Abstract:
An object of the present invention is to provide a flush toilet and a deodorizing method of the flush toilet which effectively remove a source of an offensive odor in the toilet and which can decompose the odor and also clean and sterilize a toilet bowl.  
     A flush toilet  8  is equipped with a deodorizing apparatus  1 , and the deodorizing apparatus 1 comprises: an electrolytic cell fitted with at least a pair of electrodes and storing tap water; odor suction means for sucking in an odor in the toilet; odor supply means for supplying the odor sucked in by the odor suction means into the electrolytic cell, odor adsorption means capable of adsorbing and releasing the odor; and odor supply means for supplying the odor released from the odor adsorption means to the electrolytic cell.

Description:
BACKGROUND OF THE INVENTION  
       [0001]     1. Field of the Invention  
         [0002]     The present invention relates to a flush toilet equipped with a deodorizing apparatus, and more particularly, it relates to a flush toilet and a deodorizing method of the flush toilet capable of cleaning and sterilizing a toilet bowl.  
         [0003]     2. Description of the Related Art  
         [0004]     To remove an odor during use of a flush toilet, it may be insufficient to merely flush it away after use, and various deodorizing apparatuses have heretofore been proposed to deodorize the flush toilet.  
         [0005]     Japanese Patent Publication Laid-open No. 3-286052 discloses a deodorizing apparatus wherein after an odor in a toilet bowl is sucked in by an operation of a ventilator, the odor is blown to a water containing member supplied with water in order to dissolve an offensive odor components in the water in the water containing member, and then it is discharged to sewage through drain pipes. However, this deodorizing apparatus has problems that it is necessary to provide the drain pipe in an intermediate part between a discharge part of the bowl and the sewage and it is not easy to install the drain pipe in an existing bowl, and that because the water containing member contains water, a pressure loss is caused by the water containing member when the offensive odor components are sucked in.  
         [0006]     Furthermore, Japanese Patent Publication Laid-open No. 2000-129747 discloses that sterile water is supplied to a filter having moisture retention properties, and the odor in the bowl is sucked in via this filter to adsorb and decompose the offensive odor components by the sterile water, and then new sterile water is supplied to the filter to clean the filter, and the bowl is also sterilized by this sterile water. However, such a method of supplying the sterile water to the filter has a problem that the sterile water might deteriorate the filter, and that the wet filter causes a great pressure loss to increase load in the suction of the offensive odor components.  
       SUMMARY OF THE INVENTION  
       [0007]     It is an object of the present invention to provide a flush toilet equipped with a deodorizing apparatus and a deodorizing method of the flush toilet which effectively remove a source of an offensive odor in the flush toilet and which can decompose the odor and also clean and sterilize a toilet bowl.  
         [0008]     A flush toilet of the present invention is equipped with a bowl and flushing means for flushing an inside of the bowl, and the flush toilet comprises: an electrolytic cell fitted with a pair of electrodes and storing water; a power source to electrify the pair of electrodes; odor suction means for sucking in an odor of excrement; and odor supply means for supplying the odor sucked in by the odor suction means into the electrolytic cell, wherein the electrodes are electrified by the power source to generate electrolytic water in the electrolytic cell, and the odor is removed by the electrolytic water.  
         [0009]     The flush toilet defined in claim  2  according to the invention of claim  1  further comprises: an adsorption member which adsorbs the odor sucked in by the odor suction means; and heating means for heating the adsorption member to release the odor adsorbed by the adsorption member, wherein the odor released from the adsorption member is supplied into the electrolytic cell by the odor supply means to remove the odor.  
         [0010]     In the flush toilet defined in claim  3  according to the invention of claim  1  or  2 , the odor supply means supplies the odor into the electrolytic cell from a position lower than a half of a height of the electrolytic cell.  
         [0011]     In the flush toilet defined in claim  4  according to the invention of claims  1  to  3 , the odor is supplied into the electrolytic cell by the odor supply means in a state where the electrolytic water is stored in the electrolytic cell.  
         [0012]     The flush toilet defined in claim  5  according to the invention of claims  1  to  4  comprises: a flow path to flow the water or the electrolytic water in the electrolytic cell into the bowl; and a valve which is provided in the flow path and which controls whether or not to allow the water or the electrolytic water to be flown into the bowl.  
         [0013]     In the flush toilet defined in claim  6  according to the invention of claim  5 , the flushing means comprises a flush lever or switch to flow water into the bowl, and the valve is opened in conjunction with the lever or switch.  
         [0014]     The flush toilet defined in claim  7  according to the invention of claim  5  or  6  further comprises: detection means for detecting that the bowl is in use, and when the detection means detects that the bowl is in use, the valve is opened for a predetermined period every predetermined time.  
         [0015]     The flush toilet defined in claim  8  according to the invention of claims  5  to  7  comprises a manual switch to open the valve for the predetermined period.  
         [0016]     In a deodorizing method of a flush toilet of the present invention to implement deodorization in such a manner that an odor of excrement is supplied into an electrolytic cell which stores water and which includes a pair of electrodes provided so that at least part of the pair of electrodes is immersed in the water, and the method comprises electrifying the pair of electrodes before and/or during and/or after the supply of the odor into the electrolytic cell to generate electrolytic water in the electrolytic cell, and decomposing odor components contained in the odor by the electrolytic water.  
         [0017]     In the deodorizing method of the flush toilet defined in claim  10  according to the invention of claim  9 , the electrolytic water is flown into a bowl to clean, sterilize and deodorize the bowl.  
         [0018]     According to the present invention, a source of an offensive odor in a flush toilet can be removed, and the odor can be decomposed. Moreover, according to the present invention, the bowl of the flush toilet can be cleaned and sterilized. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0019]      FIG. 1  is a schematic configuration diagram of a flush toilet equipped with a deodorizing apparatus in Embodiment 1 of the present invention;  
