JP3448530B2 - Antibacterial and antifungal ceramic products - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic porcelain having a glaze on its surface, and more particularly to a tile, sanitary ware, and other antibacterial and antifungal porcelain products whose surface has antibacterial and antifungal properties.

[0002]

2. Description of the Related Art An important function of a glaze to be applied to ceramics is that it is hard to stain, easy to clean, and hygienic. Will be even higher. By the way, a glaze having antibacterial and antifungal properties has not been known as a glaze applied to the surface of ceramics or enamel. on the other hand,
In recent years, various organic and inorganic antibacterial and antifungal agents have been developed, and these have been applied to the surface of ceramics or kneaded into a ceramic base to impart antibacterial and antifungal properties.

[0003]

However, even if these antibacterial and antifungal agents are applied to the surface of the glaze on the ceramics by the coating method, they may be peeled off by washing and the durability is poor. On the other hand, in the kneading method, antibacterial and antifungal properties cannot be imparted to the surface of the ceramic by kneading it into the ceramic body. In addition, although there is no problem in durability, it is currently impossible to knead the antibacterial and antifungal agent into the glaze instead of the ceramic base. Because the glaze is made of a glass component, it is melted and fixed on the ceramic at a high temperature of 900 to 1300 ° C. Therefore, the organic antibacterial and antifungal agent is removed by decomposition during the treatment, and is also corroded in the molten glass even in relatively heat resistant inorganic materials such as silver zeolite that has been proposed in the past. , Because it loses antibacterial and antifungal properties.

The present invention has been made in view of the above circumstances, and by fixing a glaze which does not lose antibacterial and antifungal properties even when it is melted at a high temperature of 900 ° C to 1300 ° C on a ceramic.
The purpose is to impart antibacterial and antifungal properties to the surface of ceramic products.

[0005]

The present invention provides 900-13
We found that there is an antibacterial and antifungal agent that does not lose antibacterial and antifungal properties even when it coexists with the glass component in the glaze at a high temperature of 00 ° C, and based on that, it imparts antibacterial and antifungal properties to ceramic surfaces at a practical level for the first time. It was made. Where 900 ° C
Antibacterial antifungal agent be allowed to coexist with the glass component in the glaze does not lose antimicrobial antifungal at a high temperature of to 1300 ° C. is hydroxyapatite obtained by carrying antibacterial metal. Further preferably, the hydroxyapatite supporting the antibacterial metal may contain at least one of aluminum ion and fluorine ion.

The antibacterial and antifungal ceramic product of the present invention is characterized in that a glaze containing hydroxyapatite supporting an antibacterial metal is applied to the surface of the ceramic product . Tile or sanitary ware is preferred as the ceramic product.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
As a method of imparting antibacterial and antifungal properties to the glaze, (1) a method of imparting antibacterial and antifungal properties to the glaze itself and (2) an antibacterial and antifungal agent that does not erode the molten glass There is a method of mixing with a glaze that does not contain it, but in the present invention, a glaze having antibacterial and antifungal properties was obtained by adopting the method of (2), and this glaze was applied to the surface of the ceramic product. That is, in the method (1), the glaze can be used only for a specific purpose, whereas in the method (2), the glaze can be mixed with the ready-made glaze, so that all glazes can have antibacterial and antifungal properties. Is.

The glaze used in the present invention contains an antibacterial metal.
It contains supported hydroxyapatite . Here, hydroxyapatite is one that is not corroded by molten glass and is a suitable additive for imparting antibacterial and antifungal properties to the glaze. As the antibacterial metal, one or more of silver, copper and zinc are used. In addition, when one or both of aluminum ions and fluorine ions are contained in hydroxyapatite, the corrosion resistance of hydroxyapatite to molten glass is increased, and it is possible to impart antibacterial and antifungal properties to glazes treated at higher temperatures. Is more preferable. That is, hydroxyapatite alone is stable in glaze up to about 900 ° C, but when aluminum ion or fluoride ion is contained, it is 1300 ° C.
Because it will be stable to some extent.

