JP2000257138A - Antifouling stool - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily remove stain in a toilet stool by forming, into a predetermined state, a slant face of a bowl surface from a most upstream portion to a most downstream portion, which can be flushed by water when the flush water flushes. SOLUTION: For example, bowl surfaces 2, 3 of a western style toilet stool are set to slant faces having a continuous slope of 0 to a negative value, from a rim hole 1 for discharging flush water to a portion close to a draft of a water storage portion 4, and the surfaces of the bowl are reformed to have a self-cleaning function with respect to oily stain. Then, the surface roughness of the bowl surfaces 2, 3 is set to less than 0.07 μm, based on a stylus-type surface roughness tester according to JIS-B0651, preferably to 0.05 μm or less, and more preferably to 0.03 μm or less. The surfaces 2, 3 are formed of an amorphous component. Next, a cover coat to be applied to the surfaces 2, 3 contains a metal component having a valence of 1 and/or a metal component having an electro-negativity of 1 or less. Further, the surfaces 2, 3 contains an anti-bacterial metal, and the ζ-potential of the surfaces 2, 3 are set to a negative value. Thus, stain on the bowl surfaces can be removed only by flushing water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a large urinal or urinal such as a Western-style toilet, a Japanese-style toilet, a simple toilet or the like having an antifouling property (including easy cleaning).

[0002]

2. Description of the Related Art Keeping the surface of a toilet sanitary clean is a necessary property because toilets are generally widely used as daily necessities. As a method for keeping the toilet surface clean and hygienic in general households since ancient times, a detergent such as a surfactant, acid, or alkali is attached to a scourer or brush and the toilet surface is rubbed strongly. A method has been adopted in which chemical stain removal is combined with physical removal by scrubbing with a scrub or brush.

[0003]

However, according to this method, labor for scrubbing with a scourer or a brush is required every time dirt adheres. Especially in the elderly,
It is difficult to require such labor every time. In particular, there is a strong desire of users to reduce the frequency of cleaning, especially when it comes to flushing toilets. Furthermore, in recent years, there has been a problem of river pollution due to the drainage of household wastewater containing the surfactant.

Therefore, an object of the present invention is to remove dirt on the bowl surface of a toilet bowl simply by flushing toilet flush water without using a surfactant and without rubbing strongly with a scourer or a brush. An object of the present invention is to provide a toilet bowl that can be used.

[0005]

According to the present invention, in order to solve the above-mentioned problems, an antifouling toilet bowl having a ball surface having a self-cleaning function for oily dirt, wherein the ball surface is washable with washing water, Further, the present invention provides an antifouling toilet bowl characterized in that it has a slope of 0, a negative slope or a vertical slope continuously from the most upstream part to the most downstream part when the washing water passes. . The ball surface is surface-modified so as to have a self-cleaning function against oily dirt, and the ball surface can be washed with washing water, and continuously from the most upstream portion to the most downstream portion when the washing water passes. The stools (main components are fatty dirt such as fatty acids and bacteria) that adhere to the ball surface due to the slope of any one of 0, negative slope, and vertical, etc. Moves in the direction of gravity and is removed from the ball surface. Thereby, the ball surface is always kept clean.

According to one aspect of the present invention, there is provided an antifouling toilet having a ball surface having a self-cleaning function for oily dirt, wherein the toilet has a reservoir, and the ball surface is located directly below a water discharge port. The present invention provides an antifouling toilet bowl characterized in that any one of 0, a negative slope, and a vertical slope is continuously formed up to the vicinity of a draft portion of the reservoir.
The ball surface is surface-modified so as to have a self-cleaning function against oily dirt, and the ball surface is continuously 0, from immediately below the water discharge port to near the draft portion of the reservoir.
Due to the slope being either negative or vertical, stool (main component is fatty dirt such as fatty acids and bacteria) that adheres to the ball surface, etc. As a result, it moves in the direction of gravity, and easily reaches the toilet bowl sump. Thereby, the ball surface is always kept clean.

In another aspect of the present invention, there is provided an antifouling toilet having a ball surface having a self-cleaning function for oily dirt, wherein the toilet does not have a reservoir, and the ball is located immediately below a water discharge port. The present invention provides an antifouling toilet bowl characterized in that it has a slope of any one of 0, a negative slope, and vertical from a section to a drain port. The ball surface is surface-modified so as to have a self-cleaning function against oily dirt, and the ball surface is continuously inclined from either immediately below the water discharge port to the drain port, either of 0, a negative slope or vertical. The stool attached to the ball surface (the main component is fatty dirt such as fatty acids and bacteria) moves in the direction of gravity due to its own weight or the flow of toilet flush water, and easily goes to the drain port. To reach. Thereby, the ball surface is always kept clean.

