WO2001044592A1

WO2001044592A1 - Flush toilet bowl with scale adhesion preventing function, coating composition for the function, and method of preventing adhesion of scale onto the flush toilet bowl

Info

Publication number: WO2001044592A1
Application number: PCT/JP2000/008855
Authority: WO
Inventors: Masami Ando; Masaaki Ito; Tomoyasu Ichiki; Atsushi Yoshida; Masakatsu Kiyohara; Hirotaka Ishibashi; Makoto Hayakawa; Mitsuyoshi Machida; Kenji Tabata; Koichi Hayashi
Original assignee: Toto Ltd.
Priority date: 1999-12-15
Filing date: 2000-12-14
Publication date: 2001-06-21
Also published as: AU1890001A

Abstract

A flush toilet bowl capable of effectively preventing scale from adhering thereto for long period, comprising at least a toilet bowl surface supplied with flushing water and a delivery port allowing the flushing water to be discharged to the toilet bowl surface, wherein a water repellant film and/or a hydro planing film is formed on the surfaces of the delivery port, whereby water is prevented from remaining on the surface of the film so as to prevent the residual water from being supplied to the toilet bowl surface.

Description

Description Flush-type toilet having a function of preventing scale from adhering, coating composition therefor, and method for preventing scale from adhering to a flush-type toilet

[Background of the Invention]

Field of the invention

TECHNICAL FIELD The present invention relates to a flush toilet to which scale is unlikely to adhere, a coating composition for preventing the build-up of scale in a flush toilet, and a method of preventing scale from attaching to a flush toilet. Background art

It is important for hygiene and aesthetics that the surface of the flush toilet is beautiful and clean. It is also desirable that such a condition be maintained for a long period of time.

To keep the toilet surface clean and hygienic, it is common practice to apply a detergent such as a surfactant, acid, or alcohol to the evening brush to rub the toilet surface strongly. That is, the stain on the toilet surface is removed by the chemical cleaning power of the detergent and the physical cleaning power of rubbing with a brush or a brush.

However, it is hard to say that such cleaning work is light labor, and it is desirable that the frequency is low. In particular, scale is likely to adhere to the flushing section of the flush toilet, and it is not easy to remove the scale once adhered to the flushing operation alone. In view of these circumstances, several techniques have been proposed to prevent the build-up of scale on flush toilets. For example, Japanese Utility Model Registration Publication No. 255554233 discloses that a water collecting recess is formed in a local area in the lower region of the bottom of the rim water channel provided in a ceramic toilet bowl, A technique is disclosed in which a rim hole is formed in a wall surface forming a concave portion so that residual water flows out of the rim water passage in a short time.

[Summary of the Invention] The present inventors have now found that by forming a hydrophilic film and / or a water-repellent film on a specific portion of a flush toilet, water scale can be effectively prevented over a long period of time.

Therefore, an object of the present invention is to provide a flush toilet in which the adhesion of scale is effectively prevented for a long period of time.

The flush toilet of the present invention has at least a toilet bowl surface to which flush water is supplied, and a water outlet for discharging the flush water to the toilet bowl surface. And Z or a water-slidable film is formed.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of a rim water flush toilet according to the present invention. FIG. 2 is a schematic sectional view showing an example of the open rim type toilet according to the present invention. FIG. 3 is a schematic front view showing an example of a urinal in the rim according to the present invention.

FIG. 4 is a schematic front view showing an example of a spreader type urinal according to the present invention. FIG. 5 is a schematic front view showing an example of a urinal of another embodiment according to the present invention.

[Specific description of the invention]

Flush toilet

The flush toilet of the present invention has at least a toilet bowl surface and a spout, and includes both toilets and urinals.

In the present invention, the toilet bowl surface is a surface of a flush toilet that is configured to discharge excrement from a user and to supply washing water for cleaning and removing the excrement. It is common to have a concave surface extending in the vertical direction, and a toilet bowl is generally formed in a bowl shape with an open top. In the present invention, the spout is a hole for discharging the washing water to the toilet bowl surface, and its shape can take various configurations depending on the spouting method. Here, as an example of the water discharge method, in the case of a toilet bowl, the water flow method inside the rim, the open rim method, the spray For urinals, there are a spreader method and a water flow method in the rim (slanting method).

In the flush toilet of the present invention, a water-repellent film and / or a water-slidable film is formed at the spout to prevent water from remaining on the surface of the film, and to supply water to the toilet bowl surface after washing. To prevent By adopting such a configuration, it is possible to effectively prevent the adhesion of the scale over a long period of time. Although the reason is not clear, the above configuration effectively prevents water from staying or dripping for a long time at the same position on the toilet bowl surface below the spout after washing with water. It is thought that the adhesion of ash can be effectively prevented.

The inventor carefully observed the toilet bowl surface after using the flush toilet without the water-repellent film and the Z or water-slippery film at the water outlet for a long time. As a result, a scale film was observed near the lower part of the spout, and it was found that the formation of the scale resulted in dirt on the toilet. The occurrence of scale under the water outlet was eliminated as a result of preventing water from remaining or dripping for a long time at the same position on the toilet bowl surface below the water outlet after washing. Wash water contains minerals such as Si ₂ and CaO, which are mineral components that form scale, but in the toilet bowl according to the present invention, the toilet bowl surface of the water that supplies this component Supply is cut off immediately after washing. In other words, the washing water does not stay in the place or be supplied for a long time after the washing. As a result, it is considered that the formation of the scale film was effectively prevented. Furthermore, even if a scale film is generated for any reason, in the toilet according to the present invention, since the supply of water to the toilet bowl surface is stopped immediately after washing, mold and the like propagate in the scale film and become dirty. It is thought that connection can be effectively prevented.

The flush toilet according to a preferred embodiment of the present invention further includes a rim water passage. In the present invention, the rim water passage is formed so that water can flow through the outer edge of the toilet bowl surface, and preferably, a water outlet is formed in the rim water passage. The water outlet is not limited to the one formed in the rim water passage, but may be a method of discharging the washing water through an injection nozzle.

Fig. 1 shows a schematic cross-sectional view of an example of a rim flush toilet. A toilet bowl 10 shown in FIG. 1 has a toilet bowl surface 12 formed in a bowl shape with an open top, and a toilet bowl surface outside the toilet bowl surface. The rim has a rim water passage 14 formed so as to allow water to flow therethrough, and a plurality of water outlets 16. A plurality of water outlets 16 are formed in the rim water passage 14 at a predetermined distance from each other. As a result, the washing water sent from the water pipe (not shown) into the rim water passage 14 is discharged from the water discharge port 16 to the toilet bowl surface 12 to wash the toilet bowl surface 12 over the entire surface.

Fig. 2 shows a schematic sectional view of an example of an open rim type toilet. The toilet bowl 20 shown in FIG. 2 has a toilet bowl surface 22 formed in a bowl shape with an open upper part, and an open bowl formed by being folded inside the toilet bowl at an outer edge of the toilet bowl surface. It has a rim 24 and a plurality of water outlets 26. A water outlet 26 communicates with a water supply pipe (not shown) through a water supply chamber 28, and at least an outlet is provided at the upper part on the back side of the toilet so as to discharge water toward the left and right inner walls of the open rim. Are provided. As a result, the washing water sent from the water supply pipe is discharged from the water outlet 26 to the toilet bowl surface 22 via the open rim 24, and the entire toilet bowl surface 22 is washed.

Fig. 3 shows a schematic front view of an example of a urinal with a water flow system inside the rim (didting system). The urinal 30 shown in FIG. 3 has a toilet bowl surface 32 having a concave surface extending vertically, and a rim water passage 3 formed so as to allow water to flow through an upper outer edge of the toilet bowl surface. 4 and a plurality of water outlets 36. A plurality of water outlets 36 are formed in the rim water passage 34 at a predetermined distance from each other and along the toilet bowl surface 32. As a result, the washing water sent from the water pipe (not shown) into the rim water passage 34 is discharged from the water outlet 36 along the toilet bowl surface 32, and the entire toilet bowl surface 32 is washed.

