JP2001123278A - Glazed product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glazed product capable of exhibiting sufficient antibacterial properties even under practical using conditions. SOLUTION: In this glazed product having antibacterial properties, a glaze layer has been formed on the surface of a ceramic base or a metal base material, the zeta potential in pH 7 in the surface of the above layer is negative, and also, the absolute value thereof is >=60 mV.

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 hand washers, washbasins, toilet tanks, and toilet sana, tiles such as exterior, interior, kitchen back, bathroom walls, and bathroom floors, plates, cups, and bowls Ceramics such as tableware, insulators, plugs, pots, jars, etc., enameled products such as bathtubs, washbasins, bathroom walls, system kitchen doors, kitchen sinks, kitchen counters, and glazed products such as glazed cement building materials.

[0002]

2. Description of the Related Art As an antibacterial method for ceramics, there has been conventionally proposed a method in which a mixture of a silver compound such as silver phosphate and a coloring glaze material is applied to a ceramic body and fired. Here, the silver compound such as silver phosphate is used in an amount of 0.01 to 1 part by weight with respect to the coloring glaze raw material from the viewpoint of cost and color.

[0003]

However, on a normally used toilet bowl or basin ball, a large number of bacteria adhere under actual use conditions. No sufficient amount of silver compound was present, and antibacterial activity was not sufficiently exhibited. 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 that can exhibit sufficient antibacterial properties even under actual use conditions.

[0004]

According to the present invention, in order to solve the above-mentioned problems, a glaze layer is formed on a surface of a ceramic body,
A glazed product having antibacterial properties, characterized in that the surface of the layer has a negative zeta potential at pH 7 and an absolute value of 60 mV or more. With the above configuration, fungi such as Escherichia coli are generally negatively charged in water near pH 7, so that the surface of the member and the fungi electrically repel in a state of contact with water, and Adhesion to the glazed product surface is prevented. Therefore, the glaze product surface is
Under actual use conditions, a large amount of bacteria does not adhere.

[0005] In another embodiment of the present invention, a glaze layer is formed on the surface of the ceramic body, and the surface roughness R
a is less than 0.07 μm, preferably 0.05 μm or less by a stylus type surface roughness measuring device (JIS-B0651);
More preferably, there is provided a glazed product having an antibacterial property characterized by being 0.03 μm or less. By adopting the above configuration, fungi such as Escherichia coli are less likely to be caught on the unevenness of the surface of the glazed product and remain, and therefore, the surface of the glazed product is in a state where a large amount of bacteria does not adhere under actual use conditions.

In a preferred embodiment of the present invention, a glaze layer is formed on the surface of the ceramic body, and the surface roughness Ra of the layer surface is measured by a stylus type surface roughness measuring device (JIS-B065).
According to 1) less than 0.07 μm, preferably 0.05 μm
The present invention provides a glazed product having antibacterial properties, wherein the glazed product has a zeta potential of not more than 0.03 μm, more preferably a negative zeta potential at pH 7 of the layer surface, and an absolute value of not less than 60 mV. With the above configuration, fungi such as Escherichia coli are less likely to adhere to the surface of the glazed product, so that the surface of the glazed product is in a state where a large amount of bacteria is not adhered under actual use conditions.

[0007] In a preferred embodiment of the present invention, a glaze layer to which a substance containing silver and / or copper is added is formed on the surface of the ceramic body, and the surface of the layer has a negative zeta potential at pH 7; Provided is a glazed product having antibacterial properties, the absolute value of which is 60 mV or more. With the above configuration, an antibacterial agent composed of a substance containing silver or copper is allowed to act in a state where a large amount of bacteria do not adhere under actual use conditions, so that the antibacterial function is sufficiently exhibited. . Here, in the case of the above-mentioned silver, 0.01 to 10% by weight is preferably added to the glaze layer, and more preferably 0.1 to 1% by weight.

[0008] In a preferred embodiment of the present invention, a glaze layer to which a substance containing silver and / or copper is added is formed on the surface of the ceramic body, and the surface roughness Ra of the layer surface is a stylus type surface roughness. With a measuring device (JIS-B0651).
Provided is a glazed product having antibacterial properties, which is less than 07 μm, preferably 0.05 μm or less, more preferably 0.03 μm or less. With the above configuration, an antibacterial agent composed of a substance containing silver or copper is allowed to act in a state where a large amount of bacteria do not adhere under actual use conditions, so that the antibacterial function is sufficiently exhibited. . Here, in the case of the above-mentioned silver, 0.0
It is preferably added at 1 to 10% by weight, and 0.1 to 10% by weight.
More preferably, the content is 1% by weight.

