JP2003040692A - Ceramic wear - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ceramic ware capable of reducing a frequency of cleaning. SOLUTION: In the ceramic wear, a coloring glaze layer is formed on the surface, and a overgraze layer is formed thereon, the surface roughness Ra of which is <0.07 μm. The surface overgraze layer is observed as amorphous by X-ray diffraction, and the upper most surface is observed by scanning type transmission electron microscope that it is essentially formed with a main ingredient layer of aluminum oxide.

Description

Description: BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The present invention relates to a ceramic which can maintain a surface to which dirt is unlikely to adhere for a long period of time. BACKGROUND OF THE INVENTION Keeping the surface of ceramics clean and maintaining its aesthetics over a long period of time is a property required because ceramics are generally widely used as daily necessities. . As a method of keeping the ceramic surface hygienic and aesthetically pleasing in households since ancient times, a method of applying a detergent containing a surfactant, acid, alkali or abrasive to a scourer or brush has been adopted. Have been. [0003] However, in such cleaning, if there is dirt that is difficult to remove, excessive force is applied to the dirt, so that the surface of the glaze of the ceramic is scratched by the cleaning tool or the abrasive in the detergent. May be attached. Such a flaw impairs the aesthetics of the ceramic and further makes it difficult to remove dirt. Therefore, an object of the present invention is to provide a ceramic which can reduce the frequency of the cleaning. According to the present invention, in order to solve the above problems, a coloring glaze layer is formed on the surface of a ceramic body, and a surface glaze layer is further formed thereon. The surface roughness Ra of the surface glaze layer is 0.07 μm
And the surface glaze layer is substantially amorphous when measured by X-ray diffraction on the surface, and substantially aluminum oxide is formed on the outermost surface when measured by a scanning transmission electron microscope on the surface. Provided is a porcelain characterized by having a layer as a main component. By making the surface roughness Ra of the surface glaze layer surface less than 0.07 μm, dirt is hardly adhered and dirt can be easily removed, so that cleaning with excessive force causing scratches can be performed. The need can be reduced. In addition, it is considered that the following two effects are synergistically added by forming the layer substantially containing aluminum oxide as the main component on the outermost surface, and the frequency of cleaning can be significantly reduced over a long period of time. Can be (1) The surface hardness increases, and scratches are less likely to occur. Therefore, the smooth surface is maintained for a long time, and the frequency of cleaning can be significantly reduced. (2) This layer suppresses the rapid release of monovalent metal ions such as potassium in the surface glaze layer to the outside, and acts to abundantly store monovalent metal ions like a capacitor. Thus, over a long period of time, a small and sufficient amount of 1
The valent metal ions are gradually and continuously released, and the builder effect improves the cleaning power during washing with water. Then, by this action, the frequency of cleaning can be significantly reduced. [0005] Preferred embodiments of the present invention will be described below with reference to the drawings. FIG. 2 is a conceptual diagram of a cross-sectional direction in an embodiment of the ceramics of the present invention, in which a coloring glaze layer 5 is formed on a ceramic base 4 and a surface glaze layer 6 is formed thereon. I have. The surface glaze layer 6 has a surface roughness Ra of less than 0.07 μm. FIG. 1 is a conceptual diagram of an enlarged cross section of the surface glaze layer 6 in the ceramic of FIG.
It is substantially amorphous when measured by line diffraction, and no clear crystal peak is observed. That is, the average structure at the level of about 10 μm, which is the X-ray arrival depth, is almost amorphous. However, according to measurement by a scanning transmission electron microscope, a layer of 1 to 50 nm containing a large amount of aluminum oxide on the outermost surface and having a very small amount of silicon oxide, which should be a main component of the glaze layer, is formed. Is observed. Further, in the measurement by the scanning transmission electron microscope, it can be observed that the aluminum oxide layer 2 also stores abundant monovalent metals such as potassium. It is considered that the uneven distribution of the alkali component was caused as a result of the layer 2 containing aluminum oxide as a main component suppressing rapid diffusion of the monovalent metal to the surface. Due to the above structure, the outermost surface 3 in FIG. 1 does not easily adhere to dirt, and even if it adheres, it is in a state of being easily removed by washing with water. Next, a description will be given of a basic method of manufacturing the ceramics shown in FIG. First, a ceramic molded body is made,
The surface is glazed with a coloring glaze material. Furthermore, the surface glaze raw material is glazed from above, and 800 ° C to 1300 ° C
Baking. [0010] Here, the coloring raw material for glaze is a raw material obtained by adding an emulsifier and, if necessary, a pigment to natural mineral raw materials such as silica sand, feldspar, and limestone. Examples thereof include iron compounds, vanadium compounds, tin compounds, and chromium compounds. As the emulsifier, zircon, tin oxide, bone ash, and the like can be suitably used. The surface glaze raw material is a raw material obtained by adding a natural mineral raw material, an emulsifier and a pigment to a frit raw material as required, and the frit raw material and the natural mineral raw material are added to the frit based on the sum of the two. Raw material ratio is 50-100%
It is a raw material that was made to become. Here, the frit raw material is a mixture of natural mineral particles such as quartz sand, feldspar, limestone, and the like.
Melted at a high temperature of 00 ° C. or higher and vitrified. It is considered that such a layer containing aluminum oxide as a main component is generated because a frit raw material is used as a surface glaze raw material. That is,
Thus, using the raw material once vitrified, 80
