JP2008188508A - Microorganism removing device and water treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microorganism removing device which does not use electric power and can cope with conditions where the depth of a water tank is deep or a change in a water level is large, and a water treatment method employing the same device. <P>SOLUTION: In the microorganism removing device 1, a zinc plate 2 and a copper plate 3 as two or more kinds of electrically conductive materials different in oxidation-reduction potential are brought in an electrical continuity through a short-circuit part 5, and spaces between the plates are held by a spacer 4 having a low bulk specific gravity, so that the growth of microorganisms in water can be inhibited by an energy-saving and compact structure. The water treatment method employs the above microorganism removing device. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a sterilization apparatus having a simple structure capable of sterilizing microorganisms in water. In addition, the present invention relates to a water treatment method such as a humidifier, a dehumidifier, a circulating bathtub device, a sauna device, an air conditioner, a water treatment device, and a sterilization device using the sterilization device.

  Growth of microorganisms such as Escherichia coli and Staphylococcus aureus has been observed in water storage parts such as humidifiers, circulation baths or drainage ditch members. If left untreated for an extremely long period of time, the possibility of slimy and spoiled odors may occur with the growth of microorganisms. For this reason, there has been a strong demand for techniques relating to the suppression of microbial growth and sterilization in the water storage section.

  For example, as shown in FIGS. 11 to 13, a conventional humidifier described in Patent Document 1 has an intake port 100a and an outlet 100b provided in a main body or a cover, and a water tank is provided inside the main body. A water tank 102 for receiving water supplied from 101, a heating cylinder 103 for heating the water in the water tank 102, and a water absorbing body (humidification filter) 104 that sucks up the water in the water tank 102 while surrounding the heating cylinder 103. Yes. An air path is formed from the air inlet 100a through the blower 105 to the air outlet 100b, and the air vapor from the water absorber 104 is released from the air outlet 100b together with the air from the air inlet 100a by the air blower 105. . Thereby, indoor humidification is performed. Water from the water supply tank 101 is supplied to the water tank 102, and a pair of electrodes 106 for eluting a substance having an antibacterial action is provided in any part of the water tank 102. The degree of antibacterial properties is changed by flowing electricity between the electrodes and switching the polarity at a predetermined cycle.

Patent Document 2 discloses a humidifier that can be sterilized without using electric power. A humidification mechanism including a water supply unit, a humidification filter arranged so that at least a part is immersed in water, and a blowing means for sending air through the humidification filter, and a redox potential different from that provided with a gap A first electrode and a second electrode, and a sterilization apparatus including a short-circuit portion that short-circuits the first electrode and the second electrode, and the oxidation-reduction potential of the first electrode is that of the second electrode It is higher than the oxidation-reduction potential and is disposed at a position where at least the first electrode and the second electrode are in contact with water. Since the microorganisms contained in the water of the humidifier have a certain charge, the microorganisms can move from the first electrode toward the second electrode, and the microorganisms can be physically excluded from the water between the electrodes. It is shown. Furthermore, it has been shown that microorganisms accumulated on the surface of the second electrode lose their ability to grow due to the influence of metal ions eluted from the surface of the second electrode and become inactivated.
JP 2002-89895 A JP 2004-93108 A

  Although the method described in Patent Document 1 can be sterilized using metal ions eluted from the electrode, an external power input is indispensable for elution from the electrode. When stopped, there was a problem that the bactericidal effect did not work and the bacteria would grow. Especially when the power input is stopped, metal elution does not progress, so physical contact between bacteria and metal ions can hardly be expected, and there is a problem that it is effective only in a limited area near the surface of the metal plate. there were. Furthermore, in the sterilization means, dead bodies of microorganisms may remain in the region to which metal ions have been applied, and it is desirable to remove them in order to maintain comfort, and a sterilization means is desired rather than a sterilization means.

