JP2018193708A - Water treatment article - Google Patents

Abstract

To provide a water treatment article capable of further surely sterilizing and cleaning a water contact surface, by a self-cleaning mechanism using strong oxidization effect of OH radicals, even in a case of using a "UV-LED emitting long wavelength ultraviolet rays like UVA".SOLUTION: In an article having a water contact member having an exposed surface and in which at least part of the exposed surface is a water contact surface possible to be in contact with liquid water, at least part of the water contact surface is constituted with a photocatalyst-containing layer, a part serving as a base thereof is constituted with an ultraviolet permeable member, further, after applying sterilizing and cleaning liquid generating OH radicals by the photocatalysis of hydrogen peroxide and the like onto the surface of the photocatalyst-containing layer, ultraviolet ray is emitted from an ultraviolet ray source like a UV-LED disposed behind the ultraviolet permeable member to excite the photocatalyst-containing layer to generate the OH radicals on the exposed surface, and to perform cleaning and sterilization.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an article that handles water, such as a toilet device, in which at least a part of an exposed surface is a wetted surface that can come into contact with liquid water.

  In many articles that handle water, such as toilet devices, at least a part of the exposed surface is a wetted surface that can come into contact with liquid water. When such an article (hereinafter also referred to as “water-handling article”) is a durable consumer good, it is used for a long period of time, so that dirt adheres to and accumulates on the wetted surface, and the wet environment. There is a problem that microorganisms such as molds are likely to propagate due to the tendency to be easily developed. For this reason, various devices have been made to clean the water contact surface.

  As one of such contrivances, in the case where light including ultraviolet rays such as sunlight is constantly irradiated, the photocatalytic reaction that occurs when the water contact surface is composed of a photocatalytic substance and water contacts the photocatalytic substance. There is known a method using a so-called self-cleaning mechanism in which dirt is decomposed and sterilized by the strong oxidizing power of hydroxyl radicals (also referred to as OH radicals) generated by (Patent Document 1).

  In addition, when a device used in the room or a wetted surface is present in the apparatus housing and external light irradiation cannot be expected, the wetted surface is composed of a photocatalytic substance and an ultraviolet light source such as an ultraviolet lamp. There is also known a method of disassembling and sterilizing dirt by the same mechanism as described above so that ultraviolet rays can be irradiated (Patent Document 2).

  Furthermore, a technique for performing sterilization and cleaning by spraying a cleaning liquid having a sterilizing effect on the water contact surface is also known. For example, in order to keep toilet bowl toilets clean, functional water such as hypochlorous acid water is sprayed on the bowl of the toilet bowl, and a light source device for irradiating ultraviolet rays is attached to the toilet bowl. Or what sprays the said functional water or sterilization water within the predetermined time after the irradiation of the said ultraviolet-ray is complete | finished (refer patent document 3).

  And according to the toilet apparatus described in the said patent document 3, using the flow of the air which arises by the heat_generation | fever of a light source device, the functional water sprayed from the spraying means or the sterilization water is made into the rim part of the rear part of a toilet bowl, for example It is said that it can be further spread to the back surface, and the entire surface of the bowl part of the toilet bowl can be maintained more cleanly.

  In addition, as functional water or sterilizing water used in Patent Document 3, hypochlorous acid water obtained by electrolyzing tap water with a sterilizing water generator is used.

  Further, in the toilet apparatus described in Patent Document 3, a photocatalyst layer is formed on the surface of the bowl portion, and the photocatalyst layer is irradiated with ultraviolet rays to generate active oxygen by surrounding water, oxygen, etc. The surface of the part is hydrophilized so that the functional water or sterilizing water spreads on the surface of the bowl part.

JP 2011-21396 A JP 2014-163203 A JP 2014-163162 A Japanese Patent Laid-Open No. 10-085606 Japanese Patent Laid-Open No. 2006-049518 JP 2006-049519 A JP, 2006-050291, A Japanese Patent No. 4967971 Japanese Patent Laid-Open No. 10-237928 Journal of Japan Society on Water Environment Vol.22 No.11 910-915 1999 Yoshio Nosaka, “Generation and Contribution of OH Radicals in Photocatalytic Reactions”, Proceedings of the 35th Symposium on Catalytic Chemistry Related to Light (General 1) June 10, 2016

  When a self-cleaning mechanism using a photocatalyst is used, it is necessary to irradiate the photocatalyst with excitation light. As the excitation light, natural light including ultraviolet light is generally used. However, when natural light cannot be used, it is necessary to install an ultraviolet light source as described above. However, depending on the water handling article, the installation position of the ultraviolet light source is often limited due to the internal structure thereof, and it is often impossible to irradiate the place to be purified with ultraviolet light. Even when UV irradiation is possible, the generation of OH radicals by photocatalysis is limited to the surface of the photocatalyst, so the surface or space atmosphere where no photocatalyst exists (air filling the space or stored water, etc.) Cannot be sterilized or washed. Furthermore, it is known that the lifetime of OH radicals is extremely short, and the time for obtaining the sterilizing / cleaning effect is limited to the time during which the ultraviolet rays are irradiated.

  Thus, the self-clowning mechanism using a photocatalyst is greatly restricted in the applicable area and time. In other words, in the area where the photocatalyst exists and can be irradiated with ultraviolet rays, the ultraviolet rays are actually irradiated. There is a problem that sterilization / cleaning can be performed only while it is being performed.

  If a cleaning liquid having a sterilizing effect such as hypochlorous acid water is used together as in the method described in Patent Document 3, sterilization / cleaning of the portion in contact with the cleaning liquid becomes possible, but the tap water is electrolyzed. The hypochlorous acid water obtained in this way is generally thin in concentration and its oxidizing power is weaker than that of OH radicals.

  On the other hand, when turning to the ultraviolet light source, the ultraviolet light emitting diode (hereinafter sometimes abbreviated as UV-LED) is small, power saving, long life, does not use mercury, and can be turned on and off instantaneously. It has attracted attention as an ultraviolet light source that replaces an ultraviolet lamp because it has such excellent characteristics as possible. However, “UV-LED that emits long-wavelength ultraviolet light (for example, UVA)” which is relatively inexpensive and easily available cannot emit ultraviolet light having a high ultraviolet sterilization effect called so-called sterilization line, and its energy ( Due to its low (in inverse proportion to wavelength), its practical use is limited because its effect as a driving force for photoreaction is low.

  Therefore, the present invention is more reliable by the self-cleaning mechanism that uses the strong oxidizing power of OH radicals even when the “UV-LED that emits ultraviolet light having a long wavelength such as UVA” is used as the ultraviolet light source. It is an object of the present invention to provide a water handling article that can sterilize and clean the surface in contact with water.

  As a method for generating OH radicals without using a photocatalyst, the present inventor has developed an “aqueous solution in which a substance or ions that are decomposed by ultraviolet irradiation in the presence of water to generate OH radicals or ions are dissolved” such as hydrogen peroxide. We paid attention to the known method of irradiating ultraviolet rays. Then, if it was possible to effectively irradiate the water contact surface with ultraviolet light, the above problem could be solved by attaching a sterilizing cleaning solution comprising the above aqueous solution to the water contact surface and irradiating with ultraviolet light. As a result, we have succeeded in finding a method capable of effectively irradiating the wetted surface with ultraviolet rays, and have already made proposals.

  However, it has been found that there is a new problem that the desired effect may not be obtained when long-wavelength ultraviolet rays with low energy are used.

  Therefore, the present inventor has further studied to solve the above new problem, and obtained the knowledge that the aqueous solution can generate OH radicals by photocatalytic action (see Non-Patent Document 2), thereby completing the present invention. It came to do.