In a preferred embodiment of the present invention, the surface roughness Ra of the ball surface is measured by a stylus type surface roughness measuring device (JI
According to S-B0651), the thickness is less than 0.07 μm, preferably 0.05 μm or less, more preferably 0.03 μm or less. Here, the surface roughness Ra can be obtained by measurement using a stylus type surface roughness measuring device (JIS-B0651). In the case of conventional sanitary wares, urinals, toilet sana, toilet tanks, and other sanitary wares, wash basins in wash basins, and hand washers, the surface roughness was 0.07 μm or more in Ra, and none was less than that. . As a result, the dirt gradually adheres to the irregularities, causing yellowish dirt and the like to be observed, for example, on the ball surface of the toilet bowl used for a long period of time, traps, sana, and the like. In the present invention, by making the toilet bowl surface have an unprecedented smoothness, dirt such as stool becomes hard to adhere firmly, and as a result, even if it adheres, it can be lifted up by contact with water, The raised dirt can be removed with the flush water of the toilet. Details will be described below. On the ball surface of a conventional toilet bowl, the surface roughness Ra of the glaze layer covering the surface of even a ceramic product is about 0.1 μm, and the surface has large irregularities. On the other hand, the surface of the glaze layer according to the present invention is very smooth and has only slight irregularities. Here, it is assumed that dirt of the same type and size adheres to both surfaces. At this time, when comparing the adhesion strength between the dirt and the glaze layer surface, it is considered that the conventional toilet bowl surface having a large contact area is stronger, and the smooth toilet bowl surface according to the present invention has a small contact area, so that it is weak. . Next, if the whole of the dirt is covered with water, the same size of dirt produces the same amount of buoyancy regardless of the surface condition.
As described above, dirt is less likely to float on the conventional toilet bowl surface having a large adhesion strength, and dirt is more likely to rise on the smooth toilet bowl surface of the present invention. The dirt that has risen once is removed by running water, restoring the original clean surface. In addition, since the ball surface is continuously inclined from just below the water discharge port to the vicinity of the draft portion of the water storage portion (the drainage port when there is no water storage portion), the ball surface has only a zero or negative slope. The water flow force of the washing water passing through is large, and its effect further improves the dirt removal performance.

In a preferred aspect of the present invention, the ball surface is substantially made of an amorphous (glass) component. The amorphous (glass) component is chemically stable,
It is easy to form a smooth surface. Therefore, dirt such as stool is hard to adhere firmly. As a result, even if it adheres, it can be lifted up by contact with water, and the raised dirt can be removed with the flush water of the toilet. In addition, since the ball surface continuously slopes from just below the water discharge port to the vicinity of the draft portion of the reservoir portion (the drain port if there is no reservoir portion), the ball surface has a slope of only 0 or a negative gradient. The water flow force generated by the passing washing water is large, and the dirt removing performance is further improved by the effect.

In a preferred aspect of the present invention, the ball surface is coated with a glaze, and the glaze has a monovalent metal component and / or a Pauling electronegativity scale of 1 or less. Metal component is contained. By including a monovalent metal component and / or a metal component having a Pauling electronegativity scale of 1 or less in the glaze layer, the bowl surface of the toilet bowl can exhibit a self-cleaning function against adhered stains for a long time. become. Further, the dirt once separated from the surface is prevented from being re-adsorbed. This will be described in detail below. Adhesive stains brought to the toilet bowl surface include, for example, stool (contains a large amount of oleic acid and bacteria), bacteria, fungi, and other microorganisms in toilet bowls, scales, and scales in toilet bowls.
Urinary stones, bacteria, etc., the main deposits are oily stains containing carboxyl end groups and scales. For example, when an oily soil containing a carboxyl end group is brought to the bowl surface of a toilet bowl, the presence of the above detergent component results in a metal component having a monovalent valence and / or a metal having a scale of Pauling's electronegativity of 1 or less. The components are preferentially added to or adsorbed to the oily soil by a substitution reaction. Thereby, the affinity of the dirt with water is improved, and when the dirt is a low molecular weight, the dirt is made water-soluble (saponified). Thereby, the affinity for water becomes higher than the affinity of the dirt for the pottery surface, and the dirt is easily removed by washing with water. The main component of the bowl surface is amorphous (glassy)
The above components have a tendency to be continuously released to the outside by being formed with a glaze made of the above material. Therefore, the self-cleaning function for the adhered dirt is exhibited for a long time. In addition, it is possible to prevent the dirt once detached from the surface from being re-adsorbed, because the builder of a metal component having a monovalent valence and / or a metal component having a Pauling electronegativity scale of 1 or less. Action (Yoshio Abe, "Theory of Detergent", Kindaisha Publishing Co., Ltd., 1985, Chapter 1,
1 to 102).

