JP2000192529A - Scale adhesion preventing method for flush toilet bowl surface, scale adhesion preventive flush toilet bowl and coating composition for scale adhesion preventive flush toilet bowl - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the blackening contamination by forming a water repellent film on the toilet bowl surface extending from a flushing discharge port to the part just under the flushing discharge port, and including silicone and a fluorine resin in this water repellent film. SOLUTION: A flushing method includes a spreader type for flushing the inner surface of an urinal 20 by the water ejects through a spreader nozzle 22 mounted on the upper part of the urinal inner surface and a water hanging type for flushing the inner surface with the water discharged from discharge ports 26 on the inside of the rim part 25 of the urinal 20. In the manufacture of this flush toilet bowl, a glaze is applied to a toilet bawl molded base produced by cast molding followed by baking at 1100 deg.C or higher to form a toilet bowl, and a coating material containing silicone or a coating material containing a fluorine resin is applied to the toilet bowl surface extending from the discharge port to the part just under the discharge port and hardened. According to this, scale is hardly adhered to the toilet bowl, and the blackening contamination thereof can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing scale from adhering to the surface of a flush toilet, thereby making the flush toilet hardly soiled. Further, the present invention relates to a flush-type toilet bowl which has an anti-stain adhesion property and is hardly stained. Further, the present invention relates to a coating composition for preventing scale from adhering to a flush toilet and making the flush toilet hard to stain.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for cleanliness in sanitary spaces, and it has been widely desired to keep sanitary surfaces hygienic and clean. As a method of keeping the toilet surface clean hygienically in general households since ancient times, surfactants, acids,
A method has been adopted in which a detergent such as an alkali is attached to a scourer or brush to strongly rub the surface of the porcelain, and both chemical removal by detergent and physical removal by scrubbing with a scrub brush are used.

[0003]

One of the forms of dirt on a conventional flush toilet has a problem that blackish dirt is easily generated on the surface of the pottery just below the spout. This dark stain,
The method of applying a detergent such as the above-mentioned surfactant, acid, alkali or the like to a scourer or a brush and strongly rubbing the ceramic surface could not be sufficiently removed. In view of the above, an object of the present invention is to provide a flush toilet that is unlikely to cause the above-mentioned dark stains. Another object of the present invention is to provide a coating composition for a flush toilet, which makes the above-mentioned dark stain less likely to occur in the flush toilet. Still another object of the present invention is to provide a method of using the coating composition to make the above-mentioned black toilet stain less likely to occur on the surface of a flush toilet.

[0004]

Observation of the above-mentioned dark stains reveals that a silica-based thin film is formed on the surface of the pottery, and the thin film has cracks, and microorganisms such as mold grow on the cracks. Turned out to be. From the above observations, it is estimated that the mechanism of the occurrence of dark spots is as follows. (1) On the surface of the pottery just below the water outlet, the remaining water after washing from the water outlet continues to droop for a long time and stays in the vicinity (the direction in which the residual water drips and the location where the water stays are almost the same every time) become). (2) The retained water is dried at that location to form a film of scale (a film made of an inorganic substance such as SiO2 or CaO, which is a mineral component contained in the water, is formed. Rubbing does not completely remove it). (3) When the formation of the scale film is repeated a plurality of times, and the film thickness is sufficiently large, cracks occur in the scale film due to a difference in thermal expansion between the pottery and the scale film. (4) Mold adheres to the crack. Since the crack portion is always in an environment to which water is supplied, mold easily propagates, and when the mold exceeds a predetermined number, darkening occurs. Therefore, it is considered that the best way to prevent the occurrence of dark stains is not to form a scale film, which is the root cause, directly below the water outlet.

In the present invention, based on the above observation and consideration of the mechanism, a water-repellent coating is formed on a water outlet for washing and / or a toilet surface immediately below the water outlet in order to prevent dark stains. And a water-repellent coating, wherein a water-repellent coating is formed on a flush outlet and / or a toilet surface immediately below the flush outlet. A water-repellent coating is formed on the flushing spout from which the residual water drips and / or the flushing face immediately below the flushing port, so that the flushing faucet and / or the flushing face immediately below the flushing port. The remaining water hardly stays on the surface, and the scale is hardly attached thereto, so that the black stain is hardly generated.