  That is, the present invention includes a water contact member that has an exposed surface, and at least a part of the exposed surface is a water contact surface that can come into contact with water in a liquid state, an ultraviolet light emitting means having an ultraviolet light emitting surface, A sterilizing cleaning liquid supply means capable of adhering to the water contact surface a sterilizing cleaning liquid composed of an aqueous solution in which a substance or ions that decompose by ultraviolet irradiation in the coexistence and generate hydroxyl radicals are dissolved. The water contact surface of the water contact member includes a first region composed of an exposed surface of the first photocatalyst-containing layer disposed on the ultraviolet light emission surface of the ultraviolet light emission means. In the region, the article is characterized in that the ultraviolet ray emitted from the ultraviolet ray emitting surface of the ultraviolet ray emitting means is irradiated from the non-exposed surface side of the first photocatalyst containing layer.

  Here, the number of the water contact members included in the article of the present invention may be one or plural. Moreover, when it has a some water-contact member, said 1st area | region may exist only in one water-contact member, and may exist in two or more water-contact members. Further, even in one water contact member, the first region is not limited to one location, and may be provided at a plurality of locations independent of each other.

  In the article of the present invention, the water contact surface of the water contact member further has a second region constituted by an exposed surface of the second photocatalyst-containing layer disposed on a surface that does not emit ultraviolet light, The ultraviolet rays emitted from the ultraviolet emission surface and transmitted through the first photocatalyst-containing layer, or the ultraviolet rays emitted from the ultraviolet emission surface and not transmitted through the first photocatalyst-containing layer, It is preferable that at least a part of the exposed surface of the second photocatalyst-containing layer in the second region can be irradiated. At this time, when the article of the present invention has a plurality of water contact members, there may be a water contact member that does not have the first region, and the ultraviolet light emitted from the ultraviolet light emission surface of a certain water contact member is another water contact member. The exposed surface of the second photocatalyst containing layer in the second region of the member may be irradiated.

  In these articles of the present invention, the cleaning and sterilizing solution is preferably a hydrogen peroxide solution, and further preferably includes a hydrogen peroxide solution production apparatus.

  The ultraviolet emitting means preferably further includes an ultraviolet light source including an ultraviolet light emitting diode that emits ultraviolet light having a peak in a wavelength region of more than 280 nm and not more than 400 nm, and in particular, a wavelength region of not less than 240 nm and not more than 280 nm. It is more preferable to further include an ultraviolet light source including an ultraviolet light emitting diode that emits ultraviolet light having a peak.

  Articles of the present invention are durable consumer goods, particularly flush toilet equipment, flush toilet tanks, washing machines, humidifiers, air conditioners, refrigerators, freezers, water purifiers, hand dryers, bathtubs, bathroom ceiling materials, wall materials and Floor materials, sinks for sinks, sinks for sinks, drains, drain pans or drain traps are preferred.

  Regarding sterilization / decomposition / washing using a photocatalyst, (a) a photocatalyst filter used to oxidatively decompose or kill odors, bacteria, and other contaminants in the air in an air conditioner. In the technology (Patent Document 4) that demonstrates the desired photocatalytic ability even if the entire surface cannot be irradiated with ultraviolet rays, and (b) an ultraviolet killing device for sterilizing aquatic organisms such as cultured fish and appreciation fish In addition, there is known a technique (Patent Documents 5, 6, and 7) that performs ultraviolet sterilization of water while irradiating ultraviolet rays from the back side of a window material having a photocatalyst layer to exhibit self-cleaning properties. However, these techniques relate to filters and ultraviolet irradiation devices themselves, and there is no idea of arranging a light source in a space where a light source could not be arranged. Further, Patent Documents 4, 5, 6 and 7 do not include a description relating to the application of these techniques to water handling articles as described above other than filters of air conditioners and water sterilizers.

  In the article of the present invention, the first photocatalyst-containing layer is surely excited by irradiating the ultraviolet ray emitted from the ultraviolet ray emission surface of the ultraviolet ray emission means from the non-exposed surface side of the first photocatalyst-containing layer. be able to. In the first region, the sterilizing cleaning liquid generates OH radicals by coming into contact with the excited first photocatalyst-containing layer. Therefore, sterilization and cleaning of the water contact surfaces are performed by the strong oxidizing power of the OH radicals. It can be performed. At this time, since the photocatalyst is also excited by long-wavelength ultraviolet rays, OH radicals can be generated from the sterilizing cleaning liquid even when using an ultraviolet light source that can emit only long-wavelength ultraviolet rays. Further, by using the sterilizing cleaning liquid, it is possible to greatly increase the concentration of OH radicals that are generated compared to when simple water is brought into contact with the photocatalyst (see Non-Patent Document 2). Further, even if the sterilization cleaning liquid is not subjected to ultraviolet irradiation or photocatalytic action like hydrogen peroxide water, sterilization cleaning of the water contact surface where the photocatalyst is not present is performed by using a sterilization cleaning liquid that itself has sterilization cleaning power. It is also possible.

  The UV transmittance of the photocatalyst layer excited by UV light is dependent on the wavelength of the UV light, and the longer the UV light, the harder it is to be absorbed by the photocatalyst. Non-patent document 1) that is easy to be excited). On the other hand, the effect of generating OH radicals when the sterilizing cleaning liquid is irradiated with ultraviolet rays is generally dependent on the type of dissolved substance or ions, but generally when irradiated with high energy short wavelength ultraviolet rays. high. As described above, the article of the present invention has a low OH radical generation effect when directly irradiated to the sterilizing washing liquid, and also has an ultraviolet sterilization effect (sterilization by damaging microorganism DNA by ultraviolet irradiation and depriving the reproduction ability). It is possible to efficiently generate OH radicals using ultraviolet light having a long wavelength that cannot be expected to have an effect. Therefore, the present invention uses a “long wavelength ultraviolet light (for example, UVA), which is inexpensive and easily available when an ultraviolet light emitting diode (UV-LED) is used as an ultraviolet light source, but has not been widely used for sterilization. ) Is very significant in that it is possible to obtain a high sterilizing and cleaning effect using a UV-LED "

  Furthermore, since the water contact surface of the water handling article has many opportunities to come into contact with running water, the fluid physical cleaning effect by the running water can be expected. However, in the article of the present invention, the fluid physical cleaning effect can be further enhanced. This is because, as oxidative decomposition by OH radicals progresses, the dirt substance is decomposed into a low molecular weight and highly hydrophilic substance, so that even if a decomposition residue adheres to the surface, it can be easily removed by running water. Because it becomes. That is, when a fluid physical cleaning effect by running water is obtained, such a synergistic effect makes it possible to obtain a higher self-cleaning effect simply by adding a simple process of rinsing. Therefore, in the water handling article of the present invention, it is possible to reduce the frequency of manual cleaning, and it is not necessary to rub vigorously with a brush to remove the dirt. Can be dropped. As a result, the surface is not damaged, and the life of the article and the water contact member can be extended.

  Furthermore, in the present invention, for example, the interior of the toilet body in the toilet apparatus, the outside of the pipe and the cylindrical member in the drain trap, and the cavity newly provided in the solid member, etc., are conventionally installed with an ultraviolet light source. The UV light source can be placed in a space (dead space) that could not be used as a place, so the degree of freedom of the UV light source placement location is increased, and the internal space can be used effectively to achieve compactness. Is also possible.

This figure is a schematic diagram for explaining a toilet apparatus 100 which is one of the articles of the present invention. This figure is a schematic diagram for explaining a sterilizing cleaning liquid supply means using a hydrogen peroxide production apparatus that can be used in the toilet apparatus 100. This figure is a diagram showing an ultraviolet light source that can be suitably used in the present invention. This figure is a diagram showing another ultraviolet light source that can be suitably used in the present invention.