In a preferred aspect of the present invention, the ball surface contains an antibacterial metal.
Since the antibacterial metal is contained, the antibacterial property is simultaneously exhibited.

In a preferred aspect of the present invention, the zeta potential of the ball surface is set to be negative. By making the zeta potential negative, the ball surface can have a disinfecting effect. This will be described in detail below. Fungi such as Escherichia coli are generally known to be negatively charged in water. Therefore, by making the zeta potential of the surface of the sanitary ware negative, the surface of the sanitary ware and the fungi are electrically repelled in a state where they are in contact with water, so that the adhesion of the fungi can be prevented.

In a preferred aspect of the present invention, the antifouling toilet bowl is made of earthenware. By making the toilet bowl made of pottery, it is possible to cover the toilet bowl with a substantially amorphous glaze containing a large amount of Si components.

[0014] In a preferred embodiment of the present invention, the toilet is a ceramic toilet, and the ball surface is coated with a glaze. In the glaze, a sodium component is included in all the metal components in the glaze. On the other hand, it is contained in an amount of 2.6% by weight or more in terms of oxide. By including the sodium component in a large amount of 2.6% by weight or more, the builder effect of the same component is enhanced, and the bowl surface of the toilet bowl can exhibit a self-cleaning function for adhering dirt for a long time. Further, the dirt once separated from the surface is prevented from being re-adsorbed.

In a preferred embodiment of the present invention, the toilet is a ceramic toilet, and the ball surface is coated with a glaze, and in the glaze, a potassium component is replaced by a total metal component in the glaze. On the other hand, the content is 4.1% by weight or more in terms of oxide. 3. Potassium component.
By containing a large amount of 1% by weight or more, the builder effect of the same component is enhanced, and the bowl surface of the toilet bowl can exhibit a self-cleaning function for adhering dirt over a long period of time. Further, the dirt once separated from the surface is prevented from being re-adsorbed.

In a preferred aspect of the present invention, the ball surface is fluorinated. When the fluoridation treatment is performed, the toilet surface becomes oily, and oily dirt hardly adheres.

In a preferred aspect of the present invention, the ball surface is covered with a fluororesin or a silicone resin. When the toilet bowl is covered with a fluororesin or a silicone resin, the surface of the toilet bowl becomes oily, and oily dirt hardly adheres.

In a preferred aspect of the present invention, the water outlet is a spreader type water outlet.
By using the water outlet of the spreader type, the power of flowing water passing through the ball surface is increased, and the dirt removing performance is further improved by the effect.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an embodiment of the invention according to claim 1 or 2, wherein a large number of water discharge ports (rim holes) 1 are formed on the back surface of a rim portion present at the peripheral portion of a Western style toilet. . Rinse hole 1 is a spout port for washing water.
From the water. The cleaning water discharged from the rim hole 1 flows into the reservoir 4 via the ball surface 2 or 3. Here, as shown in the figure, the shape of the ball surface 2 or 3 is an inclined surface having only zero or a negative gradient continuously from the rim hole 1 immediately below the water discharge port to the vicinity of the draft portion of the reservoir 4. Further, the ball surfaces 2 and 3 are surface-modified so as to have a self-cleaning function for oily dirt.

FIG. 2 shows another embodiment of the invention according to claim 1, which is a so-called "open rim type" Western style toilet. Wash water is supplied from the spout 11 to the ball surface 13
Or turns and flows from the rim water passage 15 to the reservoir 14 via the ball surface 12. Here, as shown in the figure, the shape of the ball surface 12 or 13 is from a portion directly below the water discharge port 11 or the rim water passage 15 which is an upstream portion in the passage of the washing water, to a reservoir portion which is a downstream portion in the passage of the washing water. A slope of only 0 or a negative slope is continuously formed up to the vicinity of the draft section 14. Further, the ball surface 12
The surface is modified to have a self-cleaning function for oily stains.