Fig. 4 shows a schematic front view of an example of a spreader type urinal. The urinal 40 shown in FIG. 4 has a toilet bowl surface 42 having a concave surface extending vertically and a water outlet 44. The spout 44 is made of a resin-made spout (spreader nozzle) having an injection port along the stool surface, and is provided near the upper end of the stool surface. As a result, the flush water is spouted from the spout 44 in various directions along the toilet bowl surface 42 to wash the toilet bowl surface 42 over the entire surface.

FIG. 5 shows a urinal of another embodiment. The urinal 50 shown in FIG. 5 includes a toilet bowl surface 52 having a concave surface extending vertically and a water outlet 5 provided in a convex shape above the toilet bowl surface and expanding downward. 4 is provided. As a result, flush water is discharged from the spout 54 The toilet bowl surface 52 is flushed downward along the toilet bowl surface 52 to wash the entire toilet bowl surface 52.

The water discharge port in the present invention means, for example, in a sprayer system, a discharge port of a spreader nozzle and an inside of a hole. In the case of the rim flow type, it means the inside of the spout and hole formed inside the rim. In the open rim type toilet, the spout means the opening that supplies water to the toilet bowl surface.

According to a preferred embodiment of the present invention, in a flush toilet having a rim water passage, it is preferable to further form a water-repellent film and a Z or water-slidable film on the inner wall surface of the rim water passage. Thus, in a flush toilet having a rim water passage, the supply of residual water to the toilet bowl surface can be more reliably prevented, and the adhesion of water scale can be more effectively prevented.

According to another aspect of the present invention, it is preferable that a water-repellent film and a Z- or water-slidable film be formed on the inner wall surface of the rim water passage regardless of whether or not a film is formed on the water outlet.

According to a preferred embodiment of the present invention, a water-repellent film and a Z or water-slidable film are further formed on the toilet bowl surface immediately below the water outlet. Thereby, the supply of the residual water to the toilet bowl surface can be more reliably prevented, and the adhesion of the scale can be more effectively prevented. According to a preferred embodiment of the present invention, it is preferable that the toilet bowl surface immediately below the spout comprises at least a region within 2 cm from the lower end of the spout, more preferably 1.5 cm. At least a region within 1 cm. As a result, the work area can be reduced by minimizing the coating area and productivity can be improved. Furthermore, it is possible to sufficiently prevent the adhesion of scale, without the user noticing the location where the film is formed.

The water-repellent film in the present invention has a contact angle with water (hereinafter, referred to as a water contact angle) measured with a contact angle measuring device of 90 degrees or more, preferably 110 degrees or more, more preferably Refers to a coating that is at least 140 degrees. Preferred examples of the water-repellent film in the present invention include a silicone-containing film, a film containing a fluororesin and a fluorine-containing or fluorine-containing compound, and a film containing silicone and a fluorine-containing resin and a fluorine-containing or a fluorine-containing compound. . Here, as the contact angle measuring device, Kyowa Interface Science, C A—XI 50 and the like are preferably usable.

The water-slidable film in the present invention refers to a film having a sliding angle of 10 ° or less, preferably 5 ° or less, more preferably 1 ° or less in terms of a falling angle of a water droplet of 50 mm ³ . According to a preferred embodiment of the present invention, the coating film has a falling angle of 20 degrees or less, more preferably 10 degrees or less, and still more preferably 5 degrees or less in terms of a falling angle of a water droplet of 20 mm ³ .

Here, the falling angle refers to the angle at which the water droplets begin to slide on the test piece when the predetermined volume of the water drop is placed on the test piece and the plate test piece is gradually inclined.

Preferred examples of the water-slidable film in the present invention include a silicone-containing film, a film containing a fluorine resin and a Z or fluorine compound, a film containing a silicone and a fluorine resin and a Z or fluorine compound, ceria and a Z or a fluorine compound. An example is a yttria-containing coating. More specific examples of the water-slidable coating include a coating in which a fluorine-based polymer and a silicon-based resin are grafted and a hydrophilic atomic group is bonded to form a nano-layer separation structure, and a cross-linking with a hydroxyl-containing siloxane polymer. A coating composed of an agent or a coating formed by modifying the surface of a coating formed by a sol-gel method with a silane derivative having a CH 3 — group and one CF 3 group.

The silicone-containing coating in the present invention is a coating obtained by curing a silicone in which one or more organic groups are bonded to a germ atom in the silicone. Specifically, such a silicone has an average compositional formula of Rp S i XqO (4-p-q) / 2

(Wherein, R is a monovalent organic group having 1 to 18 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, and p and Q are 0 <p <2, 0 <Q <4, 0 <p + Q <4).

The silicone described above is a bifunctional silane derivative monomer (a monomer that has two hydrolyzable groups per molecule and forms a bifunctional siloxane bond in which two oxygen atoms are bonded to each silicon atom) and Z or trifunctional A silane derivative monomer (a monomer that has three hydrolyzable groups per molecule and forms a trifunctional siloxane bond with three oxygen atoms bonded to each silicon atom) as an essential component, as required A composition containing a tetrafunctional silane derivative monomer (a monomer that has four hydrolyzable groups per molecule and forms a four-functional siloxane bond in which four oxygen atoms are bonded to each silicon atom) It is obtained by decomposition and condensation polymerization. Preferred examples of the bifunctional silane derivative include dimethyldimethoxysilane, dimethylethylethoxysilane, diphenyldimethoxysilane, diphenyljetoxirane, phenylmethyldimethoxysilane, phenylmethylethoxysilane, and aglycid. Xypropylmethyldimethoxysilane, aglycidoxypropylmethyljetoxysilane, a (meth) acryloxypropylmethyldimethoxysilane, a (meth) acryloxypropylmethyljetoxysilane, aaminopropyl Methyldimethoxysilane, araminopropylmethylethoxysilane, heptadecafluorooctylmethyldimethoxysilane, heptadecafluoromethylmethylethoxysilane, trifluoropropylmethyldichlorosilane, etc. I can do it.

Preferred examples of the trifunctional silane derivative include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltriisopropoxy. Silane, ethyltri-butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n_propyltri Isopropoxysilane, n_propyltri-t-butoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltributoxysilane, n-de Rutrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane, n-year-old kutadecyltrimethoxysilane, n-octane-decyltriethoxysilane, n-year-old kuta Decyltriisopropoxysilane, n-butadecyltri-t-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, glycidoxypropyltrimethoxysilane, Adalicidoxypropyltriethoxysilane, arglicidoxypropyltriisopropoxysilane, adalicidoxypropyltri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β— (3, 4_epoch Shishikuro hexyl) Echirutorietoki , Β- (3,4-epoxycyclohexyl) ethyltriisopropoxy β- (3,4-epoxycyclohexyl) ethyltri-butoxysilane, α (meth) acryloxypropyltrimethoxysilane, Ryoichi (meth) acryloxypropyltriethoxysilane, er (meth) acryloxypropyl triisopropoxysilane, ryichi (meth) acryloxypropyl trit-butoxysilane, araminoprovir Trimethoxysilane, aminopropyltriethoxysilane, aminopropyltriisopropoxysilane, τaminopropyltri-t-butoxysilane, aminocaptopropyltrimethoxysilane, aminocaptopropyltriethoxysilane, alpha Mercaptopropyltriisopropoxysilane, amercap Propyl tri-t-butoxysilane, trifluoroprop-mouth bil trimethoxysilane, trifluoropropyl triethoxy silane, trifluoro propyl triisopropoxy silane, trifluoro propyl tri-t-butoxy silane, heptadecafluoro octyl tri Examples include methoxysilane, heptadecafluorooctyltriethoxysilane, heptadecafluorooctyltriisopropoxysilane, and heptadecafluorooctyltri-t-butoxysilane.

Preferred examples of the tetrafunctional silane derivative include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-t-butoxysilane, dimethoxyethoxyethoxysilane, and the like.