  In addition, the method described in Patent Document 2 has an advantage that it can be sterilized without using electric power, but it is necessary to dispose the first electrode and the second electrode below the water surface while providing the short-circuit portion on the water surface. Therefore, installation is difficult when the water depth of the aquarium is deep or when the fluctuation of the water level is large.

  In order to solve the above-described problems, the present invention eliminates the need for electric power, and can be used even when the water depth of the aquarium is deep or when the fluctuation of the water level is large, and a water treatment method using the sterilization method. The purpose is to provide.

  In order to achieve the above object, the sterilization apparatus of the present invention is characterized in that, as described in claim 1, two or more kinds of conductive materials having different oxidation-reduction potentials are made conductive and floated on water.

  In the sterilization apparatus of the present invention, the conductive material is a metal and / or carbon.

  Further, the sterilization apparatus of the present invention is characterized in that the conductive material contains a bactericidal metal.

  In addition, the sterilization apparatus of the present invention is characterized by comprising two or more kinds of metal materials having different oxidation-reduction potentials arranged at intervals and a short-circuit portion that short-circuits the electrodes.

  Moreover, the sterilization apparatus of the present invention is characterized in that the short-circuit portion is located above the water surface.

  Moreover, the sterilization apparatus of the present invention is characterized in that the metal materials face each other via an insulating spacer.

  In addition, the sterilization apparatus of the present invention is characterized in that metal materials and insulating spacers are alternately stacked.

  In the sterilization apparatus of the present invention, the bulk density of the insulating spacer is lighter than that of water.

  In the sterilization apparatus of the present invention, the conductive material is powder and / or fibrous.

  The sterilization apparatus of the present invention is characterized in that a treatment liquid in which a conductive material is dispersed or dissolved is applied to a base material having a bulk specific gravity lighter than water.

Moreover, the sterilization apparatus of the present invention is characterized in that the surface electrical resistance of the surface treatment portion coated with the treatment liquid in which the conductive material is dispersed or dissolved is 10 ⁷ Ω / □ or less.

  In addition, the sterilization apparatus of the present invention is characterized in that the treatment liquid is applied to a place located below the water surface of a base material whose bulk specific gravity is lighter than water.

  Moreover, the sterilization apparatus of the present invention is characterized in that the substrate having a bulk specific gravity lighter than water is porous.

  The sterilization method of the present invention is characterized in that the sterilization apparatus according to any one of claims 1 to 13 is floated on water.

  In addition, the sterilization method of the present invention is characterized in that it comprises connection means for connecting the sterilization apparatus according to any one of claims 1 to 13, and the sterilization apparatus communicated by the connection means is floated on water.

  According to the present invention, there is provided a water sterilization apparatus that can cope with a case where water is deep or water level fluctuation is large without using electric power, and a water treatment method using the sterilization method. Can do.

  The invention described in claim 1 of the present invention is characterized in that two or more kinds of conductive materials having different oxidation-reduction potentials are conducted and floated on water. Since microorganisms contained in water have a constant charge as the surface charge, when an electric field is applied to water, an action of moving according to the direction of the electric field is produced. As in the present invention, by conducting two or more kinds of conductive materials having different oxidation-reduction potentials, an electromotive force is generated between the conductive materials, and as a result, microorganisms are collected on the surface of one of the conductive materials. The microorganisms in the water are sterilized.

In this configuration, since the above-mentioned sterilization effect is obtained by short-circuiting two or more kinds of conductive materials, there is no need to energize to suppress the growth of microorganisms as in Patent Document 1, and the effect that energy saving can be achieved. Have. Tap water contains positive ion substances such as Ca and Mg and negative ion substances such as Cl and NO _3, and these ionic charged substances are generated by a small electric field formed by a short-circuited conductive material. Can also be removed. Moreover, it has the effect | action that fungi, mold spores, etc. which are negatively charged in water can be collected.