In a preferred embodiment of the present invention, a glaze layer to which a substance containing silver and / or copper is added is formed on the surface of the ceramic body, and the surface roughness Ra of the layer surface is a stylus type surface roughness. With a measuring device (JIS-B0651).
Less than 07 μm, preferably 0.05 μm or less, more preferably 0.03 μm or less, the zeta potential of the layer surface at pH 7 is negative, and its absolute value is 60 m
A glazed product having an antibacterial property characterized by being V or more. By adopting the above configuration, an antibacterial agent composed of a substance containing silver or copper is allowed to act in a state where almost no bacteria are attached under actual use conditions,
The antibacterial function is sufficiently exhibited. Here, in the case of the above silver, 0.01 to 10% by weight in the glaze layer
It is preferably added, and more preferably 0.1 to 1% by weight.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below with reference to the drawings. In FIG. 1, a coloring glaze layer 2 is formed on a pottery substrate 1. In glaze layer 2,
A substance containing silver or copper is added. In addition, glaze layer 2
The surface roughness Ra of the surface is measured by a stylus type surface roughness measuring device (JIS
-B0651), it is less than 0.07 μm, preferably 0.05 μm or less, more preferably 0.03 μm or less. Further, the zeta potential at pH 7 on the surface of the glaze layer 2 is negative, and its absolute value is 60 mV or more. In FIG. 2, a coloring glaze layer 12 is formed on a metal substrate 11. A substance containing silver or copper is added to the glaze layer 12. The surface roughness Ra of the glaze layer 2 is measured by a stylus type surface roughness measuring device (JIS-B065).
According to 1) less than 0.07 μm, preferably 0.05 μm
Or less, more preferably 0.03 μm or less.
Further, the zeta potential at pH 7 on the surface of the glaze layer 2 is negative, and its absolute value is 60 mV or more.
In FIG. 3, a colored glaze layer 22 is formed on the pottery substrate 1, and a transparent glaze layer 23 is further formed thereon. A substance containing silver or copper is added to the glaze layer 23. The surface roughness Ra of the surface of the glaze layer 23 is less than 0.07 μm, preferably 0.05 μm or less, more preferably 0.03 μm or less according to a stylus type surface roughness measurement device (JIS-B0651). Further, the zeta potential at pH 7 on the surface of the glaze layer 2 is negative, and its absolute value is 60 mV or more. In FIG.
A colored glaze layer 32 is formed on a metal substrate 31, and a transparent glaze layer 33 is further formed thereon. A substance containing silver or copper is added to the glaze layer 33. The surface roughness Ra of the glaze layer 33 is 0.07 by a stylus type surface roughness measuring device (JIS-B0651).
It is less than μm, preferably 0.05 μm or less, more preferably 0.03 μm or less. Further, the zeta potential at pH 7 on the surface of the glaze layer 2 is negative, and its absolute value is 60 mV or more.

The substance containing silver or copper includes, for example, metallic silver, silver phosphate, silver oxide, calcium phosphate on silver, aluminum phosphate on silver, apatite on silver, zinc oxide on silver, titanium oxide on silver, silver on silver Zeolite, silver-supported zirconium compound, silver solid solution borosilicate glass, silver solid solution borosilicate glass, silver solid solution silicate glass, silver solid solution aluminosilicate, silver solid solution phosphoric acid compound, metallic copper, copper phosphate, copper oxide ,
Copper-supported calcium phosphate, copper-supported aluminum phosphate,
Copper-supported apatite, copper-supported zinc oxide, copper-supported titanium oxide, copper-supported zeolite, copper-supported zirconium compound, copper-dissolved borate glass, copper-dissolved borosilicate glass, copper-dissolved silicate glass, copper-dissolved aluminosilicate, A copper solid solution phosphoric acid compound or the like can be used.

