JPH0235808B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-retaining sanitary appliance, and more particularly to a sanitary appliance that prevents accumulated water from freezing by providing a heat generating layer and an insulating layer on the surface of a water storage portion of the sanitary appliance. In cold regions, the water that accumulates in the water storage areas of sanitary appliances such as toilet bowls freezes, causing the toilet bowls to break down, which is a major problem. In order to prevent this, it is sufficient to heat the entire room in which the sanitary appliances are installed, but this requires a large amount of heating costs. Therefore, it has been proposed, for example, to bury the water reservoir of a flush toilet deep underground or to drain it. However, burying water reservoirs underground requires high construction costs and is not possible for medium-to-high-rise buildings. Also, draining water is time consuming and inconvenient. It has also been proposed to heat the water storage section from the outside with a heater;
They have drawbacks such as being troublesome to install and being concerned about heat loss, wire breakage, and electrical leakage before the heat is transferred to the device surface. In view of this situation, the inventors of the present invention have conducted intensive research to develop sanitary appliances that can effectively prevent the water storage part of sanitary appliances from freezing. The inventors have discovered that freezing can be effectively prevented by the heat from the heat generating layer, and have completed the present invention. That is, the gist of the present invention resides in a sanitary appliance characterized in that a heat generating layer and an insulating layer covering the heat generating layer are provided on the surface of the appliance in the water storage section. In the present invention, the sanitary appliance has a water storage part,
Includes all sanitary appliances that need to prevent standing water from freezing, such as flush toilets, water tanks, wash basins, etc. Sanitaryware is usually made of ceramic, but may also be of other materials, such as porcelain, plastic, metal, etc. In the case of conductive materials such as metals, in order to provide insulation to the surface of the device,
It is necessary to provide an insulating layer under the heat generating layer. The heat generating layer may be formed by applying and curing a conductive paint. Examples of the conductive paint include synthetic rubbers and resins containing conductive substances such as fluorocarbon rubber, silicone rubber, silicone resin, polyimide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, and epoxy resin. In particular,
Contains fluorocarbon rubber, coupling agent, conductive material and liquid carrier, optionally amine compound and/or
Alternatively, a conductive fluororubber paint containing an inorganic fibrous substance is preferable. The insulating layer may be made of silicone rubber, silicone resin, fluorine resin, fluorine rubber, etc., and fluorine rubber is particularly preferred. Among fluororubbers, fluororubber paints containing fluororubber, a coupling agent and a liquid carrier, and optionally an amine compound and/or an inorganic fibrous substance, are particularly preferred because of their ability to impart non-stick properties to the surface. In addition, a fluoro rubber paint containing fluoro resin is applied,
A fluororubber coating film obtained by curing is preferred. The fluororubber contained in the conductive fluororubber paint and the fluororubber paint for insulating layers that are preferably used is a highly fluorinated elastic copolymer, and particularly preferred fluororubbers include Usually 40-85
Examples include elastomeric copolymers of mole percent vinylidene fluoride and at least one other fluorine-containing ethylenically unsaturated monomer copolymerizable therewith.
Further, as the fluororubber, fluororubber containing iodine in the polymer chain can also be preferably used. For example, this iodine-containing fluororubber can be used at the end of a polymer chain.
0.001 to 10% by weight, preferably 0.01 to 5% by weight of iodine, and at least one other fluorine-containing ethylenic compound which can be copolymerized with the same 40 to 85 mol% vinylidene fluoride. It is a fluororubber whose main composition is an elastic copolymer consisting of a saturated monomer (see JP-A-52-40543). Other fluorine-containing ethylenically unsaturated monomers that can be copolymerized with vinylidene fluoride to give elastic copolymers include hexafluoropropylene, pentafluoropropylene, trifluoroethylene, trifluorochloroethylene, and tetrafluoroethylene. Typical examples include ethylene, vinyl fluoride, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether).