  The article of the present invention needs to be an article (water handling article) that has an exposed surface, and has a water contact member that is a water contact surface where at least a part of the exposed surface can come into contact with liquid water. Among these items, because they are highly effective, they belong to the category of durable consumer goods, that is, water supply, water use, or wastewater disposal directly used by people in the living or living environment of people. Therefore, it is preferably an article such as equipment, apparatus, and equipment that is used for a relatively long period of time (hereinafter, also referred to as “commercial water handling article”). Here, the supply of water directly used by humans is, for example, the supply of drinking water or tap water, and the use of water is, for example, toilet flushing, washing, facial washing, hair washing, showering, bathing, washing, humidification and so on. The use of water in relation to human use of water, such as the generation of steam for ironing. Wastewater disposal means, for example, wastewater generated as a result of the use of the above water, heat exchangers for air conditioners, etc. Such as drainage generated in the room, waste water such as dew condensation in windows and bathrooms.

  Specific examples of suitable “commercial water handling articles” in the present invention include flush toilet equipment, flush toilet tank, washing machine, humidifier, air conditioner, refrigerator, freezer, hand dryer, water purifier, bathtub, bathroom And ceiling materials, wall materials and floor materials, sinks for sinks, sink sinks, drains, drain pans and drain traps.

  In addition, the water contact member in these articles is not particularly limited as long as it is a member having an exposed surface and at least a part of the exposed surface being in contact with water in a liquid state. A bowl body in the apparatus, a tank body and a hand-washing bowl body in a flush toilet tank, a water tank body and a rotating drum body in a washing machine, and the like correspond to this. One or a plurality of the water contact members are included in one article.

  The article of the present invention comprises a sterilizing cleaning liquid comprising the water-contacting member, an ultraviolet emitting means having an ultraviolet emitting surface, and an aqueous solution in which a substance or ions that decompose by irradiation with ultraviolet light in the presence of water to generate hydroxyl radicals are dissolved. A sterilization cleaning liquid supply means capable of adhering to the water contact surface, wherein the water contact surface of the water contact member is a first disposed on the ultraviolet emission surface of the ultraviolet emission means Comprising a first region composed of an exposed surface of the photocatalyst-containing layer, wherein in the first region, the ultraviolet light emitted from the ultraviolet light emitting surface of the ultraviolet light emitting means is emitted from the first photocatalyst-containing layer. Irradiated from the non-exposed surface side.

  The toilet device described in Patent Document 3 has spray means for adhering functional water having a sterilizing and cleaning function, such as a hypochlorous acid aqueous solution, to the surface of the bowl portion which is a wetted surface, and a surface of the bowl portion. A light source device that irradiates light including ultraviolet rays, and is similar to the article of the present invention in that a photocatalytic film is formed on the surface of the bowl portion. However, the mechanism of sterilization cleaning is greatly different. That is, in the toilet apparatus described in Patent Document 3, the surface of the bowl portion on which the photocatalytic film is formed is irradiated with ultraviolet rays, and the functional water sterilizing water is sprayed from the spray nozzle after the ultraviolet irradiation is completed. The sterilization and cleaning are performed by the sterilization cleaning power inherent in the functional water. On the other hand, in the article of the present invention, after a sterilizing cleaning solution such as hydrogen peroxide solution is attached onto the photocatalyst layer formed on the wet surface such as the surface of the bowl portion, ultraviolet rays are irradiated from the back side of the photocatalyst layer. The photocatalyst is excited to generate OH radicals on the water contact surface by the photocatalytic action, and sterilization and washing are performed using its strong oxidizing power. And since the ultraviolet irradiation at this time is emitted from the ultraviolet emitting surface which is the base of the photocatalyst layer, the photocatalyst layer can be surely irradiated with ultraviolet rays and excited. Further, the ultraviolet ray emitted from the ultraviolet ray emission surface and transmitted through the first photocatalyst containing layer, or the ultraviolet ray emitted from the ultraviolet ray emission surface and not transmitted through the first photocatalyst containing layer as it is, is emitted as it is. Use to activate the second photocatalyst-containing layer disposed on the surface that does not emit ultraviolet light, to generate OH radicals from the sterilizing cleaning solution on the surface, or to contact the water-contacting surface where the photocatalyst-containing layer does not exist OH radicals can be generated by directly acting on the sterilizing cleaning solution adhering to the surface. Furthermore, depending on the wavelength of the ultraviolet rays to be used, it is possible to sterilize the atmosphere with ultraviolet rays.

  At this time, by generating OH radicals on the wetted surface, OH radicals can be reliably present at a high concentration on the surface to be sterilized and cleaned, and this can be utilized. This is because the lifetime of OH radicals is extremely short when OH radicals are generated by directly irradiating ultraviolet rays onto the mist of the sterilizing cleaning solution drifting in the atmosphere and attached to the contact surface. Thus, this is one of the features of the present invention in contrast to the difficulty in increasing the surface OH radical concentration.

  Thus, the article of the present invention is (A) an aqueous solution in which substances or ions that generate OH radicals by UV irradiation in the presence of water are dissolved (this aqueous solution generates OH radicals mostly by photocatalysis. (B) a point where a photocatalyst is present on the wetted surface, and OH radicals are generated from the sterilized cleaning solution by photocatalytic action on the wetted surface where the photocatalyst is present. (C) A method of forming a photocatalyst-containing layer is adopted as a method for allowing the photocatalyst to be present on the wetted surface, and ultraviolet light for exciting (activating) the photocatalyst is applied to the photocatalyst-containing layer (non-exposed surface or back surface). There is a big feature in that it is irradiated from. Further, in connection with the feature (C) above, (D) ultraviolet rays emitted toward the (non-exposed surface or back surface) of the photocatalyst-containing layer, specifically, ultraviolet rays transmitted through the photocatalyst-containing layer, or Also characterized by irradiating the exposed surface of the photocatalyst containing layer located elsewhere and the sterilization cleaning existing on it without passing through the photocatalyst containing layer. Have.

  The sterilizing cleaning liquid used in the present invention is not particularly limited as long as it is composed of a substance that generates hydroxyl radicals (OH radicals) or ions dissolved therein by irradiating ultraviolet rays in the presence of water. When the aqueous solution is irradiated with ultraviolet rays, the substance or ions react with surrounding water to generate OH radicals, but the photocatalyst acts in the same way as ultraviolet rays to promote such a reaction. Although there are differences in degree depending on the type of substance or ion, many of the aqueous solutions can generate OH radicals also by photocatalysis.

  As a substance or ion that generates OH radicals by ultraviolet irradiation in the presence of water, a substance or ion having such a function is not particularly limited and can be used. Examples of these substances or ions include nitrate ions, nitrite ions, urethane compounds, cellulose derivatives, hydrogen peroxide, and ozone. Among these, from the viewpoint of easy handling and OH radical generation efficiency, it is preferably at least one selected from nitrate ion, nitrite ion and hydrogen peroxide, and is it nitrate ion and / or nitrite ion? Or hydrogen peroxide is more preferable. Furthermore, the effect of generating OH radicals by photocatalytic action is high, and it can be manufactured with a device that can be stored in the toilet body of a toilet device, for example, and there is no need for replenishing raw materials other than water and air, and In the case of spraying or spraying the sterilizing cleaning liquid from the nozzle, it is not necessary to use salts that precipitate when dried because it causes nozzle clogging. preferable.

  The higher the concentration of “substances or ions that generate OH radicals by UV irradiation in the presence of water” in the sterilizing cleaning solution, the easier it is to generate OH radicals. Therefore, it is not efficient and handling becomes difficult. Therefore, the concentration of the substance or ions is preferably 0.01 mM to 10 M, particularly 0.05 mM to 5 M, and most preferably 0.1 mM to 1 M. Here, M represents (mol / liter).

  From the viewpoint of safety, it is preferable that the sterilizing cleaning liquid does not substantially contain ozone. Here, “substantially not containing” means that ozone is not actively added, and inevitable mixing as an impurity is allowed. The lower the concentration when it is inevitably mixed as an impurity, the better. However, it is usually 1 ppm or less, preferably 0.1 ppm or less, most preferably 0.01 ppm or less on a mass basis.

