JPH03287965A - Ceramic building material with metal plated surface - Google Patents

Abstract

PURPOSE:To obtain a building material having a wide selective range of color tone, brilliant appearance and excellent heat resistance, fire resistance and rigidity by plating the surface of a ceramic with one or more metals. CONSTITUTION:The surface of a ceramic is plated or glazed, and a building material having a required color or pattern, etc. by plating is manufactured. In that case, after solution such as stannous chloride, palladium chloride, etc. is applied to the surface of a ceramic material less than 5 Moh's hardness, a method of electroless plating is used. After materials are sufficiently kneaded, baking is made at temperature of 1,000 - 1,300 deg.C.

Description

[Detailed Description of the Invention] (About the meaning of plating) In this specification, "plating" broadly refers to attaching an extremely thin metal film to an object, and is not limited to electrolytic plating. , silver mirror reaction, vapor deposition, metallicon, etc., and also includes methods of chemically reducing metal ions and depositing metal films on the surface of the article. Among these, plating that does not involve electrolysis is a general term. This is called electroless plating.

[Industrial application field]

The present invention relates to a building material made of ceramic. In particular, the present invention relates to ceramic building materials whose surfaces have been subjected to processing such as plating, building materials whose surfaces have been subjected to the above-mentioned surface processing on relatively low-hardness ceramic building materials, and methods for producing such low-hardness ceramic building materials.

[Conventional technology]

Ceramic is widely used as a material in various fields because it has characteristics such as durability, robustness, heat insulation, corrosion resistance, insulation, waterproofness, and fire resistance, so it is widely used as a material in various fields. Recently, it has been widely used for interior and exterior materials, floors, roofing materials, walls, etc. of buildings.

[Problems to be Solved by the Invention] However, most of the conventional ceramics have a pale monochromatic color, which lacks interest when used in architecture and usually gives a cold feeling to residents.

Furthermore, there is a problem in that those coated with decorations such as printing will fade due to sunlight, moisture, salt, etc. over a very short period of time compared to the long lifespan of ceramics.

In addition, even if such problems such as color and makeup are solved, if the ceramic material is as hard as the conventional one, it will be difficult to adjust the fit with other parts at construction sites etc. Since it is difficult to cut and process ceramics into desired sizes and shapes, this point has also been an obstacle to using ceramics as building materials.

[Means and effects for solving the problems] The present invention has been made in view of the above problems, and is a product in which a ceramic surface is plated or glazed, and a desired color or pattern is imparted by the plating. The present invention provides a plating method for applying such colors and patterns, as well as a method for manufacturing more durable plating methods and ceramic building materials with lower hardness. By eliminating the drawbacks of ceramic building materials, such as the cold feel caused by the lack of colors and patterns, and by applying the above colors and patterns to materials that are easy to cut due to their low hardness, they can be used in a wider range of applications. The purpose is to provide a building material made from ceramic that can be used for.

〔Example〕

The present invention will be described in detail below based on examples.

(Example of electroless plated ceramic material) First, a ceramic building material subjected to electroless plating will be explained.

First, the parts of the ceramic building material that do not require plating, such as the back side, are protected by pasting mask sheets such as adhesive paper, and then metal plating is applied using electroless plating. It is better to apply a catalyst using stannous chloride, palladium chloride, etc., in the same way as conventional methods for applying metal coatings to electrically nonconducting materials. That is, after applying a stannous chloride solution to ceramic building materials or immersing them in the solution, electroless plating is applied as described below using this as a catalyst. A catalyst can be easily attached to the surface of a ceramic having a catalyst.

The building materials whose surfaces have been catalyzed as described above are placed in a plating bath filled with a nickel salt solution containing hypophosphorous acid as a reducing agent, and by gradually adding hypophosphoric acid, nickel metal ions are removed. Upon reduction, a metal film of nickel adheres to the surface of the building material made of the above-mentioned Ceradan. However, when it reaches a thickness of about 5 to 30 μm, it is pulled out and washed thoroughly with boiling water.
This is a building material obtained by drying with hot air at 150°C for 2 to 3 hours. Further, by appropriately selecting the thickness of the nickel within the above range, a black to white silver color tone can be obtained, and a desired color tone can be selected from among these to produce the product.

Of course, the metal used for electroless plating is not limited to nickel; metals such as copper, gold, silver, and tin, or their alloys may also be used. It is also effective to apply it in three layers.

