WO2001044592A1 - Cuvette de toilettes a chasse d'eau dotee d'une fonction antiadhesion du tartre, composition de revetement pour la fonction et procede de prevention de l'adhesion du tartre sur la cuvette de toilettes a chasse - Google Patents

Cuvette de toilettes a chasse d'eau dotee d'une fonction antiadhesion du tartre, composition de revetement pour la fonction et procede de prevention de l'adhesion du tartre sur la cuvette de toilettes a chasse Download PDF

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Publication number
WO2001044592A1
WO2001044592A1 PCT/JP2000/008855 JP0008855W WO0144592A1 WO 2001044592 A1 WO2001044592 A1 WO 2001044592A1 JP 0008855 W JP0008855 W JP 0008855W WO 0144592 A1 WO0144592 A1 WO 0144592A1
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WO
WIPO (PCT)
Prior art keywords
water
coating
toilet
toilet bowl
repellent
Prior art date
Application number
PCT/JP2000/008855
Other languages
English (en)
Japanese (ja)
Inventor
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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toto Ltd. filed Critical Toto Ltd.
Priority to AU18900/01A priority Critical patent/AU1890001A/en
Publication of WO2001044592A1 publication Critical patent/WO2001044592A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D11/00—Other component parts of water-closets, e.g. noise-reducing means in the flushing system, flushing pipes mounted in the bowl, seals for the bowl outlet, devices preventing overflow of the bowl contents; devices forming a water seal in the bowl after flushing, devices eliminating obstructions in the bowl outlet or preventing backflow of water and excrements from the waterpipe
    • E03D11/02—Water-closet bowls ; Bowls with a double odour seal optionally with provisions for a good siphonic action; siphons as part of the bowl

Definitions

  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the flush toilet of the present invention has at least a toilet bowl surface and a spout, and includes both toilets and urinals.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • the washing water does not stay in the place or be supplied for a long time after the washing.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a discharge port of a spreader nozzle In the case of the rim flow type, it means the inside of the spout and hole formed inside the rim.
  • the spout In the open rim type toilet, the spout means the opening that supplies water to the toilet bowl surface.
  • 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.
  • a water-repellent film and a Z or water-slidable film on the inner wall surface of the rim water passage.
  • 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.
  • a water-repellent film and a Z or water-slidable film are further formed on the toilet bowl surface immediately below the water outlet.
  • 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.
  • 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.
  • 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.
  • 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 .
  • 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 .
  • 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.
  • 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.
  • a silicone has an average compositional formula of Rp S i XqO (4-p-q) / 2
  • 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, 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.
  • bifunctional silane derivative examples include dimethyldimethoxysilane, dimethylethylethoxysilane, diphenyldimethoxysilane, diphenyljetoxirane, phenylmethyldimethoxysilane, phenylmethylethoxysilane, and aglycid.
  • Preferred examples of the trifunctional silane derivative include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltriisopropoxy.
  • tetrafunctional silane derivative examples include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-t-butoxysilane, dimethoxyethoxyethoxysilane, and the like.
  • fluororesin used for the fluororesin-containing coating in the present invention include polyvinyl fluoride, polyvinylidene fluoride, polystyrene trifluoride, polytetrafluoroethylene, polytetrafluoroethylene, and hexafluoropropylene hexafluoride.
  • 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.
  • 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.
  • 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.
  • the water-repellent film and / or the water-slidable film can further contain an antibacterial agent.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Y f (x)
  • 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).
  • 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.
  • 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.
  • 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.
  • a non-frit such as frit.
  • 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.
  • a coating composition containing the above-mentioned coating component
  • 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.
  • silicone those similar to those described above for the water-repellent coating and the water-sliding coating are used.
  • those having r-glycidoxypropyl group, ⁇ - (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.
  • a curing agent when the room temperature curable silicone is used as a solute, a curing agent can be further added.
  • 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 Am
  • Aluminum 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.
  • metal oxide fine particles can be further added.
  • the hardness and scratch resistance of the cured film can be improved.
  • the glossiness can be improved by increasing the refractive index.
  • the metal oxide include silica, alumina, cerium oxide, tin oxide, zirconium oxide, hafnium oxide, antimony oxide, iron oxide, titanium oxide, and rare earth oxide.
  • 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.
  • the solvent in the coating composition of the present invention various solvents can be used.
  • 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.
  • the coating composition can further contain an antibacterial agent.
  • an 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.
  • 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.
  • 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.
  • 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.
  • a water-repellent film and a Z or water-slidable film are further formed on the toilet bowl surface immediately below the water outlet.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the excess coating composition can be easily collected by a suction process such as reverse rotation of the pump.
  • the coating composition can be passed through the rim water passage without blocking the water outlet.
  • 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.
  • 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.
  • 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.
  • 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.
  • the paint containing the fluororesin is flowed into the rim.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a set for performing a method for preventing scale adhesion Can be 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.
  • Example A the evaluation method of the flush toilet was as follows.
  • 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.
  • a stall urinal manufactured by Tohoku Kikai, U307C, pottery color: pastel ivory (# SC1)
  • 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.
  • 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.
  • 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 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 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.
  • Example A1 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.
  • 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.
  • 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.
  • 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.
  • the coating liquid was passed through the rim.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example A3 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.
  • 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 B the evaluation method of the flush toilet was as follows.
  • Test B1 Water contact angle measurement
  • 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 ⁇ 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.
  • a Western style toilet (Toseki Kiki, CS87, pottery color: pastel eye bottle (# SC1)) was prepared.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example B1 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 the evaluation method of the flush toilet was as follows.
  • the center line surface roughness Ra (JIS-B0601) of the sample surface was measured using a stylus type surface roughness measuring instrument (JIS-B0651).
  • Table 1 shows the composition of the glaze base material used in this example.
  • the composition shown in Table 1 were prepared transparent glaze substrate excluding the Z R_ ⁇ 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.
  • 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.
  • the contact angle with water of the plate-shaped test piece (referred to as plate-shaped test piece C) was 16 °.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • SAT—215 C a water-repellent material
  • X—24—94-161 a water-repellent material
  • 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.
  • 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 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 C6 The oil-based ink did not float on the water surface and remained on the surface even when the sample was tilted.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Public Health (AREA)
  • Water Supply & Treatment (AREA)
  • Sanitary Device For Flush Toilet (AREA)