FIG. 3 shows another embodiment of the invention according to claim 1 or 2, wherein a large number of water discharge ports (rim holes) 21 are provided on the back surface of a rim portion present at the periphery of a Japanese-style toilet. Is pierced. The cleaning water is discharged from a rim hole 21 which is a water discharge port. The cleaning water discharged from the rim hole 21 flows to the reservoir 24 via the ball surface 22 or 23. Here, as shown in the figure, the shape of the ball surface 22 or 23 is an inclined surface having only a zero or negative gradient continuously from the rim hole 21 immediately below the water discharge port to the vicinity of the draft of the reservoir 24. Further, the ball surface 22 or 23 is surface-modified so as to have a self-cleaning function for oily dirt.

FIG. 4 shows another embodiment of the invention according to claim 1 or 2, wherein a water outlet is provided at a portion of the Japanese toilet which is located on the side opposite to the longitudinal direction with respect to the water storage portion 34. 31 is pierced. The cleaning water is spouted from the spout 31. The washing water spouted from the spout 31 flows to the reservoir 34 via the ball surface 32. In this case, the shape of the ball surface 32 is a part of the inclined surface having only a zero or negative gradient continuously from the water discharge port 31 to the vicinity of the draft part of the reservoir part 34 as shown in the figure. Furthermore, ball surface 3
No. 2 is surface-modified so as to have a self-cleaning function for oily stains.

FIG. 5 shows another embodiment of the invention according to claim 1, which is a so-called "stand-by type" urinal having a large number of holes as water outlets. Wash water is spout 4
Water is spouted from 1. Wash water spouted from the spout 41 flows from the perforated plate 46 to the reservoir 44 via the ball surface 42. Here, as shown in the figure, the shape of the ball surface 42 is a vertical surface and 0 or continuously from the water discharge port 41 which is an upstream portion in the passage of the washing water to the perforated plate 46 which is a downstream portion in the passage of the washing water. Make the slope only negative slope. Further, the ball surface 42 is surface-modified so as to have a self-cleaning function for oily dirt.

FIG. 6 shows another embodiment of the invention according to claim 1, which is a so-called "spreader-type" urinal having a spreader nozzle as a spout. The cleaning water is spouted from the spout 51. The washing water spouted from the spout 51 flows from the perforated plate 56 to the reservoir 54 via the ball surface 52. Here, as shown in the figure, the shape of the ball surface 52 is a vertical surface and 0 or continuously from the water discharge port 51, which is the upstream part in the passage of the washing water, to the perforated plate 56, which is the downstream part in the passage of the washing water. Make the slope only negative slope. Further, the ball surface 52
Has been surface-modified to have a self-cleaning function for oily stains.

FIG. 7 shows another embodiment of the first or third aspect of the present invention, which is a simplified toilet without a reservoir. A water spout 61 is formed in the periphery of the toilet so that the flush water is spouted. The spouted washing water flows through the drain port 67 via the ball surface 62 or 63. Here, as shown in the figure, the shape of the ball surface 62 or 63 is continuously inclined from the water discharge port 61 to the drain port 67 with only a zero or negative gradient. Further, the ball surfaces 62 and 63
Has been surface-modified to have a self-cleaning function for oily stains.

In order to provide the ball surface with a self-cleaning function against oily dirt, for example, (1) a glaze layer is formed on the surface so that the surface of the glaze layer has an unprecedented smoothness. I do. (2) A glaze layer is formed on the surface, and the surface of the glaze layer contains a large amount of a monovalent metal component and / or a metal component having a Pauling electronegativity scale of 1 or less. One of
Or a method of performing both of them, or (3) fluorinating the surface. (4) A method of coating the surface with a fluororesin or a silicone resin is conceivable. The methods (1) and (2) are based on the viewpoints of sustainability of the self-cleaning function under the use environment.
It is better than (4). On the other hand, the methods (3) and (4) have an advantage in that a self-cleaning function can be provided by post-processing even to a toilet bowl that has been installed on site. The methods (1), (2) and (3), (4) may be used together from the viewpoint of utilizing the advantages of both.