Furthermore, as mentioned above, it is not an essential requirement of the present invention to apply the catalyst to the surface of the ceramic building material in advance and then perform plating. It may be a product that has been

The thus obtained electroless-plated building material has a number of advantages not found in conventional ceramic building materials, as will be described later in the section on the effects of the invention.

It goes without saying that it is not necessary to mask parts that do not require plating with adhesive paper, etc., as described above, when plating is applied to the entire front and back surfaces, but as shown in Figure 1, A mask sheet 2 is pasted and covered on the entire front and back surfaces of a tile 1 made of ceramic, and a cutout portion 3.3' that is not covered with the mask sheet is provided in a part of the surface in the shape of a desired pattern, painting, etc. By plating as above, a ceramic tile with a drawing on the surface is obtained.

Of course, the present invention can be applied to other ceramic building materials other than tiles.

Further, the electroless plating method is not limited to the above method, and various plating methods such as those described in the introduction may be employed.

(Example in which electrolytic plating was applied on electroless plating) Ceramic building materials obtained as described above or electroless plated by other methods are shown in a conceptual side cross-sectional view in Fig. 2. Then, the plating tank 4 is filled with a metal electrolytic solution 5 such as copper sulfate, and the back side of the ceramic building material 1 is covered with a mask sheet 2 as described above.
The above-mentioned electroless plating layer 6 is applied by applying a negative current to the electroless plating layer 6 formed on the surface and applying a positive current to a copper electrode plate 7 placed separately in the plating tank 4. A product is obtained in which an electrolytic plating layer 8 is further layered on top of the . That is, it is a building material obtained by electrolytic plating in the same manner as conventional metal plating, taking advantage of the fact that the surface becomes piezoelectric due to the electroless plating.

It goes without saying that the metal used in the electrolytic plating is not limited to copper, and may include various metals such as copper, cobalt, silver, gold, nickel, and chromium.

Of course, electrolytic plating of another metal may be applied on top of the electrolytic plating described above.

Building materials with drawings obtained by attaching a protective mask in the form of a drawing and plating are also effective.

(Example of durable metal plating) Using the electrolytic metal plating method described above, plating made of these metals or alloys of these metals was applied by using a solution of chromium, cobalt, etc. in the electrolytic solution. A building material is obtained, and as described in the section on effects of the invention, it is particularly durable and suitable as a building material for outdoor exterior walls or areas exposed to sea breeze.

(Example in which glaze or clear coating was applied) First, a commercially available frit (deflection point 715°C2 fire range 1050° C~1150'C)
A building material obtained by applying a mixture of 80% feldspar, 12% feldspar, and 8% frog's eye clay mixed with 70% water and firing at the above temperature. exhibits,
It is a building material that has characteristics such as not being stained by dirt.

In addition, when the glaze of the above example was applied to ceramic building materials that had been electrolessly gold plated as described above (500 A' to 100 OA° (7) Film thickness), the glaze of the above example was applied to the colloidal gold cassia.
A beautiful building material exhibiting purple (noble purple) luminescence was obtained. This is thought to be because the gold that adhered to the surface of the ceramic through electroless plating colloidally diffused into the glazed glass, creating a colloidal luminescence different from the original metallic color.

The material of the glaze does not need to be limited to the above examples, but by using a glaze with a low firing temperature as described above, there is no risk of quality loss even when applied to a ceramic with low hardness as described below.

In addition, ceramic building materials that have been electrolessly plated with various metals as mentioned above are sprayed with fluororesin, etc. in an environment of about 150°C, and then dried to give them a fluororesin clear finish. Obtained.

The thus obtained building materials coated with clear coatings have a gloss unique to metals, as well as a further gloss due to the clear coating, and the surfaces are smooth and difficult for dust, oil smoke, etc. to adhere to.

(Example of blasted building materials) Electroless plating is applied to ceramic building materials by any of the methods already explained,
Alternatively, if the surface of a product that has been further electrolytically plated is blasted by blowing compressed air mixed with wire mesh sand, etc., the surface will have a satin finish, and the luster of the metal will be replaced by the satin pattern. A very tasteful building material was obtained that harmonized with the astringency.

In addition, as mentioned above, by blasting ceramic building materials that are double plated with different metals, the color of the metal plated on the bottom surface can be changed by cutting a part of the plating layer plated on the top surface in the shape of a drawing. Building materials with drawings were obtained.