The method for producing the glazed product shown in FIG. 1 is based on, for example, a method of applying a specific coloring glaze raw material to which a substance containing silver or copper is added to a pottery molding substrate and firing it. The method for manufacturing the glazed product shown in FIG. 2 is based on, for example, a method of applying a specific coloring glaze raw material to which a substance containing silver or copper is added on a metal base material and firing the same. Here, any of the following can be used as the specific coloring glaze raw material. (1) A raw material obtained by adding a pigment and / or an emulsifier to an amorphous raw material. (2) A pigment and / or a raw material obtained by mixing 1 to 100 parts by weight of an amorphous raw material with respect to 1 part by weight of a mixture of natural minerals. Raw materials to which an emulsifier is added (3) Raw materials obtained by adding a pigment and / or an emulsifier to a mixture of fine natural minerals having a 50% particle size of less than 6 μm measured by a laser diffraction type particle size distribution analyzer or the like For example, methods such as wet spray coating, dry spray coating, dip coating, spin coating, roll coating, flow coating, printing, brush coating, and transfer can be used.

The method of manufacturing the glazed product shown in FIG. 3 is, for example, to apply a colored glaze raw material to a pottery molding base and further add a specific transparent glaze raw material to which a substance containing silver or copper is added. It depends on the method of applying and firing. In addition, the method of manufacturing the glazed product shown in FIG. 4 is, for example, to apply a coloring glaze raw material on a metal base material and further apply a specific transparent glaze raw material to which a substance containing silver or copper is added. And firing method. Here, as the coloring glaze raw material, a mixture of natural minerals such as silica sand, feldspar, and lime and / or an amorphous raw material such as a frit to which an emulsifier and / or a pigment is added can be used. Any of the following can be used for specific transparent glaze ingredients. (1) Amorphous raw material (2) A raw material obtained by mixing 1 to 100 parts by weight of an amorphous raw material with respect to 1 part by weight of a mixture of natural minerals (3) 50% measured by a laser diffraction type particle size distribution analyzer or the like Raw material mixture of fine natural minerals with a particle size of less than 6 μm. Application methods include, for example, methods such as wet spray coating, dry spray coating, dip coating, spin coating, roll coating, flow coating, printing, brush coating, and transfer. Is available. The thickness of the colored glaze layer is generally 0.05 to 1.8.
mm, preferably 0.1 to 1.2 mm, more preferably 0.2 to 0.7 mm. The thickness of the transparent glaze layer is generally 0.05 to 1.2 mm, preferably 0.1 to 0.8 mm, and more preferably 0.15 to 0.4 mm.

The glazed product of the present invention is used for sanitary ware such as toilets such as toilets, urinals, western-style toilets, and Japanese-style toilets, sanitary wares such as hand washers, washbasins, toilet tanks, and sana of toilets, and exterior, interior, and kitchen backs.・ Tile such as bathroom wall and bathroom floor, tableware such as plates, cups, bowls, etc., ceramics such as insulators, plugs, pots, jars, etc.
Suitable for antibacterial use in enamel products such as bathtubs, washbasins, bathroom walls, system kitchen doors, kitchen sinks, kitchen counters, and glazed cement building materials.

[0015]

Example (Comparative Example 1)

[0016]

[Table 1]

2 kg of glaze raw material having the composition shown in Table 1 and water 1
kg and 4 kg of cobble stone 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, and the 50% average particle size (D50) was 5.8 μm. Next, a 70 × 150 mm plate-shaped test piece was prepared using a slurry of a sanitary ware body prepared using silica sand, feldspar, clay or the like as a raw material. A sample was obtained by spray-coating glaze A on the plate-shaped test piece and then firing at 1100 to 1200 ° C. About the obtained sample, the surface roughness measurement of the glaze layer, the zeta potential measurement of the glaze layer surface, and the antibacterial test were performed. The surface roughness of the glaze layer is measured using a stylus type surface roughness meter (JI
S-B0651), the center line average roughness Ra was measured. As a result, Ra = 0.10 μm. The zeta potential of the glaze layer surface was measured using a laser zeta potentiometer (ELS-6000, manufactured by Otsuka Electronics Co., Ltd.). The measurement was performed by measuring the permeation flow and analyzing it using the Mori-Okamoto equation. As a result, the zeta potential on the glaze layer surface was -57.2.
mV. For evaluation of antibacterial properties, E. coli (Es
(Cericia coli, IFO 3972). That is, 0.2 ml of bacterial solution (the number of bacteria: 1 × 10 5 to 5 × 10 5) was applied to the surface of the glaze layer of the sample which had been sterilized and dried with 70 vol% ethanol in advance.
), Covered with a 45 × 45 mm polyethylene film and adhered closely, at a temperature of 37 ± 1 ° C. and a relative humidity of 90 °.
% For 24 hours. Thereafter, the film was peeled off, stamped with an NA medium, and cultured in an environment at a temperature of 35 ± 1 ° C. for 16 to 20 hours to measure the number of viable cells. 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 Comparative Example 1 was 25%, the growth inhibition rate was 0.12, and it was determined that the sample had no antibacterial activity.