In order to impart unprecedented smoothness (Ra <70 nm) to the surface of the glaze layer on the ball surface, first, as a glaze raw material, (A) 50% by particle size distribution measurement by a laser diffraction method. Average particle size (D50) is 1.5
Use a raw material of μm or less. Alternatively, (B) a glaze material (frit) previously vitrified is used. Or
(C) Glazing raw material which has been vitrified in advance and raw materials for glaze conventionally used (5.
A mixture of 0% average particle diameter (D50) of about 6 μm) is used. Alternatively, (D) a mixture of a pre-vitrified glaze raw material and a finer glaze raw material than before is used. After preparing any one of these glaze raw materials and applying it to a pottery (molding) substrate on the ball surface, 1000 to 1300
Firing at a temperature of ° C.

(A) A fine glaze material having a D50 of 1.5 μm or less can be prepared by pulverizing a glaze material powder with a ball mill, a cylinder mill, a vibration mill or the like. Here, the 50% average particle size (D50) of the glaze raw material can be measured by a laser diffraction type particle size distribution measuring device. (B) The vitrified frit-like glaze raw material can be obtained by melting the glaze raw material powder at a high temperature of 1300 ° C. or more. (C) The mixture of the vitrified glaze raw material and the conventionally used glaze raw material is obtained by mixing the vitrified glaze raw material obtained by the method (B) and the conventionally used glaze raw material. be able to. (D) A mixture of a pre-vitrified glaze raw material and a finer glaze raw material than before is obtained by mixing a fine glaze raw material having a D50 of 1.5 μm or less obtained by the above method (A) with the above-described method (B). It can be obtained by mixing vitrified glaze raw materials.

Further, at least silica particles (for example, silica sand in a natural raw material) in the above glaze raw material powder are D5.
0 is 6 μm or less, preferably 4 μm or less. By doing so, it is possible to reduce silica particles remaining on the surface unreacted after firing, and even when used in an environment exposed to alkaline water (ammonia-containing water) such as a toilet, priority is given to the vicinity of silica particles. A decrease in surface smoothness due to deterioration can be prevented. The reason for this is that undissolved substances (silica, zircon) that form irregularities on the glaze surface after firing preferentially dissolve in an extremely short period of about two months in the above-mentioned alkaline environment.

As a method of applying the above glaze raw material to the pottery (molding) substrate on the ball surface, general methods such as spray coating, dip coating, spin coating, roll coating, and brush coating can be used. Also,
For firing, any of a tunnel kiln, a roller hearth kiln, and a fixed firing furnace (batch furnace) can be used.

Further, in order to give the surface of the glaze layer on the ball surface an unprecedented smoothness (Ra <70 nm), a colored glaze layer is formed on the surface of the pottery substrate, and the surface of the colored glaze layer is further formed. To form a transparent glaze layer,
A so-called multilayer glaze structure may be used. The unprecedented smoothness of the ceramic surface makes it difficult for dirt to adhere firmly, and as a result, even if it adheres, it can be lifted up by contact with water, and the floating dirt is removed with running water Will be done. In addition, the production cost of ceramics can be reduced by forming a transparent glaze layer on the surface that is thinner than the glaze thickness (0.1 mm or more and 2 mm or less) that is usually coated on ceramics, and allowing the thin transparent glaze layer to have the above-mentioned smoothing performance. For this reason, when using a method in which the glaze material is applied to the ceramic forming base and then fired at once, the gas generated during firing of the forming base tends to be released to the outside as the firing of the forming base shrinks, and the The occurrence of poor appearance due to the remaining gas is prevented.

In the above structure, the ball surface may have a hydrophilic surface having a contact angle with water of less than 30 °, preferably 25 ° or less, more preferably 20 ° or less. The conventional ceramic surface has a high contact angle with water, and it is difficult for water to enter the interface between the dirt and the glaze layer surface due to a capillary phenomenon. on the other hand,
In ceramics having a hydrophilic surface, water easily penetrates into the interface by capillary action, and the dirt can be raised. Further, when the water flows, a water film is formed on the hydrophilic surface, and the effect of preventing the dirt floating in the water from adhering to the surface again and facilitating the flow is obtained.

