JPH0688844B2 - Foam ceramic plate and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a foamed ceramic plate that is lightweight, can be upsized, has rich decorativeness, and is excellent in fire resistance, fire resistance, and corrosion resistance, and the same. Regarding manufacturing method.

[Problems to be Solved by Conventional Techniques and Inventions] Conventionally, for inorganic plates such as tiles and roof tiles, raw materials are molded,
After drying, a glaze layer was provided on the surface of the molded body, and the surface was vitrified by firing to prevent water absorption on the surface and keep the appearance. However, in the case of a foam ceramic plate,
The expansion coefficient of the base material is so large that cracks are generated in the glaze layer, so that simultaneous firing cannot be performed. On the other hand, even in the case of glazeing after firing the base material, the number of manufacturing steps increases, the rebar deteriorates when the rebar is embedded, and the temperature difference between the surface layer portion and the core material portion during firing of the glaze is porous because it is porous. Since it is large, there is a problem that thermal stress occurs and cracks occur. Furthermore, since the surface is porous, pinholes are likely to occur, and the smoothness of the surface also has traces of foaming of particles, so it can be said that it is smooth on a macro scale, but it is citrus-like on a micro scale.
The smoothness such as the glass surface cannot be obtained. Also,
The surface of the foamed ceramic plate has only a thin skin having a foamed film, and thus has low strength.

Furthermore, when a pattern is given to the foam ceramic plate, for example, copper plate printing paper (etching-processed copper plate (template) is coated with ink containing paste, and the paper is laminated on it and dried after drying. A printing paper obtained by peeling off a copper plate) is used. That is, the printing paper colored with paint is leaked with water to be laminated on the foam ceramic plate, and then,
There is a method in which the paper is peeled off and the pattern is transferred and then glazed and baked. However, this method has a problem that the process is complicated, the productivity is poor, and the quality is not stable. That is, when the paper is peeled off, the transferred pattern is easily broken and the quality is not stable, and further, the pattern is broken due to foaming of the base material.

Therefore, in reality, the only way to decorate a foamed ceramic plate is to give it a relief pattern or to color the whole, and there are dense multicolored patterns and sharp patterns (clear and clear patterns). I couldn't hope at all.

In view of the above circumstances, the present invention utilizes the advantages of the foamed ceramic plate, such as lightness, heat insulation, fire resistance, workability, waterproof / moisture resistance, and the ability to make a large plate, It is an object of the present invention to provide a foamed ceramic plate in which a foamed layer and a dense ceramic layer are integrated by using porcelain paper and a method for producing the same, in order to improve surface smoothness, decorativeness, surface strength and the like, which are more disadvantageous. To do.

[Means for Solving the Problems] In the foamed ceramic plate of the present invention, the inorganic raw material layer that is foamed by heating and the porcelain paper laminated on one side or both sides of the raw material layer are simultaneously fired to be solution-integrated. This is characterized in that a dense glassy layer is formed on one side or both sides of the foam plate.

Further, the method for producing a foamed ceramic plate of the present invention, ceramic paper is laminated on one side or both sides of the inorganic raw material layer that is foamed by heating,
These are characterized in that they are simultaneously heated and fired to be melted and integrated, and immediately after that, both surfaces of the foam plate are rapidly cooled by cooled pressure rolls, and then the surface of the foam plate is heated to the softening temperature.

The foamed ceramic plate of the present invention has excellent surface smoothness and improved surface strength. In addition, porcelain paper that has been colored or printed as desired for decoration is used, which makes it possible to add very sharp and various patterns and enhance decorativeness. The foamed ceramic plate of the present invention can be suitably used for interior / exterior materials of various buildings, art porcelain plates, and the like.

[Examples] The present invention relates to a foamable inorganic substrate having alumina fibers and mullite fibers (3Al ₂ O ₃ · 2SiO ₂ as main crystals).
It has excellent mechanical strength, heat resistance and corrosion resistance), and a ceramic paper obtained by making a mixed slurry composed of inorganic powder is heated and solubilized and foamed. It is characterized in that it is integrally formed with a dense surface layer made of paper.

