JPH06144914A - Production of ceramic board and ceramic board - Google Patents

Abstract

PURPOSE:To produce a large-sized ceramic board having >=1mX1m size. CONSTITUTION:One hundred pts.wt. of a mixture of 98-80wt.% of a ceramic material and 2-20wt.% of a fiber material and a slurry contg. 1-50 pts.wt. of an org. polymer having <10 deg.C glass transition temperature are mixed. The slurry is formed into a sheet. The single sheet or the laminated sheet is pressed by a press roll, etc., to control the porosity to 0.1-0.4 or the water absorption to 10-30wt.%, and a material for the ceramic board is obtained. The material is fired at 800-1350 deg.C by a roller-hearth kiln, etc., to obtain a large-sized ceramic board and glazed ceramic board excellent in dynamical characteristic. The ceramic is excellent in dynamical characteristic and freezing and thawing resistance and is appropriately used for the building and construction materials such as wall and floor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a large ceramic plate base used mainly for construction of walls and floors, civil engineering materials, ceramic plates and glazed ceramic plates, and a method for producing the same.

[0002]

2. Description of the Related Art It is quite difficult to manufacture thin and large ceramic plates. However, due to the increased demand for building materials, etc., a method for manufacturing a large ceramic plate by manufacturing a base material for a ceramic plate using the papermaking method that has been used for manufacturing asbestos slate, etc. Came to be known. That is, a slurry containing a ceramic raw material and a fiber material is formed into a sheet, wound on a making roll, cut, and spread to produce a plate-shaped ceramic plate base.
This is a method of press-molding this and then firing it into a large ceramic plate. For example, in Japanese Examined Patent Publication No. 52-5328, a slurry containing a ceramic raw material and pulp is added with a double-sided activator to form a sheet, which is then wound on a making roll and cut and spread to obtain a plate-shaped ceramic. A method for producing a sintered body by using it as a base material for a plate and firing it is disclosed in Japanese Examined Patent Publication No. 57-3.
No. 0838 discloses that a slurry containing a ceramic raw material and a pulp is added with a viscous agent or a polymer flocculant, if necessary, to make a paper, and the obtained small sheets of several tens cm square are dried and laminated. A laminated ceramic obtained by firing a small plate-shaped molded body is disclosed in Japanese Patent Application Laid-Open No. 64-79066, in which a slurry containing a calcium silicate salt, a flux component and a fibrous substance is made into a paper and fired. Is listed.

[0003]

However, it is quite difficult to manufacture a thin and large porcelain plate even by using the above-mentioned manufacturing method. No more than 1 can be produced by these methods.
It seems that the limit is about m × 1m. For example, Japanese Patent Publication No.
It is difficult to make it thin by the method described in Japanese Patent No. 5328, and the laminated ceramics disclosed in Japanese Patent Publication No. 57-30838 has difficulty in handling because the strength of the base material is low for manufacturing a large ceramic plate. Warpage tends to occur during firing. The method described in Japanese Patent Laid-Open No. 64-79066 is difficult to give a sufficient pressure effect for pressure molding before or simultaneously with drying. The present invention has a size of more than 1 m × 1 m,
For the purpose of providing a ceramic plate base and a ceramic plate manufacturing method, and a ceramic plate base and a ceramic plate that can be easily and economically produced without warping or deformation even if the thickness is 5 mm or less. It has been completed.

[0004]

According to the present invention, 100 parts by weight of a mixture of 98 to 80% by weight of a ceramic raw material and 2 to 20% by weight of a fiber material, and an organic compound having a glass transition point not exceeding 10 ° C. Mixing a slurry containing 1 to 50 parts by weight of coalesced,
This slurry is made into a sheet into a sheet, then dried, and the dried sheet is pressed to adjust the porosity to 0.1 to 0.4, a method for producing a ceramic plate base, And 98 to 80% by weight of ceramic material and 2 to 20
After blending 100 parts by weight of a mixture with a fiber material of 1% by weight, and 1 to 50 parts by weight of an organic polymer having a glass transition point of not higher than 10 ° C., the slurry is formed into a sheet, A method for producing a base material for a ceramic plate, which comprises drying and pressing the dried sheet to adjust the water absorption rate to 10 to 30% by weight.

