JP2001019573A - Glazed product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To exhibit sufficient antimicrobial effects over the whole part subjected to antimicrobial treatment by applying a transparent glaze raw material containing formulated photocatalyst particles in which an antimicrobial metal is photoreduced and supported onto a layer of a coloring glaze raw material applied to a substrate surface. SOLUTION: A coloring glaze raw material is applied to a substrate surface and a transparent glaze raw material containing formulated photocatalyst particles in which an antimicrobial metal (silver, copper, zinc or the like) is photoreduced and supported is applied onto the colored glaze layer. The transparent glaze raw material is a solid formulation or a slurry state and 50-99 wt.% of the solid comprises an amorphous raw material and/or fine particles having <=6 μm median diameter measured by a laser diffraction apparatus. The photocatalyst particles are preferably one or more kinds selected from TiO2, ZnO and SnO2 and the surface roughness Ra (JIS-B0651) of the produced glazed product obtained by using a stylus type surface roughness measuring device (JIS-B0651) is preferably <70 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a toilet bowl, a urinal,
Toilet bowls such as Western-style toilets and Japanese-style toilets, sanitary ware such as handwashers, washbasins, toilet tanks, and toilet sana, tiles such as exterior, interior, kitchen back, bathroom walls, bathroom floors, plates, cups, and bowls Ceramics such as tableware, insulators, plugs, jars, jars, etc., enameled products such as bathtubs, washbasins, bathroom walls, system kitchen doors, kitchen sinks, kitchen counters, etc., glazed products such as glazed cement building materials, and their manufacturing methods .

[0002]

2. Description of the Related Art As an antibacterial method for ceramics, a method of applying a mixture of a silver compound such as silver phosphate and a coloring glaze raw material to a ceramic body and firing it, or a method of applying a coloring glaze to a ceramic body have been used. A method is known in which a mixture of a silver compound such as silver phosphate and a raw material for a transparent glaze is applied and fired.

[0003]

However, in a method in which a mixture of a silver compound such as silver phosphate and a coloring glaze raw material is applied to a porcelain body and fired, an emulsion agent particle such as a pigment particle or a zircon particle is used. Due to the influence, the silver compound is hardly exposed on the surface, and sufficient antibacterial properties are not exhibited. In a method in which a coloring glaze is applied to a ceramic body, and a mixture of a silver compound such as silver phosphate and a transparent glaze material is applied and baked, the silver compound is more easily exposed than in the above method. Since the silver compound is colloidally aggregated during firing, silver is unevenly distributed when viewed from the surface, and the antibacterial effect is not sufficiently exerted over the entire antibacterial treatment portion. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a glazed product capable of exhibiting a sufficient antibacterial effect over the entire antibacterial treatment section and a method of manufacturing the same.

[0004]

According to the present invention, in order to solve the above-mentioned problems, a step of applying a coloring glaze raw material to the surface of a base material and a step of forming a transparent catalyst containing photocatalytic particles carrying a photoreduced antibacterial metal are blended. Applying a raw material for a glaze to the colored glaze layer. By pre-loading antibacterial metals such as silver, copper, and zinc on the photocatalytic particles, colloid aggregation during firing of the antibacterial metals is prevented, and the antibacterial metals are uniformly dispersed when viewed from the surface. Therefore, a sufficient antibacterial effect can be exerted over the entire antibacterial treatment section.

[0005] In a preferred embodiment of the present invention, the transparent glaze raw material is a solid blend or a slurry, and 50 to 99% by weight of the solid content is an amorphous raw material and / or a laser diffraction device. Median diameter 6μm
A method for producing a glazed product characterized by the following fine particles is provided. By doing so, the surface becomes very smooth, and accordingly, it becomes difficult for bacteria to adhere to the surface. Therefore, it becomes very easy to maintain the antibacterial state. Here, the surface roughness Ra of the manufactured glazed product (JIS-B0601)
Is preferably less than 70 nm, more preferably 50 nm, according to a stylus type surface roughness measuring device (JIS-B0651).
And most preferably less than 30 nm.

In a preferred aspect of the present invention, the photocatalyst particles are at least one selected from TiO ₂ , ZnO, and SnO ₂ . The metals that make up these metal oxides are also commonly included in glaze raw materials, and are therefore easily dispersed evenly in the glaze raw materials. Therefore, antibacterial metals are more easily dispersed even when viewed from the surface. . Therefore, a sufficient antibacterial effect can be further exerted over the entire antibacterial treatment section.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Glazed products applicable to the present invention are:
For example, toilets such as toilets, urinals, Western-style toilets, and Japanese-style toilets, sanitary ware such as hand washers, washbasins, toilet tanks, and toilet sana, and exterior, interior, kitchen back, bathroom walls, and bathroom floors Tile, tableware such as plates, cups, bowls, etc., ceramics such as insulators, plugs, jars, jars, enameled products such as bathtubs, washbasins, bathroom walls, system kitchen doors, kitchen sinks, kitchen counters, glazed cement building materials, etc. It is.