Further, the present invention provides a flush toilet having a cold-setting silicone, a cold-curable fluororesin, or a fluororesin and a cold-curable silicone. And / or a coating composition for a flush toilet for forming a water-repellent film on a toilet surface immediately below the water outlet; and a coating composition for the flush toilet and / or the water discharge port of the flush toilet. The present invention provides a method of preventing the adhesion of scale to the surface of a flush toilet including the step of applying the composition directly below, the step of curing the coating composition, and the method of preventing soiling of the surface of the flush toilet. By coating the hardening component with a cold-setting material, it is possible to make it difficult for water scale to adhere to the existing flush toilet surface, and to make it difficult to generate dark stains.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a specific configuration of the present invention will be described. The flush toilet of the present invention includes a toilet bowl,
Can be used with urinals. The cleaning method does not matter.
For example, as shown in FIG. 1 (a), the urinal cleaning method includes a method of cleaning the inner surface of the urinal with water jetted from a spreader nozzle 22 attached to an upper part of the inner surface of the urinal 20 ( (Spreader method) and a method of washing the inner surface of the toilet bowl with water discharged from a water discharge port 26 formed inside the rim (didling) section 24 of the urinal 20 (idling method). Either may be used. Similarly, there are a spreader type and a resting type for toilets (not shown).
May be any of them.

In the present invention, the spout is, for example, a spout of a spreader nozzle in a spreader system, and a spout formed in a rim (stagnation) portion in a stagnation system. Immediately below the spout means several cm directly below the spout,
Preferably, it is the portion from 0 to 5 cm directly below.

The water-repellent film in the present invention means a film having a contact angle with water of 90 ° or more by a contact angle measuring device. It is preferably at least 110 degrees, more preferably 1 degree.
It is 40 degrees or more.

The silicone-containing coating in the present invention is:
Silicone having one or more organic groups bonded to silicon atoms in the silicone, that is, an average composition formula RpSIX
qO (4-p-q) / 2 (wherein, R represents 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
<This is a number that satisfies <4)).

In the coating composition for a flush toilet according to the present invention, the room-temperature-curable silicone 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 RpSiXq
O (4-pq) / 2 (where 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
<A number that satisfies <4), which is a silicone that can be cured at room temperature to form a film.

The silicone is a bifunctional silane derivative monomer (a monomer having two hydrolyzable groups per molecule and forming a bifunctional siloxane bond in which two oxygen atoms are bonded to each silicon atom) and / or 3 A functional silane derivative monomer (a monomer having three hydrolyzable groups per molecule and forming a trifunctional siloxane bond having three oxygen atoms bonded to each silicon atom) as an essential component,
Functional silane derivative monomer (having 4 hydrolyzable groups per molecule and 4 oxygen atoms bonded to each silicon atom)
A composition containing a monomer that forms a functional siloxane bond) is obtained by hydrolysis and polycondensation.

Here, as the bifunctional silane derivative, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyl Dimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, heptadecafluorooctylmethyldimethoxysilane, heptadecafluorooctylmethyldiethoxysilane, etc. Can be suitably used.

The trifunctional silane derivatives include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, and ethyltritoxysilane.
Butoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n
-Propyltriisopropoxysilane, n-propyltributoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltritbutoxysilane, n-decyltrimethoxysilane, n -Decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltrit-butoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltritbutoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane,
Phenyltriisopropoxysilane, phenyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltrit Butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethyl tributoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriisopropoxy Orchid, γ- (meth) acryloxypropyl tributoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-mercapto Propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltributoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxy Silane, trifluoropropyltributoxysilane, heptadecafluorooctyltrimethoxysilane,
Heptadecafluorooctyltriethoxysilane, heptadecafluorooctyltriisopropoxysilane, heptadecafluorooctyltributoxysilane, and the like can be suitably used.

As the tetrafunctional silane derivative, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane and the like can be suitably used.

Among the above silicones, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl)
Those having a group, a γ- (meth) acryloxy group or the like can form an organic cross-link other than the siloxane cross-link, and are preferable in obtaining room-temperature curability.