  When hydrogen peroxide water is used as the sterilizing cleaning liquid, hydrogen peroxide marketed as a disinfecting liquid or the like may be used as it is or after diluting with water, or a hydrogen peroxide water producing apparatus according to the present invention. This is used to produce hydrogen peroxide water using tap water or ion exchange water treated with ion exchange resin as a raw material and diluting it as it is or as necessary. May be used.

  As a hydrogen peroxide water production apparatus, as described in Patent Document 8, “a polymer electrolyte membrane that is an electrolyte membrane having hydrogen ion conductivity, and in contact with one surface across the polymer electrolyte membrane” An electrolytic cell comprising an anode electrode disposed and a cathode electrode disposed so as to be in contact with the other surface is provided, and an anode terminal is attached to the anode electrode, and a cathode terminal is attached to the cathode electrode, respectively. The polymer electrolyte membrane, the anode electrode, and the cathode electrode are fixed by screws through a water-tight sheet, and an anode water storage portion is provided on the electrolytic cell anode side, and a cathode water storage portion is provided on the cathode side, respectively. As described in Japanese Patent Application Laid-Open No. 2008-81760, an “electrolyte membrane having hydrogen ion conductivity” and an anode disposed in contact with the first surface of the electrolyte membrane With electrodes An electrolytic cell comprising a cathode electrode disposed in contact with the second surface of the electrolyte membrane, means for supplying water to the anode electrode, at least of an oxygen-containing gas and water supplied to the cathode electrode Means for supplying an oxygen-containing gas, gas-liquid separation means for separating the gas and liquid generated at the cathode electrode, gas supply means for supplying the gas separated by the gas-liquid separation means to the anode electrode, A hydrogen peroxide production apparatus that can be made compact, such as a hydrogen peroxide production apparatus characterized by comprising an anode electrode and a power source that applies a DC voltage to the cathode electrode, can be used without particular limitation.

  The sterilizing cleaning liquid supply means used in the present invention is not particularly limited as long as the sterilizing cleaning liquid can be attached to the exposed surface of the first region and the exposed surface of the second region of the wetted surface. Usually, it has a sterilization cleaning liquid pump, piping, and a nozzle, and the sterilization cleaning liquid stored in the sterilization cleaning liquid tank is pumped by the pump and supplied from the nozzle to the surface of the wetted surface. The nozzle is not particularly limited as long as it can supply the sterilizing cleaning liquid in contact with the surface. For example, a mist nozzle or a spray nozzle can be applied. (1) When supplying the sterilizing cleaning liquid so as to flow while in contact with the surface, the spray nozzle (2) supplies the sterilizing cleaning liquid so as to be held in contact with the surface. When performing, a mist nozzle is preferably used.

  The ultraviolet ray emitting means in the article of the present invention is not particularly limited as long as it has an ultraviolet ray emitting surface capable of emitting ultraviolet rays that excite the photocatalyst contained in the photocatalyst-containing layer. What emits the ultraviolet-ray radiate | emitted from the light source from the said ultraviolet-ray output surface is used. As such ultraviolet emitting means, (I-1) an ultraviolet light source and an ultraviolet transmissive member that transmits ultraviolet rays are provided, and the ultraviolet light source is disposed behind (on the back side) of the ultraviolet transmissive member. The ultraviolet light emitted from the ultraviolet light source is transmitted through the ultraviolet transmissive member and emitted from the surface thereof. (I-2) The ultraviolet light source is installed at an arbitrary place, and the ultraviolet light source The emitted ultraviolet rays are transmitted using an optical transmission means such as an optical fiber, and are arranged so as to face the back surface of the ultraviolet transmissive member. It is preferable that the light is emitted.

  Here, as the optical member for emitting ultraviolet light, an optical fiber collimator, a lens diffusion plate, a diffusion lens, or a light guide plate is preferably used. A lens diffusing plate, a diffusing lens or a light guide plate is particularly preferable because the irradiation area can be widened. Here, the optical fiber collimator is a member that uses collimated light (parallel light) as light emitted from the optical fiber, and a connector type in which an aspherical lens is incorporated in the ferrule for optical fiber can be suitably used. A lens diffusing plate (Light Shaping Diffuser) is also called a diffusing film, a diffusing filter, or a diffusing sheet, and diffuses and shapes light into a circular or elliptical shape by the action of small lenses randomly formed on the surface. Thus, uniform irradiation is possible. In addition, as a diffusing lens, a light enhancer cap (registered trademark) manufactured by Enplus Co., Ltd. can be suitably used. Further, as the light guide plate, for example, a surface light emitting device disclosed in JP-A-2006-237563 can be suitably used.

  The ultraviolet transmissive member used in the cases (I-1) and (I-2) is a plate-like, sheet-like, or film-like ultraviolet transmissive member that may have a curved surface made of an ultraviolet transmissive substance. A sex member is preferably used. Then, one main surface of the ultraviolet light transmissive member becomes an ultraviolet light emitting surface, and ultraviolet light emitted from the ultraviolet light source is irradiated from the other main surface side.

  The ultraviolet light transmissive material constituting the ultraviolet light transmissive member is not particularly limited as long as it is a light transmissive material capable of transmitting ultraviolet light even if it has a thickness required for the ultraviolet light transmissive member, depending on the ultraviolet light to be used. Inorganic materials such as sapphire, natural or synthetic quartz, calcium fluoride, magnesium fluoride, glass, fluorine-based resins such as PFA, FEP, ETFE, and PCTFE, ultraviolet transparent resins such as polyethylene, polypropylene, PVC, and polycarbonate, And these composite materials can be used. Among these, it is preferable to use glass or an ultraviolet transmissive resin because the molding process is easy. When the ultraviolet transmissive member is composed of an ultraviolet transmissive resin, it is preferable to coat the surface with an ultraviolet transmissive inorganic substance such as glass in order to prevent deterioration due to photocatalytic action.

  In the case of (I-1) and (I-2), the ultraviolet light source (in the case of I-1) and the optical member for ultraviolet emission (in the case of I-2) are the back side (the other main part) of the ultraviolet light transmitting member. (Surface side) It may be fixed and arranged rearward, or may be arranged so as to be movable. In the case of fixing and arranging, it is preferable to arrange a plurality of ultraviolet light sources or ultraviolet emitting optical members so that the entire back surface of the ultraviolet transmitting member can be irradiated with ultraviolet rays. In the case where the light source is movably disposed, an ultraviolet light source (light emitting member) such as a UV-LED or an optical member for emitting ultraviolet light is arranged on a base for the movable light source or the like and modularized, and the light source Ultraviolet rays are emitted while moving the substrate or casing for equalization, and the emitted ultraviolet rays scan the entire or substantially entire back surface of the ultraviolet transmitting member, or the ultraviolet irradiation region is the entire or substantially entire back surface. It is preferable to move while tracing the entire surface. From the viewpoint of reducing the number of ultraviolet light sources and ultraviolet emitting optical members, it is preferable to dispose them.

  Moreover, as an ultraviolet-ray output means, it has (II-1) an ultraviolet-ray light source, a light-guide plate, a light-guide sheet, or a light-guide film, and arrange | positions an ultraviolet-ray light source in side edge parts, such as a light-guide plate, (II-2) Ultraviolet light source, light transmission means such as an optical fiber, light guide plate, light guide sheet, and the like. Or a light guide film, the ultraviolet light source is installed at an arbitrary location, and the ultraviolet light is guided by the light transmission means and incident from a side end surface of the light guide plate or the like, and emitted from a light emitting surface (ultraviolet emitting surface). You may use what you did.

  As an ultraviolet light source, a mercury lamp or excimer lamp well known as an ultraviolet light source (hereinafter, UV may be abbreviated as UV) can be used. It is preferable to use an ultraviolet light emitting diode (UV-LED) because it is not used or can be turned on and off instantaneously.