In order to carry out these manufacturing methods, one or more of the above-mentioned dried sheets are stacked and pressed with a linear pressure of at least 100 kg / cm to obtain a porosity of 0.1.
It is more preferable to adjust to 0.4 to 0.4, or to adjust the water absorption rate to 10 to 30% by weight. And the base material for ceramic plates manufactured by these manufacturing methods is 1000 to 1350.
Provided is a method for producing a ceramic plate which is fired at 0 ° C, and further a method for producing a glazed ceramic plate which is obtained by applying a glaze to the surface of the ceramic plate base or the ceramic plate and then firing at 800-1350 ° C.

Further, 98 to 80% by weight of ceramic raw material and 2
100 parts by weight of a mixture with 20 to 20% by weight of a fiber material, and organic polymers 1 to 5 having a glass transition point not exceeding 10 ° C.
A ceramic plate comprising 0 part by weight and having a porosity of 0.1 to 0.4 or a water absorption rate of 10 to 30% by weight, and a ceramic plate made of a fired body of the ceramic plate. Further, the present invention also provides a glazed ceramic plate, in which a glaze is applied to the surface of the ceramic plate base or the ceramic plate and baked.

In the present invention, the porosity is calculated by the following equation.

Porosity = 1- [W ₀ / V ₀ ] / [(W ₁ ·
ρ ₁ + W ₂ · ρ ₂ ) / W ₀ ] However, V ₀ : 105 ° C., volume of sample after drying for 24 hours W ₀ : same weight as above W ₁ : 400 ° C., weight loss of sample after heating for 2 hours W ₂ : 400 ° C., amount of sample after heating for 2 hours ρ ₁ : Density of organic raw material contained in sample ρ ₂ : Density of inorganic raw material contained in sample (excluding water) Water absorption rate is 105 ° C., 24 Samples dried for a time
It is obtained by immersing in water at room temperature for 24 hours to absorb water, obtaining the weight before and after absorbing water, and calculating by the following formula.

Water absorption rate (%) = (weight after water absorption−weight before water absorption) / weight before water absorption There is a considerable correlation between the porosity defined here and the water absorption rate, both of which are defined in the present invention. The range of
Almost match. However, there is a case where the range is slightly deviated, and even when the effect of the present invention is exhibited, the range may be outside one of the ranges. That is, when the porosity is 0.1 to 0.4 or the water absorption is 10 to 30% by weight, the object of the present invention can be achieved. Hereinafter, the porosity will be mainly described in order to avoid complexity, but unless otherwise specified, the water absorption rate may be considered to follow this.

Further, in the present invention, the linear pressure is a value obtained by dividing the load applied to a sheet sandwiched by a roll press or the like by the width of the sheet.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described with reference to embodiments.
This will be specifically described. First, the raw materials used in the present invention will be described. Examples of the pottery raw material used in the present invention include inorganic substances such as kaolin, various clays, porcelain stone, silica stone, wollastonite, feldspar, dolomite, alumina, zirconia, and ferrite. These substances may be mixed and used. Next, as the fiber material, natural fiber, natural and synthetic pulp, rayon, vinyl alcohol polymer,
Examples include various organic synthetic fibers such as polyester, glass fibers, ceramic fibers, rock wool, and various inorganic fibers such as potassium titanate. These fibers may be mixed and used. As the organic polymer having a glass transition point of the third component not exceeding 10 ° C., natural rubber,
Examples thereof include styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, polyacrylic acid esters, and other organic polymers having a glass transition point of not more than 10 ° C., and these can be used as a mixture. In addition to the above main raw materials, various chemical agents can be added to improve the properties of the final product or to improve the operability of the manufacturing process. Examples thereof include fixing agents and aggregating agents such as anionic organic polymer electrolyte solutions, cationic organic polymer electrolyte solutions, anionic inorganic colloid solutions, cationic inorganic colloid solutions, and polyvalent metal salts. In addition, pigments, colored particles and the like can be added for coloring the product or imparting a speckled pattern.

In the production of the base material for a ceramic plate of the present invention,
Mixing ratio of ceramic raw material: fiber material 98 to 80% by weight: 2
-20% by weight means that it is difficult to fabricate a ceramic body by making paper unless the fiber material reaches 2% by weight, and when it is too large, the ceramic body is fired into a ceramic plate. At this time, shrinkage deformation and warpage of the ceramic plate due to the disappearance of the fiber material increase, and a satisfactory product cannot be obtained. Of these, the above-mentioned inorganic fibers may be used as the fiber material, or they may be mixed and used. Since the inorganic fiber does not disappear by firing, it has an action of preventing shrinkage during firing and improving the strength of the product. The blending amount of the inorganic fibers is 1 to 10% by weight, preferably 2 to 5% by weight, as the above-mentioned fiber material, and the inorganic fibers are used alone or mixed with the organic fibers. If the amount of the inorganic fibers is too large, it is difficult to increase the firing density, which is not preferable. In addition, 1 to 100 parts by weight of the above organic polymer is added to 100 parts by weight of the mixture of the ceramic raw material and the fiber material.
Use 50 parts by weight. The organic polymer has a function of lowering the porosity of the ceramic body. Details will be described later. If the amount of the organic polymer is less than 1% by weight, it is difficult to obtain the intended function and effect, and if it exceeds 50% by weight, shrinkage due to the disappearance of the organic polymer during firing becomes large, which is not preferable.