Further, a curing agent may be added to enhance the room temperature curability. 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, tetramethylammonium hydroxide and the like. Basic compounds; n-hexylamine, tributylamine, diazabicycloundecene, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenebentamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- Aminopropylmethyldimethoxysilane, γ- (2-aminomethyl) -aminopropyltrimethoxysilane, γ- (2-aminomethyl) -aminopropylmethyldimethoxysilane, etc. Titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate; aluminum compounds such as aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, and aluminum chloride; tin acetylacetonate, dibutyltin Tin compounds such as octylate; metal-containing compounds such as cobalt octylate, cobalt acetylacetonate, iron acetylacetonate; and acidic compounds such as phosphoric acid, nitric acid, phthalic acid, p-toluenesulfonic acid, and trichloroacetic acid are preferable. Available to

Further, metal oxide fine particles may be added to improve the hardness and scratch resistance of the cured film, or to improve the gloss by increasing the refractive index. As the metal oxide, silica, alumina, cerium oxide, tin oxide, zirconium oxide, hafnium oxide, antimony oxide, iron oxide, titanium oxide, rare earth oxide, and the like can be used.

In a coating composition for a flush toilet containing a room-temperature-curable silicone, it is preferable that the coating composition is dispersed in a non-aqueous solvent in order to improve the storage stability of the coating composition. As the non-aqueous solvent, alcohol, ketone, ester, toluene, xylene, hexane and the like can be suitably used.

The method for manufacturing a flush-type toilet according to claim 2 of the present invention is a method for manufacturing a flush toilet, which comprises applying a glaze to a toilet molding base made by casting and firing at a temperature of 1100 ° C. or more. And / or by applying the above-mentioned silicone-containing paint directly below the water outlet and then curing the silicone. When applying the composition to the water outlet and / or immediately below the water outlet, masking is performed on a portion not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as the method of applying. For curing the silicone, well-known methods such as standing at normal temperature, heating, and irradiation with ultraviolet rays can be used.

The fluororesin used in the fluororesin-containing coating in the present invention includes, for example, polyvinyl fluoride, polyvinylidene fluoride, poly (ethylene trichloride), poly (tetrafluoroethylene), poly (tetrafluoroethylene-propylene hexafluoride) Copolymers, ethylene-polytetrafluoroethylene copolymers, ethylene-polychlorinated ethylene trifluoride copolymers, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymers, perfluorocyclopolymers, vinyl ether-fluoroolefin copolymers, vinylester-fluoroolefin copolymers, etc. are preferably used. it can.

The fluorine compound used in the fluorine compound-containing coating of the present invention includes lithium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, scandium fluoride, yttrium fluoride, zirconium fluoride, and the like. Hafnium fluoride, manganese fluoride, iron fluoride, cobalt fluoride, nickel fluoride, copper fluoride, aluminum fluoride, gallium fluoride, indium fluoride, bismuth fluoride, lanthanum fluoride, cerium fluoride, fluoride Praseodymium, neodymium fluoride, samarium fluoride, europium fluoride, terbium fluoride, dysprosium fluoride, holmium fluoride, erbium fluoride, thulium fluoride, ytterbium fluoride, lutetium fluoride and the like can be suitably used.

In one embodiment of the flush toilet according to the third aspect of the present invention, a coating containing a fluororesin is formed on the water outlet of the toilet and / or immediately below the water outlet. One manufacturing method of the above flush toilet is that a glaze is applied to a toilet molding base made by casting and is baked at a temperature of 1100 ° C or more, and a water outlet of the toilet and / or immediately below the water outlet, After applying the paint containing the fluororesin, the fluororesin is cured. When applying the composition to the water outlet and / or immediately below the water outlet, masking is performed on a portion not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as the method of applying. For curing of fluorine resin,
Known methods such as standing at room temperature, heating, and irradiation with ultraviolet rays can be used.

In the flush toilet according to claim 3 of the present invention,
A film containing a fluorine compound is formed on the water outlet of the toilet and / or immediately below the water outlet. One manufacturing method of the above flush toilet is that a glaze is applied to a toilet molding base made by casting and is baked at a temperature of 1100 ° C or more, and a water outlet of the toilet and / or immediately below the water outlet, After applying the paint containing the above-mentioned fluorine compound, it is cured as a film. When applying the composition to the water outlet and / or immediately below the water outlet, masking is performed on a portion 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 method of applying.