As the foamable inorganic raw material, natural glass, artificial glass or the like powder, dolomite, may be used those added with a foaming agent such as silicon carbide, acid clay is a volcanic natural raw material instead of crow powder, Flux component and foaming agent are added to anti-fire stones, shirasu, etc. and finely pulverized (44μ-90%), and this powder is granulated to 0.2 to 1 m / m. It is preferable because it is excellent in gas divergence.

Flux components are substances that lower the melting point of other substances when mixed with other substances, such as Na ₂ CO ₃ and Na ₂ SiO _2.
3 , NaNO ₃ , Na ₂ HPO ₄ , Pb ₃ O ₄ , 2PbCO ₃ · Pb (OH) ₂ , BaCO ₃ ,
NaB ₄ O ₇・ 10H ₂ O, H ₃ BO ₃ , ZnO, glass powder, frit, etc.

Porcelain paper is a sheet-like substance obtained by making a slurry by mixing inorganic powder raw materials such as feldspar, glass powder, and frit with inorganic fibers, an organic binder, an inorganic binder, and an aggregating agent. Examples of the compounding include, for example, inorganic powder raw material mixed with alumina fiber and / or mullite fiber, inorganic powder raw material mixed with inorganic fiber and pulp fiber, inorganic raw material mixed with pulp fiber, and the like. There is. As described above, porcelain paper contains an inorganic powder raw material and a fibrous raw material as essential components, but when alumina fiber and / or mullite fiber is used as the fibrous raw material, shrinkage of the porcelain paper during firing can be reduced. It is preferable because it is possible. Further, the shrinkage is further reduced by using the calcination raw material. Although it is possible to use glass fiber, pulp fiber or the like as the fibrous raw material, these do not cause a problem in sheet formation, but they shrink by heating (in this case,
The base material layer is foamed and expanded, and there are disadvantages that there are many portions without porcelain paper (and thus portions without a dense surface layer) in the peripheral portion of the foam ceramic plate. Therefore, it is preferable that the raw material of porcelain paper contains 4 to 8% by weight of inorganic fibers such as alumina fibers and mullite fibers.

The porcelain paper is obtained by making a slurry having the above-mentioned composition into a sheet and making it into a sheet, and a continuous paper machine can be used for making the sheet. It is possible to give a desired pattern such as a multicolored pattern to the porcelain paper by printing the dried sheet with a printing machine or the like by pressing the porcelain paper into a sheet formed by a paper machine. Further, in the case of printing, a desired color can be added in addition to a clear pattern which cannot be realized by the conventional method.

Further, a colored sheet can be obtained by blending a metal oxide such as Cr, Mn, Co, Ni, or Cu with a colorant such as a pigment in the slurry. The metal oxide dissolves in the glass phase during firing to develop a color (the colored element dissolves as an ion). A pigment is one that is suspended in glass without dissolving in the glass phase like a metal oxide,
The metal oxide as described above is mixed with kaolin, feldspar, etc., calcined, washed with water and crushed. The pigment must be flux stable.

Next, a method for manufacturing the foam ceramic plate of the present invention will be described.

The foamed ceramic plate of the present invention is obtained by laminating the above-mentioned pellet-like expandable inorganic raw material, and placing porcelain paper on the upper surface thereof, or laminating the expandable inorganic raw material on porcelain paper,
Furthermore, it is manufactured by firing a piece of ceramic paper on top of it to make it integral. As the firing furnace, it is preferable to adopt a transfer tunnel furnace equipped with a heat resistant mesh belt. When the mesh belt is used, the volatile components can be uniformly diffused from the upper and lower surfaces during foaming, and the heat can be uniformly transferred to the upper and lower surfaces.

The firing temperature is determined by the ratio of SiO ₂ , Al ₂ O ₃ , and flux components of the compounding raw materials, but when using metal parts for mesh belts, rolls, etc., fire at the lowest possible temperature for the sake of maintenance. Preferably, specifically 750
Firing is preferably carried out in the range of ℃ to 850 ℃.