  Further, in the method of Patent Document 2, it is necessary to dispose the first electrode and the second electrode below the water surface while providing the short circuit portion on the water surface. Therefore, when the water level fluctuates, the short circuit portion is submerged and the electric charge escapes. In some cases, the disinfection performance was not exhibited. In the method of the present invention, since the sterilization unit is floated on the water, the depth of the sterilization unit is kept constant even if the water level fluctuates, and the sterilization apparatus is stably maintained at a desired potential difference to ensure sterilization performance. can do. Further, in the conventional method, when the water depth of the water tank is deep, it is necessary to take a long distance from the electrode to the short-circuit portion, and problems such as disconnection are likely to occur, but in the present invention, the distance between the electrode and the short-circuit portion is shortened. Therefore, it is possible to provide a water sterilization apparatus that can cope with a case where the water depth of the aquarium is deep or a large fluctuation in water level, and a water treatment method using the sterilization method.

  Further, the conductive material is characterized in that it is a metal and / or carbon, and a sterilization apparatus can be easily obtained by utilizing the conductivity of the metal and / or carbon. Examples of conductive metals include Au, Pt, Ag, Cu, Pb, Ni, Sb, Co, W, Fe, Sn, Cr, Zn, V, Al, Ti, Zr, Mg, K, and alloys thereof. Can be mentioned. In particular, Ag, Cu, and Zn are preferable because the antibacterial property of the metal itself is strong. Fe, Zn, and Al are relatively inexpensive and easy to use. The selection of two or more metals is not particularly limited in consideration of the use, life and economy, but hydrogen is generated from the electrode in the vicinity of water electrolysis start voltage of 1.2 V. This is not preferable because of the tendency of corrosion.

  Further, when two or more kinds of metals having different oxidation-reduction potentials come into contact with water in a state where a potential difference is generated, the metal having a lower oxidation-reduction potential is eluted into water. The eluted metal acts on microorganisms and exerts a sterilizing effect. Here, since the metal having a higher oxidation-reduction potential is difficult to elute, it is better to increase the compounding ratio of the metal having a higher oxidation-reduction potential and a lower oxidation-reduction potential for long-term use.

  Examples of the conductive carbon material include graphite, carbon black, carbon fiber, fullerene, carbon nanotube, carbon nanohorn, carbon microcoil, carbon nanocoil, and conductive polymer having an unsaturated bond. Graphite and carbon black are the most commonly used conductive carbon materials and are highly economical. Moreover, what mixed resin emulsion and carbon as a conductive paint is marketed, and it can obtain easily. Carbon fibers, fullerenes, carbon nanotubes, carbon nanohorns, carbon microcoils, carbon nanocoils, etc. are often added to resins for the purpose of improving the strength of the resins, reducing their weight, and preventing electromagnetic waves. Thus, the sterilization effect of the present invention can be obtained. In addition, a conductive polymer that is being developed as an electrode can similarly obtain a sterilizing effect.

  In addition, the conductive material is characterized by containing a bactericidal metal, and after microorganisms are collected on the surface of the conductive material, the microorganisms in the water are quickly killed by the bactericidal action of the metal. Have. Examples of the bactericidal metal include Ag, Cu, Zn, and Ni. Moreover, it has the effect | action that the water with bactericidal property can be obtained by discharge | releasing the metal ion with bactericidal property in water.

  Moreover, it is comprised from the short circuit part which short-circuits two or more types of metal materials with which the oxidation-reduction potentials arrange | positioned at intervals and the said electrodes are short-circuited, and 2 with different oxidation-reduction potentials. By conducting more than one kind of metal material, an electromotive force is generated between the metal materials. As a result, microorganisms are collected on the surface of one metal material, so that microorganisms in water are sterilized. This is a simple method of short-circuiting the electrodes, and there is no need to energize from the outside, and there is an effect that energy can be saved. In addition, there is an effect that the energization circuit and the control mechanism are not required and the apparatus can be simplified. In addition, the same material may be sufficient as a metal material and a short circuit part.