         [0020]      FIG. 2  is a schematic configuration diagram of the flush toilet equipped with the deodorizing apparatus in Embodiment 2 of the present invention;  
         [0021]      FIG. 3  is a schematic configuration diagram of the flush toilet equipped with the deodorizing apparatus in Embodiment 3 of the present invention;  
         [0022]      FIG. 4  is a schematic configuration diagram of the flush toilet equipped with the deodorizing apparatus in Embodiment 3 of the present invention;  
         [0023]      FIG. 5  is a schematic configuration diagram of the flush toilet equipped with the deodorizing apparatus in Embodiment 4 of the present invention;  
         [0024]      FIG. 6  is a schematic configuration diagram of the flush toilet equipped with the deodorizing apparatus in Embodiment 4 of the present invention;  
         [0025]      FIG. 7  is a schematic configuration diagram of the flush toilet equipped with the deodorizing apparatus in Embodiment 5 of the present invention;  
         [0026]      FIG. 8  is a schematic configuration diagram of the flush toilet equipped with the deodorizing apparatus in Embodiment 6 of the present invention;  
         [0027]      FIG. 9  is a schematic configuration diagram of an experimental apparatus to explain a decomposition treatment mechanism of odor components by electrolysis of the present invention; and  
         [0028]      FIG. 10  is a schematic configuration diagram of a hot water cleaning device using ozone water as one example of a hot water cleaning device of the flush toilet equipped with the deodorizing apparatus of the present invention. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION  
       [0029]     Preferred embodiments of a flush toilet of the present invention will hereinafter be described in detail with reference to the drawings.  
       Embodiment 1  
       [0030]     One embodiment of the present invention will be described in detail with reference to the drawings.  FIG. 1  shows a schematic configuration diagram of a flush toilet  8  equipped with a deodorizing apparatus  1  as the one embodiment of the present invention.  
         [0031]     In the present embodiment, the flush toilet  8  includes the deodorizing apparatus  1  comprising an odor adsorption device  100  and an electrolysis device  20 ; a bowl  2 ; a seat  3 ; a water storage tank  4  to flush the bowl  2 ; a water supply pipe  5  coupled to an unshown water pipe to supply water to the water storage tank  4 ; and a hot water cleaning device  30  comprising an unshown hot water tank and the like.  
         [0032]     The odor adsorption device  100  comprises a disk-shaped adsorption member  11  rotated at a predetermined speed; an air intake fan  12  which takes in an odor in the bowl  2  and an odor in a toilet room from an odor suction port  29  and an odor suction port  29 A via an odor flow path  15  to pass air containing the odors to the adsorption member  11  and which passes and circulate the air; an electric heater  13  which heats the adsorption member  11  to +60° C. to +120° C.; a circulation path  14  which circulates the odors heated by the electric heater  13  while passing the air through the adsorption member  11  in a reproduction portion  14 A in the vicinity of the adsorption member  11 ; a circulation fan  16  provided in the circulation path  14 ; a throttle portion  17  provided in the circulation path  14 ; etc.  
         [0033]     The adsorption member  11  comprises an odor absorbent such as zeolite, and the odor of the flush toilet passed through the odor flow path  15  is adsorbed and collected in the adsorption member  11 . Here, the odor to be removed by the present invention includes hydrogen sulfide (H 2 S), methyl mercaptan (CH 3 SH), ammonia (NH 3 ) and the like emitted from excrement or vomit and wafting in the bowl and the toilet room.  
         [0034]     The adsorption member  11  is rotated at a predetermined speed in a direction of an arrow in  FIG. 1 , and a part which has adsorbed the odor through the odor flow path  15  will soon be turned to be located in the vicinity of the reproduction portion  14 A. In the reproduction portion  14 A, air heated to a high temperature by the electric heater  13  is circulated in the circulation path  14 , and the part turned to the reproduction portion  14 A is heated to the above-mentioned temperature by the high-temperature air. The adsorption member  11  releases the adsorbed odor when it is heated. Then, the released odor is carried to the throttle portion  17  in the circulation path  14  on the high-temperature air. It is to be noted that an odor adsorption function of the adsorption member  11  is restored by releasing the odor in the reproduction portion  14 A. Then, this is continuously performed along with the rotation of the adsorption member  11 .  
         [0035]     On the other hand, one end of an intake pipe line  18  is connected to the circulation path  14  on an upstream side of the throttle portion  17 , while the other of the intake pipe line  18  is connected to an air diffusing pipe  26  of the electrolysis device  20  described later. Furthermore, an air pump  19  and a check valve  21  (directed forward to the air diffusing pipe  26 ) located on the air diffusing pipe  26  side of the air pump  19  are interposed in the intake pipe line  18 , and the air containing the odor stopped before the throttle portion  17  in the circulation path  14  by an operation of the air pump  19  is taken into the intake pipe line  18 , and then fed to the air diffusing pipe  26  via the check valve  21 .  
         [0036]     The electrolysis device  20  comprises an electrolytic cell  23 ; a pump  6  which supplies water from the water storage tank  4  or the unshown water pipe into the electrolytic cell  23  via a supply pipe  7 ; the air diffusing pipe  26  which discharges (bubbles) the odor sent from the odor adsorption device  100  into the water in the electrolytic cell  23 ; at least one pair of electrolytic electrodes  24 ,  25  provided in the electrolytic cell  23 ; an electrolytic water flow path  27  which is a flow path to flow the water in the electrolytic cell  23  into the bowl  2  through an outlet port  28 A; a valve  31  which controls water flowing from the electrolytic cell  23  to the electrolytic water flow path  27 ; a controller  22  which includes a microcomputer or the like, has a predetermined direct-current power source, electrifies the electrolytic electrodes  24 ,  25  and controls an operation of an unshown motor to rotate the fans  12 ,  16 , the electric heater  13  and the adsorption member  11  and operations of the air pump  19 , the valve  31  and the like; etc.  
         [0037]     Both of the electrolytic electrodes  24 ,  25  comprise insoluble metal electrodes based on, for example, platinum-iridium (Pt—Ir), and a distance between them is 3 mm, for example. It is to be noted that in the present invention, the electrolytic electrode means an electrode which is immersed in a water solution as water to be electrolyzed and which contributes directly to the electrolysis, and the electrolytic electrode also includes part of an electrode which is immersed to contribute directly to the electrolysis. Moreover, the electrolytic electrodes  24 ,  25  comprise the pair of electrodes, but a plurality of electrolytic electrodes may be provided instead.  