On the toilet bowl surface, a glaze layer is formed on the surface, and the surface of the glaze layer contains a large amount of a monovalent valent metal component and / or a metal component having a scale of Pauling's electronegativity of 1 or less. Also, a self-cleaning function for oily dirt can be provided. Here, the valence is 1
Li, Na, K, Rb, Cs,
Ag, Cu, Au and the like can be suitably used. Further, as a metal component having a scale of Pauling's electronegativity of 1 or less,
Li, Na, K, Rb, Cs, Ba, Sr and the like can be suitably used. When Na is used, it is 2.6% by weight or more, preferably 3% by weight, in terms of oxide based on all metal components of the glaze.
Add by weight or more. In the case of K, the amount of oxide is 4.1% by weight or more, preferably 5% by weight, based on the total metal components of the glaze.
Add by weight or more. Further, among the above metal components, L
With respect to alkali metal components such as i, Na, K, Rb, Cs, etc., it is necessary to reduce the amount of oxides to less than 20% by weight, preferably 15% by weight or less, based on the entire metal components constituting the glaze. preferable.

The self-cleaning function for oily dirt can also be provided by coating the bowl surface of the toilet bowl with a fluororesin or silicone resin. Here, as the fluororesin, polyvinyl fluoride, polyvinylidene fluoride, polychlorinated ethylene trifluoride, polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, Ethylene-polychlorinated ethylene trifluoride copolymer, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, and the like can be suitably used. Examples of the silicone resin include a bifunctional hydrolyzable silane, a trifunctional hydrolyzable silane, a siloxane resin composed of a dehydration-condensed polymer of a tetrafunctional hydrolyzable silane, and an organic-inorganic hybrid resin having an organic crosslink in addition to the siloxane crosslink. It can be suitably used.
In particular, in addition to siloxane cross-linking, organic cross-linking based on condensation polymerization of an acrylic group is preferable because it exhibits strong resistance to ammonia base in a toilet environment.

The glaze layer may have an additional function by adding an additive other than the glaze. Here, the additive to be added to the glaze is preferably one that forms a compound by reaction with the glaze or atmosphere during firing. For example, antibacterial metals such as silver, copper, zinc or its compounds, solid solutions, and photocatalysts such as titanium oxide, zinc oxide, tin oxide, ferric oxide, tungsten trioxide, strontium titanate, and bismuth trioxide are added. The effect is exhibited.
In addition, the photocatalyst also has an effect of having photoreducing properties in which hydrophilicity is promoted, and the like.

[0036]

Example (Comparative Example 1)

[0037]

[Table 1]

2 kg of a glaze raw material having the composition shown in Table 1 and water 1
kg 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, and the 50% average particle size (D50) was 6.2 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 stain resistance test by a pseudo (oil) dirt, and the zeta potential measurement of the glaze layer surface were performed. As for the surface roughness of the glaze layer, the center line surface roughness Ra was measured using a stylus type surface roughness measuring device (JIS-B0651). As a result, Ra = 0.10 μm
m. In the stain resistance test with pseudo (oil) dirt, first, a pseudo dirt composed of 200 parts by weight of oleic acid, 1 part by weight of engine oil, and 1 part by weight of oil black was prepared. Here, oleic acid is a main component in stool, and engine oil and oil black are additives for making the oil easily visible. Next, 0.3 cc of pseudo dirt of the above components was dropped on the glaze layer surface of a horizontally placed plate-shaped sample, and then tilted at 45 ° or 90 ° so that the tip of the oil droplet was spaced 10 cm apart for several seconds. The flow was measured to see if it was falling, and the falling speed of the oil droplet was calculated. Further, the time until the entire pseudo-stain was removed was measured. As a result, the oil droplet falling velocity at a 45 ° inclination was 0.76 cm / sec, and the oil droplet falling velocity at a 90 ° inclination was 1.4 cm / sec. In both cases of 45 ° and 90 °, the fall time could not be measured because an oil film having a wide width in the up-down direction remained even after 5 minutes. The zeta potential of the glaze layer surface was measured using a laser zeta potentiometer (manufactured by Otsuka Electronics Co., Ltd., ELS-6000), using an aqueous solution of NaCl having a pH of 7.0 and a concentration of 10 mM as an electrolyte, and using polystyrene latex as light scattering monitor particles. 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 -53.8 mV.

Example 1 From Table 1, it was found that the emulsifier ZrO
2 and a glaze substrate having a composition excluding the pigment were 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, 400 g of water and 1 kg of alumina balls were put into a 2 liter pottery pot, and pulverized 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 × 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 glaze A was spray-coated as a lower layer on the plate-shaped test piece, and a glaze B 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 measurement result of the surface roughness was Ra = 0.03.
μm. As for the result of the stain resistance test by the pseudo dirt, the oil droplet falling speed at the time of 45 ° inclination was 0.85 c.
m / sec and the fall time was 131 seconds. The oil droplet falling speed at the time of 90 ° inclination was 1.5 cm / sec, and the falling time was 114 seconds. The measurement result of the zeta potential on the glaze layer surface is -61.
It was 2 mV.