Preferred examples of the fluororesin used for the fluororesin-containing coating in the present invention include polyvinyl fluoride, polyvinylidene fluoride, polystyrene trifluoride, polytetrafluoroethylene, polytetrafluoroethylene, and hexafluoropropylene hexafluoride. Copolymer, ethylene-polytetrafluoroethylene copolymer, ethylene-polychlorinated trifluorene ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether cobolomer, perfluorocyclopolymer, vinyl ether-fluorene Refin copolymers, vinyl ester-fluorofluorin copolymers and the like. Preferred examples of the fluorine compound used in the fluorine compound-containing coating film of the present invention include lithium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, scandium fluoride, yttrium fluoride, and yttrium fluoride. Zirconium fluoride, hafnium fluoride, manganese fluoride, iron fluoride, cobalt fluoride, nickel fluoride, copper fluoride, aluminum fluoride, gallium fluoride, indium fluoride, bismuth fluoride, lanthanum fluoride, fluorine Cerium fluoride, brasedium fluoride, neodymium fluoride, samarium fluoride, europium fluoride, terbium fluoride, dysprosium fluoride, holmium fluoride, erbium fluoride, thulium fluoride, ytterbium fluoride, lutetium fluoride, etc. Can be As the silicone, fluorine resin, and fluorine compound used in the coating containing the silicone and the fluorine resin and the fluorine or fluorine compound in the present invention, those similar to the above can be suitably used. In particular, when the weight of the fluorine resin and the fluorine compound is at least 40% based on the total weight of the silicone and the fluorine resin and the fluorine compound, the contact angle with water is 150 ° or more, which is preferable because of exhibiting super water repellency. No.

The coating containing ceria and Z or yttria according to the present invention exhibits hydrophilicity immediately after the formation of the coating, but exhibits water repellency when left for a while. Therefore, the residual water hardly stays on the toilet bowl surface, and the scale is hardly adhered to the toilet bowl.

According to a preferred embodiment of the present invention, the water-repellent film and / or the water-slidable film can further contain an antibacterial agent. Preferred examples of the antibacterial agent include antibacterial metals such as silver, copper and zinc and fine particles of the compound or a carrier supported on a carrier such as silica gel zeolite, a quaternary ammonium salt, a nitrile derivative, an imidazole derivative, and a benzothiazole. Derivatives, isothiazole derivatives, thiazithiazole derivatives, triazine derivatives, sulfone derivatives, phenol derivatives, phenol ester derivatives, pyrrole derivatives and the like.

When an antimicrobial agent is used in combination with a water-repellent or water-slip coating, water repellency or water-slidability makes it difficult for water droplets to remain, and bacteria cannot grow in places without water. The effect can be expected.

According to a preferred aspect of the present invention, the water-repellent coating and the water-sliding coating are not formed on the toilet bowl surface except for the toilet bowl surface immediately below the water outlet. As a result, it is possible to reduce the work load by minimizing the film formation and improve productivity, Adhesion of scale can be sufficiently prevented. Further, the antifouling property of the toilet bowl itself can be further improved without impairing the antifouling function originally possessed.

According to a more preferred aspect of the present invention, the contact angle of water on the toilet bowl surface where the water-repellent film and the water-slidable film are not formed is less than 30 degrees over substantially the entire surface. Yes, more preferably less than 20 degrees, and even more preferably less than 10 degrees. Accordingly, it is possible to semipermanently and effectively prevent the attachment of oily dirt such as stool to the toilet bowl surface and the attachment and growth of fungi. Further, in combination with the prevention of the supply of residual water by the water repellent film and the water-slidable film, the adhesion of scale can be more effectively prevented.

According to a more preferred embodiment of the present invention, the center line average roughness Ra of the non-coating-formed portion measured by a stylus type surface roughness measuring device based on JIS-B0651 (1996) is 0. It is less than 07 m, more preferably less than 0.05 m. This makes it possible to semipermanently and effectively prevent the adhesion of dirt on the toilet bowl surface and the adhesion and growth of fungi. Further, in combination with the prevention of the supply of residual water by the water repellent coating and the water-sliding coating, it is possible to more effectively prevent the adhesion of scale.

Here, in the present invention, “surface roughness (Ra)” means that a portion having a measurement length of 1 is extracted from a roughness curve in the direction of the center line, and the center line of the extracted portion is defined as the X axis and the vertical magnification. When the direction is defined as the Y axis and the roughness curve is represented by Y = f (x), it means the value obtained by the following equation.

In the present invention, the measurement of the surface roughness Ra is carried out by a stylus type surface roughness measuring device conforming to JIS-B 0651 (1996) according to the definition and display according to JIS-B 0601 (1994). Is done. These JIS standards are readily available along with their English translations from Japanese Industrial Standards (4-11-124, Akasaka, Minato-ku, Tokyo, Japan). According to a preferred aspect of the present invention, the surface condition satisfying the water contact angle and Ra is such that a hydrophilic layer substantially composed of a transparent glaze layer is exposed and formed on the outermost surface of the non-film-forming portion. This can be achieved. Specifically, a coloring glaze layer containing an emulsifier such as zircon and a pigment is formed on the surface of the pottery substrate, and a transparent glaze layer is formed on top of the coloring glaze layer. Is covered with transparent glaze.

According to another preferred embodiment of the present invention, the surface condition satisfying the water contact angle and Ra is such that the main component of the glaze raw material used when forming the surface glaze layer on the toilet bowl surface is a non-frit such as frit. This can be achieved by using a crystalline material or by using a fine material having an average particle size of less than 6 ^ m and baking at 110 to 130 ° C after application.

Coating composition-The water-repellent coating and the Z or water-sliding coating according to the present invention are formed by applying a coating composition containing the above-mentioned coating component to a toilet bowl and curing the composition. Can be. As the coating composition, those containing a solvent and a solute, and those containing the components of the water-repellent film and Z or the water-slidable film as the solute can be preferably used. Preferred examples of the solute include a curable silicone, a curable fluororesin, a combination of a curable silicone and a fluororesin, ceria and Z or yttria. Room temperature curable silicones are preferable among the curable silicones, and room temperature curable fluororesins are more preferable among the curable fluororesins, since they can easily form a coating.

The room temperature-curable silicone in the coating composition of the present invention is a silicone in which one or more organic groups are bonded to a silicon atom in the silicone, that is, an average composition formula R p S i X q O (4− p-q) / 2 (wherein, R is a monovalent organic group having 1 to 18 carbon atoms, X is an alkoxy group having 1 to 4 carbon atoms, p and q are 0 <p <2, This is a number that satisfies 0 <q <40 <p <Q + 4) and can be cured at room temperature to form a film.

As the silicone, those similar to those described above for the water-repellent coating and the water-sliding coating are used. Among these silicones, those having r-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) group, tertiary (meth) acryloxy group, etc., have organic crosslinks other than siloxane crosslinks. Possible, room temperature hard It is preferable from the viewpoint of obtaining chemical properties.

According to a preferred embodiment of the present invention, when the room temperature curable silicone is used as a solute, a curing agent can be further added. Thereby, the room temperature curability can be further enhanced. Preferred examples of the curing agent include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, potassium acetate, potassium formate, potassium propionate, tetramethylammonium chloride, Basic compounds such as tetramethylammonium hydroxide; n-hexylamine, triptylamine, diazabicycloundecene, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramamine, tetraethylenebenthamine, ethanolamine , Aminopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, amino (2-aminomethyl) aminopropyltrimethoxysilane, amino (2-aminomethyl) aminopropyl Amine compounds such as tildimethoxysilane; Titanium compounds such as tetraisobutylpyrutitanate and tetrabutyl titanate; aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, etc. Aluminum compounds; Tin compounds such as tin acetylacetonate and dibutyltin octylate; Metal-containing compounds such as cobalt octylate, cobalt acetyl acetonate, iron acetyl acetonate; phosphoric acid, nitric acid, and phthalate Acidic compounds such as acid, P-toluenesulfonic acid, and trichloroacetic acid.

According to a preferred embodiment of the present invention, when the room temperature curable silicone is used as a solute, metal oxide fine particles can be further added. Thereby, the hardness and scratch resistance of the cured film can be improved. Also, the glossiness can be improved by increasing the refractive index. Preferred examples of the metal oxide include silica, alumina, cerium oxide, tin oxide, zirconium oxide, hafnium oxide, antimony oxide, iron oxide, titanium oxide, and rare earth oxide.

In the coating composition of the present invention, a cold-curable fluororesin, a combination of a cold-curable silicone and a fluororesin, and ceria and / or yttria are the same as those described above for the water-repellent film and the water-slidable film. Use Can be.