Abstract

L'invention concerne une cuvette de toilettes à chasse d'eau capable d'empêcher efficacement l'adhésion du tartre sur celle-ci pendant une durée prolongée, comprenant au moins une surface de cuvette de toilettes alimentée en eau de chasse ainsi qu'un orifice d'amenée permettant la décharge de l'eau de chasse sur la surface de la cuvette de toilettes, dans laquelle une couche mince hydrophobe et/ou une couche mince d'hydroplanage est formée sur les surfaces de l'orifice d'amenée, de manière que l'eau ne puisse pas rester sur la surface de la couche mince, de manière à empêcher que de l'eau résiduelle ne soit amenée sur la surface de la cuvette des toilettes.
PCT/JP2000/008855 1999-12-15 2000-12-14 Cuvette de toilettes a chasse d'eau dotee d'une fonction antiadhesion du tartre, composition de revetement pour la fonction et procede de prevention de l'adhesion du tartre sur la cuvette de toilettes a chasse WO2001044592A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18900/01A AU1890001A (en) 1999-12-15 2000-12-14 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

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP35569899 1999-12-15
JP11/355698 1999-12-15
JP2000-33724 2000-02-10
JP2000033724 2000-02-10
JP2000-119880 2000-04-20
JP2000119880 2000-04-20

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WO2001044592A1 true WO2001044592A1 (fr) 2001-06-21

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PCT/JP2000/008855 WO2001044592A1 (fr) 1999-12-15 2000-12-14 Cuvette de toilettes a chasse d'eau dotee d'une fonction antiadhesion du tartre, composition de revetement pour la fonction et procede de prevention de l'adhesion du tartre sur la cuvette de toilettes a chasse

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008146880A1 (fr) 2007-05-31 2008-12-04 Sumitomo Osaka Cement Co., Ltd. Produit sanitaire et son procédé de fabrication
JP2013167060A (ja) * 2012-02-14 2013-08-29 Toto Ltd トイレ装置
US8709616B2 (en) 2007-01-30 2014-04-29 Sumitomo Osaka Cement, Co., Ltd. Cooking device and method of manufacture of the same
WO2017130595A1 (fr) * 2016-01-29 2017-08-03 パナソニックＩｐマネジメント株式会社 Urinoir

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01174480U (fr) * 1988-05-19 1989-12-12
JPH0565733A (ja) * 1991-09-05 1993-03-19 Matsushita Electric Ind Co Ltd 便器及び便座装置
EP0649887A2 (fr) * 1993-10-22 1995-04-26 DOW CORNING ASIA, Ltd. Composition de revêtement hydrofuge et antiseptique
US5466486A (en) * 1990-10-25 1995-11-14 Matsushita Electric Industrial Co., Ltd. Chemically adsorbed monomolecular lamination film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01174480U (fr) * 1988-05-19 1989-12-12
US5466486A (en) * 1990-10-25 1995-11-14 Matsushita Electric Industrial Co., Ltd. Chemically adsorbed monomolecular lamination film
JPH0565733A (ja) * 1991-09-05 1993-03-19 Matsushita Electric Ind Co Ltd 便器及び便座装置
EP0649887A2 (fr) * 1993-10-22 1995-04-26 DOW CORNING ASIA, Ltd. Composition de revêtement hydrofuge et antiseptique

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8709616B2 (en) 2007-01-30 2014-04-29 Sumitomo Osaka Cement, Co., Ltd. Cooking device and method of manufacture of the same
WO2008146880A1 (fr) 2007-05-31 2008-12-04 Sumitomo Osaka Cement Co., Ltd. Produit sanitaire et son procédé de fabrication
JP2013167060A (ja) * 2012-02-14 2013-08-29 Toto Ltd トイレ装置
US10738453B2 (en) 2012-02-14 2020-08-11 Toto Ltd. Toilet device
WO2017130595A1 (fr) * 2016-01-29 2017-08-03 パナソニックＩｐマネジメント株式会社 Urinoir

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