(Example 2) A glaze base material prepared such that the Na2O component was increased relative to the composition of the glaze B prepared in Example 1 (the weight of Na2O was 8.0 with respect to the total weight of the glass components) % By weight using an electric furnace.
Melted at 1400 ° C. and quenched in water to obtain a glass frit. This was pulverized by a stamp mill to obtain 600 g of the obtained powder, 400 g of water and 1 kg of alumina balls.
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 C. When the particle size of the glaze C obtained after the pulverization was measured using a laser diffraction type particle size distribution meter, 68% was found to be 10 μm or less, and 50% average particle size (D50).
Was 6.0 μm. Next, using a sanitary ware body slurry prepared using silica sand, feldspar, clay, etc. as raw materials, a 70 ×
A 150 mm plate specimen was prepared. After the glaze A is spray-coated as a lower layer on the plate-shaped test piece and the glaze C is spray-coated as an upper layer,
A sample was obtained by firing at 1100 to 1200 ° C. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the measurement result of surface roughness was Ra = 0.04 μm. Regarding the result of the stain resistance test performed by the pseudo dirt, the oil droplet falling velocity at a 45 ° inclination was 0.87 cm / sec.
The fall time was 112 seconds. The oil droplet falling speed at the time of 90 ° inclination was 2.5 cm / sec, and the falling time was 101 seconds.
The measurement result of the zeta potential on the glaze layer surface was −66.5 mV.

(Example 3) A glaze base material prepared so that the K2O component is increased with respect to the composition of the glaze B prepared in Example 1 (the weight of K2O is 12.2 with respect to the total weight of the glass components) % By weight using an electric furnace.
It was melted at 1400 ° C. and quenched in water to obtain a glass frit. This was pulverized by a stamp mill to obtain 600 g of the obtained powder, 400 g of water and 1 kg of alumina balls.
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 C. When the particle size of the glaze C obtained after the pulverization was measured using a laser diffraction type particle size distribution meter, 68% was found to be 10 μm or less, and 50% average particle size (D50).
Was 6.0 μm. Next, using a sanitary ware body slurry prepared using silica sand, feldspar, clay, etc. as raw materials, a 70 ×
A 150 mm plate specimen was prepared. After the glaze A is spray-coated as a lower layer on the plate-shaped test piece and the glaze C is spray-coated as an upper layer,
A sample was obtained by firing at 1100 to 1200 ° C. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the measurement result of surface roughness was Ra = 0.04 μm. Regarding the result of the stain resistance test performed by the pseudo dirt, the oil droplet falling velocity at a 45 ° inclination was 0.87 cm / sec.
The fall time was 133 seconds. The oil droplet falling speed at the time of 90 ° inclination was 1.4 cm / sec, and the falling time was 79 seconds. The measurement result of the zeta potential on the glaze layer surface was -60.9 mV.

Example 4 The entire surface of the glaze layer of the plate-like sample obtained in Comparative Example 1 was spray-coated with Glaska B603 manufactured by JSR. After drying at room temperature for 30 minutes, it was heated and cured at 200 ° C. for 30 minutes to form a film composed of silicone and acrylic. When the obtained sample was evaluated in the same manner as in Comparative Example 1, the measurement result of surface roughness was Ra = 0.02 μm. With respect to the result of the stain resistance test performed by the pseudo soil, the oil droplet falling speed at the time of 45 ° inclination was 0.95 cm / sec, and the falling time was 61 seconds. The oil drop speed at the time of 90 ° inclination is 2.5 cm /
Seconds and the fall time was 54 seconds. The measurement result of the zeta potential on the glaze layer surface was -30.4 mV.

[0043]

[Table 2]

Table 2 summarizes the evaluation results of the examples of the present invention. Thus, in the embodiment of the present invention,
It is a glaze layer surface where oily dirt on the inclined surface is hard to remain, so even in actual use as sanitary ware,
It is estimated that the filth is easily removed. Also,
In the examples of the present invention, it is estimated that the zeta potential on the glaze layer surface has a large negative value and a large electric repulsion is generated against fungi such as Escherichia coli, so that a disinfection effect can be obtained. Is done.