As the solvent in the coating composition of the present invention, various solvents can be used. In the case where a room temperature curable silicone is used as a solute, a non-aqueous solvent is used to improve the storage stability of the coating composition. It is preferable to use the solvent of Preferred examples of the non-aqueous solvent include alcohols, ketones, esters, toluene, xylene, and hexane.

According to a preferred embodiment of the present invention, the coating composition can further contain an antibacterial agent. As the antibacterial agent that can be added to the coating composition, those similar to those described above for the water-repellent film and the water-slidable film can be used.

Water scale prevention method

The method for preventing scale adhesion of the present invention comprises: forming a water-repellent film and a water-repellent film at a water discharge port of a flush toilet to prevent water from remaining on the film surface; To prevent the supply of residual water to the water. As a result, as a result of the above-described operation of the flush toilet, it is possible to effectively prevent water stains from adhering to the toilet bowl surface for a long time.

According to a preferred aspect of the present invention, in a flush toilet having a rim water passage, a water-repellent coating and a Z or water-slippery coating are further formed on the inner wall surface of the rim water passage, whereby the surface of the coating is formed. And the supply of residual water to the toilet bowl surface is prevented. This makes it possible to more reliably prevent the residual water from being supplied to the toilet bowl surface and more effectively prevent the adhesion of water scale in the rim flush type flush toilet.

According to another aspect of the present invention, it is preferable that a water-repellent film and a Z or water-slidable film be formed on the inner wall surface of the rim water passage regardless of whether or not a film is formed on the water outlet.

According to a preferred embodiment of the present invention, a water-repellent film and a Z or water-slidable film are further formed on the toilet bowl surface immediately below the water outlet. Thereby, the supply of the residual water to the toilet bowl surface can be more reliably prevented, and the adhesion of the scale can be more effectively prevented.

According to a preferred embodiment of the present invention, formation of a water-repellent film and / or a water-slidable film The coating can be performed by applying the coating composition described above and then curing the coating composition. This makes it possible to very easily perform the scale prevention treatment.

According to a more preferred embodiment of the present invention, the coating composition is applied to the toilet bowl surface immediately below the water outlet by impregnating the fabric with the coating composition, and the impregnated fabric is placed immediately below the water outlet. This is done by contacting the toilet bowl surface. This makes it possible to very easily perform the scale prevention treatment, and is particularly effective when performing on-site maintenance. In the case of a flush toilet with a coating formed by such a coating method, the supply of residual water can be performed within a short time of 1 minute or less, for example, in the case of the CS87 type (manufactured by TOTO Kiki Co., Ltd.). (It takes about 15 minutes to stop the supply of residual water in a CS87-type flush toilet that does not perform the scale prevention treatment of the present invention).

According to a more preferred embodiment of the present invention, the coating of the coating composition at the water outlet is impregnated with a coating material in a rod-like material that can be inserted into the water outlet, and the impregnated rod-like material is brought into contact with the water outlet. It is done by doing. This makes it very easy to apply the anti-scalding treatment, which is especially effective for on-site maintenance. In the case of a flush toilet with a coating formed by such a coating method, the supply of residual water can be performed within a short time of 1 minute, for example, in the case of the CS87 type (manufactured by TOTO Kiki Co., Ltd.). It can be stopped (it takes about 15 minutes to stop the supply of residual water in a CS87 type flush toilet that does not perform the anti-scaling treatment of the present invention).

According to a more preferred embodiment of the present invention, the application of the coating composition on the inner wall surface of at least the rim water passage, after the flushing toilet upside down, re through ^spout: The coating composition in arm water passage It can be done by pouring and dipping. This makes it possible to very easily perform the scale prevention treatment on the inner wall surface of the rim water passage. In the case of a flush toilet with a coating formed by such a coating method, for example, in the case of the CS87 type (manufactured by TOTO Kiki Co., Ltd.), the supply of residual water can be performed within an extremely short time of 15 seconds. (In the case of the CS 87 type flush toilet which is not subjected to the scale prevention process of the present invention, it takes 15 Takes about a minute).

Various methods can be adopted for injecting the coating composition into the rim water channel through the water outlet, for example, by inserting an injection device such as a syringe or a spray into the water outlet, and directly injecting the coating composition. May be. Alternatively, the toilet may be held upside down, and the tube may be inserted into the spout, and then injected directly into the rim water passage using an injection means such as a pump. In this case, the excess coating composition can be easily collected by a suction process such as reverse rotation of the pump. Further, by masking the inside of the stool bowl, the coating composition can be passed through the rim water passage without blocking the water outlet.

Hereinafter, an example of a method of preventing scale adhesion when each of the above-described coating compositions is used will be specifically described.

The production of a flush toilet in which the water-repellent coating and the water- or water-sliding coating of the present invention are silicone-containing coatings can be performed, for example, as follows. First, a glaze is applied to a toilet molding substrate manufactured by built-in molding and fired at a temperature of 110 ° C or more. The above silicone-containing paint is applied to the water outlet of the resulting toilet bowl, immediately below the water outlet, and on the inner wall surface of the no or rim water passage. Then, the silicone is cured.

When applying to the spout and Z or just below the spout, mask the area that is not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as a method of applying. As a method of applying the paint in the rim, a method of flowing the above-mentioned silicone-containing paint into the rim, spraying the paint into the rim, or the like can be used.

For curing the silicone, well-known methods such as standing at room temperature, heating, and ultraviolet irradiation can be used.

The production of a flush toilet in which the water-repellent coating and the water- or water-sliding coating of the present invention are coatings containing a fluororesin can be carried out, for example, as follows. First, a glaze is applied to the base of the toilet bowl formed by the injection molding and fired at a temperature of 110 ° C or higher. The coating composition containing the fluororesin is applied to the water outlet of the resulting toilet bowl, immediately below the water outlet, and on the inner wall surface of the Z or rim water passage. And The fluororesin is cured.

When applying to the spout and / or immediately below the spout, mask the area that is not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as a method of applying. Further, as a method of applying the paint in the rim, a method of flowing the paint containing the fluororesin into the rim, spraying the paint into the rim, or the like can be used.

Well-known methods such as standing at room temperature, heating, and UV irradiation can be used for curing the fluororesin.

The production of a flush toilet in which the water-repellent coating and the Z or water-sliding coating of the present invention are coatings containing a fluorine compound can be carried out, for example, as follows. First, a glaze is applied to the toilet body made by casting and fired at a temperature of 110 ° C or more. The paint containing the above-mentioned fluorine compound is applied to the water outlet of the resulting toilet bowl, immediately below the water outlet, and on the inner wall surface of the Z or rim water passage. Then, the coating composition is cured as a film.

When applying to the water spout and the nozzle or just below the water spout, mask the area not to be applied as necessary. Well-known methods such as spray coating, brush coating, sponge coating, flow coating, and bar coating can be used as a coating method. In addition, as a method of applying the paint inside the rim, a method of flowing the paint containing the fluororesin into the rim, spraying the paint into the rim, or the like can be used.

The production of a flush toilet in which the water-repellent coating and / or the water-sliding coating of the present invention is a coating containing silicone and a fluororesin can be carried out, for example, as follows. First, a glaze is applied to a toilet body formed by casting and fired at a temperature of 110 ° C or higher. The coating composition containing the silicone and the fluororesin is applied to the water outlet of the resulting toilet bowl, immediately below the water outlet, and / or on the inner wall surface of the rim water passage. Then, the silicone is cured.

When applying to the spout and Z or just below the spout, mask the area that is not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as a method of applying. In addition, as a method of applying the inside of the rim, the paint containing the fluororesin is flowed into the rim. For example, a method such as spraying a paint can be used.

The water-repellent coating and the water-sliding coating of the present invention, which are coatings containing silicone and a fluorine compound, can be produced, for example, as follows. First, a glaze is applied to a toilet body formed by casting and fired at a temperature of 110 ° C or higher. Curing the silicone after applying the coating composition containing the silicone and the fluorine compound to the water outlet of the resulting toilet bowl, immediately below the water outlet, and on the inner wall surface of the Z or rim water passage. by.

When applying to the spout and Z or just below the spout, mask the area that is not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as a method of applying. Further, as a method of applying the paint in the rim, a method of flowing the paint containing the fluororesin into the rim, spraying the paint into the rim, or the like can be used.