(Example of building material subjected to wire brush processing) As in the above-mentioned blasting example, a building material having an elegant hairline pattern on the surface was obtained by cutting the surface with an electric wire brush.

In this case as well, by layering two or more types of metal plating with different tones and then applying the wire brush cutting as described above, the upper layer plating is cut in a hairline shape, and the color tone of the lower layer metal is changed. Since it is visible, a building material with an elegant drawing due to the change of color tone is obtained.

(Example of manufacturing low-hardness ceramics) It is desirable that ceramic building materials with plated surfaces as described above be easy to process, such as cutting, at construction sites. An example will be described below.

Raw materials are natural wollastonite (main component Ca○・5iO2) frog's eye clay (main component A1□03 ・2StO2・2H20) talc (
Powders such as the main components (3Mg0, 4Si○2, H2O) are mixed, 15 to 25% water is added to the mixture, and the clay obtained by sufficiently layering is formed into the desired shape. Here, to give an example of forming a ceramic thin plate, a vacuum kneading machine is used to extrude it into a cylindrical shape with a diameter of 400 ff IIn and a wall thickness of 30 ff 1111, cut along the generatrix of the cylindrical shape, and unfolded into a flat plate. , and further roll rolling is repeated until the final thickness is 4 to 6 m.

After being formed in this way, it is dried using an infrared heater or the like, and then heated to 1000°C to 13°C in a roller hearth furnace.
When fired at a temperature of 0.000C, the hardness of the product did not become as high as that of ordinary ceramics, and it was possible to obtain a product with a Mohs hardness of 5 or less.

The reason for this is that by using the above manufacturing method, the material composition is first made uniform by sufficient kneading, and then the crystals within the material are given orientation by repeated rolling as described above. Since the crystals are bonded by a phase reaction between crystals that are in close contact with each other due to their orientation, even if they are formed into a thin plate as described above, they can be prevented from deforming or cracking during the drying or firing process, and even at relatively low temperatures as described above. It is thought that the ceramic with low hardness as described above was obtained because the formation of glassy particles was kept extremely small by firing.

Therefore, if the firing temperature is lower than 1000°C, the firing will be premature and hardening will be insufficient, resulting in a brittle product, which will easily weather due to water, temperature changes, etc. Also, when fired at a temperature higher than 1300℃,
A large amount of glass is produced, resulting in high hardness.

The present invention is a building material obtained by subjecting the ceramic building material obtained as described above to the above-mentioned surface treatment, but the present invention is not limited thereto. This includes those that have undergone surface treatment.

〔Effect of the invention〕

As described above, the present invention is a ceramic building material that is plated, so its color tone can be selected from a wide range as described above, and its appearance has the brilliance characteristic of metals. It becomes a beautiful example and enhances the artistic aesthetics of the building.

Further, due to the characteristics of metal, it has conductivity, so if it is used for wall tiles, etc., the wall surface will have less dust adhesion due to static electricity.

Furthermore, since it is metal plated, there is no risk of generation of harmful gases or fading compared to conventional coloring using paint.

Furthermore, those with various patterns etc. as mentioned above,
It can also be used in place of wood by preparing it in the same manner as combustible building materials such as wood, and in that case, it has superior heat resistance, fire resistance, and robustness compared to wood. Furthermore, it is possible to obtain a building that has the same appearance as a building made of wood or other materials.

In addition, building materials with electrolytic plating layered on top of electroless plating are
A product can be obtained in which the plating is strong and difficult to peel off, and if necessary, the plating is applied to a desired thickness.

Building materials with paintings, etc. obtained by cutting out protective masks in the form of paintings or patterns are effective as wall materials as building materials that are layered and familiar, and can also be used as decorative items in rooms. It can also be used as a wall surface.

Building materials coated with hard and durable metals such as cobalt, nickel, and chromium are highly durable, so even when used for floor tiles, etc., the plating may peel off or wear off. Therefore, it is extremely useful for, for example, floor tiles in station premises on which information displays are written.

In addition, glazed metal-plated surfaces have excellent chemical resistance and can be used in buildings near chemical factories or the coast without worrying about deterioration due to chemical reactions. It is also effective when ceramic building materials are used in tanks, chemical reaction tanks, etc., and even when used in ordinary buildings, it reduces the adhesion of soot and smoke and makes it easy to clean adhering dirt.