The solubilization temperature of porcelain paper can be changed appropriately depending on the raw material formulation, but the firing temperature of the base material is more important for the performance of the product and it is necessary to select it with priority, so it is slightly lower than the base material. It is preferable to adjust so that the solution dissolves.

When the temperature of the base material layer and the porcelain paper is increased in the firing furnace, the base material layer and the porcelain paper begin to soften, and at the same time, the base material layer expands while generating gas to increase its volume and foam. move on. In this case,
Softening the ceramic paper on top or bottom,
It melts and becomes integral with the foam layer.

After foaming, the foamed ceramic plate in which the base material layer and the porcelain paper are integrated is cooled, but in this case, the surface is rapidly cooled by the cooled roll and then reheated so that the surface is resoftened (for example, Reheat according to the ambient temperature in the firing furnace)
Preferably. The preferable number of rolls depends on the thickness of the foamed ceramic plate and the type of raw material, and is not particularly limited in the present invention. Lightness or luster (JIS JIS
Z 8722) can be increased. The reason for reheating after pressing and quenching with a roll is that even a glass surface having a luster by heating and heating becomes a matte surface (matte surface) that does not lose gloss when pressed by a roll while hot. Therefore, the surface is heated again to be melted to give a luster, and then transferred to a cooling zone and sequentially cooled so as to remove the "strain" stress, so that the dense layer and the foamed substrate are integrated. In this way, a smooth and glossy ceramic foam plate can be manufactured.

The temperature of the quenching pressure roll can be prevented from fusion of the roll by pressing with a roll having a temperature 60 to 70 ° C. lower than the product surface temperature, but it is preferable to lower the temperature to the solidification temperature in order to improve the productivity. According to the general method, for example, the surface of the foamed ceramic plate fired at a surface temperature of 880 ° C. is rapidly cooled to 600 ° C. and then reheated at about 850 ° C.

Next, the foamed ceramic plate of the present invention and the method for producing the same will be described based on Examples, but the present invention is not limited to such Examples.

Example 1 69% feldspar (wt%, the same applies below), 17% soda ash, ZrSiO ₄
A blended raw material consisting of 10% and sodium nitrate 4% was wet pulverized using a pot mill so that the particle size was 250 mesh. Alumina fiber 5% (outer split.
Based on the blended raw materials), starch 5%, acrylic emulsion 2%, and anions or cations as coagulants are added so that the papermaking concentration (concentration of raw materials produced by a paper machine) is adjusted to 1% or less. did. The obtained liquid material was applied to a papermaking machine to make a sheet having a papermaking dimension of 50 cm × 50 cm × 0.1 cm.

A surface pressure of 29 kg / cm ² was applied to the paper making roll to finish it, and far infrared rays were radiated for 2 hours to dry. After drying, the six color pigments adjusted to a melting temperature of 850 ° C were used as 201 cerazole (pigment kneading oil manufactured by Mitamura Shoten Co., Ltd.).
The squeegee (elastic rubber or resin) was directly printed on the porcelain paper using the respective screens in which the pattern was decomposed into 6 colors, and dried to obtain the patterned porcelain paper. It should be noted that the porcelain paper was adjusted so that the firing solution temperature was 850 ° C.

Next, acid clay 71%, soda ash 10%, sodium nitrate 4
%, Zircon flower (crushed zircon sand, particle size 74μ or less), dolomite 5%, dry-milled with a pot mill to a particle size of 44μ / 90%, and then into a bread-type granulator. Granulate with a particle size of 1-2 m / m
I got a pellet. The pellets are used as a foaming base material and are compounded so that the foaming temperature is 870 ° C.