  The short-circuit portion is located above the water surface. In the method of Patent Document 2, it is necessary to dispose the first electrode and the second electrode under the water surface while providing the short-circuit portion on the water surface. Bacterial performance may not be demonstrated. In the method of the present invention, since the sterilization unit is floated on water, the short-circuit portion is not submerged, and the sterilization apparatus can be stably maintained at a desired potential difference to ensure sterilization performance. The surface of the short-circuit portion is preferably subjected to an electrical insulation treatment and / or a water repellent treatment.

  In addition, the metal materials are opposed to each other through an insulating spacer, so that the metal materials do not come into contact with each other in water and the charge does not escape, so that the sterilization apparatus can have a desired potential difference. It has the effect | action that it can be kept at. Further, it is possible to prevent variation in the interval between the metal materials due to the bending or deformation of the metal material, and to increase the potential of the portion where the metal material is in close proximity, thereby suppressing the problem that the disinfection performance varies depending on the location.

  In addition, the bulk density of the insulating spacer is lighter than that of water, and it is not necessary to prepare a separate float, and a sterilization apparatus that floats on water can be easily obtained. Here, the bulk specific gravity refers to the weight per unit volume.

  Further, the conductive material is characterized in that it is powder and / or fibrous. By using a fine powder and / or a fibrous conductive material, the surface area can be increased and the sterilization action becomes stronger than in the case of a metal plate or metal wire. In addition, by miniaturization, conductive material can be mixed into the resin pellets when molding, and a sterilization effect can be obtained simply by molding a mold. It is not necessary to ensure, and it has the effect | action that it can be set as a compact structure. Moreover, it has the effect that a disinfection site | part can be comprised in a free shape rather than a metal plate by resin molding. In the case of powder, when the conductive carbon material and the metal are dispersed in the resin, it is possible to obtain an effect of good dispersibility and easy processing. In addition, since it is easy to obtain a uniform state as compared with the fibrous form, there are advantages in appearance such as suppression of uneven color and unevenness. In the case of a fibrous form, when dispersed, the number of conductive carbon materials or contact points between fibers increases, and the number of places where a local potential difference occurs on the resin surface can be increased. Moreover, the strength of the resin can be improved by the fiber serving as a filler. There is no problem even if mixing of powder and fiber or mixing of dissimilar metals depending on the application.

  Further, the treatment liquid in which the conductive material is dispersed or dissolved is applied to a base material whose bulk specific gravity is lighter than water. By miniaturizing the conductive material to a size that can be dispersed or dissolved in the liquid, a treatment liquid having a sterilizing action can be created. A treatment liquid in which a conductive material is dispersed in a resin can obtain a sterilization effect simply by applying a sterilization material on the surface, and does not require a space for a sterilization apparatus as in Reference 2, and is compact. It has the effect that it can be configured. Moreover, it has the effect that a disinfection site | part can be comprised in a free shape rather than a metal plate by coating. In addition, only the part exposed on the surface of the resin exerts the sterilizing action, and the effect that the effect can be exerted in a smaller amount compared to the method of mixing a conductive material in the resin. Have.

  When using the powder, the carbon material is easily mixed if it is pulverized in advance. Further, when a liquid in which a carbon material is dispersed is used, mixing is easier. At this time, if the solvent in which the resin is dissolved or dispersed is aqueous, carbon black dispersed in water using a surfactant may be used. If the solvent for dissolving or dispersing the resin is an organic solvent system, a commercially available conductive paint in which a resin emulsion and carbon are mixed in advance may be used. When an organic solvent-based material is used, it is excellent in volatility, so that the material can be easily molded and dried.

  The conductive carbon material is preferably 0.02% or more in terms of the mixing ratio with respect to the total amount of metal powder in the sterilizing material. As a result, a potential difference is generated in the sterilization material, and a higher electrical attraction effect can be obtained. Therefore, sufficient sterilization performance can be obtained.