  By the way, as described above, it is known that the ultraviolet light permeability to the layer containing the photocatalyst excited by the ultraviolet light and the bactericidal effect by the ultraviolet light itself have a wavelength dependency of the ultraviolet light. That is, the longer the wavelength, the more easily the exposed surface of the photocatalyst layer is activated when irradiated with the back surface (back surface) (see Non-Patent Document 1), and the ultraviolet light in the wavelength region around 265 nm has a high bactericidal effect. For this reason, from the viewpoint of surely exciting the surface (exposed surface) of the photocatalyst layer by irradiating the photocatalyst-containing layer with ultraviolet rays from the back surface (back surface), the long wavelength, for example, more than 280 nm, 400 nm or less, particularly 290 nm or more. It is preferable to irradiate ultraviolet rays having a wavelength region of 390 nm or less. On the other hand, if the photocatalyst-containing layer is made to be UV permeable, and the transmitted UV light is used for activation by sterilizing the atmosphere and irradiating from the exposed surface of the photocatalyst-containing layer (of other parts), 240 nm or more It is preferable to irradiate ultraviolet rays having a wavelength region of 280 nm or less, particularly 250 nm or more and 270 nm or less. Furthermore, in order to obtain both effects, it is preferable to simultaneously irradiate ultraviolet rays having a wavelength region of more than 280 nm and not more than 400 nm and ultraviolet rays having a wavelength region of not less than 240 nm and not more than 280 nm. For these reasons, when UV-LEDs are used, UV-LEDs that emit ultraviolet light having a peak in the wavelength region of 240 nm or more and 280 nm or less, and ultraviolet rays that have a peak in the wavelength region of more than 280 nm and 400 nm or less are used. It is preferable to use UV-LED that emits light in combination. Further, from the viewpoint of preventing ozone generation for safety, it is preferable that the irradiated ultraviolet rays do not include ultraviolet rays having a wavelength of less than 200 nm.

  The water contact surface of the water contact member used in the article of the present invention includes a first region composed of an exposed surface of the first photocatalyst-containing layer disposed above the ultraviolet light emission surface of the ultraviolet light emission means. Become.

Here, as the first photocatalyst-containing layer, a thin film layer made of only a photocatalyst substance or a thin film layer having a structure in which fine particles of a photocatalyst substance are dispersed in an organic and / or inorganic base material is suitably employed. As the photocatalytic substance, a substance known to exhibit a photocatalytic action, such as TiO ₂ , SrTiO ₂ , ZnO, CdS, SnO ₂ , WO _{3 and the} like can be used without particular limitation, but from the viewpoint of high photocatalytic effect, It is preferable to use a TiO ₂ or TiO ₂ -based photocatalytic material.

  A thin film layer made of only a photocatalytic substance can be formed by sputtering or vapor deposition using a photocatalytic substance, or CVD. In this case, a general film thickness of the thin film layer is 100 nm to 10 μm, and a preferable film thickness is 150 nm to 5 μm.

  On the other hand, a thin film layer having a structure in which fine particles of a photocatalytic substance are dispersed in an organic or inorganic base material is applied and cured by applying a so-called photocatalytic coating agent in which the fine particles of the photocatalytic substance are dispersed in an organic and / or inorganic binder. Can be formed. In this case, a general film thickness of the thin film layer is 0.3 to 50 μm, and a preferable film thickness is 0.5 to 10 μm. The organic or inorganic substrate is usually a cured product of the binder component of the photocatalyst coating agent, and the concentration of the photocatalytic substance dispersed in such a substrate is 0.5 to 20 mass on a mass basis. %, Particularly 1 to 15% by mass. The particle diameter of the fine particles of the photocatalytic substance may be in the range of 5 nm to 1 μm for the primary particles obtained by image analysis of the transmission electron microscope image. From the viewpoint of the high photocatalytic function, the primary particles are used. The particle diameter is preferably 5 to 50 nm.

  As described above, when the first photocatalyst-containing layer is excited by ultraviolet rays and has ultraviolet transparency, not only can the first photocatalyst-containing layer be activated by backside (back) irradiation, Activation by UV sterilization in the surrounding atmosphere and irradiation from the exposed surface of the photocatalyst containing layer (of other parts) through the first UV transmitting photocatalyst containing layer (hereinafter also referred to as “transmitted UV”) Can be used. For the reason that such merits can be obtained, it is preferable that at least a part of the first photocatalyst-containing layer has ultraviolet light transmittance. In order to provide the first photocatalyst-containing layer with ultraviolet transparency, the organic or inorganic substrate, particularly the substrate in the photocatalyst-containing layer in the first region, may be composed of a substance having ultraviolet transparency. In view of the ease of forming the photocatalyst-containing layer, it is preferable that the cured body is a “cured body that is transparent to ultraviolet rays and ultraviolet rays of the photocatalytic substance”. As the binder, an inorganic binder such as a silicate binder, an inorganic colloid binder, a metal alkoxide binder, an organic binder such as a fluororesin binder, or a combination thereof can be used.

  For the reason that the ultraviolet light transmittance is further increased, the first photocatalyst-containing layer is made of “the photocatalyst substance and its cured product with respect to the ultraviolet light and the ultraviolet light of the photocatalytic substance, as disclosed in Patent Document 6”. Composite photocatalyst particles obtained by pulverizing a cured product obtained by curing a curable composition comprising a transparent binder, and the cured product is permeable to ultraviolet rays and ultraviolet rays of the photocatalytic substance. And a cured product of a “photocatalyst coating composition characterized by comprising a binder comprising:

  In the present invention, even when the first photocatalyst-containing layer does not have ultraviolet transmissivity, ultraviolet rays emitted from the ultraviolet emission surface can be sterilized from the surface exposed to the photocatalyst-containing layer by ultraviolet sterilization of the surrounding atmosphere or (other parts). It can also be used for activation by irradiation. That is, when the ultraviolet light impervious first photocatalyst containing layer is disposed on the ultraviolet light emitting surface, the entire surface of the ultraviolet light emitting surface is not disposed so as to be covered with the first photocatalyst containing layer, but is emitted from the ultraviolet light. By exposing a part of the surface, ultraviolet rays emitted from the exposed portion to the outside (hereinafter also referred to as “non-transmissive ultraviolet rays”) can be used for the above purpose. Because the effect of the first photocatalyst-containing layer and the effect of the non-transmitting ultraviolet rays can be obtained uniformly and uniformly, as shown in Patent Document 5, a plurality of independent firsts are provided on the ultraviolet emission surface. One photocatalyst-containing layer is formed so as to be substantially uniformly dispersed, or the first photocatalyst-containing layer is formed in a punched net shape so that the punched portion is substantially uniformly dispersed on the effective surface. Thus, it is preferable that the coverage defined by the ratio (%) of the total area of the first photocatalyst containing layer to the total area of the ultraviolet emission surface is 2 to 95%. At this time, in order to make the surface a smooth surface without unevenness, an ultraviolet light transmissive layer is formed in the same thickness as the first photocatalyst containing layer on the portion where the first photocatalyst containing layer is not formed. Also good.

  The transmitted ultraviolet light and the non-transmitted ultraviolet light have the following effects. First, when activation of the first photocatalyst-containing layer by backside (backside) irradiation is insufficient, transmitted ultraviolet rays (transmitted ultraviolet rays) and non-transmitted ultraviolet rays (non-transmitted ultraviolet rays) emitted from different positions By irradiating from the exposed surface side of the first photocatalyst-containing layer, there is an effect that a high activation state can be obtained. Secondly, a wetted surface in which an ultraviolet light source (ultraviolet light source) cannot be installed at the opposite position, and an ultraviolet emitting surface (ultraviolet emitting surface) cannot be disposed on the back surface (back surface). Specifically, because the space facing the water contact surface is narrow or fulfills the function of an article or the like, it is impossible to install an external light source, and the thickness of the main body part where the water contact surface exists is small. Effect of enabling activation of a photocatalyst-containing layer (hereinafter also referred to as “photocatalyst-containing layer that is difficult to irradiate front and back”) formed on a wetted surface where an internal light source cannot be installed because it is thin Is brought about.