In particular, as mentioned above, when glaze is applied to gold-plated ceramic building materials, it has a brilliant color tone such as cassia purple (noble purple) that cannot be obtained with other materials. When used in buildings, these building materials create a very luxurious atmosphere.

Alternatively, ceramic building materials coated with clear coating can also be used as building materials with even higher artistic aesthetics. Blast-finished or brushed plated surfaces give the viewer a more elegant feel, thereby broadening the range of uses for ceramic building materials.

Plating only the desired parts of building materials in the form of a drawing using methods such as mask sheets or mask painting allows the building materials to have the desired drawing drawn on them, so it can be used, for example, for murals, etc. By using tiles or bricks subjected to this treatment on the outer wall, it can be used for wall advertisements and displays, and a wall surface with a display that does not easily disappear even when exposed to wind and rain can be obtained.

Items that have been blasted have a calming effect due to the brilliance unique to metal that harmonizes with the bitterness of the satin pattern.
It can be used as a building material that gives a soft feel.

The above-mentioned building materials treated with wire also give an elegant feel, so if used for indoor walls, etc., they can also serve as decoration and have the effect of relaxing the mood of residents.

Building materials made of low-hardness ceramics with the above-mentioned surface treatment can be easily cut without using diamond tools like conventional ceramics and tiles, so they can be easily cut into spaces at construction sites, etc. After looking at it for a while,
It can be cut to exact dimensions on the spot and used, making it convenient for building buildings with no gaps, etc., and is less prone to cracking during these on-site processing.

[Brief explanation of the drawing]

Fig. 1 is a conceptual side cross-sectional view of a ceramic tile surface in which the present invention can be applied by electroless plating by cutting a mask sheet into the shape of a painting, etc., and Fig. 2 is a side cross-sectional conceptual diagram of a state where electroless plating is applied to the surface of a ceramic tile in which the present invention can be carried out by cutting a mask sheet into the shape of a painting or the like. FIG. 2 is a conceptual side cross-sectional view of the vicinity of a plating tank in which building materials are further plated by an electrolytic plating method. In the figure, l: tile, 2: mask sheet, 3: cutout part of mask sheet, 4: plating bath, 5: metal electrolyte solution such as copper sulfate, 6: electroless plating layer, 7: copper plate , 8: Indicates an electroplated layer, respectively. Figure 1 Figure 2 Procedural Amendment 1, Display of the Case 1990 Patent Application No. 88748 2 Name of the Invention "Seradan Ivy Building Materials with Metal Plating on the Surface 3, Person Making the Amendment Relationship with the Case Patent Application Address: 1-8-7 Oyama Higashimachi, Itabashi-ku, Tokyo Contents of amendment (1) Line 7 on page 6 of the specification: ``By placing it in a plating bath and gradually adding hyboric acid.'' of,
"If you put it in a plating bath," I corrected. (2) Replace Figure 2 of the drawings with the attached drawings. 8. Attached documents (1) Drawing 1 copy 4. Agent address L-14-6 Ginza, Chuo-ku, Tokyo (2) Drawing (Figure 2)

Claims (10)

[Claims] (1) Ceramic building materials whose surfaces are plated with one or more metals. (2) The ceramic building material according to claim 1, wherein the surface is electroless plated and further electrolytically plated. (3) The ceramic building material according to claim 1 or 2, wherein the surface is plated with a highly hard and durable metal such as chromium or cobalt. (4) The ceramic building material according to any one of claims 1 to 3, wherein the surface is coated with glaze or clear coating. (5) The ceramic building material according to any one of claims 1 to 3, wherein the plated surface is given a satin finish by blasting. (6) The ceramic building material according to any one of claims 1 to 3, wherein the plated surface is finished in a hairline pattern obtained by wire brushing. (7) The ceramic building material according to any one of claims 1 to 6, which has a surface plated in the shape of a pattern, painting, etc. only on the other surface by means of pasting a mask sheet, mask painting, printing, or the like. (8) The method for producing a ceramic building material according to any one of claims 1 to 7, characterized in that the surface is plated by an electroless plating method after applying a solution of stannous chloride, palladium chloride, or the like to the surface. (9) The ceramic building material according to any one of claims 1 to 8, comprising a ceramic material having a Mohs hardness of 5 or less. (10) After thoroughly kneading the materials, the temperature is 1000℃ or 1
The method for manufacturing a ceramic building material according to claim 9, characterized in that the firing is performed at a temperature of 300°C.