  Examples of the resin include resins such as nylon, polyester, polyether, acrylic, epoxy, polyurethane, polycarbonate, and silicone, or resins containing these. If the resin is blended so that the blending ratio with respect to the total solid content in the sterilizing material is 7% or more, sufficient adhesion between the materials and the material application surface can be obtained. However, if it exceeds 35%, the adhesion and strength are good, but the continuity between the metal and the conductive material is hindered, so the sterilization performance decreases. The amount of resin to be mixed with the sterilizing material may be arbitrarily selected depending on the balance between the sterilizing performance, adhesion, and strength within a range of 7% or more. Further, if the resin can be dissolved or dispersed in a solvent, it is easy to adjust the viscosity of the sterilizing material, and it becomes easy to handle.

  The metal particle size is desirably larger than the size of the microorganism to be removed. In order to collect microorganisms by the potential difference, at least the interval between the portions to which the potential is applied needs to be larger than the size of the microorganisms. Even when the particle size is small, it is considered that a potential is generated in a state where a plurality of particles are connected and spaced apart from each other, but it is expected that the potential is not high in terms of probability. In order to ensure a sufficient distance, it is preferably 10 μm or more, which is sufficiently larger than 1 μm, which is the average size of microorganisms as various bacteria. When the shape is fibrous, the above-described conditions may be used in the length direction, not the thickness.

  Specifically, it is desirable that the metal particle diameter is 0.3 μm to 100 μm. Particles larger than 100 μm have a smaller contact area with the conductive material and other metal particles, and the sterilization efficiency is lowered. Therefore, the metal particle diameter is preferably 100 μm or less. In addition, when particles of 100 μm or less, particularly powders or fibers smaller than 10 μm are used, when the conductive carbon material and the metal are dispersed in the resin, the dispersibility is good and the processing becomes easy. On the other hand, fine particles smaller than 0.3 μm can obtain good dispersibility, but they are easily scattered as dust and easily get into the fine irregularities of the mixing container at the time of mixing. The diameter is preferably 0.3 μm or more.

  Moreover, if the particle diameter ratio of two or more kinds of metals having different oxidation-reduction potentials is 1 to 8, high sterilization performance can be obtained because contact efficiency with the conductive material and other metal particles is good. Here, the particle size ratio of the metal is the length ratio of large particles / small particles.

Further, the surface electrical resistance of the surface-treated portion where the treatment liquid in which the conductive material is dispersed or dissolved is applied is 10 ⁷ Ω / □ or less. If the surface electric resistance is too high, an insulating film is formed, and the strength of the electric field is lowered, so that the sterilization action is lowered, which is not preferable. Moreover, it has the effect | action that the adhesion of the microbe and the microorganisms in air by electrification can be reduced by making surface electrical resistance low.

  In addition, it is characterized in that the treatment liquid is applied to a base material with a bulk specific gravity lighter than water and located below the surface of the water. The effect that there is no waste of material can be obtained.

  In addition, the substrate having a lighter specific gravity than water is porous. Since the base material is porous, the surface area of the base material can be increased and more bacteria can be collected. As the porous substrate, natural fibers such as cotton, rayon, nylon, wood and pulp, and synthetic fibers such as resin-impregnated paper and polyester / polyurethane / polyether can be used. For example, any shape such as a fiber shape, a net shape, a bead shape, a slit shape, a straw shape, a plate shape, a honeycomb shape, a sponge shape, and a foam shape can be used. In the foamed shape, the finer the surface, the higher the surface area.

  The sterilization apparatus according to any one of claims 1 to 13 is floated on water. By floating the sterilization apparatus on the water, the area of the portion having the sterilization performance under the surface of the water becomes constant regardless of the fluctuation of the water level, so that a sterilization effect can always be obtained. Moreover, in the method described in Patent Document 2, since it is necessary to dispose the first electrode and the second electrode below the water surface while providing the short-circuit portion on the water surface, the installation is performed when the water depth of the aquarium is deep. Although it was difficult, in the present invention, since the sterilization apparatus floats on water, it has an effect that the sterilization performance can be easily exerted when the water depth is deep.