  In the article or member of the present invention, at least a part of the first photocatalyst-containing layer in the first region is made of an ultraviolet ray emitted from the ultraviolet ray emission surface because the first effect is easily obtained. The ultraviolet transmissive photocatalyst-containing layer that partially transmits, the ultraviolet transmissive photocatalyst-containing layer has a curved shape or a bent portion, and a part of the ultraviolet transmissive photocatalyst-containing layer is (Or obliquely) facing each other, the ultraviolet rays transmitted through the ultraviolet transmissive photocatalyst containing layer (transmitted ultraviolet rays), or emitted from the ultraviolet ray emitting surface, and without passing through the ultraviolet transmissive photocatalyst containing layer, The emitted ultraviolet light (non-transparent ultraviolet light) can be irradiated (mutually) to the exposed surface of the first photocatalyst containing layer (facing each other) in the first region. It is preferable to have.

  Further, for the reason that the second effect is easily obtained, the water contact surface of the water contact member is a second surface constituted by the exposed surface of the second photocatalyst containing layer disposed on the surface that does not emit ultraviolet light. It is preferable that at least a part of the exposed surface of the second photocatalyst-containing layer in the second region can be irradiated with the transmitted ultraviolet light or the non-transmitted ultraviolet light.

  In the water contact member included in the water handling article, depending on the shape of the water contact member or the combination state when a plurality of water contact members are used in combination, an ultraviolet ray transmissive member is attached to these water contact members. In many cases, it is unavoidable that a second region made of an ultraviolet opaque material is present on the wetted surface.

  In the article of the present invention, the surface of the second region can be irradiated with ultraviolet rays due to the second effect. At this time, it is possible to irradiate the surface of the second region having an area larger than that of the first region due to the influence of the directivity angle and scattering of the emitted ultraviolet light. In addition, it is possible to further widen the irradiable region by providing an ultraviolet diffusing function in the ultraviolet transmitting region. Further, by using a hydrogen peroxide solution or the like that exhibits its own sterilizing and cleaning effect as a sterilizing and cleaning liquid, it is possible to perform cleaning and sterilization of a portion that is not irradiated with ultraviolet rays. For this reason, it is not always necessary to make the entire wetted surface the first ultraviolet light transmitting region.

  From the viewpoint of making the area of the water contact surface that can be reliably irradiated with ultraviolet rays as wide as possible, the first region is preferably as wide as possible. However, since there is the situation as described above, at least dirt substances are likely to adhere. The first region may be appropriately determined so that ultraviolet rays can be irradiated to the region, the region where dirt substances are likely to accumulate, or the narrow space or the inside of the article and difficult to clean manually. Depending on the type of article, the ratio of the area of such a region to the entire wetted surface is often not so large, and the region that cannot be made the first region is also limited. In the article of the present invention, a sufficient sterilization and cleaning effect can be obtained by self-cleaning by considering the emission intensity of ultraviolet rays and the positional relationship between the first region and the second region.

  Hereinafter, the article of the present invention will be described in detail with reference to the drawings.

  A toilet device 100 that is an article of the present invention shown in FIG. 1 basically has the same structure as the toilet device described in FIG. 1 of Patent Document 9 (Japanese Patent Laid-Open No. 10-237928). That is, the toilet apparatus 100 is a siphon-jet flush toilet apparatus, and the toilet bowl body 10 is formed by integrally forming the bowl section 11 and a low tank (not shown) serving as a water supply source. A drainage channel 30 is formed integrally with the lower part of the slab. The toilet body 10 includes a zette waterway 20, a rim waterway 40, and a water supply chamber 50. Here, the jet conduit 20 is a jet of washing water directed from the jet hole 21 opened at the bottom of the bowl portion 11 toward the drainage passage 30, from the jet conduit inlet 22 to the jet hole 21. In addition, it is formed in an arc shape along the outer peripheral surface of the bowl portion 11. The rim water passage 40 allows the washing water to flow along the inner surface of the bowl 11 from a rim spray hole 41 perforated on the lower surface of the rim 12 formed on the upper edge of the bowl portion 11. .

  The water supply chamber 50 is for supplying the wash water supplied from the low tank to the Zet water conduit 20 and the rim water conduit 40, with the rim water conduit inlet 42 at the upper part and the Zet water conduit inlet 22 at the lower part. Is formed. In the water supply chamber 50, water flow deflecting means 60 for deflecting the wash water toward the rim water passage inlet 42 is provided, and a part of the wash water supplied into the water supply chamber is supplied to the Zet conduit inlet. It is possible to distribute water to the rim waterway at almost the same timing as it flows into the rim. That is, the water supply chamber 50 forms a descending passage gradually narrowed from the upper space on the side of the cleaning water supply port to the lower space on the side of the inlet 22 of the jet conduit, and the cleaning water supplied into the water supply chamber 50 is supplied with the jet guide. It flows down toward the water channel inlet 22 and is distributed to the jet conduit 20, and is directly ejected from the jet hole 21 toward the inlet of the drainage channel 30. At this time, part of the water supplied into the water supply chamber 50 is supplied to the rim water passage 40 from the rim water passage inlet 42, and the washing water flows down from the rim spray hole 41, Clean the sides.

  In the toilet device 100, the lower surface of the rim 12 and the exposed surface inside the bowl portion 11 serve as the water contact surface 14. A partial enlarged view of the periphery of the rim 12 is shown on the right side of FIG. 1, and the lower partition including the periphery of the rim spray hole 41 of the rim 12 is composed of the ultraviolet transmitting member 13, and the first partition is formed on the exposed surface. One photocatalyst containing layer 15 is formed. The exposed surface of the first photocatalyst-containing layer 15 is an exposed surface (surface) 16 of the first region. That is, most of the lower surface of the rim 12 provided in a ring shape at the peripheral edge of the opening of the bowl portion is an exposed surface (surface) 16 of the first region composed of the exposed surface of the first photocatalyst containing layer 15. Further, a second second photocatalyst containing layer 17 is formed on the inner exposed surface of the lower bowl portion body from the corner portion where the rim 12 and the bowl portion 11 are joined, and the exposed surface is a second region. The exposed surface 18 (which is also a part of the contact water surface 14). And the ultraviolet light source 70 is arrange | positioned at the back surface side of the ultraviolet transmissive member 13, and can irradiate an ultraviolet-ray toward the said back surface. In the ultraviolet transmitting member 13, a through hole is provided in a portion corresponding to the rim spray hole 41.

  In the toilet apparatus 100 of the present invention, hydrogen peroxide 81 is used as the sterilizing cleaning liquid, and the sterilizing cleaning liquid supply means 80 uses the hydrogen peroxide 81 to expose the exposed surface (surface) 16 in the first region and the exposed surface 18 in the second region. It can be made to adhere to the surface of the water contact surface 14 containing.

  In FIG. 1, only the sterilization cleaning liquid nozzle 86 is shown as the sterilization cleaning liquid supply means 80 for the sake of simplification, and other portions are omitted. One or a plurality of sterilizing cleaning liquid nozzles 86 are arranged along the circumference of the elliptical ring-shaped corner portion where the rim 12 and the edge of the bowl portion 11 are joined, and the sterilizing cleaning liquid is provided therefrom. Is sprayed on the exposed surface 16 of the first region and the exposed surface 18 of the second region. The sterilization cleaning liquid supply means 80 supplies a sterilization cleaning liquid tank (not shown) as it is or diluted with water as a sterilization cleaning liquid prepared externally in advance, for example, hydrogen peroxide commercially available as a disinfecting liquid. What sprayed from the nozzle 86 for sterilization washing | cleaning liquid using the pump for washing | cleaning liquid may be used. Moreover, it is good also as what uses the hydrogen peroxide solution 81 manufactured using the sterilization washing | cleaning liquid supply means 80 which has the hydrogen peroxide solution manufacturing apparatus 82 shown in FIG. In FIG. 2, a sterilizing / cleaning liquid supply means 80 having two sterilizing / cleaning liquid nozzles 86 and 86 ′ is shown for convenience.