Well-known methods such as standing at room temperature, heating, and UV irradiation can be used to cure silicone.

The production of a flush toilet in which the water-repellent coating and / or the water-sliding coating of the present invention is a coating containing seria and / or yttria can be carried out, for example, as follows. First, a glaze is applied to a toilet body formed by casting and fired at a temperature of 110 ° C or more. The paint containing the cerium and / or yttrium alkoxide is applied to the water outlet of the obtained toilet, directly below the water outlet, and / or to the inner wall surface of the rim water passage. Then, it is fired at a temperature of 300 to 700 degrees.

When applying to the spout and Z or just below the spout, mask the area that is not to be applied as necessary. As a method of applying, well-known methods such as spray coating, brush coating, sponge coating, flow coating, bar coating and the like can be used. In addition, as a method of applying the paint inside the rim, a method of flowing the paint containing the fluororesin into the rim, spraying the paint into the rim, or the like can be used.

According to a preferred aspect of the present invention, a portion where a water-repellent film and a water-slidable film are not formed A transparent glaze layer is formed almost all over the minute. This makes it possible to semipermanently and effectively prevent the attachment of dirt to the toilet bowl surface and the attachment and growth of fungi. In addition, the water repellent film and the water-slidable film prevent the residual water from being supplied, so that the adhesion of water scale can be more effectively prevented.

According to a preferred embodiment of the present invention, a cloth for applying the coating composition on the toilet bowl surface immediately below the water outlet is combined with the above-described coating composition to form a set for performing a method for preventing scale adhesion. Can be provided. By using this set, it is possible to easily perform on-site maintenance treatment for preventing scale from adhering to a flush toilet.

According to a preferred aspect of the present invention, there is provided a set for performing a method for preventing scale adhesion by combining a rod-shaped material for applying a coating composition at a water outlet and the above-described coating composition. Can be. By using this set, it is possible to easily perform on-site maintenance processing for preventing scale adhesion in flush toilets.

[Examples] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example A

In Example A, the evaluation method of the flush toilet was as follows.

Test A1: Measurement of water contact angle

Droplets of distilled water were dropped on the surface of the plate-shaped test piece from the micro syringe. Thirty seconds after the dropping, the contact angle between the surface of the plate-shaped test piece and water was measured using a contact angle measuring device (CA-X150, manufactured by Kyowa Interface Science).

Test A2: Water fall angle measurement

Topped with 5 0 water droplets mm ³ or 2 0 mm ³ in piece plate test was inclined plate specimen gradually. The angle at which the water droplet began to slide on the specimen was measured.

Test A3: Observation of water droplet adhesion The state of water droplets adhering to the outlet of the toilet sample and its surroundings was checked by visual observation of the state of water flow and the remaining state of water droplets when the flash valve was opened and closed.

Test A4: Observation of scale adhesion

After leaving for 30 days under normal use conditions (average number of uses: 20 times a day for urinals, average number of uses: 10 times Z days for toilets), spitting of toilet sample The scale of the water port and its surroundings was observed as follows. Healthtech dental plaque dyeing jewel "DENTCLUB" was diluted with distilled water. Here, if this plaque-stained jewel is used, the portion with a large amount of scale is dyed strongly red, and the portion without the scale is not colored. Therefore, it is possible to visually evaluate the amount of scale attached. Next, the diluted solution obtained was sprayed on the spout and its surroundings, and the amount of scale attached was evaluated based on the intensity of the red color.

Example A 1

As a sample, a stall urinal (manufactured by Tohoku Kikai, U307C, pottery color: pastel ivory (# SC1)) was prepared. A 70 × 150 mm plate-shaped test piece prepared by firing from the same base and glaze as the urinal was prepared. Spray coating of JSR glass power B603 was applied to the area around the water discharge port provided in the water flow section (slanting area) in the urinal rim and a range of 5 cm directly below the water discharge port. After drying at room temperature for 30 minutes, the mixture was heated and cured at 200 ° C. for 30 minutes to form a silicone-containing coating. In addition, the entire glaze surface of the plate-shaped test piece was spray-coated with glass power B603 made by JSR, and treated in the same manner as a urinal to form a silicone-containing coating. The above tests A 1, A 3 and A 4 were performed on the urinals and test pieces obtained. The results are shown below.

Test A1: The water contact angle was 100 degrees, indicating water repellency.

Test A3: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water did not flow in a belt shape but dropped after falling into a water droplet. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered.

Test A4: Sprayed plaque stained jewel, but the spout and immediately below it stain red. In addition, it was possible to confirm the prevention of scale adhesion.

Example A 2

A urinal and a plate-like test piece similar to those in Example A1 were prepared. A coating liquid was obtained by mixing PTF (Tefylene tetrafluoride) powder Lubron L-12 manufactured by Daikin Industries and glass power B603 manufactured by JSR so that the weight ratio of the solid content was 7: 3. The above coating solution was spray-coated on the area around the water outlet provided in the stagnant part of the urinal and within 5 cm immediately below the spout. After drying at room temperature for 30 minutes, it was heated and cured at 200 for 30 minutes to form a film containing a fluororesin and silicone. The coating liquid was spray-coated on the entire glaze surface of the plate-shaped test piece, and the same treatment as that of a urinal was performed to form a film containing a fluororesin and silicone. The above-mentioned tests A1, A3, and A4 were performed on the obtained urinals and test pieces. The results are shown below.

Test A1: The water contact angle was 150 °, indicating super water repellency.

Test A4: Spraying the plaque stained jewel did not stain the spout and the area immediately below the spout, confirming the prevention of the adhesion of plaque.

Comparative Example A 1

The same urinal and plate-like test piece as in Example A1 were prepared, and the above-mentioned tests Al, A3 and A4 were performed. The results are shown below.

Test A1: The water contact angle was 30 degrees, indicating hydrophilicity.

Test A3: A small amount of water continued to flow for 3 minutes after closing the flash valve, and many large water droplets remained on the water path.

Test A4: The flow path of the water flow was dyed red at the water discharge part and the lower part, and it was found that scale was attached.

Example A 3

As a sample, Western-style toilet (made by Tohoku Kikai, CS971B, pottery color: pastel Ivory (# SC1)) was prepared. A 70 × 150 mm plate specimen was prepared by firing from the same base and glaze as the toilet. The area around the spout provided on the rim of the toilet and within 5 cm immediately below the spout was spray-coated with JSR glass power B603. After drying at room temperature for 30 minutes, the mixture was heated and cured at 200 ° C. for 30 minutes to form a silicone-containing coating. Also, the entire glaze surface of the plate-shaped test piece was spray-coated with JSR glass power B603, and treated in the same manner as a toilet bowl to form a silicone-containing coating. The above tests A1, A3, and A4 were performed on the obtained toilet bowl and test pieces. The results are shown below. Test A1: The water contact angle was 100 degrees, indicating water repellency.

Test A3: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water did not flow in a belt shape but dropped after falling into a water droplet. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered. In addition, since the water outlet was coated with a water repellent material, the drainage was good, and it was confirmed after 30 minutes that the supply of residual water was stopped and no adhesion of water was confirmed.

Example A 4

A toilet bowl and a plate-shaped test piece similar to those in Example A3 were prepared. A coating liquid was obtained by mixing PTFE (rubber tetrafluoroethylene) Lubron L-2 manufactured by Daikin Industries and glass strength B603 manufactured by JSR so that the weight ratio of the solid content was 7: 3. After closing the hole in the rim of the toilet bowl, the coating liquid was passed through the rim. Furthermore, the coating liquid was spray-coated on the area around the spout provided on the rim and within 5 cm immediately below the spout. After drying at room temperature for 30 minutes, the film was heated and cured at 200 ° C. for 30 minutes to form a film containing a fluororesin and silicone. In addition, the coating liquid was spray-coated on the entire glaze surface of the plate-shaped test piece, and the same treatment as that of a toilet bowl was performed to form a film containing a fluororesin and silicone. The above tests A1, A3 and A4 were performed on the obtained toilet bowl and test pieces. The results are shown below. Test Al: The water contact angle was 150 °, indicating super water repellency.