         [0038]     Furthermore,  FIG. 10  shows a schematic configuration diagram of the hot water cleaning device  30  using ozone water as one example of the hot water cleaning device  30  of the flush toilet  8  in the present invention. This hot water cleaning device  30  comprises a shower nozzle  52  and a jet  51  which jets water to and wash a pubic region; a water passage  56  which supplies jet water to the jet  51 ; a heater  50  which heats water to produce warm water between the water passage  56  and the shower nozzle  52 ; an electrolysis device  55  which generates ozone water; electrolytic electrodes  53 ,  54  which are immersed in the water flowing through the water passage  56  placed in the electrolysis device  55 ; and a controller  57  which includes a microcomputer or the like, has a predetermined direct-current power source, electrifies the electrolytic electrodes  53 ,  54  and controls electrification of the heater  50  and the like; etc.  
         [0039]     Of the electrolytic electrodes  53 ,  54 , the electrolytic electrode  54  which serves as an anode comprises, for example, an electrode based on platinum-tantalum (Pt—Ta) as an ozone generating electrode, while the electrolytic electrode  53  which serves as a cathode comprises an insoluble metal electrode based on, for example, platinum-iridium as described above, and a distance between the electrodes is 6 mm, for example. It is to be noted that the platinum-tantalum-based electrode is an electrode in which an intermediate layer containing platinum is formed on a surface of a conductive base substance such as titanium, and a surface layer comprising a dielectric such as tantalum oxide and niobium oxide is formed on a surface of the intermediate layer. By using such a platinum-tantalum-based electrolytic electrode  54  as the anode, generation of hypochlorous acid can be restrained and ozone water of high concentration can be produced even when tap water containing chloride ions is electrolyzed.  
         [0040]     In the above configuration, an operation of the flush toilet  8  equipped with the deodorizing apparatus  1  in the present embodiment will be described. It is to be noted that the tap water has been previously stored in the water storage tank  4  and the electrolytic cell  23  before use of the flush toilet in the present embodiment. In addition, about 5 to 200 mg/l in general, about 17 mg/l on average of chloride ions is contained in the tap water for sterilization depending on regions and seasons.  
         [0041]     Deodorization Mode  
         [0042]     First, a deodorization mode to deodorize the flush toilet will be described. When the flush toilet  8  is used and excrement such as human waste is discharged into the bowl  2 , an odor caused by hydrogen sulfide, methyl mercaptan, ammonia and the like is produced in the bowl  2  and the toilet room as described above. Here, by sensing the use of the toilet, for example, by an unshown odor sensor or by an unshown seating sensor for the seat  3 , or by a manual switch, the controller  22  operates the fan  12  and also operates a rotating motor of the adsorption member  11  to rotate the adsorption member  11  at the predetermined speed. By the operation of the fan  12 , the air containing the odor in the bowl  2  and the toilet room is passed from the odor suction port  29  and the odor suction port  29 A to the adsorption member  11  via the odor flow path  15 , whereby hydrogen sulfide, methyl mercaptan, ammonia and the like which are odor components are sucked and collected in the adsorption member  11 .  
         [0043]     Such an operation of collecting the odor into in the adsorption member  11  is generally performed for a predetermined period, for example, five minutes every time the flush toilet is used.  
         [0044]     Odor Component Decomposition Mode  
         [0045]     Furthermore, the flush toilet is used a predetermined number of times, for example, three times, and the odor collection is performed the predetermined number of times, and a certain amount of the odor components is thus collected in the adsorption member  11 . Then, an odor component decomposition mode is executed.  
         [0046]     When the odor component decomposition mode is executed, the controller  22  operates the fan  16  and the air pump  19 , and also operates the rotating motor of the adsorption member  11  to rotate the adsorption member  11  at the predetermined speed, thereby electrifying the electric heater  13  for heat generation.  
         [0047]     The adsorption member  11  which has adsorbed and collected the odor components in the above-mentioned deodorization mode will soon reach the reproduction portion  14 A by the rotation, where the adsorption member  11  is heated by the high-temperature air circulated by the fan  16  and heated by the electric heater  13 . By heating the adsorption member  11  in this manner, the odor components adsorbed by the adsorption member  11  are released, and moved to the throttle portion  17  of the circulation path  14  together with the high-temperature air. The air containing a large amount of the released odor components is taken into the intake pipe line  18  by the air pump  19 , and arrives at the air diffusing pipe  26  provided at the bottom of the electrolytic cell  23  of the electrolysis device  20  via the check valve  21 . The air containing the large amount of the odor components fed to the air diffusing pipe  26  is bubbled in an amount of 0.1 to 50.01/min, preferably an amount of 0.5 to 1.01/min in the water within the electrolytic cell  23 , and passes between the electrolytic electrodes  24 ,  25  and around them in a form of bubbles.  
         [0048]     On the other hand, the controller  22  supplies electric power to the electrolytic electrodes  24 ,  25 . At this time, the electrolytic electrode  24  to which a positive potential is applied serves as the anode, while the electrolytic electrode  25  to which a negative potential is applied serves as the cathode. Further, the controller  22  may change polarities of the electrolytic electrodes  24 ,  25  every predetermined time, for example, three minutes. If the polarities of the electrolytic electrodes  24 ,  25  are changed in this manner, the electrolytic electrode  24  serves as the cathode and the electrolytic electrode  25  serves as the anode, and moreover, scale such as calcium sticking to surfaces of the electrodes can be removed.  
         [0049]     Furthermore, since the tap water generally containing about 17 mg/l of chloride ions as described above is stored in the electrolytic cell  23  in which the odor components have dissolved, the chloride ions emit electricity to produce chlorine in the electrolytic electrode  24  which serves as the anode (Reaction Formulas (1), (2)). Subsequently, chlorine dissolves in the water, and hypochlorous acid is produced (Reaction Formula (3)). Reaction Formulas (1), (2), (3) are shown below. 
 