  As the hydrogen peroxide solution production apparatus 82, for example, a hydrogen peroxide solution production apparatus having a structure similar to that disclosed in Patent Document 8 as shown in FIG. 2, that is, “an electrolyte having hydrogen ion conductivity” is shown. A polymer electrolyte membrane 82b which is a membrane, an anode electrode (not shown) disposed so as to be in contact with one surface across the polymer electrolyte membrane 82b, and a cathode electrode which is disposed so as to be in contact with the other surface (Not shown), and an anode terminal (not shown) is attached to the anode electrode, and a cathode terminal (not shown) is attached to the cathode electrode. The molecular electrolyte membrane 82b, the anode electrode, and the cathode electrode are fixed by screws through a water-tight sheet (not shown), the anode reservoir 82c on the electrolytic cell anode side, and the cathode reservoir on the cathode side 82d provided Is, it is possible to use hydrogen peroxide production apparatus 82 '.

According to Patent Document 8, the hydrogen peroxide production apparatus 82 produces the hydrogen peroxide solution 81 as follows. That is, a DC power source is connected to the anode terminal and the cathode terminal, and the electrolytic cell 82a is operated while a DC voltage of 1.5 to 10 V is applied between the positive and negative electrodes continuously or intermittently. At this time, the water collected in the anode storage part 82c passes through the anode electrode and comes into contact with the polymer electrolyte membrane 82b. Then, water is absorbed by the polymer electrolyte membrane 82b and diffuses and is retained in the polymer electrolyte membrane 82b. In the anode electrode, the supplied water is divided into oxygen (O ₂ ) and hydrogen ions (H ⁺ ) as shown in the following reaction formula (1). When a voltage is applied by a direct current power source, a current flows and oxygen molecules are generated from the surface of the anode electrode. The polymer electrolyte membrane 82b does not transmit gas, is electrically insulating, and has a property of conducting only water and hydrogen ions (H ⁺ ), and therefore contains oxygen (O ₂ ) such as air from the cathode side. When gas and water (H ₂ O) are supplied, the hydrogen ions (H ⁺ ) and hydrogen ions (H ⁺ ) conducted from the anode electrode reaching the interface with the polymer electrolyte membrane 82b on the cathode electrode The reducing substance that reacts with oxygen gas (O ₂ ) reacts to generate hydrogen peroxide (H ₂ O ₂ ) by a reduction reaction represented by the following reaction formula (2). This hydrogen peroxide solution 81 is stored in the cathode water storage part 82d, and the concentration increases as time passes.

Anode: 2H ₂ O → O ₂ + 4H ⁺ + 4e ⁻ (1)
Cathode: O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O ₂ (2)
Tap water can be used as the raw water for the hydrogen peroxide solution. As the tap water used as a raw material, for example, water stored in a raw tank (not shown) can be used, and a raw material water supply pipe 87 connected to the raw tank via a flow path switching valve is newly provided and stored. What is necessary is just to supply the tap water which was made to the anode water storage part 82c of the hydrogen peroxide solution manufacturing apparatus 82 arrange | positioned in the dead space in the toilet bowl main body 10, for example. Thereafter, the hydrogen peroxide solution production apparatus 82 is operated, and the produced hydrogen peroxide solution 81 is stored in the cathode water storage part 82d. At this time, the supply amount of tap water and the operating conditions of the hydrogen peroxide solution production apparatus are controlled by a control means (not shown) so that the hydrogen peroxide solution can be produced continuously for a predetermined time. The hydrogen peroxide solution 81 stored in the cathode reservoir 82d in this way is stored as it is or once in the sterilization / cleaning liquid tank (not shown), and then the sterilization / cleaning liquid pump 83 is activated to supply the sterilization / cleaning liquid supply pipe 84. The inside is pumped. The sterilizing cleaning liquid supply pipe 84 is made of a flexible pressure-resistant tube, and is connected to the sterilizing cleaning liquid nozzles 86 and 86 ′ so as not to interfere with other members, from which the hydrogen peroxide solution 81 is sprayed. The The amount of spraying (spraying speed) at this time is controlled by flow rate adjusting valves 85 and 85 ′ arranged upstream of the sterilizing cleaning liquid nozzles 86 and 86 ′. Thus, specifically, the hydrogen peroxide solution 81 (sterilization cleaning liquid) is uniformly attached to the water contact surface 14 including the exposed surface 16 of the first region and the exposed surface 18 of the second region.

  Thus, the hydrogen peroxide solution 81 is formed on the surfaces of the exposed surface (surface) 16 of the first region in the lower surface of the rim 12 and the exposed surface 18 of the second region in the bowl portion 11, which are the targets for sterilization and cleaning. Self-cleaning is started by turning on the ultraviolet light source 70 and emitting ultraviolet rays with the (sterilization cleaning liquid) uniformly attached. That is, as shown in FIG. 1, by turning on the ultraviolet light source 70, the ultraviolet rays are emitted toward the back surface of the ultraviolet transmitting member 13. The emitted ultraviolet light passes through the ultraviolet transmissive member 13, decomposes the hydrogen peroxide solution 21 (sterilization cleaning liquid) adhering to the exposed surface (surface) 16 of the first region, and generates OH radicals. A portion thereof is irradiated onto the exposed surface 18 of the second region to excite the photocatalyst contained in the second photocatalyst-containing layer 17 and is attached to the exposed surface 18 of the second region. Irradiated to water 21 (sterilization cleaning liquid), it is decomposed by photocatalysis and / or photoreaction by ultraviolet irradiation to generate OH radicals. The soiling substance adhering to the surface of the exposed surface is decomposed and sterilized at the same time by the oxidizing power of the generated OH radicals.

  The ultraviolet light source 70 is an LED module 710 as shown in FIG. Here, the LED module is generally a mechanical or electrical control circuit or a part thereof, in which an LED package is mounted on a substrate or the like, or a plurality of LEDs (light emitting diodes) are arranged in a plane or three-dimensionally. , And optically composed of a large number of elements so that it can be handled as a single unit, or an aggregate thereof.

  FIG. 3 shows a front view (schematic diagram) when the LED module 710 is viewed from the lower side when the lower surface of the rim portion 12 is viewed from the lower side, and a partially enlarged view is shown in the upper side. As shown in FIG. 4, in the LED module 710, the ultraviolet light transmitting member 714 for emitting ultraviolet light that covers substantially the entire back surface of the ultraviolet light transmitting member 13 having a shape (elliptical ring shape) substantially the same as the bottom surface of the rim 12. The UV-LEDs 713 are arranged in a plurality of rows horizontally in the U-shaped ultraviolet light source unit housing 712 whose opening is closed, and accommodated so that the angle of the optical axis of the UV-LED differs in each row. Has been. By doing so, the entire back surface of the ultraviolet transmitting member 13 can be irradiated with ultraviolet rays. In the LED module 710, a through hole is provided in a portion corresponding to the rim spray hole 41.