In the flush toilet according to claim 4 of the present invention,
A coating containing silicone and a fluororesin is formed on the water outlet of the toilet and / or immediately below the water outlet. Here, those exemplified above can be suitably used for the silicone and the fluororesin. In particular, when the weight of the fluororesin is 40% or more of the total weight of the silicone and the fluororesin,
It is preferable because it exhibits super water repellency with a contact angle with water of 150 degrees or more. The method for producing a flush toilet according to claim 4 of the present invention is characterized in that a glaze is applied to a toilet bowl formed by casting and fired at a temperature of 1100 ° C. or more, and / or the water outlet of the toilet. By applying a coating containing the silicone and the fluororesin just below the water outlet, and then curing the silicone. When applying the composition to the water outlet and / or immediately below the water outlet, masking is performed on a portion not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as the method of applying. For curing silicone, leave it at room temperature,
Known methods such as heating and ultraviolet irradiation can be used.

In the flush toilet according to claim 5 of the present invention,
A coating containing silicone and a fluorine compound is formed on the water outlet of the toilet and / or immediately below the water outlet. here,
As the silicone and the fluorine compound, those exemplified above can be suitably used. In particular, it is preferable that the weight of the fluorine compound is 40% or more based on the total weight of the silicone and the fluorine compound, since the contact angle with water exhibits a super water repellency of 150 degrees or more. The method for producing a flush toilet according to claim 4 of the present invention is characterized in that a glaze is applied to a toilet bowl formed by casting and fired at a temperature of 1100 ° C. or more, and / or the water outlet of the toilet. By applying a paint containing the silicone and the fluorine compound immediately below the water outlet, and then curing the silicone. When applying the composition to the water outlet and / or immediately below the water outlet, masking is performed on a portion not to be applied as necessary. Well-known methods such as spray coating, brush coating, and sponge coating can be used as the method of applying. For curing silicone,
Known methods such as standing at room temperature, heating, and irradiation with ultraviolet rays can be used.

In the flush toilet according to claim 6 of the present invention,
A coating containing ceria and / or yttria is formed on the water outlet of the toilet and / or immediately below the water outlet. When a film containing ceria and / or yttria is formed, the film exhibits hydrophilicity immediately after production, but exhibits water repellency when left for a while. Therefore, residual water hardly stays on the water outlet of the toilet and / or the toilet surface immediately below the water outlet, and it is difficult for water scale to adhere to the water outlet. The method for manufacturing a flush toilet according to claim 6 of the present invention comprises:
The cerium and / or yttrium alkoxide is contained immediately below the water outlet and / or immediately below the water outlet of a toilet bowl obtained by applying a glaze to a toilet body formed by casting and firing at a temperature of 1100 ° C or higher. After applying a coating material to be applied, baking is performed at a temperature of 300 to 700 degrees. When applying the composition to the water outlet and / or immediately below the water outlet, masking is performed on a portion 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 method of applying.

The water repellent film or the coating composition for a flush toilet of the flush toilet of the present invention may contain an antibacterial agent. Antibacterial agents, silver, copper, antibacterial metals such as zinc and its compound fine particles or a carrier such as silica gel or zeolite, a quaternary ammonium salt,
Nitrile derivatives, imidazole derivatives, benzothiazole derivatives, isothiazole derivatives, thiazithiazole derivatives, triazine derivatives, sulfone derivatives, phenol derivatives, phenol ester derivatives, pyrrole derivatives and the like can be suitably used. Also, when using an antibacterial agent in combination with a water-repellent coating, water droplets are unlikely to remain because of the water repellency, and bacteria cannot grow in places without water,
A higher antibacterial effect can be expected.