NaCl→Na + +Cl −   (1) 
 
2Cl − →Cl 2 +2e −   (2) 
 
Cl 2 +H 2 O→HClO+HCl   (3) 
 
         [0050]     Furthermore, the air fed into the electrolytic cell  23  as described above easily contacts the water, and the odor components contained in the air therefore dissolve in the water. Thus, hydrogen sulfide, methyl mercaptan, ammonia and the like which are the odor components dissolve in the water and are decomposed by the electrolytic water containing hypochlorous acid, thereby releasing air in a cleaned state into the toilet room.  
         [0051]     It is to be noted that regarding the electrolysis by the electrification of the electrolytic electrodes  24 ,  25  in accordance with the controller  22  described above, the tap water in the electrolytic cell  23  may be electrolyzed in advance for a predetermined period before the bubbling of the odor components so that the electrolytic water containing hypochlorous acid may be produced in the electrolytic cell  23 , or the tap water may be electrolyzed during the bubbling, or the tap water may be electrolyzed after the odor components are dissolved in the tap water.  
         [0052]     Here, a decomposition treatment mechanism of the odor components using the electrolysis of the water solution will be described with reference to  FIG. 9 . In addition,  FIG. 9  is a schematic configuration diagram of an experimental apparatus to explain the decomposition treatment mechanism of the odor components.  
         [0053]     This experimental apparatus comprises a sealed glass vessel  43  which stores 300 ml of test water; the air diffusing pipe  26  which bubbles the odor components in the test water; an odor sealing pack  41  and an air pump  42  which feed test odor components to the air diffusing pipe  26 ; a recovery pack  45  to collect a gas over a surface of the water in the glass vessel  43 ; a liquid gathering syringe  44  which gathers the test water; the electrolytic electrodes  24 ,  25  which are immersed in the test water; and the controller  22 .  
         [0054]     The test water used includes the following two kinds: a water solution in which sodium chloride (NaCl) is dissolved in purified water to have a chloride ion concentration of 5 mg/l (hereinafter referred to as Cl − 5 mg/l water), and a water solution in which sodium chloride (NaCl) is dissolved in purified water to have a chloride ion concentration of 17 mg/l (hereinafter referred to as Cl − 17 mg/l water).  
         [0055]     Furthermore, the odor components to be evaluated in the present experiment include three kinds of odor components: hydrogen sulfide, methyl mercaptan and ammonia. These odor components are diluted with argon gas so that a gas concentration of hydrogen sulfide may be 3 ppm, that a gas concentration of methyl mercaptan may be 3.2 ppm, and that a gas concentration of ammonia may be 4.8 ppm, and these are then sealed into separate odor sealing packs  41 . These components are bubbled in the test water at a flow volume of 0.5 ml/min by the air pump  42  via the air diffusing pipe  26 . Then, the odor components which have passed through the test water are collected by the recovery pack  45 , and gas concentration measurement of the odor components is made by a gas chromatograph and a detector tube, while the test water is gathered by the liquid gathering syringe  44 , and solution components of the test water are analyzed by an ion chromatograph. It is to be noted that the gas concentrations of the odor components are about ten times as high as the gas concentrations of the odor contained in the odor in general flush toilets.  
         [0056]     Then, the platinum-iridium-based electrolytic electrodes  24 ,  25  similar to the ones described above are immersed in the test water. It is to be noted that the electrolytic electrodes  24 ,  25  used in the experiment have dimensions including a length of 60 mm, a width of 35 mm and a thickness of 2 mm, and the distance between the electrodes is 3 mm as above. Then, a constant current having a current density of 20 mA/cm 2  is applied to the electrolytic electrodes  24 ,  25  by the controller  22 .  
         [0057]     Since the chloride ions are contained in the test water as described above, the chloride ions emit electricity to produce chlorine (Cl) in the electrolytic electrode  24  which serves as the anode. Subsequently, chlorine dissolves in the water, and hypochlorous acid (HClO) is produced (Reaction Formulas (1), (2), (3)).  
         [0058]     Table 1 shows the concentration (mg/l) of hypochlorous acid in the test waters before and after bubbling and the concentration (ppm) of hydrogen sulfide as the gas concentration of the odor component in a recovery gas pack. In this case, the following test waters were used: the above-mentioned Cl − 5 mg/l water electrolyzed for three minutes before five-minute bubbling of the odor components described later (hereinafter referred to as Cl − 5 mg/l electrolytic water), and the above-mentioned C − 17 mg/l water electrolyzed for three minutes before five-minute bubbling of the odor components described later (hereinafter referred to as Cl − 17 mg/l electrolytic water). Then, 3 ppm of hydrogen sulfide was sealed as the odor component into the odor sealing pack  41 , and the hydrogen sulfide gas was bubbled for five minutes in the respective test waters. Table 2 shows the concentration of hypochlorous acid and the concentration of hydrogen sulfide in a case where the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water are also electrolyzed during the five-minute bubbling.  
         [0059]     As apparent from Table 1 and Table 2, 1 ppm of hydrogen sulfide was also detected in the Cl − 5 mg/l water after the bubbling, and when the odor in the recovery gas pack was smelled, an unpleasant odor of hydrogen sulfide was perceived. On the contrary, hydrogen sulfide was not detected from the recovery pack after the bubbling in the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. Further, in accordance with the solution analysis by the ion chromatograph, sulfate ions (SO 4   2− ) were detected from the test waters after the bubbling in the case of the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. It was presumed from the above that hydrogen sulfide was decomposed by hypochlorous acid into odorless sulphuric acid. A degradation reaction of hydrogen sulfide by hypochlorous acid is shown below in Reaction Formula (4). 
 