Particularly desirable fluororubbers are vinylidene fluoride/hexafluoropropylene dielastic copolymers and vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene terelastic copolymers. The coupling agent contained in conductive fluororubber paint and fluororubber paint for insulation layers acts on the interface between organic and inorganic materials, forming a strong bridge between the two materials through chemical or physical bonding. It is usually a compound of silicon, titanium, zirconium, hafnium, thorium, tin, aluminum or magnesium, and has a group capable of bonding an organic material and an inorganic material. Among these coupling agents, preferred are silane coupling agents and orthoacid esters of Group transition elements of the periodic table (such as titanium or zirconium) and derivatives thereof, with aminosilane compounds being most preferred. Examples of the silane coupling agent include the general formula: R ¹・Si ・R ² _3-a・R ³ _a [wherein R ₁ is a chlorine atom, an amino group, an aminoalkyl group, a ureido group, a glycidoxy group, an epoxycyclohexyl group] , an alkyl group having 1 to 10 carbon atoms or a vinyl group having at least one functional atom or group selected from acryloyloxy group, methacryloyloxy group, mercapto group, and vinyl group, R ² and R ³ are each a chlorine atom , hydroxyl group,
An atom or group selected from an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 15 carbon atoms, a hydroxyalkyloxy group having 2 to 4 carbon atoms, and an acyloxy group having 2 to 15 carbon atoms, a is 0 , 1 or 2. ] Examples include silane compounds represented by the following. R ¹ is an alkyl group having a functional substituent, and preferable examples include β-aminoethyl group, γ-aminopropyl group, N-(β-aminoethyl)-γ-aminopropyl group. , γ-ureidopropyl group, γ-glycidoxypropyl group, β-
(3,4-epoxycyclohexyl)ethyl group,
Examples include γ-acryloyloxypropyl group, γ-methacryloyloxypropyl group, γ-mercaptopropyl group, β-chloroethyl group, γ-chloropropyl group, and γ-vinylpropyl group.
Further, R ¹ may be a vinyl group. Specific examples of the silane compounds preferably used include γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, and γ-glycidoxypropyl. Trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethylsilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltris(β-methoxyethoxy) Silane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, β-aminoethyl-β-aminoethyl −γ
-aminopropyltrimethoxysilane and the like. Among these silane coupling agents, aminosilane compounds such as γ-aminopropyltriethoxysilane (hereinafter referred to as A-1100), N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-(trimethoxysilylpropyl) Ethylenediamine, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, β-aminoethyl-β-aminoethyl-γ-
Compounds such as aminopropyltrimethoxysilane not only function as vulcanizing agents for fluorocarbon rubber, but also greatly contribute to improving adhesion to substrates, and are also safe to use with liquid carriers, so they are especially useful. preferable. Examples of compounds of titanium, zirconium, hafnium and thorium include the general formula: T(OR) ₄ [wherein T represents titanium, zirconium, hafnium or thorium, and R represents an alkyl group, a cycloalkyl group or an aryl group. ] Examples include derivatives obtained by reacting an orthoacid ester represented by the following and one or more compounds having at least one functional group therewith. Examples of the above-mentioned compounds having at least one functional group include glycerin, ethylene glycol, 1,
3-butanediol, 2,3-butanediol,
Polyhydric alcohols such as hexylene glycol and octylene glycol, oxyaldehydes such as salicylaldehyde and glucose, oxyketones such as diacetone alcohol and fructose, glycolic acid, lactic acid, dioxymaleic acid,
Oxycarboxylic acids such as citric acid, diketones such as diacetylacetone, ketonic acids such as acetoacetic acid, esters of ketonic acids such as ethyl acetoacetate, oxyamines such as triethanolamine and diethanolamine, oxyphenols such as catechol and pyrogallol. Compounds etc. can be used. Examples of specific compounds when T is titanium include tetraalkyl titanate (e.g., tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate), tetraethylene glycol titanate, triethanolamine titanate, titanium acetylacetonate. , isopropyl trioctanoyl titanate, isopropyl trimethacryl titanate, isopropyl triacryl titanate, isopropyl tri(butyl, methyl pyrophosphate) titanate, tetraisopropyl di(dilauryl phosphite) titanate,
Examples include dimethacryloxyacetate titanate, diacryloxyacetate titanate, di(dioctyl phosphate) ethylene titanate, and the like. As the zirconium compound, a compound similar to the above titanium compound can be used. Specific examples include tetraalkyl zirconates such as tetraethyl zirconate and tetrabutyl zirconate, n-propyl zirconate, isopropyl zirconate, n-butyl zirconate, isobutyl zirconate, zirconium acetylacetonate, and the like. As the hafnium and thorium compounds, compounds similar to titanium and zirconium can be used. organic or inorganic compounds, such as tin compounds;
For example, SnCl ₄ etc. can be used. Examples of aluminum compounds include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethylacetoacetate). Examples of the magnesium compound include magnesium alcoholates such as magnesium methylate and magnesium ethylate. Liquid carriers contained in paints include organic solvents such as lower ketones, lower esters, and cyclic ethers, water,
and a mixture of water and a water-soluble organic liquid, and examples of the water-soluble organic liquid include alcohols. Among these liquid carriers, water is most preferred since it does not impair coating workability. Furthermore, other inorganic fibrous substances contained in both fluoro rubber coatings are used to improve the compression recovery properties of the fluoro rubber coatings, and typical examples include glass fiber, carbon fiber, and asbestos. Examples include fibers and potassium titanate fibers.
