JPH04175281A - Glazed molded article of cement having transfer decoration and production thereof - Google Patents

Abstract

PURPOSE:To obtain a glazed molded article of cement having transferred decoration by glazing the surface of molded article of cement comprising a heat- resistant cement-based binder, further painting by raw glaze transfer and burning. CONSTITUTION:100 pts.wt. heat-resistant cement-based binder prepared by blending a cement (e.g. fluorine-containing boron-containing specific cement) with 5-35wt.% fine powder silica is blended with 15-500 pts.wt. total amounts of an heat-resistant aggregate (e.g. shamotte), inorganic fibers and optionally, a hardening retarder, a hardening accelerator, a water reducing agent, etc., kneaded with water as less as possible, molded by extrusion molding and dried. The surface of the molded article is glazed by a proper method, then subjected to water-impermeable treatment with a filling solution (e.g. resin emulsion) and then transferred by transfer paper. Then the molded article is burnt by a tunnel furnace, etc., at 500-1,100 deg.C to give the title molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a cement molded product whose surface is decorated by transfer decorative glazing, and a method for producing the same.

More specifically, the present invention relates to a cement molded product suitable for interior or exterior building panels, etc., by applying a transfer-decorated glaze to the surface of the cement molded product in order to enhance its durability and aesthetic appearance.

[Prior Art] Conventionally, there have been known a large number of various cement molded products, so-called so-called cement two-blow products, using Portland cement as a binder, and methods for producing the same.

In particular, in order to increase the added value of cement two-blown products, high-performance molded bodies have been manufactured with advances in molding technology and modifiers, and recently, these molded bodies have been surface decorated with glaze. It has been proposed (for example, Japanese Unexamined Patent Publication No. 52-12
No. 1019, JP-A-56-160366, JP-A-61
-219748, JP 62-12682, JP 62-223077, JP 63-1277, JP 63-35475, JP 63-159274,
JP-A-63-107878, etc.).

On the other hand, recently, instead of ordinary Portland cement, a heat-resistant cement useful as a binder for inorganic molded bodies and a molded body using the same have been proposed (Japanese Patent Laid-Open No. 63-1667).
No. 39, JP-A No. 1-131046, JP-A No. 2-164
No. 749, Japanese Unexamined Patent Publication No. 184750.

[Problems to be Solved by the Invention] Glazed cement molded products as described above are being actively developed to meet the recent demands for tile-like or ceramic-like building materials based on extrusion molding.

However, it is not only difficult for glazed cement molded products to have a clean glazed surface like tiles made of glazed ceramic plates, but also that the strength of the molded product inevitably deteriorates as it is fired. It is thought that the crystallization water in the hydraulic reaction product is released during firing.Incidentally, as is well known, in our everyday living environment, glazed ceramic products with transfer decoration, such as tableware, etc. , furniture or tiles are used as essential items.

By using a mass production system for transfer-decorated glazed articles, the same product glazed with any desired pattern can be supplied in large quantities and at low cost.

However, such transfer glaze decoration has not been obtained for building materials other than tiles, such as large-sized interior and exterior panels. In particular, although glazed cement molded products have been developed as described above, there are still many technical problems to be solved, and glazed products with transfer decorations have not yet been obtained. Not there.

There are various reasons for this, but the base material, which is based on cement, has a high water absorption rate and is difficult to transfer, and large panels may suffer from heat shrinkage, warpage, or other deformation after firing, or cracks. This is thought to be due to the lack of reproducibility of the decorative surface by glazing.

If a building material panel whose surface is decorated with a transfer decorative glaze can be obtained, it will enrich the living space as an interior/exterior building material with arbitrary patterns, and it will also be extremely advantageous for industrial development.

In view of the above-mentioned problems, the inventors of the present invention have completed the present invention as a result of intensive research into applying transfer decorative glazes to cement molded products.

That is, an object of the present invention is to provide a cement molded product having a glazed decorative surface with a transfer painting, and a method for industrially producing the same in large quantities.

[Means and effects for solving the problem] That is, the transfer-decorated glazed cement molded product provided by the present invention is a cement molded product using heat-resistant cement as a binder. The cement molded product is characterized by being glazed and fired based on top transfer.Furthermore, the present invention relates to an industrially advantageous method for manufacturing such a cement molded product.