H 2 S+4HClO→6H + +SO 4   2− +4Cl −   (4) 
 
         [0060]     In addition, no difference was recognized in the concentration of hydrogen sulfide after the bubbling between the case where the electrolysis was also implemented during the bubbling (Table 2) and the case where the electrolysis was not implemented (Table 1). However, the concentration of hypochlorous acid after the bubbling was higher in the case where the electrolysis was also implemented during the bubbling. It is thus considered that more hydrogen sulfide can be decomposed in the case where the electrolysis is implemented, and that sterilizing and odor eliminating effects are improved when the electrolytic water in the electrolytic cell  23  of the present invention is flown into the bowl  2  as described later.  
                                                                       TABLE 1                                       Hypochlorous acid   Hydrogen sulfide           concentration (mg/l)   concentration (ppm)                Before   After   Before   After           bubbling   bubbling   bubbling   bubbling                        Cl − 5 mg/l   0   0   3.0   1.0       water       Cl − 5 mg/l   3.0   1.5   3.0   Undetected       electrolytic       water       Cl − 17 mg/l   7.0   4.0   3.0   Undetected       electrolytic       water                  
 
         [0061]    
       
         
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
             
             
               
                   
                   
               
               
                   
                   
               
               
                   
                 Hypochlorous acid 
                 Hydrogen sulfide 
               
               
                   
                 concentration (mg/l) 
                 concentration (ppm) 
               
             
          
           
               
                   
                 Before 
                 After 
                 Before 
                 After 
               
               
                   
                 bubbling 
                 bubbling 
                 bubbling 
                 bubbling 
               
               
                   
                   
               
             
          
           
               
                 Cl − 5 mg/l 
                 0 
                 0 
                 3.0 
                 1.0 
               
               
                 water 
               
               
                 Cl − 5 mg/l 
                 3.0 
                 5.7 
                 3.0 
                 Undetected 
               
               
                 electrolytic 
               
               
                 water 
               
               
                 Cl − 17 mg/l 
                 7.0 
                 15.5 
                 3.0 
                 Undetected 
               
               
                 electrolytic 
               
               
                 water 
               
               
                   
               
             
          
         
       
     
         [0062]     Table 3 shows the concentration (mg/l) of hypochlorous acid in the test waters before and after bubbling and the concentration (ppm) of methyl mercaptan as the gas concentration of the odor component in the recovery gas pack. In this case, the test waters used were: the Cl − 5 mg/l water, the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. Then, 3.2 ppm of methyl mercaptan was sealed as the odor component into the odor sealing pack  41 , and the methyl mercaptan gas was bubbled for five minutes in the respective test waters. Table 4 shows the concentration of hypochlorous acid and the concentration of methyl mercaptan in a case where the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water are also electrolyzed during the five-minute bubbling.  
         [0063]     As apparent from Table 3 and Table 4, 0.9 ppm of methyl mercaptan was also detected in the Cl − 5 mg/l water after the bubbling, and when the odor in the recovery gas pack was smelled, an unpleasant odor of methyl mercaptan was perceived. On the contrary, methyl mercaptan was not detected from the recovery pack after the bubbling in the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. Further, in accordance with the solution analysis by the ion chromatograph, metal sulfonic acid (SO 4   2− ) was detected from the test waters after the bubbling in the case of the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. It was presumed from the above that methyl mercaptan was decomposed by hypochlorous acid into metal sulfonic acid which was an odorless component. A degradation reaction of methyl mercaptan by hypochlorous acid is shown below in Reaction Formula (5). 
 
CH 3 SH+3HClO→CH 3 SO 3 H+3HCl   (5) 
 
         [0064]     In addition, no difference was recognized in the concentration of methyl mercaptan after the bubbling between the case where the electrolysis was also implemented during the five-minute bubbling (Table 2) and the case where the electrolysis was not implemented (Table 1), as in the case of hydrogen sulfide described above. However, the concentration of hypochlorous acid after the bubbling was higher in the case where the electrolysis was also implemented during the bubbling. It is thus considered that more methyl mercaptan can be decomposed in the case where the electrolysis is implemented, and that the sterilizing and odor eliminating effects are improved when the electrolytic water in the electrolytic cell  23  of the present invention is flown into the bowl  2  as described later.  
                                                                       TABLE 3                                       Hypochlorous acid   Methyl mercaptan           concentration (mg/l)   concentration (ppm)                Before   After   Before   After           bubbling   bubbling   bubbling   bubbling                        Cl − 5 mg/l   0   0   3.2   0.9       water       Cl − 5 mg/l   2.6   1.2   3.2   Undetected       electrolytic       water       Cl − 17 mg/l   7.0   4.5   3.2   Undetected       electrolytic       water                  
 
         [0065]    
       
         
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
             
             
               
                   
                   
               
               
                   
                   
               
               
                   
                 Hypochlorous acid 
                 Methyl mercaptan 
               
               
                   
                 concentration (mg/l) 
                 concentration (ppm) 
               
             
          
           
               
                   
                 Before 
                 After 
                 Before 
                 After 
               
               
                   
                 bubbling 
                 bubbling 
                 bubbling 
                 bubbling 
               
               
                   
                   
               
             
          
           
               
                 Cl − 5 mg/l 
                 0 
                 0 
                 3.2 
                 0.9 
               
               
                 water 
               
               
                 Cl − 5 mg/l 
                 2.6 
                 4.8 
                 3.2 
                 Undetected 
               
               
                 electrolytic 
               
               
                 water 
               
               
                 Cl − 17 mg/l 
                 7.0 
                 15.2 
                 3.2 
                 Undetected 
               
               
                 electrolytic 
               
               
                 water 
               
               
                   
               
             
          
         
       
     