Test A3: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water did not flow in a belt shape but dropped after falling into a water droplet. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered. In addition, since the rim was coated with a water-repellent material, the remaining water in the rim drained well, and after 30 minutes it was confirmed that the supply of the remaining water was stopped and no water adhesion was confirmed.

Example A 5

A toilet bowl and a plate-shaped test piece similar to those in Example A3 were prepared. After closing the hole in the rim part of the toilet bowl, pass the Shinko Giken S AT-215 C solution into the rim and at room temperature.

After drying for 30 minutes, the film was heated at 140 ° C. for 15 minutes to form a film. In addition, Shin-Etsu Silicone X—2

4-9 4 16 was spray coated and dried at room temperature for 2 days to form a coating. In addition, one of the plate-shaped test pieces is made of a water-repellent material (SAT-215C), and the other piece of the plate-shaped test piece is made of a water-repellent material (X-224-94). ) Was separately spray-coated on the entire glaze surface and treated in the same manner as a toilet bowl to form a coating. The above tests A1 to A4 were performed on the obtained toilet bowl and test pieces. The results are shown below. Test A1: The contact angle of the test piece coated with the water repellent material with water was measured and found to be 110 °, indicating water repellency.

Test A 2: For water slip material, with the coated test piece, when the sliding angle of water with water drops were at 5 0 mm ³ measured was 7 degrees, the use of the 2 0 mm ³ water drops 1 It was 8 degrees and showed slipperiness.

Test A3: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water did not flow in a belt shape but dropped after falling into a water droplet. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered. Also, because the rim is coated with water-slippery material, the remaining water in the rim drains well, and after 30 minutes it was confirmed that the supply of residual water was stopped. No adhesion of water was confirmed.

Comparative Example A 2

The same toilet bowl and plate-shaped test piece as in Example A3 were prepared, and the above tests A1, A3, and A4 were performed. The results are shown below.

Test A1: The water contact angle was 30 degrees, indicating hydrophilicity.

Test A 2: If using 5 0 mm ³ of water droplets was measured sliding angle of water is 2 0 degrees, when using the 2 0 mm ³ water droplets was 3 9 degrees.

Test A3: It was confirmed that a small amount of water continued to flow in the same place for about one and a half hours until the residual water in the rim disappeared even after the flash valve was closed.

Example B

In Example B, the evaluation method of the flush toilet was as follows.

Test B1: Water contact angle measurement

Test B2: Observation of water droplet adhesion

The state of water droplets adhering to the outlet of the toilet sample and its surroundings was checked by visual observation of the state of water flow and the remaining state of water droplets when the flash valve was opened and closed.

Test B 3: Observation of scale adhesion

The remote control toilet cleaning unit TES 90 was attached to the mouth tank. The remote control transmitter was connected to a timer, and the water was flushed into the toilet once every 1 Ί to force the scale to adhere. Once every two days, the back of the rim was rubbed with a soft sponge to keep the surface clean. After standing for 10 days, a solution prepared by diluting methylene blue with distilled water was sprayed, and the amount of scale attached was evaluated based on the intensity of the blue color. Example B 1

\ A Western style toilet (Toseki Kiki, CS87, pottery color: pastel eye bottle (# SC1)) was prepared. In addition, a 70 x 150 mm plate specimen prepared by firing from the same base and glaze as the toilet bowl was prepared. GE Toshiba Silicone XC98—B2472 (Fluoroalkylsilane 1% solution; solvent is isopropyl alcohol 7.8 parts with propylene glycol monomethyl) around the water discharge port installed in the rim of the toilet bowl (20 parts of ether were added). It was dried at room temperature for 2 days to form a fluorine-containing film. In addition, the plate-shaped test piece was subjected to Westcoating of XC98-B2472 made by GE Toshiba Silicone on the entire surface of the glaze, and treated in the same manner as a toilet bowl to form a fluorine-containing coating. The above tests B1 to B3 were performed on the obtained toilet bowl and test pieces. The results are shown below.

Test B1: The water contact angle was 105 degrees, indicating water repellency.

Test B2: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water began to drop after falling into a water droplet instead of flowing in a band. In addition, since the water outlet was coated with a water repellent material, the drainage was good, and when checked after 1 minute, the supply of residual water was stopped, and no adhesion of water was confirmed. Test B3: After leaving for 10 days, even if the methylene blue aqueous solution was sprayed, the spout and the area immediately below the spout were not stained blue, confirming the prevention of scale adhesion.

Example B 2

A toilet bowl and a plate-shaped test piece similar to those in Example B1 were prepared. A GE Toshiba Silicone XC98-B2472 was coated with a cotton swab on the inner wall of the water outlet installed on the rim of the toilet bowl. It was dried at room temperature for 2 days to form a fluorine-containing film. The plate-shaped test piece was coated on the entire glaze surface with GE Toshiba Silicone XC98_B2472 with a cotton swab, and treated in the same manner as a toilet bowl to form a fluorine-containing coating. The above tests B1 to B3 were performed on the obtained toilet bowl and test pieces. The results are shown below.

Test B1: The water contact angle was 105 degrees, indicating water repellency.

Test B2: Regarding the state of water droplet adhesion, since the water outlet is water-repellent, the amount of water When the number of water drops, water began to drop after falling into water droplets instead of flowing in a band. In addition, since the water outlet was coated with a water repellent material, the drainage was good, and when checked after 1 minute, the supply of residual water was stopped, and no adhesion of water was confirmed. Test B3: After leaving for 10 days, spraying with an aqueous solution of methylene bull did not stain the spout and immediately below it, confirming the prevention of scale adhesion.

Example B 3

A toilet bowl and a plate-shaped test piece similar to those in Example B1 were prepared. Turn the toilet upside down and dip the GE Toshiba Silicone XC988-B2472 into the inside of the rim, the inner wall of the spout provided on the rim, around the spout, and within 1 cm below the spout. I did. It was dried at room temperature for 2 days to form a fluorine-containing film. The plate-like test piece was dip-coated with GE Toshiba Silicone XC98-B2472 on the entire glaze surface, and treated in the same manner as a toilet bowl to form a fluorine-containing coating. The above tests B1 to B3 were performed on the obtained toilet bowl and test pieces. The results are shown below.

Test B1: The water contact angle was 105 degrees, indicating water repellency.

Test B2: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water began to drop after falling into a water droplet instead of flowing in a band. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered. In addition, since the water outlet was coated with a water repellent material, the drainage was good and the drainage was good. After one minute, it was confirmed that the supply of residual water had stopped and no adhesion of water was confirmed.

Test B3: After leaving for 10 days, even if the methylene blue aqueous solution was sprayed, the spout and the area immediately below the spout were not stained blue, confirming the prevention of scale adhesion.

Comparative Example B 1

A toilet bowl and a plate-like test piece similar to those in Example B1 were prepared, and the above tests B1 to B3 were performed. The results are shown below.

Test B1: The water contact angle was 25 degrees, indicating hydrophilicity.

Test B2: It was confirmed that a small amount of water continued to flow in the same place for about 15 minutes until the residual water in the rim disappeared even after the flush valve was closed. Test B3: At the outlet and below, the path of the water flow was dyed blue, and it was found that scale was attached.

Example C

In Example C, the evaluation method of the flush toilet was as follows.

Test C1: Water contact angle measurement

Test C2: Measurement of water fall angle

Put the water droplets 50 mm ³ on a piece plate test was gradually inclined plate specimen. The angle at which the water droplet began to slide on the specimen was measured.

Test C3: Observation of water droplet adhesion

Test C4: Observation of scale adhesion

After leaving for 30 days under normal use conditions (average number of uses: 20 times a day for urinals, average number of uses: 10 times Z days for urinals), the spout of the toilet sample and its The surrounding scale was observed as follows. Healthtech dental plaque dyeing jewel "DENTCLUB" was diluted with distilled water. Here, if this plaque-stained jewel is used, the portion with a large amount of scale is dyed strongly red, and the portion without the scale is not colored. Therefore, it is possible to visually evaluate the amount of scale attached. Next, the diluted solution obtained was sprayed on the spout and its surroundings, and the amount of scale attached was evaluated based on the intensity of the red color.