(Example 1) From Table 1, ZrO as an emulsifier was used.
The glaze base material having the composition excluding 2 and the pigment was melted at 1300 to 1400 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass frit. This was pulverized by a stamp mill to obtain 600 g of the obtained powder, 3.0 g of silver powder (0.5% by weight based on the glaze), 400 g of water and 1 g of alumina balls.
kg was placed in a 2 liter pottery pot and ground by a ball mill for about 24 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 analyzer, 68% was found to be 10 μm or less, and 50% average particle size (D5
0) was 6.0 μm. Next, using sanitary ware body slurry prepared from silica sand, feldspar, clay, etc. as raw materials,
A 0x150 mm plate test piece was prepared. Spray-coat glaze A as a lower layer on this plate-shaped test piece,
Subsequently, a sample was obtained by spray-coating glaze B as an upper layer, followed by firing at 1100 to 1200 ° C. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the surface roughness of the glaze layer was Ra = 0.02 μm. The measurement result of the zeta potential at pHｐＨ7 of the glaze layer surface was −68.3 mV. Antibacterial test results
The sterilization rate was 99.994% and the growth inhibition rate was 4.2, and it was determined that there was antibacterial activity.

(Example 2) From Table 1, it was found that ZrO as an emulsifier was used.
The glaze base material having the composition excluding 2 and the pigment was melted at 1300 to 1400 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass frit. This was pulverized by a stamp mill, and 600 g of the obtained powder, 6.0 g of copper oxide powder (1.0% by weight based on the glaze), 400 g of water and 1 kg of alumina balls were placed in a pot of 2 liters in pottery. And ground by a ball mill for about 24 hours. The glaze slurry obtained here is designated as glaze C. When the particle size of the glaze C obtained after the pulverization was measured using a laser diffraction type particle size distribution analyzer, 68% was found to be 10 μm or less, and the 50% average particle size (D50) was found to be 6.0 μm. Next, a 70 × 150 mm plate-shaped test piece was prepared using a slurry of a sanitary ware body prepared using silica sand, feldspar, clay or the like as a raw material. On this plate-shaped test piece, glaze A was spray-coated as a lower layer, then glaze C was spray-coated as an upper layer, and then fired at 1100 to 1200 ° C to obtain a sample. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the surface roughness of the glaze layer was Ra = 0.0.
It was 3 μm. The measurement result of the zeta potential at pHｐＨ7 of the glaze layer surface was −60.2 mV. The antibacterial test results show that the sterilization rate is 99.0% and the growth inhibition rate is 2.0,
It was determined to be antibacterial.

Example 3 The frit glaze prepared in Example 1 above (containing no emulsifier and pigment, D50 = 6.0 μm)
m) 80 parts by weight of the slurry and a glaze (D50 = 5.9 μm) containing no emulsifier and pigment before fritting (D50 = 5.9 μm) 2
After mixing with 0 parts by weight, the solid content of the glaze was 0.5%.
Weight percent silver powder and stir using a plunger.
Mixed. The glaze slurry obtained here is designated as glaze D. The particle size of the glaze D obtained after mixing was measured using a laser diffraction type particle size distribution analyzer.
The 7% and 50% average particle size (D50) was 6.0 μm. Next, a 70 mm × 150 mm plate-like molded body was produced using a slurry of a sanitary ware body prepared using silica sand, feldspar, clay and the like as raw materials. On this plate-like molded piece, glaze A is spray-coated as a lower layer, and then glaze D is spray-coated as an upper layer.
A sample was obtained by firing at 00 ° C. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the surface roughness of the glaze layer was Ra = 0.05 μm. The measurement result of the zeta potential at pH 釉 7 of the glaze layer surface was −61.3.
mV. The antibacterial test results show that the sterilization rate is 99.991
%, The growth inhibition rate was 4.0, and it was determined that there was antibacterial activity.