         [0066]     Table 5 shows the concentration (mg/l) of hypochlorous acid in the test waters before and after bubbling and the concentration (ppm) of ammonia as the gas concentration of the odor component in the recovery gas pack. In this case, the test waters used were: the Cl − 5 mg/l water, the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. Then, 4.8 ppm of ammonia was sealed as the odor component into the odor sealing pack  41 , and the ammonia gas was bubbled for five minutes in the respective test waters. Table 6 shows the concentration of hypochlorous acid and the concentration of ammonia in a case where the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water are also electrolyzed during the five-minute bubbling.  
         [0067]     As apparent from Table 5 and Table 6, 0.5 ppm of ammonia was also detected in the Cl − 5 mg/l water after the bubbling, and when the odor in the recovery gas pack was smelled, an unpleasant odor of ammonia was perceived. On the contrary, ammonia was not detected from the recovery pack after the bubbling in the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. Further, in accordance with the solution analysis by the ion chromatograph, ammonium ions (NH 4   + ) were not detected from the test waters after the bubbling in the case of the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water. It was presumed from the above that ammonia dissolved in the test waters was decomposed by hypochlorous acid due to a so-called break point. Degradation reactions of ammonia by hypochlorous acid are shown below in Reaction Formulas (6) to (8). 
 
NH 4   + +ClO − →NH 2 Cl+H 2 O   (6) 
 
NH 2 Cl+ClO − →NHCl 2 +H 2 O   (7) 
 
NH 2 Cl+NHCl 2 →N 2 ↑+ 2 3H 2 Cl   (8) 
 
         [0068]     In addition, no difference was recognized in the concentration of ammonia after the bubbling between the case where the electrolysis was implemented during the five-minute bubbling (Table 2) and the case where the electrolysis was not implemented (Table 1), as in the cases of hydrogen sulfide and methyl mercaptan described above. However, the concentration of hypochlorous acid after the bubbling was higher in the case where the electrolysis was also implemented during the bubbling. It is thus considered that more ammonia can be decomposed in the case where the electrolysis is implemented, and that the sterilizing and odor eliminating effects are improved when the electrolytic water in the electrolytic cell  23  of the present invention is flown into the bowl  2  as described later.  
                                                                       TABLE 5                                       Hypochlorous acid   Ammonia concentration           concentration (mg/l)   (ppm)                Before   After   Before   After           bubbling   bubbling   bubbling   bubbling                        Cl − 5 mg/l   0   0   4.8   0.5       water       Cl − 5 mg/l   3.0   1.5   4.8   Undetected       electrolytic       water       Cl − 17 mg/l   7.0   5.0   4.8   Undetected       electrolytic       water                  
 
         [0069]    
       
         
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 6 
               
             
             
               
                   
                   
               
               
                   
                   
               
               
                   
                 Hypochlorous acid 
                 Ammonia concentration 
               
               
                   
                 concentration (mg/l) 
                 (ppm) 
               
             
          
           
               
                   
                 Before 
                 After 
                 Before 
                 After 
               
               
                   
                 bubbling 
                 bubbling 
                 bubbling 
                 bubbling 
               
               
                   
                   
               
             
          
           
               
                 Cl − 5 mg/l 
                 0 
                 0 
                 4.8 
                 0.5 
               
               
                 water 
               
               
                 Cl − 5 mg/l 
                 2.4 
                 4.3 
                 4.8 
                 Undetected 
               
               
                 electrolytic 
               
               
                 water 
               
               
                 Cl − 17 mg/l 
                 7.0 
                 15.0 
                 4.8 
                 Undetected 
               
               
                 electrolytic 
               
               
                 water 
               
               
                   
               
             
          
         
       
     