The pelletized foamable inorganic raw material is laminated on a continuous mesh belt so as to form a layer of 50 cm × 50 cm × 1 cm,
A lath net was buried in the middle. The ceramic paper is placed on the base material layer and conveyed into the furnace at a speed of 28 cm / min, and the maximum temperature is 8
It was heated at 70 ° C. for 20 minutes to be melted and integrated. Then 160mm
It was pressed and quenched with four φ rolls. Then, it was heated and melted again at 850 ° C. for 5 minutes, then gradually cooled, and after 150 minutes after being carried into the furnace, firing was completed. The temperature of the foam after quenching was 600 ° C (surface) to 850 ° C (central part).

Specific gravity and bending strength (JIS A 14
08), smoothness (by scanning electron microscope), gloss (JIS Z 8741) and abrasion resistance (JIS A 5209)
Was measured. The results are shown in Table 1.

Moreover, when the shrinkage rate of the porcelain paper was measured with a caliper, it was 4%.
Met.

Example 2 A foamed ceramic plate was produced in the same manner as in Example 1 except that pulp fiber was used instead of alumina fiber as a raw material for porcelain paper.

The shrinkage ratio of the porcelain paper of the obtained ceramic foam plate was measured with a caliper as in Example 1, and it was 50%.

Example 3 A foam ceramic plate was manufactured in the same manner as in Example 1 except that reheating was not performed.

When the gloss of the obtained ceramic foam plate was measured in the same manner as in Example 1, it was 7.1 (sample 1 = 6.2, sample 2 = 7.2, sample 3 = 7.8).

Comparative Example 1 A foamed ceramic plate was prepared in the same manner as in Example 1 except that a decorative layer having a thickness of 5 mm having the following composition was provided on the base material layer in place of the porcelain paper of Example 1, and no reheating was performed. Manufactured.

Composition of makeup layer ^* Acid clay 71% Soda ash 10% Sodium nitrate 4% Zircon flower 10% Dolomite 5% Colorant M142 (outer) 6% Silica powder (particle size: 200 mesh) 4% * Makeup layer is the above composition Mix and pulverize things with a pot mill,
It was granulated and used as a cosmetic raw material.

The foam ceramic plate thus obtained was subjected to the same measurement as in Example 1. The results are shown in Table 1.

Example 4 Fly Ash 801 Frit (manufactured by Nisto Sangyo Co., Ltd.) 70
%, Glass powder 10%, water cullet 10%, and feldspar 10% were wet-milled using a pot mill so that the total particle size was 250 mesh. Alumina fiber 5% (outer percentage; based on the above-mentioned blended raw materials), starch 5 on the obtained slip
%, Acrylic emulsion 2%, and an anion and a cation as a coagulant were added to adjust the papermaking concentration to 1% or less. The obtained liquid material was applied to a papermaking machine to make a sheet having a papermaking dimension of 50 cm × 50 cm × 0.1 cm.

A surface pressure of 20 kg / cm was applied to the paper making roll to finish it, and far infrared rays were radiated for 2 hours for drying. After drying, the six color pigments adjusted to the melting temperature of 880 ° C were kneaded with 201 cerazole, and the patterns were decomposed into 6 colors. The screens were directly printed on the squeegee with a squeegee and dried to give the patterned ceramics. I got a piece of paper. It should be noted that the porcelain paper was adjusted so that the firing solution temperature was 880 ° C.

Next, 55% Kuroganite, 20% soda ash, 15 bentonite
%, Sodium nitrate 5%, and lime 5% were dry pulverized with a pot mill to a particle size of 44 μ / 90%, and then granulated with a pan-type granulator to a particle size of 1 to 2 m / I got m pellets. The pellets are used as a foaming base and are compounded so that the foaming temperature is 900 ° C.

Using the above-mentioned ceramic paper and pellets, the maximum firing temperature
A foamed ceramic plate was produced in the same manner as in Example 1 except that the temperature was 900 ° C. and the reheating temperature after rapid cooling was 880 ° C.

The foam ceramic plate thus obtained was subjected to the same measurement as in Example 1. The results are shown in Table 1.

Example 5 A foam ceramic plate was measured in the same manner as in Example 4 except that reheating was not performed.