Test C5: Measurement of center line average roughness Ra

The center line surface roughness Ra (JIS-B0601) of the sample surface was measured using a stylus type surface roughness measuring instrument (JIS-B0651).

Test C6: Removal of oily dirt

Φ ΐ θηιηι with black oil-based ink (magic ink # 700) on the sample surface The inside of the sample was filled and dried at room temperature for about 1 minute. Then, 3 ml of water was added dropwise to examine whether the oil-based ink was lifted and whether the oil-based ink was washed away when the sample was tilted.

Example C 1

Table 1 shows the composition of the glaze base material used in this example.

1

Glaze base weight%

S i〇 ₂ 55〜 80

A 12 O 3 5 ~ 13

F e 2 O 3 0 .1 to 0.4

Mg〇 0.8-3.0

C aO 8 ~ 17

Z ηθ 3〜8

K2O 1-4

N a ₂₀ .05 to 2.5

ZrO2 0.:! ~ 15

Pigment :! ~ 20

2 kg of glaze base material, 1 kg of water and 4 kg of sphere were placed in a 6-liter pottery pot and crushed by a ball mill for about 18 hours. When the particle size of the glaze slurry obtained after pulverization was measured using a laser-diffraction particle size distribution analyzer, 65% or less and 50% average particle size (D50) of less than lOm were 6.2 m. Was. This is Glaze A.

Next, the composition shown in Table 1, were prepared transparent glaze substrate excluding the Z R_〇 ₂ and pigments. This transparent glaze substrate was melted at 1300 to 1450 ° C using an electric furnace, and then rapidly cooled in water to obtain a glass frit. This glass frit was ground by a stamp mill. 600 g of the obtained powder, 400 g of water and l kg of alumina balls were placed in a 2 liter pottery pot, and ground by a ball mill for about 18 hours. The particle size of the frit glaze slurry obtained after grinding was measured using a laser diffraction particle size distribution analyzer. 50) was 6. O ^ m. This is called glaze B.

Next, using a sanitary ware body slurry prepared from raw materials such as clay sand, feldspar and clay, a 70 × 150 mm plate-shaped molded product and a toilet bowl molded product were produced. Glaze A was applied on the plate-shaped molded body and the molded toilet bowl by a spray coating method, and then glaze B was spray-coated thereon. The obtained molded body was fired at 110 to 1200 ° C. to obtain a plurality of plate-shaped test pieces and a toilet. At this time, the contact angle with water of the plate-shaped test piece (referred to as plate-shaped test piece C) was 16 °.

Further, a glass coating B603 made by JSR was spray-coated around the water discharge port provided in the rim portion of the toilet bowl and within a range of 5 cm directly below the water discharge port. After drying at room temperature for 30 minutes, the mixture was heated and cured at 200 ° C. for 30 minutes to form a silicone-containing film. Some plate-shaped test pieces (plate-shaped test piece D) were spray-coated with JSR glass power B603 on the entire glaze surface, treated in the same way as a toilet bowl, and contained silicone. A coating was formed. The above tests C1 and C3 to C6 were performed on the obtained toilet bowl and test pieces. The results are shown below.

Test C1: The water contact angle of the obtained plate-shaped test piece D was 100 °, indicating water repellency.

Test C3: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water did not flow in a belt shape but dropped after becoming a water droplet. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered. In addition, since the water outlet was coated with a water repellent material, the drainage was good, and it was confirmed after 30 minutes that the supply of residual water was stopped and no adhesion of water was confirmed.

Test C4: After leaving for 30 days, even if the plaque stained jewel was sprayed, the spout and immediately below the spout did not stain red, confirming the prevention of adhesion of scale.

Test C 5: Center line surface roughness Ra was 0 · 05 m.

Test C6: Approximately 30 seconds after the dropping of the water, the oil-based ink floated on the surface of the water. When the sample was tilted, it was washed away with water, and all the oil-based ink on the surface was lost.

Example C 2

A toilet and a plate-shaped test piece C similar to that in Example C1 were prepared. Daikin Industries P A coating solution was obtained by mixing TFE (tetrafluoroethylene tylene) powder rubron L-2 and JSR glass power B603 so that the weight ratio of the solid content was 7: 3. After closing the hole in the rim of the toilet, the above coating liquid was passed through the rim. Further, the above-mentioned coating solution was spray-coated on the area around the water outlet provided in the rim portion and a range of 5 cm immediately below the water outlet. After drying at room temperature for 30 minutes, the film was heated and cured at 200 at room temperature for 30 minutes to form a film containing a fluororesin and silicone. In addition, the coating liquid was spray-coated on the entire glaze surface of the plate-shaped test piece, and the same treatment as that of a toilet bowl was performed to form a film containing a fluororesin and silicone. The above-mentioned tests Cl, C3 and C4 were performed on the obtained toilet bowl and test pieces. The results are shown below.

Test C1: The water contact angle was 150 degrees, indicating super water repellency.

Test C3: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water did not flow in a belt shape but dropped after becoming a water droplet. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered. In addition, since the inside of the rim was coated with a water-repellent material, the remaining water in the rim drained well, and when checked after 30 minutes, the supply of the remaining water was stopped, and no adhesion of water was confirmed.

Example C 3

A toilet bowl and a plate-shaped test piece C similar to those in Example C3 were prepared. After closing the hole in the rim of the toilet bowl, a SAT-2015C solution manufactured by Shinko Ichigiken was passed through the rim. The toilet was dried at room temperature for 30 minutes, and then heated at 140 for 15 minutes to form a coating. Furthermore, the area around the spout provided on the rim and a range of 5 cm directly under the spout are spray-coated with Shin-Etsu Silicon X-24-94 16 and dried at room temperature for 2 days to form a film. I let it. In addition, a water-repellent material (SAT—215 C) is applied to one of the plate-shaped test pieces, and a water-repellent material (X—24—94-161) is applied to the other sheet of the plate-shaped test piece. Was spray-coated separately on the entire glaze surface and treated in the same way as a toilet bowl to form a coating. The above tests C1 to C4 were performed on the obtained toilet bowl and test pieces. That The results are shown below.

Test C1: The contact angle with water was measured on a test piece coated with a water-repellent material in the same manner as in Comparative Example 2, and it was 110 °, indicating water repellency.

Test C2: The slip angle of water was measured on a test piece coated with a water-sliding material and found to be 7 degrees, indicating a water-sliding property.

Test C3: Regarding the state of water droplet adhesion, the water outlet became water-repellent, so when the amount of water was reduced, the water did not flow in a belt shape but dropped after becoming a water droplet. In addition, the water path immediately below the water outlet was water-repellent, so the path of water was undefined, and no large water droplets adhered. In addition, since the rim was coated with water-slippery material, the remaining water in the rim drained well, and it was confirmed after 30 minutes that the supply of the remaining water was stopped and no adhesion of water was confirmed.

Comparative Example C 1

As a sample, a Western-style toilet (Tosoh Kikki, CS971B, pottery color: pastel ivory (# SC1)) was prepared. A 70 × 150 mm plate specimen was prepared by firing from the same base and glaze as the toilet. The above tests Cl and C3 to C6 were performed on these toilet bowls and test pieces. The results are shown below.

Test C1: The water contact angle was 30 degrees, indicating hydrophilicity.

Test C3: It was confirmed that a small amount of water continued to flow in the same place for about one hour and a half until the residual water in the rim disappeared even after the flash valve was closed.

Test C4: The flow path of the water flow was dyed red at the water outlet and its lower part, and it was found that scale was attached.

Test C5: Center line surface roughness Ra was 0.1 m.

Test C6: The oil-based ink did not float on the water surface and remained on the surface even when the sample was tilted.

Claims

The scope of the claims

1. A toilet bowl surface to which washing water is supplied, and at least a water outlet for discharging the washing water to the toilet bowl surface,

A water-washing type i¾ «ff in which a water-repellent film and / or a water-slidable film is formed on the water outlet.

2. The rim has a rim water passage formed at an outer edge of the toilet bowl surface so that water can pass therethrough, and the water discharge port is formed in the rim water passage,

The flush toilet according to claim 1, wherein a water-repellent coating and a Z or water-sliding coating are further formed on an inner wall surface of the rim water passage.