         [0070]     Thus, the Cl − 5 mg/l electrolytic water and the Cl − 17 mg/l electrolytic water were used as the test waters so that hydrogen sulfide, methyl mercaptan, and ammonia could be decomposed in a significantly short time by simply bubbling them in the test waters.  
         [0071]     In the flush toilet  8  of the present embodiment, the odor components bubbled in the electrolytic cell  23  as described above are decomposed with the electrolytic waters containing hypochlorous acid by the electrolysis. Further, in accordance with the electrolytic electrodes  24 ,  25  of the embodiment, there are also produced, in the water solution by the electrolysis, ozone, oxygen, hydrogen peroxide, or hydrogen peroxide radical, superoxide radical (O 2   − ), hydroxy radical (•OH) and singlet oxygen radical (′O 2 ). These can be used to decompose the odor components contained in the air discharged into the water in the electrolytic cell  23 . It is to be noted that in order to electrify the electrolytic electrodes  24 ,  25 , there are provided an unshown hypochlorous acid concentration sensor, an ozone concentration sensor and the like, and control may thus be performed so that the electrolysis is stopped when detection values of these concentration sensors reach predetermined values.  
         [0072]     Furthermore, in the electrolysis device  20  of the present invention, deodorized air in which the odor components are decomposed rises in the form of bubbles in the electrolytic cell  23 , and bursts in an upper part of the electrolytic cell  23  including hypochlorous acid, ozone and the like. Thus, an unshown air outlet is provided in the upper part of the electrolytic cell  23  so that hypochlorous acid and the like contained in the burst bubbles are discharged into the toilet room. Thus, the odor components are also decomposed which are contained in the ambient air and which could not be collected by the odor adsorption device  100 , and the air is also sterilized.  
         [0073]     Moreover, in the odor component decomposition mode described above, a total amount or a predetermined amount of the electrolytic water in the electrolytic cell  23  after the odor component decomposition is drained from the outlet port  28 A via the electrolytic water flow path  27  in conjunction with the unshown flush lever, flush switch or the like to flow flushing water for the bowl  2  stored in the water storage tank  4  or in accordance with opening of the valve  31  every predetermined time by the controller  22 , thereby flushing the bowl  2  using the flushing water together. Thus, the bowl  2  is, for example, bleached, cleaned, deodorized, sterilized, by hypochlorous acid and the like contained in the electrolytic water, and capacity of cleaning the bowl can be improved as compared with a case where the inside of the bowl is cleaned with the flushing water alone as in ordinary flush toilets.  
         [0074]     It is to be noted that the valve  31  may be opened for a predetermined period every predetermined time when it is detected that the bowl  2  is in use by detection means detecting the use of the bowl  2 , for example, by the unshown seating sensor for the seat, thereby flowing the electrolytic water in the electrolytic cell  23  into the bowl  2 .  
         [0075]     Furthermore, in accordance with the hot water cleaning device  30  of the present embodiment, the electrolysis device  55  can electrolyze the water before jet to the pubic region from the jet  51  provided at the tip of the shower nozzle  52  as described above in order to form the water into ozone water. Thus, regions around the pubic region are sterilized by ozone, and effects in, for example, hemorrhoid treatments are also expected.  
         [0076]     It is to be noted that in a case of a configuration wherein changes can be made by an unshown switch or the like in an amount or time of the electrification of the electrolytic electrodes  53 ,  54  by the controller  57 , a concentration of the ozone water to wash the pubic region can be changed to, for example, a low concentration as required. Further, the ozone water of high concentration can be produced and used for, for example, sterilization and cleaning of, for example, the jet  51  or the bowl  2 .  
       Embodiment 2  
       [0077]      FIG. 2  shows a schematic configuration diagram of a flush toilet  8  equipped with a deodorizing apparatus  1  in a second embodiment of the present invention. It is to be noted that those assigned with the same numbers in  FIG. 2  as those in Embodiment 1 have the same or similar functions and effects. In this case, a configuration similar to that in Embodiment 1 is provided except that an adsorption member  11  is provided in a circulation path  14  without a rotation mechanism such as the motor described above, that an odor flow path  15  communicates with a circulation path  14 , and that lids  32 A,  32 B are provided at a portion where the odor flow path  15  is connected to the circulation path  14 . It is to be noted that the adsorption member  11  in the present embodiment does not have the rotation mechanism, but when capacity of the adsorption member  11  to adsorb and release odor components is to be increased, the rotary adsorption member  11  similar to that in Embodiment 1 can be provided in the circulation path  14 .  
         [0078]     In the present embodiment, an odor in the flush toilet sucked in by a fan  12  from the odor suction port  29  passes through the adsorption member  11  provided in the circulation path  14  as described above, thereby gathering the odor in the adsorption member  11 .  
         [0079]     Furthermore, in a deodorization mode, the lids  32 A,  32 B are opened by a controller  22  so that the odor is adsorbed by the adsorption member  11 , but the controller  22  closes the lids  32 A,  32 B as soon as the deodorization mode is terminated. Subsequently, an odor component decomposition mode is performed, and in this case, an operation similar to that in Embodiment 1 is performed, that is, air in the circulation path  14  is circulated by a fan  16 , and the air heated by a heater  13  heats and restores the adsorption member  11 , so that the adsorption member  11  releases the adsorbed the odor components. Then, the released odor substances are carried on high-temperature air to be sucked in by an air pump  19  at an upstream portion of a throttle portion  17 , and then taken into an intake pipe line  18  to be fed to an air diffusing pipe  26  via a check valve  21 . According to such a configuration, it is also possible to collect the odor components in the flush toilet and decompose them by electrolysis. Subsequently, cleaning and the like of a bowl  2  are also performed by electrolytic water in an electrolytic cell  23  as in Embodiment 1.  
         [0080]     It is to be noted that in the flush toilet  8  equipped with the deodorizing apparatus  1  in the present embodiment, for example, even when the odor components are released from the adsorption member  11  in the odor component decomposition mode, it is possible to avoid a disadvantage that the released odor components are again diffused in a toilet room and the like because the adsorption member  11  is housed in the circulation path  14 . Moreover, it is possible to reduce a size of the deodorizing apparatus  1  of the present invention since the rotation mechanism or the like of the adsorption member  11  is not needed.  
       Embodiment 3  
       [0081]     Next,  FIGS. 3 and 4  show schematic configuration diagrams of a flush toilet  8  equipped with a deodorizing apparatus  1  in a third embodiment of the present invention. It is to be noted that those assigned with the same numbers in  FIGS. 3 and 4  as those in the above embodiments have the same or similar functions and effects. In this case, a configuration similar to those in the above embodiments is provided except that an electrolytic water flow path  27  branches into outlet ports  28 B and  28 C in addition to an outlet port  28 A at a downstream portion of a valve  31 .  
         [0082]     Thus, in the flush toilet  8  equipped with the deodorizing apparatus  1  in the present embodiment, electrolytic water from an electrolytic cell  23  is flown into a bowl  2  in three directions by the outlet ports  28 A,  28 B and  28 C, so that cleaning and the like inside the bowl  2  can be implemented more uniformly and in a wider range than in a case where the cleaning and the like inside the bowl  2  are implemented with the electrolytic water using the outlet port  28 A alone as in the embodiments described above. It is to be noted that the three outlet ports  28 A,  28 B and  28 C are provided in the present embodiment, but the number of outlet ports can naturally be increased or decreased as required.  