Next, a base material for a ceramic plate and a method for manufacturing the ceramic plate of the present invention will be described. First, a ceramic raw material and a fiber material having a predetermined mixing ratio are added to water, and further a predetermined amount of the organic polymer is added, and the mixture is stirred and mixed to form a slurry. The procedure of adding the raw materials and water and stirring can be arbitrarily selected depending on the situation. A known material such as pulper may be used for stirring and mixing. The solid content concentration in the slurry is usually
0.5 to 10% by weight, preferably 1 to 5% by weight.
This slurry is formed into a sheet and formed into a sheet. A known fourdrinier or round-net machine can be used for papermaking. The produced sheet may be wound into a making roll, laminated and then cut into a rectangular sheet as in the case of producing asbestos slate. The thickness of the sheet is generally 10 to 30 mm. But,
In the present invention, the belt-shaped long sheet can be wound as it is without being laminated or cut into short pieces. In this case, the thickness of the sheet is generally 2-5 mm. A known roll dryer or tunnel dryer can be used for drying. The water content is in a range such that it can be easily handled in a later step and a predetermined porosity can be imparted to the base material for ceramics, but it cannot be unconditionally specified because it varies depending on the type of raw material and its mixing ratio.
However, in the case of the present invention, the moisture content is usually 1.7% by weight.
Hereafter, it may be suppressed to preferably 1% by weight or less. The obtained dried sheet is wound or cut into a sheet having an appropriate length and pressed to adjust the porosity to the range of 0.1 to 0.4 to obtain the base material for a ceramic plate of the present invention. .

A known hydraulic press or mechanical press can be used for the pressing operation, but in the present invention, it is preferable to use a roll press capable of uniformly and continuously applying a large linear pressure to the long sheet. The applied linear pressure is at least 100 kg
/ Cm, preferably 300 kg / cm or more, more preferably 500 kg / cm. Linear pressure is 100kg / c
When it is m or less, it is difficult to adjust the porosity to the range of 0.1 to 0.4. Adjusting the porosity in the range of 0.1 to 0.4 is important for the present invention.
By setting the porosity to 0.4 or less, shrinkage during firing is suppressed, and it is possible to manufacture a ceramic plate with a smooth surface that is not affected by firing conditions and is not warped or deformed. On the other hand, when the porosity is 0.1 or less, the ceramic plate base material is excessively compressed, and residual stress in the base material easily causes cracking or warpage during firing, which is not preferable. The water absorption rate is 10-30
The weight may be adjusted to 15% by weight, preferably 15 to 25% by weight.

Further, it is preferable to heat the sheet in advance at the time of applying pressure. This is because it is possible to obtain a base material for a ceramic plate that is dense and has less distortion at a lower pressure. Usually, it is 50 ° C higher than the glass transition temperature of the organic polymer blended as a raw material.
As described above, it is preferable to heat to a high temperature. It is considered that the organic polymer is sufficiently softened and the tackiness is improved to obtain a preferable result.

The blending of the organic polymer used in the present invention makes it possible to easily adjust the porosity of the base material for a ceramic plate to a low range of 0.1 to 0.4, and it is large that the porosity is low. It facilitates the manufacture of ceramic plates. That is, by blending an organic polymer having a glass transition point of 10 ° C. or lower, the above-mentioned dry sheet is easily deformed and highly compressed, and when the sheets are laminated,
Uniform integration at a given pressure without the use of a binder. Further, in the conventional ceramic body, when the porosity is low in this way, it becomes very difficult to handle as a large plate that is hard, brittle and thin, but in the present invention, an organic polymer having a low glass transition point is blended. Therefore, the flexibility is maintained and the handling becomes easy. Such an action cannot be expected in an organic polymer having a high glass transition point.