It is considered that by re-firing at about 0 to 1300 ° C., appropriate phase separation is promoted in the amorphous portion, and such a layer is formed. (Comparative Example) 2 kg of natural mineral particles having the composition shown in Table 1, 1 kg of water and 4 kg of cobblestone were put into a 6-liter pottery pot and ground by a ball mill for about 24 hours. The glaze slurry obtained here is designated as glaze A. When the particle size of the glaze A obtained after the pulverization was measured using a laser diffraction type particle size distribution analyzer, 65% was 10 μm or less,
The 50% particle size was 5.8 μm. Next, a plate having a size of 70 × 150 mm was prepared by using a slurry of a sanitary ware body prepared using silica sand, feldspar, clay or the like as a raw material. Glaze A was applied on the plate-shaped test piece by spray coating by a wet-blowing method so as to have a thickness of 0.5 mm, and then fired at 1100 to 1200 ° C to obtain a sample. Let the obtained plate-shaped test piece be A1. About the obtained sample, the cross section near the surface of the glaze was observed using the scanning transmission electron microscope (STEM). FIG. 3 shows a Z contrast image. (Examples) From Table 1, it was found that the emulsifier ZrO2
Was melted at 1300 to 1500 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass frit. This is crushed by a stamp mill,
The obtained powder (1.8 kg) and the emulsifier Zr from Table 1 were used.
0.2 kg of natural mineral particles having a composition excluding O2 were placed in a ceramic pot having a capacity of 6 liters with 1.2 kg of water and 4 kg of cobblestone, and pulverized by a ball mill for about 36 hours. The glaze slurry obtained here is designated as glaze B. When the particle size of the glaze B obtained after the pulverization was measured using a laser diffraction type particle size distribution meter, 10% or less was 68%,
The 50% particle size was 6.0 μm. Further, after the glaze A was applied to the plate-shaped test piece by spray coating by a wet-blowing method so as to have a thickness of 0.5 mm, the glaze B was further applied thereon by spray coating by a dry-blowing method to a thickness of 0.4 mm. It applied so that it might become. This is 1100
A sample was obtained by firing at 1200 ° C. The obtained plate-shaped test piece is designated as B1. For the obtained sample, a cross section near the surface of the glaze was scanned with a scanning transmission electron microscope (STEM).
Observation was performed using. FIGS. 4 and 5 show Z contrast images, FIG. 6 shows the distribution of aluminum elements in the region of FIG. 5, and FIGS. 7 to 9 similarly show the distribution of silicon, calcium and potassium elements. [Table 1] As a result of comparing the samples A1 and B1 by observation with a scanning transmission electron microscope, the existence of a layer made of aluminum oxide was not recognized on the surface of the sample A1 in which no frit raw material was used (FIG. 3). On the other hand, in the sample B1 using the frit raw material, a thin layered structure 2a, 2a
b was observed. This layered structure was a layer containing a large amount of aluminum oxide and having a very small amount of silicon oxide, which should be the main component of the glaze layer (FIG. 6, FIG. 6).
7). It was also confirmed that a large amount of potassium was present in this layer (FIG. 9). Further, measurement of B1 by X-ray diffraction was also performed, but no clear crystal peak was observed. In FIG. 4, a columnar structure was also confirmed inside the surface glaze layer.
From FIG. 7, this portion also contains a large amount of aluminum oxide, whereas the amount of silicon oxide, which should be the main component of the glaze layer, is extremely small. Therefore, it is considered that the particle dispersion strengthening mechanism due to the presence of this portion is also involved in hardening the surface. According to the present invention, it is possible to provide a ceramic which can reduce the frequency of cleaning.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing one embodiment of the present invention. FIG. 2 is a diagram showing a configuration of a product having the embodiment shown in FIG. FIG. 3 is a photograph obtained by observing an amorphous portion on a glaze surface of a sample A1 using a scanning transmission electron microscope. FIG. 4 is a photograph obtained by observing an amorphous portion on the glaze surface of Sample B1 with a scanning transmission electron microscope. FIG. 5 is a photograph obtained by observing an amorphous portion on the glaze surface of Sample B1 with a scanning transmission electron microscope. FIG. 6 is a photograph showing a distribution of an aluminum element in a region of FIG. 3; FIG. 7 is a photograph showing a distribution of a silicon element in a region of FIG. 8 is a photograph showing the distribution of calcium element in the region of FIG. FIG. 9 is a photograph showing the distribution of potassium in the region of FIG. 3; [Description of Signs] 1, 1a, 1b, 1c, 1d Amorphous portion 2, 2a, 2b Layer made of aluminum oxide 3 Top surface of glaze 4 Base 5 Colored glaze layer 6 Amorphous glaze layer

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Masaaki Ito             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka             No. Toto Kiki Co., Ltd. (72) Inventor Toshihiro Aoshima             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka             No. Toto Kiki Co., Ltd. (72) Inventor Koichi Hayashi             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka             No. Toto Kiki Co., Ltd. (72) Inventor Shin Hayakawa             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka             No. Toto Kiki Co., Ltd. (72) Inventor Aki Urano             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka             No. Toto Kiki Co., Ltd. (72) Inventor Junichi Iwasawa             2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka             No. Toto Kiki Co., Ltd.

Claims (1)

Claims: 1. A coloring glaze layer is formed on a surface of a ceramic body, and a surface glaze layer is further formed thereon. The surface glaze layer has a surface roughness Ra. 0.07 μm
And the surface glaze layer is substantially amorphous when measured by X-ray diffraction on the surface, and substantially aluminum oxide is formed on the outermost surface when measured by a scanning transmission electron microscope on the surface. Ceramics characterized by forming a layer as a main component.