It is desirable that the inorganic fibrous material has an average length of at least 1μ, preferably 1 to 100μ. In addition, the amine compound added to both fluororubber paints, if desired, primarily functions as a vulcanizing agent for the fluororubber, and together with the coupling agent, improves mechanical properties. Examples of such compounds include monoamines such as ethylamine, propylamine, butylamine, benzylamine, allylamine, n-amylamine, and ethanolamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 3,9-bis(3- diamines such as (aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (hereinafter referred to as V-11), polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine Among these, amine compounds having two or more terminal amino groups are preferred. Fluororesins preferably included in the fluororubber paint for insulation layers include polytetrafluoroethylene,
Tetrafluoroethylene and at least one other ethylenically unsaturated monomer copolymerizable with it (e.g. ethylene, olefins such as propylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, vinyl fluoride) Copolymers with halogenated olefins, perfluoroalkyl vinyl ethers, etc.), polychlorotrifluoroethylene, polyvinylidene fluoride, etc. Among these, preferred fluororesins include at least one of polytetrafluoroethylene, tetrafluoroethylene and hexafluoropropylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, and perfluoropropyl vinyl ether.
Seeds (usually 40 mol% based on tetrafluoroethylene)
(included below). As the conductive substance added to the conductive paint including the above-mentioned conductive fluororubber paint, conventionally used substances such as carbon, graphite, and metal are used. Channel black, furnace black, thermal black, etc. are included, and metals include gold, silver, copper, aluminum, titanium, etc. To prepare such conductive fluororubber paints and fluororubbers for insulating layers, pigments, acid acceptors, fillers and If necessary, an inorganic fibrous substance and, in the case of a conductive fluororubber paint, a conductive substance are blended in a conventional manner, and the coupling agent and, if necessary, an amine compound are added to the resulting dispersion. (Additives such as surfactants, pigments, acid acceptors, fillers, etc. may be added as necessary.) By thoroughly mixing using a conventional method,
Make a uniform fluoro rubber paint. The amount of coupling agent added is usually fluoro rubber.
1 to 50 parts by weight per 100 parts by weight, preferably 1 to 50 parts by weight
It is 20 parts by weight. When an amine compound is added as desired, it is blended so that the total sum of the coupling agent and the amine compound takes the above value. in this case,
The molar ratio of the coupling agent to the amine compound is selected from the range of 1:99 to 99:1. The reason why fluororesin is added to the fluororubber paint for the insulating layer is to impart excellent non-adhesive properties to the surface of the fluororubber coating. Therefore, when adding a fluororesin, it is desirable that the ratio of fluororubber to fluororesin is 95:5 to 35:65 by weight, and if the ratio of fluororesin is less than the above lower limit, Improvements in non-adhesiveness and lubricity are not sufficient, and conversely, when the amount exceeds the above upper limit, a coating film of the desired thickness cannot be obtained.
Cracks and pinholes are likely to occur in the paint film. The amount of the conductive substance added to the conductive paint may be such that the cured paint film becomes a surface heating element and has a volume resistivity of 10 ² Ω-cm or less. As the acid acceptor, those commonly used in the vulcanization of fluororubber can be similarly used, such as one or more divalent metal oxides or hydroxides. Specific examples include oxides or hydroxides of magnesium, calcium, zinc, lead, and the like. Further, as the filler, silica, clay, diatomaceous earth, talc, carbon, etc. are used. The conductive paint is applied to either the internal or external surface of the sanitary appliance using a conventional paint coating method, under conditions suitable for each paint, such as room temperature to 400°C for the preferred conductive fluororubber paint, Preferably 100~
A heating layer coating can be obtained by curing at a temperature of 400°C for an appropriate period of time. When forming this heat generating layer, appropriate electrodes and lead wires are coated on the coating film. After forming the heat generating layer, various paints for the insulating layer are applied thereon under conditions suitable for each, for example, for the preferred fluoro rubber paint for the insulating layer, the temperature is between room temperature
An insulating layer coating can be formed by curing at a temperature of 400°C, preferably 100 to 400°C for an appropriate time. The heat-generating layer provided on the surface of the device of the present invention generates heat when energized, heats the water storage portion, and prevents water from freezing. Further, if such a heat generating layer and an insulating layer are provided on the surface of the toilet seat of a Western-style toilet bowl, use in cold weather becomes more comfortable. Furthermore, if the insulating layer is formed from the above-mentioned fluororubber paint for insulating layers containing a fluororesin, non-adhesive properties will be imparted to the surface and an antifouling effect will be obtained. The antifreeze sanitary appliance of the present invention will be explained with reference to drawings showing an example of a toilet bowl. FIG. 1 is a cross-sectional view of a Western-style toilet bowl 1, and FIG. 2 is a cross-sectional view of a Japanese-style toilet bowl 1'. Each toilet has a water reservoir 2, 2', and a heat generating layer 4 and an insulating layer 5 are provided on the outer surface of the wall 3 or the inner surface of the wall 3', as shown partially enlarged in FIG. is provided. As shown in FIG. 4, a heating effect can be obtained by providing a heat generating layer/insulating layer 7 on the surface of the toilet seat 6. The enlarged view of this surface is also similar to FIG. 4. Next, the present invention will be explained by showing Examples and Comparative Examples. Note that parts are by weight. Example 1 (1) to (6) A paint (carrier) containing fluorocarbon rubber, conductive carbon/graphite (4:6) and V-11 in a solid content ratio of 100:45:2 was applied to a 150 mm square ceramic plate. : A mixture of methyl ethyl ketone and methyl isobutyl ketone in a weight ratio of 1:1) was applied and cured to form a heat generating layer coating. On top of this, add 100 parts of the following liquid A and 5 parts of liquid B.