The present invention will be explained in detail below.

The cement molded product according to the present invention has a surface decorated by glazing and firing, and is characterized by the fact that it has patterns and decorations created by transfer.

Transferring is used as a means of mass production of decorations on shells and ceramics. That is, after molding with china clay, unglazed firing, glazing and final firing, then transfer the pattern or picture shown on the transfer paper to the surface of the ceramic using transfer paper,
It is baked and used for makeup.

Transfer paper is made by applying a water-soluble glue such as dextrin to the surface of high-quality paper that has water absorption properties, and printing patterns or pictures on the coated surface using ink containing an inorganic pigment and synthetic resin. A layer is formed and the surface is further coated with an oil-based lacquer (clear lacquer).

The thickness of a pattern or the like printed with pigment is usually about 30 μm, but is not particularly limited, and may be about 200 μm depending on the case.

Although the transfer glazed cement molded product according to the present invention is basically the same as the transfer technique using the transfer paper described above, the same pattern as described above is transferred onto the unfired glazed ring on the surface of the cement molded product, that is, it is not produced. It is characterized by the fact that the glaze is transferred onto the glaze (12), and the glaze and transfer film are fired at the same time to provide strength and surface decoration.

In the present invention, the base material of the cement molded product, which is the object to be transferred, is composed of heat-resistant cement as a binder and aggregate, inorganic fibers, etc. as the main ingredients, and after firing, it is strongly sintered and becomes a kind of ceramic body. As such, it has fire resistance or heat resistance.

Although there are no particular limitations on the size or shape of the cement molded product, in most cases it is preferable to have a shape that can be used as interior or exterior panels for not only general houses but also all types of buildings.

The transfer-decorated glazed cement molded article according to the present invention can be produced by the following method.

That is, the first step is to knead a heat-resistant cement binder, aggregate, and inorganic fibers with a small amount of water as the main raw materials, then shape and dry them, then glaze the surface of the obtained cement molded product, and then apply raw glaze. The second part that performs the upper transfer processing
step, and then a third step of firing the surface-treated cement molded product.

First Step The main raw materials used in the present invention must all be heat resistant because the cement molded product must be able to withstand the temperature of glazing and firing as described above.

A heat-resistant cementitious binder is one in which finely powdered silica is pre-blended or used in combination with a hydraulic material.6 Hydraulic materials include, for example, Portland cement,
In addition to known cements such as alumina cement and slag cement, fluorine-containing boron-containing special cements such as the modified slag cement described in JP-A-61166739 and the special cement described in JP-A-2-164749 are also available. However, in the present invention, the above-mentioned special cement is particularly advantageous.

This cement has a chemical composition of Ca0 = 40 to 65% by weight.
, S i O2 = 10-32 wt%, A1203 = 7
~24% by weight, F=1.5-12% by weight and B203=
A powder containing a boron-containing melt in the range of 0.2 to 3% by weight, containing a hydraulic component of 11CaO 7^1203CaF and/or β-2CaO 5in2 and 3C.
a0 ・2SiO2・CaF2.2CaO^1zO*
This is a special cement containing at least one stable mineral selected from 5iOz and CaFz. Further, as other special cements, phosphorous-containing improved slag cements containing the above-mentioned hydraulic mineral components can also be advantageously applied.

The cementitious binder in the present invention is made by blending 5 to 35% by weight, preferably 10 to 25% by weight, of finely powdered silica as SiO2 in such cement, and has heat resistance so as to develop strength after firing. It is. Suitable examples of the fine powder silica include so-called fumed silica and fine powder silica produced as a by-product during the production of ferroalloys.

Heat-resistant aggregates include materials that have already been subjected to a heat history, such as slag powder, chamotte, refractory brick waste, and various types of ceramics.
Examples include pottery scraps and igneous blue powder like anti-firestone.

Examples of inorganic fibers include rock wool, slag wool, glass fiber, ceramic silica fiber, and asbestos.

In addition to these main raw materials, curing retarders, curing accelerators, water reducing agents, etc. can be added as necessary.