When the gloss of the obtained ceramic foam plate was measured in the same manner as in Example 1, it was 7.1 (Sample 1 = 6.7, Sample 2 = 7.2, Sample 3 = 7.5).

Comparative Example 2 A foamed ceramic plate was prepared in the same manner as in Example 4 except that a decorative layer having a thickness of 5 mm and having the following composition was provided on the base material layer in place of the porcelain paper of Example 4, and no reheating was performed. Manufactured. The decorative layer was manufactured in the same manner as in Comparative Example 1.

Composition of decorative layer 69% feldspar 12% soda ash 12% sodium nitrate 4% zircon 5% dolomite 10% The same measurement as in Example 1 was performed on the obtained ceramic foam plate. The results are shown in Table 1.

From Example 1 and Comparative Example 1, and Example 4 and Comparative Example 2,
It can be seen that bending strength, smoothness, and abrasion resistance are improved and gloss is increased by placing porcelain paper on the upper surface of the base material layer to melt and integrate both. More importantly, when the decorative layer was used (Comparative Examples 1 and 2), printing was impossible, and the obtained ceramic foam plate had poor decorativeness, but when using porcelain paper, it was not It is possible to perform color printing, and it is possible to obtain a foamed ceramic plate that is extremely decorative.

Further, it is understood from Examples 1 and 2 that when alumina fiber is used as a raw material for porcelain paper, the shrinkage rate of porcelain paper can be made extremely small.

Further, according to Examples 1 and 3 and Examples 4 and 5, it is possible to significantly improve the surface gloss of the foamed ceramic plate by rapidly cooling the foamed ceramic plate with a roll and then heating it again. Recognize.

[Effects of the Invention] As described above, the foamed ceramic plate of the present invention has the glass-like layer formed by melting and solidifying the porcelain paper on the surface, and can exert the following effects.

Due to the glassy layer the surface is very smooth and the mechanical strength is improved.

By coloring or printing porcelain paper, or by adding an embossed pattern, it is possible to attach a wide variety of patterns such as multicolored patterns and uneven patterns to the foam ceramic plate, and to enhance the decorativeness of the foam ceramic plate. It can be significantly increased. In this case, the applied pattern is extremely sharp and sharp.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Kitagawa 1-1-12 Shinsenri Nishimachi, Toyonaka City, Osaka Prefecture National Housing Industry Co., Ltd. (72) Inventor Takatoshi Miyazawa 1-1, Shinsenri Nishimachi, Toyonaka, Osaka Prefecture No. 12 National Housing Industry Co., Ltd.

Claims (9)

[Claims] 1. A dense glass is formed on one or both sides of a foam plate by cofiring an inorganic raw material layer that is foamed by heating and porcelain paper laminated on one side or both sides of the raw material layer for solution integration. Foam ceramic plate with a quality layer formed. 2. The foam ceramic plate according to claim 1, wherein the porcelain paper is composed of an inorganic powder raw material and alumina fibers and / or mullite fibers. 3. The foamed ceramic plate according to claim 1, wherein the porcelain paper comprises an inorganic powder raw material, and inorganic fibers and pulp fibers. 4. The foam ceramic plate according to claim 1, wherein the porcelain paper has a coloring agent. 5. The foamed ceramic plate according to claim 4, wherein the coloring agent is a metal oxide. 6. The foam ceramic plate according to claim 4, wherein the colorant is a pigment. 7. The foam ceramic plate according to claim 1, wherein the surface of the porcelain paper is provided with a stamp pattern. 8. The foam ceramic plate according to claim 1, wherein a pattern is printed on the surface of the porcelain paper with an inorganic pigment. 9. Ceramic paper is laminated on one or both sides of an inorganic raw material layer which is foamed by heating, and these are simultaneously heated and fired to be melted and integrated. Immediately after that, both sides of the foam plate are rapidly cooled with cooled pressure rolls. After that, a method for producing a foam ceramic plate in which the surface of the foam plate is heated to a softening temperature.