As described above, the slope of the embodiment 4 is
The best antifouling properties were confirmed. On the other hand, it was confirmed that the inclined surfaces in the embodiments of Examples 1 to 3 of the present invention also had excellent antifouling properties. Example 1
The inclined surface in the third embodiment is more excellent in abrasion resistance than the embodiment of Example 4, and it is considered that the antifouling performance is maintained for a longer period of time even when the toilet or the washbasin is used.

[0046]

According to the present invention, dirt on the bowl surface of a toilet bowl can be easily removed by, for example, flushing toilet flush water without using a surfactant and without rubbing strongly with a scourer or a brush. A toilet bowl that can be provided can be provided.

[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.

FIG. 5 is a diagram showing another embodiment of the present invention.

FIG. 6 is a diagram showing another embodiment of the present invention.

FIG. 7 is a diagram showing another embodiment of the present invention.

[Explanation of symbols]

1, 11, 21, 31, 41, 51, 61 ... outlets 2, 3, 12, 13, 22, 23, 32, 42, 52,
62, 63: ball surface 4, 14, 24, 34, 44, 54: pool part 15: rim water passage 46, 56: plate 67: drain port

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masaaki Ito 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Tochiki Kiki Co., Ltd. Koichi Hayashi 2-1-1 Nakashima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture 1-1-2 Totoki Equipment Co., Ltd. (72) Inventor Shin Hayakawa Kokura, Kitakyushu-shi, Fukuoka Prefecture 2-1-1 Nakajima, Kita-ku Toto Kiki Co., Ltd. (72) Inventor Kenichiro Aoyama 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka F-term (reference) 2D039 AA01 AA04 DB04

Claims (16)

[Claims] 1. An antifouling toilet having a ball surface having a self-cleaning function for oily dirt, wherein the ball surface is washable with washing water, and the ball surface is the most downstream from the most upstream portion when the washing water passes. An antifouling toilet bowl, characterized in that only one of the slopes of 0, negative slope or vertical is continuously provided up to the part. 2. The antifouling toilet having a ball surface having a self-cleaning function for oily dirt, wherein the toilet has a water storage portion, and the ball surface has a draft of the water storage portion from immediately below a water discharge port. An antifouling toilet bowl characterized in that the slope is any one of 0, a negative slope, and a vertical slope continuously near the part. 3. The antifouling toilet having a ball surface having a self-cleaning function for oily dirt, wherein the toilet does not have a reservoir, and the ball surface is continuous from immediately below a water discharge port to a drain port. An antifouling toilet characterized by having a slope of any one of 0, a negative slope, and a vertical slope. 4. The surface roughness Ra of the ball surface is set to 0.0 by a stylus type surface roughness measuring device (JIS-B0651).
The antifouling toilet according to any one of claims 1 to 3, wherein the thickness is less than 7 µm. 5. The surface roughness Ra of the ball surface is determined to be 0.0 by a stylus type surface roughness measuring device (JIS-B0651).
The antifouling toilet according to any one of claims 1 to 3, wherein the thickness is 5 µm or less. 6. The surface roughness Ra of the ball surface is set to 0.0 by a stylus type surface roughness measuring device (JIS-B0651).
The antifouling toilet according to any one of claims 1 to 3, wherein the thickness is 3 µm or less. 7. The antifouling toilet according to claim 1, wherein the ball surface is substantially composed of an amorphous component. 8. The ball surface is coated with a glaze, and the glaze contains a monovalent metal component and / or
The antifouling toilet according to any one of claims 1 to 7, wherein a metal component having a Pauling electronegativity scale of 1 or less is contained. 9. The antifouling toilet according to claim 1, wherein the ball surface contains an antibacterial metal. 10. The antifouling toilet according to claim 1, wherein the zeta potential of the ball surface is negative. 11. The antifouling toilet according to claim 1, wherein the antifouling toilet is made of earthenware. 12. The ball surface is covered with a glaze, and the glaze contains at least 2.6% by weight of an oxide equivalent with respect to all metal components in the glaze. The antifouling toilet bowl according to claim 11, characterized in that: 13. The ball surface is coated with a glaze, and the glaze contains at least 4.1% by weight of a potassium component in terms of an oxide with respect to all metal components in the glaze. The antifouling toilet according to claim 11 or 12, wherein: 14. The antifouling toilet according to claim 1, wherein the ball surface is fluorinated. 15. The antifouling toilet according to claim 1, wherein the ball surface is coated with a fluororesin or a silicone resin. 16. The antifouling toilet according to claim 1, wherein the spout is a spreader-type spout.