(Example 4) 600 g of a glaze base material having the composition shown in Table 1, 3.0 g of silver powder (0.5% by weight based on the glaze), 400 g of water and 1 kg of alumina balls were placed in a 2 liter pottery. The mixture was placed in a pot and ground by a ball mill for about 65 hours. The glaze slurry obtained here is
Make it glaze E. Using a laser diffraction particle size analyzer,
The particle size of the glaze E obtained after the pulverization was measured.
98% or less and 50% average particle diameter (D50) of 1.2
μm. Next, using a sanitary ware body slurry prepared using silica sand, feldspar, clay, etc. as a raw material, 70 × 150 m
m was prepared, and the glaze E obtained as described above was applied to the plate-like molded body by a spray coating method, and was fired at 1100 to 1200 ° C to obtain a sample. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the surface roughness of the glaze layer was Ra = 0.02 μm. The measurement result of the zeta potential at pHｐＨ7 of the glaze layer surface was −62.4 mV. Antibacterial test results
The sterilization rate was 99.990% and the growth inhibition rate was 4.0, and it was determined that there was antibacterial activity.

(Comparative Example 2)

[Table 2]

The glaze raw material having the composition shown in Table 2 was melted at 1100 to 1400 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass frit. 2 kg of this glass frit, an emulsifier (antimony oxide), a few g of pigment and 4 kg of cobblestone were put into a 6-liter pottery pot and pulverized by a ball mill so as to pass through a 150-mesh sieve. I got a glaze. The glaze powder obtained here is designated as glaze A. Next, a 100 × 100 mm plate-shaped metal test piece was prepared, the lower glaze was wet-glazed, and fired at 800 to 1100 ° C.
The glaze A obtained as described above in a hot state was dry-glazed and fired at 800 to 1100 ° C to obtain a sample. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the surface roughness of the glaze layer was Ra = 0.06 μm. The measurement result of the zeta potential at pHｐＨ7 of the glaze layer surface was −51.1 mV. As a result of the antibacterial test, the sterilization rate was 35% and the growth inhibition rate was 0.19, and it was determined that there was no antibacterial property.

Example 5 A glaze raw material having the composition shown in Table 2 was melted at 1100 to 1400 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass frit. This glass frit 2
kg, 10 g of silver powder (0.5% by weight based on glass frit) and 4 kg of cobblestone were put into a 6-liter pottery pot and pulverized by a ball mill so as to pass through a 150-mesh sieve. I got a glaze. The glaze powder obtained here is designated as glaze B. Next, 100 × 100
mm plate-shaped metal test piece was prepared, and the lower glaze was wet-glazed.
After firing at 0 to 1100 ° C, the glaze A obtained as described above in a hot state is dry-glazed and fired at 800 to 1100 ° C. Further, a glaze B was dry-glazed in the same hot state and fired at 800 to 1100 ° C to obtain a sample. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the surface roughness of the glaze layer was Ra = 0.03 μm.
Met. The measurement result of the zeta potential at pHｐＨ7 of the glaze layer surface was −61.5 mV. As a result of the antibacterial test, the sterilization rate was 99.99% and the growth inhibition rate was 4.0, and it was determined that there was antibacterial activity.

[0025]

[Table 3]

Table 3 summarizes the evaluation results in the examples of the present invention. Thus, in the embodiment of the present invention,
Because the surface irregularities are very small, Escherichia coli is less likely to be caught by the glaze layer surface irregularities and remains, and the surface zeta potential has a large negative value. Is charged), it is presumed that a large amount of fungi does not adhere to the electric repulsion. Furthermore, when an antibacterial agent is acted on in a state where a large amount of fungi are not attached, it is considered that a very high antibacterial effect is obtained.

According to the present invention, it is possible to provide a glazed product which can exhibit sufficient antibacterial properties even under actual use conditions.

[Brief description of the drawings]

FIG. 1 is a diagram showing one embodiment of the present invention.

FIG. 2 is a diagram showing another embodiment of the present invention.

FIG. 3 is a diagram showing another embodiment of the present invention.

FIG. 4 is a diagram showing another embodiment of the present invention.