[0029]

EXAMPLES (Comparative Example 1) As a sample, a stall urinal (U307C) made by Totoki Kiki and a pottery color: pastel ivory (# SC1) were prepared. A 70 × 150 mm plate-shaped test piece prepared by firing from the same base and glaze as the urinal was prepared. Using this plate-shaped test piece, the contact angle with water was measured, and the urine sample was used to observe the state of attachment of water droplets and scale near the water discharge section provided in the stagnation section and the surrounding area. The contact angle between the surface of the plate-shaped test piece and water was measured 30 seconds after a droplet of distilled water was dropped on the sample surface from a micro syringe using a contact angle measuring device (CA-X150, manufactured by Kyowa Interface Science). . As a result, the contact angle with water was 30 °. The observation of the state of water droplets adhering to the water outlet of the urinal sample and its surroundings was performed by visually observing the state of water flow and the state of remaining water droplets when the flash valve was opened and closed. As a result, a small amount of water continued to flow even after 3 minutes from when the flash valve was closed, and many large water droplets remained in the water passage. Regarding the observation of the scale attached to the water discharge section of the urinal sample and the surrounding area, the specimen was left under normal use conditions (average use number: 20 times / day) for 30 days,
A solution prepared by diluting a plaque dye gel “DENTCLUB” made by Healthtech with distilled water was sprayed, and the amount of the scale added was evaluated based on the intensity of the red color. When this plaque dyed gel is used, a portion with much scale is strongly dyed red, and a portion without scale is not colored. Therefore, it is possible to visually evaluate the scale adhesion amount. As a result, it was found that the path of the water stream was dyed red at the water discharge part and the lower part thereof, and that water scale was attached.

(Example 1A) The same urinal and plate-shaped test piece as in Comparative Example 1 were prepared. The urinal was spray-coated with Glaska B603 manufactured by JSR in the area around the water outlet provided in the stagnation area and in a range immediately below the water outlet. 3 at room temperature
After drying for 0 minutes, the mixture was cured by heating at 200 ° C. for 30 minutes to form a silicone-containing coating. The plate-like test piece was spray-coated with Glaska B603 made by JSR on the entire glaze surface and treated in the same manner as a urinal to form a silicone-containing coating. When the contact angle with water of the obtained plate-shaped test piece was measured in the same manner as in Comparative Example 1, it was 100 °, indicating water repellency. Moreover, about the obtained urinal, the adhesion state of water droplets and the adhesion state of scale were observed in the same manner as in Comparative Example 1. Regarding the state of attachment of water droplets, since the water outlet is water-repellent, when the amount of water is reduced, the water does not flow in a band shape but drops after being formed into water droplets. In addition, since the water just below the spout is water repellent,
The path of the water was not determined, and no large water droplets adhered.
As a result, even after spraying the plaque stained gel after standing for 30 days, the spout and the area immediately below the spout were not stained red, and it was possible to confirm the prevention of the adhesion of the scale.

(Example 1B) The same urinal and plate-shaped test piece as in Comparative Example 1 were prepared. The urinal has a PTFE (tetrafluoroethylene) powder Rubron L-2 manufactured by Daikin Industries and a glass jar B603 manufactured by JSR with a weight ratio of solids of 7 in the vicinity of the water outlet provided in the stagnant portion and within a range of 5 cm below the water outlet. : 3 was spray-coated with the mixed solution.
After drying at room temperature for 30 minutes, the film was cured by heating at 200 ° C. for 30 minutes to form a film containing a fluororesin and silicone. The plate-like test piece was spray-coated with the above-mentioned mixed solution on the entire glaze surface and treated in the same manner as a urinal to form a film containing a fluororesin and silicone. The obtained plate-shaped test piece was measured for the contact angle with water in the same manner as in Comparative Example 1, and was found to be 150 °, indicating super-water repellency. Moreover, about the obtained urinal, the adhesion state of water droplets and the adhesion state of scale were observed in the same manner as in Comparative Example 1.
Regarding the state of attachment of water droplets, since the water outlet is water-repellent, when the amount of water is reduced, the water does not flow in a band shape but drops after being formed into water droplets. Further, since the water-repellent area immediately below the water outlet was also water-repellent, the path of water was not determined, and large water droplets did not adhere. As a result, even after spraying the plaque stained gel after standing for 30 days, the spout and the area immediately below the spout were not stained red, and it was possible to confirm the prevention of the adhesion of the scale.