For the base material of the present invention, for example, a ceramic body such as a ceramic molded body or a ceramic fired body, or a metal such as cement, concrete, cast iron, stainless steel, or aluminum can be suitably used.

The coloring raw material for glaze refers to a raw material for glaze obtained by adding a pigment and / or an emulsifier to a mixture of natural minerals such as silica sand, feldspar and limestone and / or an amorphous raw material such as frit.

The transparent glaze raw material in the present invention is a mixture of natural minerals such as silica sand, feldspar and limestone and / or an amorphous raw material such as frit mixed with photocatalyst particles in which an antibacterial metal is photoreduced and supported. And a glaze raw material to which no pigment or emulsifier is added.

As a method for applying the coloring glaze raw material or the transparent glaze raw material in the present invention, a general glaze method can be used, for example, a spray coating method such as wet blowing and dry blowing, a dip coating method, and a roll coating method. , Flow coating method, bar coating method,
A printing method, a brush coating method, a spin coating method and the like can be suitably used.

The photocatalyst particles include particles such as anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide, tin oxide, strontium titanate, ferrous oxide, tungsten trioxide, and bismuth trioxide. It can be suitably used, and its preferred average particle size is 5-1.
00 nm.

As the antibacterial metal, at least one of silver, copper and zinc can be used.

The method of photoreducing and supporting an antibacterial metal on photocatalyst particles includes, for example, silver nitrate, silver acetate, silver lactate, silver sulfate, silver citrate, cuprous nitrate, cuprous acetate, cuprous lactate, and sulfuric acid. Cuprous, cuprous citrate, cupric nitrate, cupric acetate, cupric lactate, cupric sulfate, cupric citrate, zinc nitrate, zinc acetate, zinc lactate, zinc sulfate, citric acid By irradiating a mixed liquid obtained by mixing an aqueous solution of a salt containing an antibacterial metal such as zinc and a photocatalyst particle dispersion with light including ultraviolet rays.

In the glazed product of the present invention, the contact angle of the surface with water is preferably less than 30 °, more preferably less than 25 °, and most preferably less than 20 °. The contact angle with water can be measured by a contact angle measuring device.

[0016]

EXAMPLES (Example 1) First, ultrafine zinc oxide powder ZnO-350 manufactured by Sumitomo Osaka Cement was placed in a 1% by weight aqueous solution of silver nitrate placed in a beaker. Black light blue fluorescent light F
By irradiating L20S-BLB from a distance of 10 cm for 30 minutes, silver was photoreduced and supported on the zinc oxide powder. Thereafter, the powder was filtered, washed several times with distilled water, and then dried to obtain a powder for addition to the glaze. SiO ₂ -Al ₂ O _3-
# 1 glaze raw material 2k composed of a composition mainly composed of Na ₂ O
g, 1 kg of water and 4 kg of cobblestone were placed in a 6-liter pottery pot and ground by a ball mill for about 18 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 meter, 65% was 10 μm or less,
The 50% average particle size (D50) was 5.8 μm. Further, a transparent glaze base material having a composition obtained by removing the emulsifier and the pigment from the above # 1 glaze raw material was prepared by using an electric furnace at 1300-1.
It was melted at 400 ° C., quenched in water, and pulverized by a stamp mill to obtain a transparent glaze frit. Transparent glaze frit and non-frit transparent glaze raw material in a weight ratio of 7:
3, 600 g of this mixed powder, 6.0 g of silver-carrying zinc oxide powder obtained as described above (1.0% by weight added to the glaze base material), 400 g of water and 1 kg of alumina balls. And placed in a 2 liter pottery pot and ground by a ball mill for about 18 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, it was 68% for 10 μm or less, and the 50% average particle size (D50) was 6.0 μm. Next, a 70 x 150 mm plate-like molded body was produced using a slurry of a sanitary ware body prepared using silica sand, feldspar, clay, or the like as a raw material. A glaze A was spray-coated as a lower layer on the formed body, and a glaze B was spray-coated as an upper layer, and then fired at 1100 to 1200 ° C to obtain a sample.