Separately purify and apply the mixture using a 200 mesh wire mesh, cure at 300℃ for 15 minutes to form an insulating layer,
Got a test piece. A liquid fluororubber ¹⁾ Aqueous dispersion (fluororubber content 60% by weight, including nonionic HS-208)
166 parts fluororesin ²⁾ Aqueous dispersion (fluororesin content 50% by weight, including nonionic HS-208)
150 parts Magnesium oxide 3 parts Medium thermal carbon 20 parts Nonionic HS-210 2 parts Water 50 parts B liquid A-1100 40 parts V-11 20 parts Water 40 parts Notes (1) Vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene Elastic copolymer. Note (2) Tetrafluoroethylene/hexafluoropropylene copolymer For (1), (2), and (3), the heating layer of the obtained test piece was heated at a power density of 0.1 W/cm ² for 10 minutes each.
Electricity was applied for 30 minutes and 60 minutes, and in (4), (5), and (6), electricity was applied for 10 minutes, 30 minutes, and 60 minutes at a power density of 0.2 W/cm ² to generate heat, respectively. Table 1 shows the surface temperature at each point. Note that the surface temperature before heat generation was 23°C.

[Table] Example 2 One drop of pure water was dropped onto the insulating layer coating film obtained in Example 1 at 24°C, and the contact angle was measured using a goniometer (manufactured by Elma Optical Co., Ltd.). The contact angle was 110°. For comparison, the contact angle of water on ceramics was similarly measured and found to be 63°. As described above, the coating film obtained from the fluororubber paint of Example 1 has non-adhesive properties and can be provided with excellent antifouling properties.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a Western-style toilet bowl with a heat-generating layer and an insulating layer provided on the outer surface of the water reservoir, and FIG. 2 is a cross-sectional view of a Japanese-style toilet bowl with a heat-generating layer and an insulating layer provided on the inner surface.
FIG. 3 is a sectional view of a toilet seat provided with a heat generating layer/insulating layer, and FIG. 4 is a partially enlarged view showing the surface condition of the water reservoir wall of the toilet bowl or the toilet seat shown in FIGS. 1 to 3. 1, 1'... Toilet bowl, 2, 2'... Water storage part, 3,
3'... Wall, 4... Heat generating layer, 5... Insulating layer, 6...
...Toilet seat, 7... Heat generating layer/insulating layer.

Claims (1)

[Scope of Claims] 1. A sanitary appliance in which a heat generating layer and an insulating layer covering the heat generating layer are provided on the surface of the appliance in a water storage part, wherein the heat generating layer is a conductive material containing fluorocarbon rubber, a coupling agent, a conductive substance, and a liquid carrier. The insulating layer is a coating layer formed by applying and curing a fluorocarbon rubber paint containing fluorocarbon rubber, a fluorocarbon resin, a coupling agent, and a liquid carrier. Sanitary utensils characterized by: 2. The sanitary appliance according to claim 1, wherein the conductive fluororubber paint or fluororubber paint further comprises an amine compound having at least one terminal amino group directly connected to an aliphatic hydrocarbon group. 3. The sanitary appliance according to claim 2, wherein the amine compound has at least two terminal amino groups. 4. The sanitary appliance according to claim 1, wherein the conductive substance contained in the conductive fluororubber paint is selected from the group consisting of carbon, graphite, and metal. 5. The sanitary appliance according to any one of claims 1 to 3, wherein the conductive fluororubber paint or the fluororubber paint further contains an inorganic fibrous substance.