(Comparative Example 2) As a sample, a Western style toilet made by Totoki Kiki: CS971B, 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 toilet was prepared. The contact angle between the surface of the plate-shaped test piece and water was measured using a contact angle measuring instrument (CA-X150, manufactured by Kyowa Interface Science).
The measurement was performed 30 seconds after a droplet of distilled water was dropped on the sample surface from the microsyringe using a micro syringe. As a result, the contact angle with water was 30 °. Observation of the state of water droplets adhering to the water outlet of the toilet bowl sample and its surroundings was performed by visually observing the state of water flow and the state of remaining water droplets when the flash valve was opened and closed. As a result, even after the flush valve was closed, a small amount of water continued to flow until the tank was full, and many large water droplets remained on the water path. Observation of the scale attached to the water outlet of the toilet bowl sample and its surroundings was performed under normal use conditions (average use: 10 times /
) Was left for 30 days and sprayed with a solution obtained by diluting a plaque-dyeing gel “DENTCLUB” manufactured by Healthtech with distilled water, and the amount of scale attached was evaluated based on the intensity of the red color. As a result, it was found that the path of the water flow was dyed red at the water outlet and the lower part thereof, and that water scale was attached.

(Example 2A) The same toilet bowl and plate-shaped test piece as in Comparative Example 2 were prepared. The toilet bowl was spray-coated with JSR Glaska B603 in the vicinity of the water outlet provided in the rim part and in a range of 5 cm immediately below the water outlet. 30 at room temperature
After drying for 20 minutes, the composition was heated and cured at 200 ° C. for 30 minutes to form a silicone-containing coating. The plate-like test piece was spray-coated with JSR Glaska B603 on the entire glaze surface, and treated in the same manner as a toilet bowl to form a silicone-containing coating. About the obtained plate-shaped test piece, the contact angle with water was measured in the same manner as in Comparative Example 2.
00 °, indicating water repellency. Further, the obtained toilet bowl was observed for the state of water droplet adhesion and the state of water scale adhesion in the same manner as in Comparative Example 2. Regarding the state of attachment of water droplets, since the water outlet is water-repellent, when the amount of water is reduced, the water does not flow in a belt shape but drops after being formed into water droplets. Further, since the water-repellent area immediately below the water outlet was also water-repellent, the path of water was not determined, and large water droplets did not adhere. As a result, even after spraying the plaque-dyeing gel after standing for 30 days, the spout and the area immediately below the spout were not stained red, and it was possible to confirm the prevention of the adhesion of scale.

Example 2B The same toilet bowl and plate-shaped test piece as in Comparative Example 2 were prepared. The toilet bowl has PTFE (tetrafluoroethylene) powder Lubron L-2 and J in the area around the water discharge port provided in the rim part and within 5 cm immediately below it.
A solution obtained by mixing SR Glaska B603 so that the weight ratio of the solid content was 7: 3 was spray-coated. After drying at room temperature for 30 minutes, the film was cured by heating at 200 ° C. for 30 minutes to form a film containing a fluororesin and silicone. The plate-like test piece was spray-coated with the above mixed solution on the entire glaze surface, and treated in the same manner as a toilet bowl to form a film containing a fluororesin and silicone. When the contact angle with water of the obtained plate-shaped test piece was measured in the same manner as in Comparative Example 2, the contact angle was 150 °, indicating super-water repellency. Further, the obtained toilet bowl was observed for the state of water droplet adhesion and the state of water scale adhesion in the same manner as in Comparative Example 2. Regarding the state of attachment of water droplets, since the water outlet is water-repellent, when the amount of water is reduced, the water does not flow in a band shape but drops after being formed into water droplets. Further, since the water-repellent area immediately below the water outlet was also water-repellent, the path of water was not determined, and large water droplets did not adhere. As a result, even after spraying the plaque stained gel after standing for 30 days, the spout and the area immediately below the spout were not stained red, and it was possible to confirm the prevention of the adhesion of the scale.

As described above, in the embodiment, the water droplet does not remain in a certain place for a long period of time.
It is presumed that almost no scale is attached, so that dark stains are unlikely to occur.

[0036]

According to the present invention, it is possible to provide a flush toilet which hardly causes dark stains. In addition, it is possible to provide a flush toilet and a coating composition for flush toilets, which hardly cause dark stains. Furthermore, it becomes possible to provide a method of using the above-mentioned coating composition to make the above-mentioned black toilet stain less likely to occur on the surface of a flush toilet.