The ceramic plate body thus obtained is, for example, 1000 to 1000 by using a known roller hearth kiln.
The ceramic plate of the present invention can be manufactured by firing at 1350 ° C, preferably 1000 to 1300 ° C. When glazed, it is usually possible to manufacture a glazed ceramic plate by firing at 800 to 1350 ° C.

The ceramic plate of the present invention has excellent freezing and thawing resistance despite having a relatively high water absorption rate of about 1 to 7%, but in particular, the following α is 0.8 or less, When it is preferably 0.7 or less, it has excellent freeze-thaw resistance.

Α = (W _t0 −W _t1 ) / (W _t0 −W _t2 ), where W _t0 : the weight of the sample (ceramic plate) after being dried at 105 ° C. for 24 hours W _t1 : immersed in water at room temperature for 24 hours weight of the sample after W _t2: after immersing for 24 hours in room temperature water, then immersed under 4 hours of -740MmHg, further 2 hours the weight W of the sample after standing _t0 -W _t1: water absorption W ceramic plate _t0- W _t2 : Saturated water absorption of ceramic plate

[0020]

EXAMPLES The present invention will be described in more detail with reference to examples. In the measuring methods used in the following examples and comparative examples, the porosity and the water absorption rate were as described above, and the bending strength and the freeze-thaw resistance were in accordance with the method described in JIS A-5209. Examples 1 and 2 Fiber materials, porcelain raw materials, and styrene-butadiene rubber latex (SBR) having a glass transition point of -20 ° C or acrylic emulsion (AE) having a glass transition point of 4 ° C are shown in Table 1 as organic polymers, respectively. A slurry having a concentration of 2% by weight at the compounding ratio shown was prepared. This slurry was used to make an endless sheet having a width of 120 cm using a Fourdrinier paper machine, and was further passed through a multi-cylinder dryer to adjust the water content to 0.5% by weight and wound up. The thickness of the dry sheet was 3.0 mm. Then, this dry sheet is passed through a hydraulic type calander roll having a linear pressure of 300 kg / cm in one step and cut at intervals of 3 m, and the size is 3 m × 1 m and the thickness is 2 mm. Was manufactured. Table 1 shows the measurement results of the porosity and water absorption of this substrate. Further, the base material for a ceramic plate was fired in a roller hearth kiln having a furnace temperature of 1280 ° C. for 30 minutes to obtain a ceramic plate of the present invention. The firing shrinkage and the properties of the obtained ceramic plate were measured and are shown in Table 1. Comparative Example 1 A base material for a ceramic plate and a ceramic plate were manufactured under the same conditions as in Example 1 except that a slurry was used to prepare an organic polymer and papermaking was performed using a wet machine, and the characteristics of each were measured and shown in Table 1. It was Comparative Example 2 A base material for a ceramic plate and a ceramic plate were produced under the same conditions as in Example 1 except that the linear pressure of the roll press was adjusted so that the water absorption rate of the base material for ceramics was 50%. The measured values are shown in Table 1. The linear pressure of the roll press at this time was 50 kg / cm.

[0021]

[Table 1] Examples 3 to 5 and Comparative Example 3 Using the dry sheet produced in Example 1, the linear pressure of the roll press was changed to produce the ceramic plate base materials having different porosities as shown in Table 1. This ceramic plate base is 1250 ℃
It was baked for 40 minutes with a roller hearth kiln of No. 1 to produce a ceramic plate. The firing shrinkage and the characteristics of the obtained ceramic plate were measured and are shown in Table 2.

[0022]

[Table 2] Examples 6 to 8 The dry sheets produced in Example 2 were laminated to produce a ceramic plate substrate. That is, a predetermined number of dry sheets are stacked and pressed by a roll press having a roll temperature of 55 ° C. and a linear pressure of 1000 kg / cm, and the size is 3 m × 1 m and the thickness is 2 m.
A ~ 8 mm substrate for a ceramic plate was produced. This ceramic plate base was fired for 60 minutes at 1220 ° C. roller hearth kiln to produce a ceramic plate. The firing shrinkage and the properties of the obtained ceramic plate were measured and are shown in Table 3.