  The sterilization apparatus connected to the sterilization apparatus according to any one of claims 1 to 13 is provided, and the sterilization apparatus communicated by the connection means is floated on water. By using a plurality of sterilization apparatuses, it is easy to adjust to the desired sterilization performance. In addition, since the sterilization apparatuses are connected to each other, the sterilization apparatus can be easily increased or decreased and collected.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(Embodiment 1)
As shown in FIG. 1, the sterilization apparatus 1 includes a zinc plate 2 that is an electrode as a conductive material, and a copper plate 3 that is an electrode as a conductive material arranged at intervals. The zinc plate 2 and the copper plate 3 are connected to each other by a copper wire serving as a conductive short-circuit portion at the upper portion, and are held at a constant interval by a spacer 4. The spacer 4 is made of styrene foam, and its bulk specific gravity is lighter than water. Therefore, the sterilization apparatus floats on the water while holding the short-circuit portion on the water surface.

  Here, the standard electrode potential of the metal is shown in Table 1.

  Since the standard electrode potentials of copper and zinc are 0.34 V and −0.76 V, respectively, the redox potential is 1.11 V from the difference between the standard electrode potentials. By short-circuiting the copper plate and the zinc plate, a potential difference occurs in the water, and negatively charged microorganisms existing between the metal plates are attracted to the zinc plate and sterilized. The sterilized microorganisms lose their charge on the surface of the zinc plate and die by the sterilization action of zinc. By repeating the same process, water is sterilized.

  As described above, in Embodiment 1 of the present invention, the distance of the copper wire as the short-circuit portion between the zinc plate 2 as the electrode and the copper plate 3 as the electrode can be shortened, that is, zinc Since the distance between the plate 2 and the copper plate 3 can be shortened, the water disinfection device that can cope with the case where the water depth of the aquarium is deep or the fluctuation of the water level is large, and the water treatment using the disinfection method A method can be provided.

(Embodiment 2)
As shown in FIG. 2, the sterilization apparatus 11 includes a hollow sphere 13 inside a frame 12. On the surface of the hollow sphere 13, a treatment liquid in which zinc powder and silver powder as a conductive material and a commercially available carbon paste are mixed is applied. The hollow sphere 13 is made of ABS resin, and its bulk specific gravity is lighter than that of water. Therefore, the sterilization apparatus 11 floats in a state where a part thereof is submerged in water. Here, since the zinc powder and the silver powder are electrically connected by conductive carbon particles, a potential difference is generated in the water, and negatively charged microorganisms are attracted to the zinc powder and sterilized. The sterilized microorganisms lose their charge on the surface of the zinc powder and die by the sterilization action of zinc. By repeating the same process, water is sterilized.

(Embodiment 3)
As shown in FIG. 3, the sterilization apparatus 21 has a net-like resin net 23 attached around a foam body 22 made of styrene, and copper powder and brass as a conductive material are formed on the surface of the resin net 23. A treatment liquid in which powder and a commercially available carbon paste are mixed is applied. Since the foam body 22 has a bulk specific gravity lower than that of water, the sterilization apparatus floats in a state where the resin net 23 is submerged in water. The sterilizer 21 is connected by a connecting rod 24. Here, since the copper powder and the brass powder are electrically connected by conductive carbon particles, a potential difference is generated in the water, and negatively charged microorganisms are attracted to the brass powder and sterilized. The sterilized microorganisms lose their charge on the surface of the brass powder and are killed by the sterilizing action of brass. By repeating the same process, water is sterilized.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is limited to the following description and is not interpreted at all.

A bacterial solution was prepared by adding Escherichia coli (IFO 3972) to a normal bouillon medium diluted 400 times with purified water. ^Two metal plates prepared so as to be 30 cm ² (60 cm ^{2 on both} sides as the metal surface) were electrically joined on the water surface and placed in a plastic petri dish. The metal plate was a combination of copper and copper and a combination of copper and zinc. The changes in the number of bacteria were compared by putting each bacterial solution in a plastic petri dish and collecting 0.1 ml of the solution at regular intervals and culturing.

