 75μ.

From this table, it is understood that the adhesion amount is preferably 70 g or more (（), but even an adhesion amount of about 30 g can be used (（).

  As described above, and further exhibiting excellent technical effects as shown in the results of Examples and Comparative Examples described later, they are new compositions of ceramic glazes according to the present invention, composition of ceramic products, and novel manufacturing methods thereof. It can be said that it is extremely remarkable in that it can be obtained for the first time by adopting various conditions, and as a result, a product such as a new traditional ceramic tile that is not inferior to a natural product can be obtained.

  Hereinafter, the features of the glaze for the traditional ceramics according to the present invention, the ceramic product for the traditional ceramics, and the manufacturing method thereof will be described in more detail by way of examples. However, the present invention is not limited to these examples.

Example 1
Components of Table 4 using raw materials such as frit (glass), feldspar, silica, kaolin, clay, aluminum phosphate, alumina, calcium phosphate, zinc oxide, magnesium carbonate, barium carbonate, strontium carbonate, calcium carbonate, iron oxide, etc. The glaze was blended so that the unit was mol, and wet pulverized with a pot mill for 3 hours to obtain a glaze slip. The particle size of this slip was 1.7% when 75μ or more. This slip was glazed on a dried tile white background with an adhesion amount of 100 g per sheet and fired at 1180 ° C. As a result, a good roof tile with a texture similar to that of a traditional waiting house was obtained. As a result of observation with a stereomicroscope, red flaky crystals were seen on the surface of the glaze. When the surface of this glaze was evaluated for weather resistance and penetration by a predetermined method, extremely good results were obtained as tile tiles. The results are as shown in Table 4, and the evaluation method is as follows.
Evaluation Method The evaluation methods employed in the above Examples, Comparative Examples, and Confirmation Examples are as follows.
Observe the color of the glaze surface by changing the color development angle, judging whether the color change when viewed from the front is the same as the traditional visit glaze,
Weather resistance Immerse in 3% hydrochloric acid for 8 hours according to JIS A5209 Observe surface changes,
Immerse the roof tile in water for more than 15 hours, then hold it in a dryer for 24 hours, keep it completely dry, put it back into 30 ° C water, and observe the glaze surface for cracks

Examples 2-35
Also in Example 2 and later, the glaze raw materials were blended so as to have the components shown in Table 4 of the above Example, and the same experiment as in Example 1 was performed under the conditions of Table 4, and the results were also in Example 1. Displayed after.
In the table, R ¹ represents lithium, potassium and / or sodium, and R ² represents strontium, barium and / or lead.

Comparative Examples 1-11
Next, using the same raw materials as in the example, the ingredients shown in Table 5, the particle size, the amount of adhesion, and the glaze at the firing temperature were blended, and the same experiment as in the example was performed, but it did not melt sufficiently, Even if it is melted, it does not produce a unique color of the visiting glaze, or even if the coloring is similar to the example, the weather resistance is insufficient compared to the example, or penetration occurs, etc. I couldn't get a glaze with a texture resembling that of a spider.

  According to the present invention, due to the technical effects of the above-mentioned novel glaze for porcelain ceramics, porcelain porcelain products and the manufacturing method thereof, the parcels are not inferior to natural parcel products with a constant target or target quality. It can be said that it is extremely useful industrially in that it enables mass production of wind porcelain products, especially new waiting porcelain tiles, and can also contribute to energy saving.

Claims (10)

In the Zegel representation, CaO is more than 0 mol, maximum 0.6 mol, MgO is more than 0 mol, maximum 0.5 mol, ZnO is more than 0 mol, maximum 0.5 mol, Al ₂ O ₃ is minimum 0 .5 mol, maximum 1.5 mol, P ₂ O ₅ has a composition containing a minimum of 0.2 mol, a maximum of 0.6 mol, and SiO ₂ has a minimum of 1.0 mol and a maximum of 3.0 mol , Glaze for coming-in-style ceramics. Further, the glaze for a traditional ceramics according to claim 1, further comprising R ¹ ₂ O (R ¹ : Na, K and / or Li) and R ² O (R ² : Sr, Ba and / or Pb).   Furthermore, an appropriate amount of at least one of oxides of B, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sn, Sb and Bi, and / or Mo, W, Ta, Nb, and The glaze for a traditional Chinese ceramics according to claim 1 or 2, which contains a trace amount of at least one of oxides of Y and lanthanoid rare earth elements. CaO is 0.3 to 0.5 mol, MgO is 0.3 to 0.5 mol, ZnO is 0.1 to 0.3 mol, and Al ₂ O ₃ is 0.8 to 1.0 mol. , P ₂ O ₅ is 0.3 to 0.5 mol, SiO ₂ is 1.8 to 2.2 mol, R ¹ ₂ O is 0.2 mol at maximum, and R ² O is 0.1 to 0.2 mol. The glaze for incoming ceramics according to claim 2, comprising 0.3 mol. In the Zegel representation, CaO is more than 0 mol, maximum 0.6 mol, MgO is more than 0 mol, maximum 0.5 mol, ZnO is more than 0 mol, maximum 0.5 mol, Al ₂ O ₃ is minimum 0 Glazed ceramic glaze having a composition including 0.5 mol, 1.5 mol maximum, 0.2 mol minimum of P ₂ O ₅ , 0.6 mol maximum, SiO ₂ minimum 1.0 mol, maximum 3.0 mol Coming-of-age ceramic products made by firing.   6. The traditional ceramic product according to claim 5, wherein the ceramic product is a ceramic tile. In the Zegel representation, CaO is more than 0 mol, maximum 0.6 mol, MgO is more than 0 mol, maximum 0.5 mol, ZnO is more than 0 mol, maximum 0.5 mol, Al ₂ O ₃ is minimum 0 0.5 mol, 1.5 mol maximum, P ₂ O ₅ minimum 0.2 mol, maximum 0.6 mol, SiO ₂ minimum 1.0 mol, maximum 3.0 mol composition, particle size + 75μ The ceramic glaze crushed to 10% or less is applied to a white background for ceramic products so that the amount of adhesion per tile is 150 g or less and fired at a firing temperature of 1250 ° C. or less. A method for manufacturing a traditional ceramic product. ^{_{Furthermore, R 1 2 O (R 1}} : Na, K and / or Li) and ^{R 2 O (R 2: Sr} , Ba and / or Pb) using ceramics for glaze having a composition containing, according to claim 7 Manufacturing method for traditional ceramic products.   Furthermore, an appropriate amount of at least one of oxides of B, Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Sn, Sb and Bi, and / or Mo, W, Ta, Nb, and The method for producing a traditional ceramic product according to claim 7 or 8, comprising a trace amount of at least one of oxides of Y and a lanthanoid rare earth element.   The method for producing a traditional ceramic product according to claim 7, 8 or 9, wherein the firing temperature is 1050 to 1250 ° C.