The obtained sample was subjected to surface roughness measurement and antibacterial test. The center line surface roughness Ra (JIS-B0601) was measured by using a stylus type surface roughness meter (JIS-B0651) for the surface roughness of the sample surface. As a result, Ra = 0.03 μm. For the antibacterial test, Escherichia coli (IFO)
3972) was evaluated for its bactericidal effect. That is, 0.2 ml of a bacterial solution (the number of bacteria: 1 × 10 ^{5 to} 5 × 10 ⁵ ) was dropped on the surface of the glaze layer of the sample previously sterilized with 70 vol% of ethanol and dried, and dried at 45 × 45m
m, and then allowed to stand for 24 hours in an atmosphere at a temperature of 37 ± 1 ° C. and a relative humidity of 90% or more. Thereafter, the film was peeled off, stamped with an NA medium, cultured in an environment at a temperature of 35 ± 1 ° C. for 16 to 20 hours, and the viable cell count was measured. At the same time, by comparing the number of bacteria tested and cultured with a blank sample without antibacterial activity (control product) and the number of bacteria tested and cultured on the sample (test sample), the bacteria reduction rate and growth inhibition rate were compared. Was calculated, and the antibacterial property was determined. The sterilization rate is calculated by the following equation. Bacterial reduction rate (%) = 100 × ([count of surviving bacteria of control product] − [number of surviving bacteria of test sample]) / [number of surviving bacteria of control product] The growth inhibition rate is calculated by the following formula. Is done. Growth inhibition rate = log ([control product surviving cell count] / [test sample surviving cell count]) The criteria for judging the presence or absence of the antibacterial effect is that the above-mentioned sterilization rate is 99%.
% Or the growth inhibition rate is 2.0 or more, it is determined that "there is an antibacterial effect";
As a result, the sterilization rate of the sample of Example 1 was 99.999991.
% And the growth inhibition rate were 6.0, and it was determined that "there was an antibacterial effect".

(Example 2) An anatase-type titanium oxide powder ST-01 manufactured by Ishihara Sangyo Co., Ltd. was placed in a 1% by weight aqueous solution of silver nitrate in a beaker, and while stirring with a stirrer, black light blue fluorescence manufactured by Sankyo Electric Co., Ltd. Light FL20S
By irradiating -BLB from a distance of 10 cm for 20 minutes, silver was photoreduced and supported on the titanium oxide powder. afterwards,
The powder was filtered, washed several times with distilled water, and then dried to obtain a powder for addition. Further, a transparent glaze base material having a composition obtained by removing the emulsifier and pigment from the # 1 glaze raw material used in Example 1 above was melted at 1300 to 1400 ° C. using an electric furnace, and rapidly cooled in water. Then, the mixture was pulverized with a stamp mill to obtain a transparent glaze frit. A transparent glaze frit and a non-frit transparent glaze raw material were mixed in a weight ratio of 7: 3, and 600 g of the mixed powder and 6.0 g of the silver-supported titanium oxide powder obtained as described above (glaze base material) were used. 1.0% by weight of water), 400 g of water and 1 kg of alumina balls,
It was placed in a 2 liter pottery pot and ground by a ball mill for about 18 hours. The glaze slurry obtained here is designated as glaze C. When the particle size of the glaze C obtained after pulverization was measured using a laser diffraction type particle size distribution meter,
10% or less was 68%, and 50% average particle diameter (D50) was 6.0 μm. Next, using a slurry of sanitary ware body prepared using silica sand, feldspar, clay, etc. as raw materials, 70 × 1
A 50 mm plate-shaped molded body was produced. A sample was obtained by spray-coating the glaze A prepared in Example 1 as a lower layer on the molded body, spray-coating the glaze C as an upper layer, and firing at 1100 to 1200 ° C.

When the surface roughness of the obtained sample was measured in the same manner as in Example 1, Ra = 0.05 μm. When an antibacterial test was conducted in the same manner as in Example 1, the sterilization rate of the sample of Example 2 was 99.994%, and the growth inhibition rate was 4.2, which was determined to be "antibacterial".

Example 3 Tin oxide powder TDS manufactured by Dowa Mining Co., Ltd. was placed in a 1% by weight aqueous solution of silver nitrate in a beaker.
The mercury-xenon lamp UXM-200H manufactured by Ushio Inc. was irradiated from a distance of 30 cm for 30 minutes while N-1 was charged and stirred with a stirrer, whereby silver was photoreduced and supported on the tin oxide powder. Thereafter, the powder was filtered, washed several times with distilled water, and then dried to obtain a powder for addition. Also,
A transparent glaze substrate having a composition obtained by removing the emulsifier and pigment from the # 1 glaze raw material used in Example 1 above was melted at 1300 to 1400 ° C. using an electric furnace, quenched in water, and then stamped. The resultant was pulverized by a mill to obtain a transparent glaze frit. A transparent glaze frit and a non-frit transparent glaze raw material were mixed in a weight ratio of 7: 3, and 600 g of the mixed powder and 6.0 g of silver-supported tin oxide powder obtained as described above were mixed.
(1.0% by weight based on the glaze base material), 400 g of water and 1 kg of alumina balls were placed in a 2 liter pottery pot and ground by a ball mill for about 18 hours.
The glaze slurry obtained here is designated as glaze D. Glaze D obtained after grinding using a laser diffraction type particle size distribution meter
When the particle size of 10 μm or less was measured, 68% was 50%.
% Average particle size (D50) was 6.0 μm. Next, a 70 x 150 mm plate-like molded body was produced using a slurry of a sanitary ware body prepared using silica sand, feldspar, clay, or the like as a raw material. On this molded product, the glaze A prepared in Example 1 was spray-coated as a lower layer, and the glaze D was spray-coated as an upper layer.
A sample was obtained by firing at 200 ° C.