  As the ultraviolet light source 70, a plurality of LED modules 710 ′ having a basic structure as shown in FIG. 4 is a schematic diagram showing a state in which the LED module 710 ′ is arranged on the back surface of the ultraviolet ray transmitting member 13 arranged on the rim 12, and a schematic diagram of each LED module 710 ′ is shown above. It was. As shown in the upper part of FIG. 4, the LED module 710 ′ is a module using a light guide plate. When the shape (elliptical ring shape) substantially the same as the bottom surface of the rim 12 is divided into several parts, A plurality of UV-LEDs 713 are arranged in a row on a plate-like substrate 715 having a shape corresponding to the peripheral edge, and a unit surrounded by a protective frame 716 is arranged on the side end face of the vertically long light guide plate 717. The UV light emitted from the UV-LED 713 is emitted from the light exit surface 717a of the light guide plate 717. In the upper diagram of FIG. 4, the state seen from the front is represented by a rectangle for convenience, but in reality, as shown in the lower portion of FIG. 4, each bow has a different curvature depending on the location. It has a curved shape in the mold. Further, as shown in the lower part of FIG. 4, twelve LED modules 710 ′ are arranged so as to avoid the rim spray hole 41.

  In the toilet apparatus 100 which is an article of the present invention, as shown in the partially enlarged view of FIG. 1, in the first region, ultraviolet rays are irradiated from the back surface (back surface) side of the ultraviolet transmitting member 13 which is the base. Then, the transmitted ultraviolet light transmitted through the ultraviolet light transmitting member 13 is irradiated to the hydrogen peroxide solution 81 (sterilization cleaning liquid) attached to the exposed surface (surface) 16 of the first region. Further, transmitted ultraviolet light (indicated by a dotted arrow in the figure) is the inner surface of the bowl portion below the corner portion where the rim 12 and the bowl portion 11 are joined (the surface of the exposed surface 18 in the second region). The photocatalyst contained in the second photocatalyst containing layer 17 is excited and irradiated with hydrogen peroxide 81 (sterilization cleaning liquid) adhering to the exposed surface 18 of the second region.

  As shown in the partially enlarged view, the corner portion is generally a narrow gap space, is difficult to see from the outside, and is difficult to clean because a brush or the like is difficult to reach. For this reason, mold and the like tend to grow and become stubborn dirt (dirty dirt that is difficult to remove), and when trying to remove it by manual cleaning, the surface is often rubbed with a brush. In contrast, in the toilet apparatus of the present invention, it is possible to reliably perform advanced self-cleaning using such a high oxidizing power of OH radicals in such a place. In addition, the irradiation region of the transmitted ultraviolet rays in the second region is relatively wide. For example, by providing the ultraviolet transmitting member 13 with a light diffusion function, the region is further expanded, and the application range of the self-cleaning by the mechanism as described above is increased. It can be further expanded. Further, even if there is a place where the transmitted ultraviolet rays do not reach, purification by the sterilization / cleaning power inherent in the hydrogen peroxide solution can be performed there. Therefore, for example, it is possible to detect that a person is not in the toilet using sensing technology and automatically turn on the UV source for a predetermined time, or turn on the UV source periodically for a predetermined time every day at midnight. By doing so, it is possible to always keep the part clean. And even if dirt accumulates, since the dirt is decomposed by the action of OH radicals and has low molecular weight and hydrophilicity, it can be easily removed even with a soft cleaning instrument such as a sponge. . Therefore, the surface of the article or member is not damaged.

  As mentioned above, although this invention was demonstrated to the toilet apparatus as an example, this invention is not limited to this, It is applicable to above-mentioned various water handling articles and members. For example, if it is applied to the ceiling or wall material of a unit bath that is prone to mold and difficult to clean, an ultraviolet light source can be installed in an unused space on the back side of the ceiling or the back side of the wall, so the degree of freedom in wiring is also high. Large and does not impair the interior appearance. In addition, since these spaces are waterproof, the ultraviolet light source does not come into contact with water in a liquid state, and the risk of leakage etc. can be reduced. Even in a drain trap or the like, the same effect can be obtained by installing an ultraviolet light source outside the piping section. Furthermore, when the water contact surface to be sterilized and washed, such as a drain trap pipe portion, is the inner surface of a water contact member having a cylindrical shape, the entire constant portion in the length direction of the water contact member , Which is composed of a cylindrical ultraviolet light transmitting member having a certain height, and a longitudinally long UV-LED module having substantially the same height (height) is disposed on the outside thereof, and this is disposed on the outer periphery of the cylinder. By making it move around, it is possible to efficiently irradiate ultraviolet rays using a small number of UV-LEDs.

DESCRIPTION OF SYMBOLS 100 ... Toilet apparatus 10 ... Toilet body 11 ... Bowl part 12 ... Rim 13 ... Ultraviolet transparent member 14 ... Water contact surface 15 ... First photocatalyst containing layer 16 ..Exposed surface 17 of first region ... Second photocatalyst containing layer 18 ... Exposed surface 20 of second region ... Zet conduit 21 ... Zet hole 22 ... Zet conduit Entrance 30 ... Drain channel 40 ... Rim passage 41 ... Rim spray hole 50 ... Water supply chamber 60 ... Water flow deflecting means 70 ... UV light source 710, 710 '... LED module 712 ... Ultraviolet light source unit housing 713 ... Ultraviolet light emitting diode (UV-LED)
714... UV transmissive member 715 for emitting ultraviolet rays... Base 716 .. protective frame 717 .. light guide plate 717 a. Sterilization cleaning liquid (hydrogen peroxide solution)
82 ... Hydrogen peroxide water production apparatus 82a ... Electrolytic cell 82b ... Polymer electrolyte membrane 82c ... Anode water storage part 82d ... Cathode water storage part 83 ... Sterilization cleaning liquid pump 84 ... Sterilization cleaning liquid supply pipe 85... Flow adjustment valve 86... Sterilization cleaning liquid nozzle 87.

Claims (8)

By a water contact member having an exposed surface, at least a part of the exposed surface being a water contact surface that can come into contact with water in a liquid state, an ultraviolet light emitting means having an ultraviolet light emitting surface, and ultraviolet irradiation in the presence of water. A sterilizing cleaning liquid supply means capable of adhering a sterilizing cleaning liquid composed of an aqueous solution in which a substance or ions that decompose to generate hydroxyl radicals are dissolved, to the wetted surface;
The water contact surface of the water contact member comprises a first region constituted by an exposed surface of the first photocatalyst-containing layer disposed on the ultraviolet light emission surface of the ultraviolet light emission means,
In the first region, the article is characterized in that the ultraviolet ray emitted from the ultraviolet ray emitting surface of the ultraviolet ray emitting means is irradiated from the non-exposed surface side of the first photocatalyst containing layer. The water contact surface of the water contact member further has a second region composed of an exposed surface of the second photocatalyst containing layer disposed on a surface that does not emit ultraviolet light,
The ultraviolet rays emitted from the ultraviolet emission surface and transmitted through the first photocatalyst-containing layer, or the ultraviolet rays emitted from the ultraviolet emission surface and not transmitted through the first photocatalyst-containing layer, The article according to claim 1, wherein at least a part of the exposed surface of the second photocatalyst-containing layer in the second region can be irradiated.   The article according to claim 1 or 2, wherein the cleaning sterilizing solution is a hydrogen peroxide solution.   The article according to claim 3, further comprising an apparatus for producing hydrogen peroxide solution.   5. The ultraviolet light source according to claim 1, further comprising an ultraviolet light source including an ultraviolet light emitting diode that emits ultraviolet light having a peak in a wavelength region of more than 280 nm and not more than 400 nm. Goods.   The article according to claim 5, wherein the ultraviolet light source further comprises an ultraviolet light emitting diode that emits ultraviolet light having a peak in a wavelength region of 240 nm or more and 280 nm or less.   The article according to any one of claims 1 to 6, wherein the article is a durable consumer good.   The durable consumer goods are flush toilet equipment, flush toilet tank, washing machine, humidifier, air conditioner, refrigerator, freezer, water purifier, hand dryer, bathtub, bathroom ceiling material, wall material and flooring, sink for washing The article of claim 7, wherein the article is a sink sink, drain, drain pan or drain trap.

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