[Brief description of the drawings]

FIG. 1 is a view showing a flush type urinal. (A) The figure which shows the urinal of a spreader system. (B) The figure which shows the urinal of the stagnation method.

[Explanation of symbols]

 20 urinal 22 spreader nozzle 24 stagnant part 26 spout

Claims (27)

[Claims] 1. A method for preventing scale from adhering to the surface of a flush-type toilet, comprising forming a water-repellent coating on a flush outlet for flushing and / or a toilet surface immediately below the flush outlet. 2. The method according to claim 1, wherein the water-repellent coating is a silicone-containing coating. 3. The method according to claim 1, wherein the water-repellent film is a film containing a fluororesin and / or a fluorine compound. 4. The water-repellent film according to claim 1, wherein the water-repellent film is a film containing silicone and a fluororesin.
3. The method for preventing scale from adhering to the surface of a flush toilet according to 4. 5. The method according to claim 1, wherein the water-repellent coating is a coating containing silicone and a fluorine compound. 6. The method according to claim 1, wherein the water-repellent coating is a coating containing ceria and / or yttria. 7. The method according to claim 1, wherein the water-repellent coating further contains an antibacterial agent. 8. The water repellent film according to claim 1, wherein the water repellency of the water repellent film is 90 degrees or more in terms of a contact angle with water.
8. The method for preventing scale from adhering to the surface of a flush toilet according to any one of Items 1 to 7. 9. The method according to claim 1, wherein the toilet bowl is a toilet bowl. 10. The method according to claim 1, wherein the toilet is a urinal. 11. A water-repellent flush toilet, wherein a water-repellent coating is formed on a flush outlet and / or a toilet surface immediately below the flush outlet. 12. The flush toilet according to claim 11, wherein the water-repellent coating is a silicone-containing coating. 13. The water-repellent film according to claim 13, wherein the water-repellent film comprises a fluororesin and / or
The flush toilet according to claim 11, wherein the flush toilet is a film containing a fluorine compound. 14. The flush toilet according to claim 11, wherein the water-repellent film is a film containing silicone and a fluororesin. 15. The flush toilet according to claim 11, wherein the water-repellent coating is a coating containing silicone and a fluorine compound. 16. The film according to claim 11, wherein the water-repellent film is a ceria- and / or yttria-containing film.
A flush-type toilet bowl according to the above item. 17. The flush toilet according to claim 11, wherein the water-repellent coating further contains an antibacterial agent. 18. The flush toilet according to claim 11, wherein the water repellency of the water repellent coating is 90 degrees or more in terms of a contact angle with water. 19. The flush toilet according to claim 11, wherein the toilet is a toilet. 20. The flush toilet according to claim 11, wherein the toilet is a urinal. 21. Water scale for forming a water-repellent film on a flush water outlet and / or a toilet surface immediately below the water discharge port of a flush toilet characterized by containing a cold-setting silicone. An anti-adhesive flush toilet coating composition. 22. A water-repellent film for forming a water-repellent coating on a flushing spout of a flush-type toilet and / or a toilet surface immediately below the spout, characterized by comprising a cold-setting fluororesin. A coating composition for flush toilets which has anti-scale adhesion properties. 23. A water-repellent coating is formed on a flush water outlet of a flush toilet and / or a toilet surface immediately below the water discharge port, characterized by containing a room-temperature-curable silicone and a fluororesin. , A coating composition for a flush-type toilet bowl having anti-scale adhesion. 24. The coating composition for a flush toilet bowl according to claim 21, further comprising an antibacterial agent. 25. The water-repellent water-repellent rinse according to claim 21, wherein the surface of the water-repellent film formed by the coating composition exhibits a contact angle with water of 90 degrees or more. Coating composition for toilet bowl. 26. A step of applying the coating composition for a flush toilet according to claim 21 to a flush faucet of a flush flush toilet and / or a toilet bowl surface immediately below the flush faucet.
An antifouling method for a flush-type toilet surface, comprising a step of curing the coating composition. 27. A step of applying the coating composition for a flush toilet according to claim 21 to a flush faucet of a flush flush and / or a toilet surface immediately below the flush faucet.
A method for preventing scale from adhering to the surface of a flush toilet, comprising a step of curing the coating composition.