[0023]

[Table 3]

[0024]

[Effects of the Invention] Using the method for producing a base material for a ceramic plate of the present invention, the glass transition point of a predetermined amount is 1 in the ceramic raw material and the fiber material.
A slurry containing an organic polymer that does not exceed 0 ° C is formed into a paper, dried, and then strongly pressed to have a porosity of 0.1 to 0.4,
Alternatively, it is possible to manufacture a ceramic plate base material having a water absorption adjusted to 10 to 30% by weight. This base material for ceramic plates has a higher density, greater bending strength, and more flexibility than conventional ones.
Even if it is a large thin substrate having a size of m × 1 m or more, for example, 1 m × 3 m and a thickness of 4 mm, it is hard to break and easy to handle, and is suitable for actual production. Furthermore, this ceramic base material of the present invention suppresses the shrinkage rate due to the disappearance of organic components during firing and the sintering of ceramic raw materials to a minimum, and the firing shrinkage rate in the width direction,
Both in the length direction are small, and normally the average value of the firing shrinkage in the width direction and the length direction is 0.8 or less of the firing shrinkage in the thickness direction. Therefore, it is possible to manufacture the ceramic plate of the present invention that is less affected by the firing conditions and is less likely to warp, distort, or crack. Further, since this ceramic plate base has good dimensional stability during firing, it can be directly glazed to produce a glazed ceramic plate by one firing.

The porcelain plate of the present invention thus manufactured generally has a water absorption of about 1 to 7% and is slightly high, but has a dense structure with few voids, high strength, and freeze resistance. It has excellent melting properties. Since it has an appropriate water absorption, the adhesive easily penetrates when it is adhered to the base, and it has good adhesiveness. In addition, the glaze is well applied and it is easy to apply the glaze uniformly.

As described above, according to the present invention, the size is 1 m.
Even if the ceramic plate has a thickness of more than 1 m and a thickness of 5 mm or less, the ceramic plate base and the ceramic plate can be easily and economically produced without warping or deformation. Also,
The characteristics of the ceramic plate and the glazed ceramic plate of the present invention are suitable as a material for construction and civil engineering.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Shimizu 1-1-1, Sonoyama, Otsu-shi, Shiga Toray Co., Ltd. Shiga Plant (72) Innovator Mitsunobu Otani 1-1-1, Sonoyama, Otsu-shi, Shiga Prefecture Toray Co., Ltd. Shiga Business Site (72) Inventor Seio Noda 1-1-1, Sonoyama, Otsu City, Shiga Prefecture Toray Co., Ltd. Shiga Business Site

Claims (9)

[Claims] 1. A ceramic raw material of 98 to 80% by weight and 2 to 20.
After blending 100 parts by weight of a mixture with a fiber material of 1% by weight, and 1 to 50 parts by weight of an organic polymer having a glass transition point of not higher than 10 ° C., the slurry is formed into a sheet, A method for producing a base material for a ceramic plate, which comprises drying and pressing the dried sheet to adjust the porosity to 0.1 to 0.4. 2. The one or more of the dried sheets are pressed with a linear pressure of at least 100 kg / cm to adjust the porosity to 0.1 to 0.4. 1. The method for manufacturing a base material for a ceramic plate according to 1. 3. Ceramic material of 98 to 80% by weight and 2 to 20
After blending 100 parts by weight of a mixture with a fiber material of 1% by weight, and 1 to 50 parts by weight of an organic polymer having a glass transition point of not higher than 10 ° C., the slurry is formed into a sheet, A method for producing a base material for a ceramic plate, which comprises drying and pressing the dried sheet to adjust the water absorption rate to 10 to 30% by weight. 4. The water absorption rate is adjusted to 10 to 30% by weight by pressurizing one or more of the dried sheets with a linear pressure of at least 100 kg / cm. A method for producing a base material for a ceramic plate as described. 5. A ceramic plate base material produced by the method according to claim 1, 2, 3 or 4 is 1000 to 1350 ° C.
A method for manufacturing a ceramic plate, which comprises firing at. 6. A substrate for a ceramic plate manufactured by the method according to claim 1, 2, 3 or 4, or 800 after applying a glaze to the surface of the ceramic plate manufactured by the method according to claim 5. A method for producing a glazed ceramic plate, which comprises firing at 1350 ° C. 7. A ceramic raw material of 98 to 80% by weight and 2 to 20
100 parts by weight of a mixture with a weight percentage of a fiber material, and 1 to 50 parts by weight of an organic polymer having a glass transition point not exceeding 10 ° C., and a porosity of 0.1 to 0.4 or a water absorption rate. A base material for a ceramic plate, which is 10 to 30% by weight. 8. A ceramic plate comprising the fired body of the ceramic plate base according to claim 7. 9. A glazed ceramic plate, characterized in that a glaze is applied to the surface of the ceramic plate base according to claim 7 or the surface of the ceramic plate according to claim 8 and fired.