To obtain hydroxyapatite carrying an antibacterial metal, first adjust the pH value to a range of 5 to 7 and react calcium hydroxide with phosphoric acid to precipitate hydroxyapatite. Here, in order to support the antibacterial metal, after reaching a predetermined pH, a water-soluble salt of silver, copper or zinc is added and sufficiently mixed. The addition amount of these antibacterial metals is 10 with respect to hydroxyapatite.
% Or less, preferably 0.001 to 5%. Because
This is because if it is less than 0.001%, the antibacterial and antifungal properties are not sufficiently exhibited, and if it exceeds 5%, it is impossible to support more metal.

In order to contain aluminum ions or fluorine ions, these ions are added at the same time as the antibacterial metal is added. Aluminum nitrate and aluminum sulfate are preferable as the aluminum ion source, and sodium fluoride is used as the fluorine ion source.
Potassium fluoride is preferred. Next, the thus obtained hydroxyapatite carrying an antibacterial metal, and further thoroughly washed the precipitate of hydroxyapatite containing one or both of aluminum ion and fluorine ion, and then dried to obtain a powder. The body.

To obtain the glaze having antibacterial and antifungal properties used in the present invention, the above hydroxyapatite is added to and mixed with a conventional glaze raw material. The amount of hydroxyapatite added is preferably 1 to 20% by weight with respect to the glaze raw material. That is, if the amount is less than 1% by weight, the antibacterial and antifungal activity is weakened, and if the amount is more than 20% by weight, the properties of the glaze may be impaired. Regarding the method of baking such a glaze having antibacterial and antifungal properties on the surface of the ceramic product, the same method as the conventional method in which the hydroxyapatite is not mixed can be adopted.

[0012]

EXAMPLES The present invention will be described more specifically by way of examples. Hydroxyapatite with antibacterial and antifungal properties was synthesized under various conditions. The synthesis was carried out by dropping 80 g / l phosphoric acid into a 37 g / l calcium hydroxide suspension. The pH during the synthesis of hydroxyapatite is 4
The range was from ˜7, and silver ion was used as the antibacterial metal source. The concentration of silver ions was 2% by weight with respect to hydroxyapatite. Aluminum ions or fluorine ions were added to some of the samples. These concentrations are also 2 for each of hydroxyapatite.
It was set to% by weight.

Next, the obtained synthetic hydroxyapatite was dried into a powder, and 5% by weight of this powder was added to the glaze to obtain the glaze of the present invention. Here, as the glaze, enamel glaze (melting point 700 ° C.) and pottery glaze (melting point 1100)
C) and were used respectively. The glaze was melted at a temperature in the range of 700 to 1300 ° C. for 10 minutes, further cooled and solidified, and then the glaze was finely pulverized. The finely ground product was evaluated for antibacterial and antifungal properties, and the results are shown in Table 1. Escherichia coli was used as the bacterium, and black mold was used as the mold. In addition, for the evaluation, x was given to the ones in which the fungus or mold was grown, and ◯ was given to the ones which were not grown and were observed to have antibacterial or antifungal properties.

[0014]

[Table 1] From Table 1, it was confirmed that the glaze used in the present invention has antibacterial and antifungal properties.

[0015]

As described above, according to the present invention, 9
Since the antibacterial and antifungal agent that does not lose antibacterial and antifungal properties even when coexisting with the glass component in the glaze at a high temperature of 00 to 1300 ° C is applied to the surface of the ceramic product, the ceramic product with surface antibacterial and antifungal property is obtained. Can be provided. Therefore, antibacterial and antifungal ceramic products such as tiles and sanitary ware with improved hygiene can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyuki Kumakura 585 Tomimachi, Funabashi, Chiba Sumitomo Osaka Cement Co., Ltd. Central Research Laboratory (56) References JP-A-5-201747 (JP, A) (58) Survey Areas (Int.Cl. ⁷ , DB name) C04B 41/86 C03C 1/00-14/00

Claims (2)

(57) [Claims] 1. A hydroxya carrying an antibacterial metal.
An antibacterial and antifungal ceramic product characterized in that a glaze containing patte is applied to the surface of the ceramic product. 2. The ceramic product is a tile or sanitary ware.
Antibacterial and antifungal property according to claim 1, which is a container.
Ceramic products.