3. A toilet bowl surface to which washing water is supplied, a water outlet for discharging the washing water to the toilet bowl surface, and at least a rim water passage formed so as to be able to flow to an outer edge of the toilet bowl surface. Become

A flush toilet, wherein a water-repellent coating and a Z or water-sliding coating are formed on an inner wall surface of the rim water passage.

The flush toilet according to any one of claims 1 to 3, wherein a water-repellent coating and Z or a water-slip coating are further formed on a toilet bowl surface immediately below the water outlet.

5. The formation of the water-repellent film and the Z or water-slidable film prevents water from remaining on the surface of the film and prevents water from being supplied to the toilet bowl after washing. Item 7. A flush toilet according to any one of Items 1 to 4.

6. The water-repellent film and / or the water-slidable film are formed so as to prevent water from remaining on the surface of the film and prevent supply of water to the toilet bowl surface after washing. The flush toilet according to any one of to 4.

7. The flush toilet according to any one of claims 1 to 6, wherein the toilet bowl surface immediately below the spout comprises at least an area within 2 cm from a lower end of the spout.

8. The flush toilet according to any one of claims 1 to 7, wherein the water-repellent coating and the water-sliding coating are silicone-containing coatings.

9. The flush toilet according to any one of claims 1 to 7, wherein the water-repellent coating and the water-sliding coating are coatings containing a fluororesin and Z or a fluorinated compound.

10. The flush toilet according to any one of claims 1 to 7, wherein the water-repellent coating and the water-sliding coating are coatings containing silicone, a fluororesin, and Z or a fluorine compound.

1. The flush toilet according to claim 1, wherein the water-repellent coating is a coating containing seria and rhodium or yttria.

12. The flush toilet according to any one of claims 1 to 11, wherein the water-repellent coating and the water-sliding coating further contain an antimicrobial agent.

13. The flush toilet according to any one of claims 1 to 12, wherein a contact angle of water on the surface of the water-repellent coating is 90 degrees or more.

14. The at the surface of the planing coat, sliding angle of 50 mm ³ water droplets is under 10 degrees or, flushing toilet according to any one of claims 1 to 13.

15. The at the surface of the planing coat sliding angle of a water drop of 20 mm ³ are at 20 degrees or, flushing toilet according to any one of claims 1 to 14.

16. The toilet bowl according to any one of claims 1 to 15, wherein a water-repellent coating and a water-sliding coating are not formed on a portion other than the toilet bowl immediately below the water outlet. The flush toilet described.

17. The contact angle of water at a portion of the toilet bowl surface where the water-repellent coating and the water-sliding coating are not formed is less than 30 degrees over substantially the entire surface. A flush-type toilet bowl according to item 1.

18. The center line average roughness Ra of the uncoated portion, measured with a stylus type surface roughness measuring device according to JI SB 0651 (1996), is less than 0.07 m. The flush toilet according to 16 or 17.

19. The flush toilet according to any one of claims 16 to 18, wherein the outermost surface of the uncoated portion is substantially made of a transparent glaze layer.

20. The flush toilet according to any one of claims 1 to 19, wherein the toilet is a toilet.

21. The flush toilet according to any one of claims 1 to 19, wherein the toilet is a urinal.

22. The water-repellent toilet according to any one of claims 1 to 21. A coating composition used to form a coating and a water or water-slidable coating, comprising:

A coating composition for a flush toilet, comprising a solvent and a solute, wherein the solute comprises a curable silicone.

23. A coating composition used for forming a water-repellent coating and a Z or water-sliding coating in the flush toilet according to any one of claims 1 to 21,

A coating composition for a flush toilet, comprising a solvent and a solute, wherein the solute comprises a room temperature curable silicone.

24. The coating composition used to form a water-repellent coating and / or a water-sliding coating in the flush toilet according to any one of claims 1 to 21,

A coating composition for a flush toilet, comprising a solvent and a solute, wherein the solute comprises a curable fluororesin.

25. A coating composition used to form a water-repellent coating and a Z or water-sliding coating in the flush toilet according to any one of claims 1 to 21,

A coating composition for a flush-type toilet, comprising a solvent and a solute, wherein the solute comprises a cold-setting fluororesin.

26. The flushing toilet according to any one of claims 1 to 21, wherein the coating composition is used to form a water-repellent coating and a Z or water-sliding coating.

A coating composition for a flush toilet, comprising a solvent and a solute, wherein the solute comprises a curable silicone and a fluororesin.

27. The coating composition used to form a water-repellent coating and / or a water-sliding coating in the flush toilet according to any one of claims 1 to 21,

A coating composition for a flush toilet, comprising a solvent and a solute, wherein the solute comprises a room temperature curable silicone and a fluororesin.

28. In the flush toilet according to any one of claims 1 to 21, a coating composition used to form a water-repellent coating,

A coating composition for a flush toilet, comprising a solvent and a solute, wherein the solute comprises ceria and / or ittria.

29. The coating composition of any one of claims 22 to 28, further comprising an antimicrobial agent.

30. By forming a water-repellent film and a Z or water-slippery film at the water discharge port of the flush toilet, the water on the surface of the film is prevented from remaining and the supply of the remaining water to the toilet bowl surface is prevented. How to prevent scales on flush toilets.

31. The method according to claim 30, further comprising forming a water-repellent film and / or a water-slidable film on the inner wall surface of the rim water passage of the flush toilet.

32. By forming a water-repellent film and / or a water-slidable film on the inner wall surface of the rim water passage of the flush toilet, water is prevented from remaining on the surface of the film, and water remaining on the toilet bowl surface is prevented. A method of preventing scale from adhering to flush toilets to prevent the supply of water.

33. The scale-adhesion prevention method according to any one of claims 30 to 32, further comprising forming a water-repellent coating and a Z or water-sliding coating on the toilet bowl surface immediately below the water outlet.

34. The formation of the water-repellent film and / or the water-slidable film is performed by applying the coating composition according to any one of claims 22 to 29, and thereafter curing the coating composition. The method for preventing scale adhesion according to any one of claims 30 to 33, wherein the method is performed by the following.

35. The application of the coating composition on the toilet bowl surface immediately below the water outlet impregnates the fabric with the coating composition, and brings the impregnated fabric into contact with the toilet bowl surface immediately below the water outlet. The method of preventing scale adhesion according to claim 34, which is performed by:

36. The application of the coating composition at the water outlet is performed by impregnating the coating composition into a rod that can be inserted into the water outlet, and bringing the impregnated rod into contact with the water outlet. The method for preventing scale adhesion according to claim 34 or 35.

37. At least the coating agent composition on the inner wall surface of the rim water channel The application is performed by injecting and dipping the coating composition into the rim water passage through the water outlet after the flush toilet is turned upside down, The coating composition according to any one of claims 34 to 36, The method for preventing scale from adhering to the item.

38. The scale prevention according to any one of claims 33 to 37, wherein the toilet bowl surface immediately below the water outlet comprises at least an area within 2 cm from the lower end of the water outlet. Method.

39. The scale-adhesion prevention method according to any one of claims 30 to 38, wherein a contact angle of water on the surface of the water-repellent coating is 90 degrees or more.

4 0. The at the surface of the planing coat, 5 0 sliding angle mm ³ of water drops to 1 0 degrees or below, water stain preventing adhesion method according to any one of claims 3 0-3 9.

4 1. The the surface of the planing coat, 2 0 mm ³ of the sliding angle of the water droplet and 2 0 degrees or below, water stain preventing adhesion method according to any one of claims 3 0-4 0.

42. A transparent glaze layer is formed on substantially the entire surface of the toilet bowl surface where the water-repellent film and the water-slidable film are not formed. The method for preventing scale from adhering to the item.

43. The method of preventing scale adhesion according to any one of claims 30 to 42, wherein the toilet is a toilet.

44. The method of preventing water stains according to any one of claims 30 to 42, wherein the toilet is a urinal.

45. A cloth used in the method for preventing scale adhesion according to any one of claims 35 to 44, and a coating composition according to any one of claims 22 to 29. Set for performing the scale prevention method.

46. The rod-shaped material used in the method for preventing scale adhesion according to any one of claims 36 to 45, and the coating composition according to any one of claims 22 to 29. A set for performing a method for preventing scale adhesion.