The mixing ratio of the cementitious binder and other raw materials varies depending on the product's use, physical properties of the binder, molding method, firing method, etc., but in most cases, the ratio of the cementitious binder to the other raw materials is 100%.
The amount is in the range of 15 to 500 parts by weight, preferably 50 to 300 parts by weight.

These raw material mixtures are kneaded and molded with an appropriate amount of water, but it is better to use as little water as possible.

For example, in the case of the special cement, water-cement ratio (w
Knead with a very small amount of water, 7' c > or 10 to 40.

There are no particular limitations on the method of molding the product, and any desired method such as extrusion molding, hollow extrusion molding, vibration molding, pressure molding, or cast molding can be applied.

Thus, after the molding process, the molded product is dried by natural curing or heating until a certain strength is obtained.

To Iko 1 In this step, the surface of the molded body obtained in the previous step is glazed,
Furthermore, the painting process of transferring onto the raw glaze is applied.

That is, the surface of the molded body is glazed by a desired method such as spraying, impregnation or brushing.

The glazes may be either glazes made from raw materials or glazes containing frits, and furthermore, they may be either bright glazes or matte glazes.

Next, it is transferred to the glazed lower surface, but in this case, the object to be transferred needs to have a water-impermeable surface.

When transferring to ceramics, as mentioned above, the transfer is done after glazing and firing, so since the object to be transferred is water-impermeable, the transfer paper can be applied very smoothly, and when fired, the transferred pattern is transferred to the glaze. It moves and becomes fixed colorfully.

In the present invention, since the lower glazed surface is water permeable, the transfer paper cannot be used in the above-mentioned formulation as it is.

Therefore, in the present invention, water impermeability treatment is performed using a resin emulsion or resin solution called "filler".

Examples of the sealant include (meth)acrylate resin emulsion, vinyl acetate resin emulsion,
PVA1! ! One or two types of fat-based emulsion (
If necessary, a predetermined amount of a solvent such as xylene or butyl cellosolve may be added.

In addition, as a filler for a resin solution, for example, a synthetic resin such as poly(meth)acrylate, polyvinyl butyral, ethyl cellulose, or acetyl cellulose may be mixed with a compatible solvent such as hydrocarbon such as toluene or xylene, methyl cellosolve, butyl cellosolve, etc. Dissolved in a solvent such as an ether compound, an ester compound such as methyl acetate, ethyl acetate, or ethyl lactate, or a ketone compound such as acetone or methyl ethyl ketone.

The sealing liquid is applied onto the glazed surface by spraying or brushing, dried to form a water-impermeable film, and transferred onto the film using the above-mentioned transfer paper.

Therefore, in the present invention, the transfer treatment on raw glaze means a series of operations from such a water-impermeable treatment of the glazed surface to a transfer treatment using a transfer paper.

Furthermore, in the above, the glaze and the sealing liquid are used separately, and although it is used in boat fishing, depending on the case, it may be possible to process using a glaze mixed with the sealing liquid. It is possible.

1st, 3rd Step - This step is to fire the cement molded body, which has been surface-treated by transfer on raw glaze in the previous step, to impart strength to the molded body as it becomes ceramic and to fix the glaze and transfer decoration. It is in.

The firing conditions vary depending on the physical properties of the molded body, the firing method, the glaze, etc., but in most cases the firing temperature is 500 to 1100℃.
, preferably 0.5 at a temperature of 700-1050°C
~6 hours.

Note that the firing furnace is not particularly limited, and it is sufficient to install a furnace according to the size and shape of the compact, such as a shuttle furnace or a tunnel furnace.In particular, in the latter case, a roller hearth furnace is suitable for industrial use. preferred.

In the case of cement molded bodies using the special boron-containing cement binder mentioned above, the molded bodies turn into ceramic and are fire resistant, and there is no decrease in strength due to thermal deterioration, but other cement binders In some cases, thermal deterioration may occur, and in this case, if necessary, after firing, hydration curing may be performed to recover strength.

[Example] The present invention will be explained in more detail with reference to Examples.