[Explanation of symbols]

 1,21: Pottery base 11, 31: Metal substrate 2, 12, 22, 32: Colorable glaze layer 32, 33: Transparent glaze layer

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C23D 5/00 C23D 5/00 Z E03D 11/02 E03D 11/02 Z // C04B 41/86 C04B 41/86 R ( 72) Inventor Masaaki Ito 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Tohoku Kiki Co., Ltd. (72) Inventor Masami Ando 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Totoki Inside (72) Inventor Koichi Hayashi 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Touchi Kiki Co., Ltd. (72) Inventor Shin Hayakawa 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka No. F-term (reference) in TOTO KOGYO CO., LTD.

Claims (28)

[Claims] 1. An antibacterial property, wherein a glaze layer is formed on a surface of a pottery substrate or a metal base material, and the surface of the layer has a negative zeta potential at pH 7 and an absolute value of 60 mV or more. Glazed products with. 2. A glaze layer is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is 0.07 μm by a stylus type surface roughness measuring device (JIS-B0651).
A glazed product having antibacterial properties, characterized by being less than m. 3. A glaze layer is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is 0.05 μm by a stylus type surface roughness measuring device (JIS-B0651).
m, which is less than m. 4. A glaze layer is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is 0.03 μm by a stylus type surface roughness measuring device (JIS-B0651).
m, which is less than m. 5. A glaze layer is formed on the surface of a ceramic or metal substrate, and the surface roughness Ra of the surface of the layer is 0.07 μm by a stylus type surface roughness measuring device (JIS-B0651).
m, the zeta potential at pH 7 of the layer surface is negative, and the absolute value thereof is 60 mV or more. 6. A glaze layer is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the surface of the layer is 0.05 μm by a stylus type surface roughness measuring device (JIS-B0651).
m, the zeta potential at pH 7 of the surface of the layer is negative, and the absolute value is 60 mV or more. 7. A glaze layer is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is 0.03 μm by a stylus type surface roughness measuring device (JIS-B0651).
m, the zeta potential at pH 7 of the surface of the layer is negative, and the absolute value is 60 mV or more. 8. The method according to claim 8, wherein silver and / or
Or a glaze layer having an antibacterial property, wherein a glaze layer to which a substance containing copper is added is formed, and the surface of the layer has a negative zeta potential at pH 7 and an absolute value of 60 mV or more. . 9. The method according to claim 9, wherein silver and / or
Or, a glaze layer to which a substance containing copper is added is formed, and the surface roughness Ra of the surface of the layer is less than 0.07 μm by a stylus type surface roughness measuring device (JIS-B0651). Glazed products with antibacterial properties. 10. A glaze layer to which a substance containing silver and / or copper is added is formed on a surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is measured by a stylus type surface roughness measurement. A glazed product having antibacterial properties, characterized in that the thickness is 0.05 μm or less according to an apparatus (JIS-B0651). 11. A glaze layer to which a substance containing silver and / or copper is added is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is measured by a stylus type surface roughness measurement. A glazed product having antibacterial properties, characterized in that the thickness is 0.03 μm or less according to an apparatus (JIS-B0651). 12. A glaze layer to which a substance containing silver and / or copper is added is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is measured by a stylus type surface roughness measurement. A glazed product having antibacterial properties, characterized in that it has a zeta potential of less than 0.07 μm according to an apparatus (JIS-B0651), a negative zeta potential of the layer surface at pH 7, and an absolute value of 60 mV or more. 13. A glaze layer to which a substance containing silver and / or copper is added is formed on the surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is measured by a stylus type surface roughness measurement. A glazed product having antibacterial properties, wherein the glazed product is 0.05 μm or less according to an apparatus (JIS-B0651), has a negative zeta potential at pH 7 on the surface of the layer, and has an absolute value of 60 mV or more. 14. A glaze layer to which a substance containing silver and / or copper is added is formed on a surface of a pottery substrate or a metal substrate, and the surface roughness Ra of the layer surface is measured by a stylus type surface roughness measurement. A glazed product having antibacterial properties, wherein the glazed product has a zeta potential of 0.03 μm or less according to an apparatus (JIS-B0651), a zeta potential of the layer surface at pH 7 of negative, and an absolute value of 60 mV or more. 15. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a ceramic. 16. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is an enamel product. 17. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a glazed cement building material. 18. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is sanitary ware. 19. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a tile. 20. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is tableware. 21. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is an insulator. 22. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a toilet bowl. 23. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a wash basin. 24. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a toilet bowl. 25. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a hand-washing machine. 26. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a toilet bowl sana. 27. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a bathtub. 28. The glazed product having antibacterial properties according to claim 1, wherein the glazed product is a sink.