When the surface roughness of the obtained sample was measured in the same manner as in Example 1, Ra = 0.03 μm. When an antibacterial test was conducted in the same manner as in Example 1, the sterilization rate of the sample of Example 3 was 99.9995%, the growth inhibition rate was 5.3, and the sample was determined to be "antibacterial".

[0022]

According to the present invention, it is possible to provide a glazed product capable of exhibiting a sufficient antibacterial effect over the entire antibacterial treatment section and a method for producing the same.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23D 5/00 C23D 5/00 J // B01J 35/02 B01J 35/02 J (72) Inventor Masaaki Ito Inside Totoki Equipment Co., Ltd. 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture (72) Inventor Masami Ando 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Totoki Equipment Co., Ltd. (72) Inventor Koichi Hayashi 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture Inside Totoki Equipment Co., Ltd. (72) Inventor Shin Hayakawa 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Totoki Equipment Co., Ltd. F term (reference) 4G069 AA03 AA08 BA00 BA04A BA04B BA13A BA13B BA14A BA17 BA48A BB02B BB04A BB04B BC22A BC22B BC32B BC35A BC35B CA01 CA11 EA07 EB05 EB18X EB18Y EC22Y EC26 ED02 FA03 FA03 06 FB07 FB15 FB23 FB24 FC08 4H011 AA02 BA01 BB18 BC18 BC20 DA01

Claims (22)

[Claims] 1. A step of applying a coloring glaze raw material to the surface of a base material, and a step of applying a transparent glaze raw material containing photocatalyst particles in which an antibacterial metal is photoreduced and supported on the colored glaze layer. A method for producing a glazed product, comprising: 2. The transparent glaze raw material is in the form of a solid compound or a slurry, and 50 to 99% by weight of the solid content is an amorphous raw material and / or a median diameter of 6 μm or less in a laser diffraction device. The method for producing a glazed product according to claim 1, comprising fine particles. 3. The photocatalyst particles include TiO ₂ , ZnO, S
method for producing a glazed product according to claim 1 or 2, characterized in that at least one selected from nO _2. 4. A stylus type surface roughness measuring device (JIS) which can be produced by the production method according to claim 1 and has a surface roughness Ra.
A glazed product having an antibacterial property of less than 70 nm according to -B0651). 5. A stylus type surface roughness measuring apparatus (JIS) which can be produced by the production method according to claim 1 and has a surface roughness Ra.
-A glaze product having a particle size of less than 50 nm according to B0651) and having antibacterial properties. 6. A stylus type surface roughness measuring device (JIS) which can be produced by the production method according to claim 1 and has a surface roughness Ra.
-A glaze product having an antibacterial property of less than 30 nm according to B0651). 7. The glazed product according to claim 4, wherein the surface has a contact angle with water of less than 30 °. 8. The glazed product according to claim 4, wherein the surface has a contact angle with water of less than 25 °. 9. The glazed product according to claim 4, wherein the surface has a contact angle with water of less than 20 °. 10. The glazed product according to claim 4, wherein the glazed product is a ceramic. 11. The glazed product according to claim 4, wherein the glazed product is an enamel product. 12. The glazed product according to claim 4, wherein the glazed product is a glazed cement building material. 13. The glazed product according to claim 4, wherein the glazed product is sanitary ware. 14. The glazed product according to claim 4, wherein the glazed product is a tile. 15. The glazed product according to claim 4, wherein the glazed product is tableware. 16. The glazed product according to claim 4, wherein the glazed product is an insulator. 17. The glazed product according to claim 4, wherein the glazed product is a toilet bowl. 18. The glazed product according to claim 4, wherein the glazed product is a wash basin. 19. The glazed product according to claim 4, wherein the glazed product is a toilet tank. 20. The glazed product according to claim 4, wherein the glazed product is a hand-washing machine. 21. The glazed product according to claim 4, wherein the glazed product is a toilet bowl sana. 22. The glazed product according to claim 4, wherein the glazed product is a bathtub.