Example 1 Neocement "fluorine-containing boron-containing special cement manufactured by Nihon Kagaku Kogyo Co., Ltd.: CaO: 52.5% by weight, 5i02.19.
2% by weight, F: 10.9% by weight, Mg0.68% by weight,
B20. : 0.47% by weight, 1100 parts by weight, finely powdered silica (manufactured by Japan Heavy Chemical Industry, 07.6 parts by weight, aggregate (chamotte, 48% of 149-300 μm), 74-14
9μ steel 29%, 74μ ring or less 23%) 10
0 parts by weight, 5.5 parts by weight of inorganic fibers (a mixture of alkali-resistant glass fibers and asbestos), and 2 parts by weight of methylcellulose were dry mixed in a mixer, and then the water reducing agent and setting retarder were dissolved. After adding 15 parts by weight of water and kneading for about 5 minutes, an extrusion molding machine [Model HDE100 manufactured by Honda Iron Works Co., Ltd.] was used to form a mold with a width of 200 mm and a length of 1 mm.
A cement-molded hollow plate having a thickness of 150 m+a and a hollow ratio of about 40% was obtained.

This molded plate was kept in a constant temperature room at 20° C. and 80% RH for 18 hours, and then air-dried in a room at 70° C. and 50% RH, and the bending strength was 107 Kgf/e+a2.

Spray borosilicate frit glaze on one side of this board.
After 7 hours, it was dried. Next, a resin emulsion prepared by mixing 40% by weight of a copolymer emulsion of methyl ester and ethyl ester of methacrylic acid (resin content: 45% by weight) and 60% by weight of water was used as a filler to seal the surface of the glazed layer. The sealant was applied uniformly and dried.

Next, a flower pattern was transferred onto the water-impermeable surface using a printed transfer paper.

That is, the transfer paper was immersed in water to dissolve the dextrin, and the pattern layer was peeled off from the high-quality paper together with the oil-based lacquer layer while being transferred onto the water-impermeable glazed layer.

After the transfer, after sufficiently drying, the temperature is 1030℃ in a tunnel furnace.
When fired at ℃, a good transfer glazed cement board with a flower pattern was obtained. The bending strength of this molded plate is 172
It was 5f/Cm2.

Example 2 Portland cement [110 manufactured by Nippon Cement Co., Ltd.
Using the following main raw materials:
After creating a cement molded board in the same manner as in Example 1 except that the firing temperature was set at 850°C, transfer was performed on the raw glaze, and this was fired.

The fired product was a good transfer glazed cement molded board.

Next, this plate was cured in an autoclave at 125° C. for 5 hours to recover its strength, but the transferred glazed surface did not show any change and was stable.

[Effects of the Invention] The cement molded product according to the present invention is a cement molded product that is glazed and fired based on transfer on raw glaze, and has a surface decoration by transfer glazing.

Since the glazed surface is decorated with desired patterns, pictures, etc., it is effective for interior and exterior architectural panels.

Further, according to the present invention, such transfer glazed cement molded products can be advantageously produced in terms of T industry using a mass production system.

Patent applicant: Nippon Chemical Industry Co., Ltd. Same as above Takenaka Corporation Same as above Nozawa Co., Ltd. Same as above Setec Co., Ltd.

Claims (1)

[Scope of Claims] 1. A glazed cement molded product made of a heat-resistant cement-based binder, characterized in that the surface decoration of the molded product is obtained by glazing and firing based on transfer onto raw glaze. . 2. The transfer-decorated glazed cement molded article according to claim 1, wherein the heat-resistant cement binder is a fluorine-containing, boron-containing special cement containing finely powdered silica. 3. The glazed cement molded product with transfer decoration according to claim 1 or 2, wherein the cement molded product is an interior/exterior building material panel. 4. The first step is to knead a heat-resistant cement binder, aggregate, and inorganic fibers with an appropriate amount of water as the main raw materials, then mold and dry them.Then, the surface of the obtained cement molded product is glazed, and A method for producing a glazed cement molded article with transfer decoration, comprising a second step of performing a transfer decoration treatment on the raw glaze, and then a third step of firing the surface-treated cement molded article. 5. The method for producing a glazed cement molded article with transfer decoration according to claim 4, wherein the first step is performed by extrusion molding. 6. The method for producing a glazed cement molded article with transfer decoration according to claim 4, wherein the third step of firing is performed in a tunnel furnace at a temperature of 500 to 1100°C.