       Embodiment 4  
       [0083]      FIGS. 5 and 6  show schematic configuration diagrams of a flush toilet  8  equipped with a deodorizing apparatus  1  in a fourth embodiment of the present invention. It is to be noted that those assigned with the same numbers in  FIGS. 5 and 6  as those in the above embodiments have the same or similar functions and effects. In this case, a configuration similar to those in the above embodiments is provided except that an electrolysis device indicated by  40  in  FIGS. 5 and 6  is partially different from the electrolysis device  20  in the above embodiments. That is, the electrolysis device  40  in the present embodiment uses a water storage tank  4  as an electrolytic cell thereof instead of an electrolytic cell  23  in the above embodiments.  
         [0084]     Thus, in the flush toilet  8  equipped with the deodorizing apparatus  1  in the present embodiment, the water storage tank  4  installed in an ordinary flush toil is used similarly to the electrolytic cell  23  without separately providing the electrolytic cell  23  in the electrolysis device  40 , thereby allowing a further reduction in size of the deodorizing apparatus  1 . Further, since electrolysis is performed in the water storage tank  4  in the present embodiment, electrolytic water containing hypochlorous acid is generated in water contained in the water storage tank  4 , so that, for example, propagation of mold and miscellaneous germs in the water storage tank  4  can be prevented to keep the inside of the water storage tank  4  clean, and a toilet room can be better deodorized.  
         [0085]     It is to be noted that in the present embodiment, cleaning of a bowl  2  with the electrolytic water can be performed by opening/closing a valve  31  every flush or every predetermined time as in the embodiments described above.  
       Embodiment 5  
       [0086]      FIG. 7  shows a schematic configuration diagram of a flush toilet  8  equipped with a deodorizing apparatus  1  in a fifth embodiment of the present invention. It is to be noted that those assigned with the same numbers in  FIG. 7  as those in the above embodiments have the same or similar functions and effects.  
         [0087]     In the deodorizing apparatus  1  in the present embodiment, an odor generated in the flush toilet is sucked into an intake pipe line  18  provided with a check valve  21  from an odor suction port  29  via an odor flow path  15  by an operation of an air pump  19 , and also fed to an air diffusing pipe  26 . Then, air containing odor components fed to the air diffusing pipe  26  is subjected to a decomposition treatment of the odor components using electrolytic water in an electrolytic cell  23  as in the embodiments described above.  
         [0088]     In such a configuration, the odor in the flush toilet can be removed in the present embodiment without using an adsorption member  11  or the like described above. Thus, further reductions in size and cost of the deodorizing apparatus  1  can be achieved.  
         [0089]     However, in this case, it is required that as soon as the odor caused by hydrogen sulfide, methyl mercaptan, ammonia and the like is generated in a bowl  2  and a toilet room as described above, use of the flush toilet be sensed, for example, by an unshown odor sensor or by an unshown seating sensor for a seat  3 , or a controller  22  drive the air pump  19  and electrify electrolytic electrodes  24 ,  25  of an electrolysis device  20  by use of a manual switch so that the odor is introduced to the electrolytic cell  23  of the electrolysis device  20 . The electrolysis device  20  is usually operated every time the flush toilet is used, which may decrease operation efficiency of the electrolysis device. However, significant reductions in size and cost of the deodorizing apparatus  1  can be achieved as described above, and it is therefore needless to say that this configuration may be effective depending on a form in which it is used.  
         [0090]     It is to be noted that the odor in the flush toilet is sucked in by the air pump  19  in the present embodiment, but the odor in the flush toilet may be sucked using, for example, a fan.  
       Embodiment 6  
       [0091]      FIG. 8  shows a schematic configuration diagram of a flush toilet  8  equipped with a deodorizing apparatus  1  in a sixth embodiment of the present invention. It is to be noted that those assigned with the same numbers in  FIG. 8  as those in the above embodiments have the same or similar functions and effects. The deodorizing apparatus  1  in this case comprises a buffer tank  33  and an air valve  34  in an intake pipe line  18  between a check valve  21  and an air diffusing pipe  26 , in addition to the configuration of the deodorizing apparatus  1  in Embodiment 5.  
         [0092]     Thus, in the deodorizing apparatus  1  of the present embodiment, an odor generated in the flush toilet can be stored for a predetermined time or in a predetermined amount even though the deodorizing apparatus  1  does not comprise an odor adsorption portion such as an adsorption member  11 , and the stored odor can be decomposed by an electrolysis device  20  as necessary. That is, according to the deodorizing apparatus  1  of the present embodiment, when the odor caused by hydrogen sulfide, methyl mercaptan, ammonia and the like during use of the flush toilet as described above is generated in a bowl  2  and a toilet room, the use of the flush toilet is sensed, for example, by an unshown odor sensor or by an unshown seating sensor for a seat  3 , or a controller  22  drives an air pump  19  and keeps the air valve  34  closed by use of a manual switch so that the odor can be stored in the buffer tank  33 . The stored odor can be fed to an electrolytic cell  23  and decomposed thereby if necessary as described above. Thus, the odor can be stored without providing the adsorption member  11  or the like, and an operation of the electrolysis device  20  can be controlled as required, thereby allowing further energy saving and a size reduction of the deodorizing apparatus  1 .  
         [0093]     It is to be noted that in the embodiments described above, cleaning by draining the electrolytic water from the electrolytic cell  23  into the bowl  2  is performed when the bowl  2  of the flush toilet is washed after termination of the odor component decomposition mode. However, this is not a limitation. The tap water in the electrolytic cell  23  can be always electrolyzed by the controller  22  every predetermined time to store the electrolytic water, and a predetermined amount of the electrolytic water can be drained every time the bowl  2  is washed to accomplish the cleaning of the bowl  2 . Further, the use of the flush toilet is sensed, for example, by the odor sensor or by the unshown seating sensor for the seat  3 , or the manual switch is operated, so that the odor of excrement discharged in the bowl  2  can be directly removed during the use of the flush toilet owing to hypochlorous acid and the like contained in the electrolytic water by draining the electrolytic water every predetermined time or in accordance with the operation of the valve  31  using the unshown switch during the use of the flush toilet. Thus, the unpleasant odor during the use of the flush toilet can be reduced.  
         [0094]     Furthermore, a so-called Western-style toilet equipped with the seat  3  has been described in the above embodiments, but the present invention is not limited thereto. The deodorizing apparatus  1  of the present invention may be provided in a so-called Japanese-style toilet without the seat or in a urinal for men.  
         [0095]     Still further, the platinum-iridium-based material is used for the electrolytic electrodes  24 ,  25  in the embodiments described above, but the material is not limited thereto, and carbon, for example, can also be used. Moreover, hydrogen sulfide, methyl mercaptan and ammonia have been described as the odor components by way of example in the above embodiments, but it is needless to say that these are not the only odor components which can be removed by the deodorizing apparatus  1  of the present invention.