  The results are shown in FIG. Even with the combination of copper and copper, the number of bacteria decreased due to the antibacterial action of copper, but on the 6 hour scale, there was no significant difference compared to the blank without metal. On the other hand, with copper-zinc, a large decrease in the number of bacteria was observed after 6 hours. From this, it can be seen that when a conductive material having a redox potential is electrically joined, a high sterilization effect can be obtained.

A copper plate and a zinc plate were placed on a slide glass and arranged at an interval entering the field of view of the microscope. Escherichia coli (IFO 3972) is added to a normal bouillon medium diluted 400 times with purified water, and about 10 ⁶ cfu / ml of bacterial solution is added to the slide glass so that it touches the copper plate and the zinc plate. 2 ml was dropped. As soon as observed with a microscope, E. coli moved to the zinc plate and aggregated. From this, it was found that when materials having different ionization tendencies are electrically joined, Escherichia coli in the bacterial solution is sterilized.

  When a similar experiment was performed using two zinc plates, Escherichia coli was in a normal movement state and was not seen to be attracted to either metal.

  (1) A zinc powder having an average particle diameter of 50 μm as a metal and a commercially available conductive carbon coating material (conductive carbon and polyester resin dispersed in a solvent), the weight ratio of zinc to carbon being 11: 5 The resulting mixture was well kneaded into a paste to prepare a treatment liquid. The prepared treatment liquid was spread on a PET film and dried at 100 ° C. for 1 hour to prepare a sterilization film Zn.

  (2) A sterilizing film Cu was prepared by the same method as (1) except that the metal was changed to 75 to 150 μm copper powder.

(3) A comparative film TiO ₂ was prepared in the same manner as in (1) except that a metal oxide 0.1-0.3 μm TiO ₂ powder was added instead of metal.

  (4) A comparative film C without spreading a metal and mixing a commercially available conductive carbon paint (conductive carbon and polyester resin dispersed in a solvent) on a PET film and drying it overnight. It was created.

Each of the films prepared by the methods (1) to (4) was cut into a circle having a diameter of 85 mm (about 57 cm ² ) and placed in a plastic petri dish so that the coating surface of the treatment liquid was facing upward.

A bacterial solution was prepared by adding Escherichia coli (IFO 3972) to 10 ⁵ (cfu / ml) in a normal bouillon medium diluted 400 times with purified water. 20 ml of each bacterial solution was placed in a plastic petri dish, and 0.1 ml of the solution was collected at regular intervals and cultured to compare changes in the number of bacteria. In order to prevent the sterilizing action of ultraviolet rays, the experiment was conducted with the petri dish shielded from light.

The results are shown in FIG. In the sterilization film to which the metal is added, the number of bacteria is reduced and it can be said that there is a sterilization effect. The effect was especially strong in the film which added Cu. On the other hand, in the comparative film C, the decrease in the number of bacteria was slight, and the difference in the effect was clearly seen from the sterilization film. The comparative film TiO ₂ , which is a metal oxide, seems to have a slightly smaller number of bacteria than the comparative film C and has an adsorption action on TiO ₂ particles, but it cannot be said to have a sterilization action.

(1) A zinc powder having an average particle diameter of 50 μm as a metal and a commercially available conductive carbon coating material (conductive carbon and polyester resin dispersed in a solvent), the weight ratio of zinc to carbon being 11: 5 The resulting mixture was well kneaded into a paste to prepare a treatment liquid. The prepared treatment liquid was spread on a PET film molded into a circle having a diameter of 85 mm (about 57 cm ² ) and dried at 60 ° C. for 2 hours to prepare a sterilization plate A.

  (2) A copper powder of 75 to 150 μm as a metal and a commercially available conductive carbon paint (conductive carbon and polyester resin dispersed in a solvent) have a copper: carbon weight ratio of 11: 5. Thoroughly kneaded at a ratio to make a paste to prepare a treatment liquid. The prepared treatment liquid was spread on a PET film and dried at 60 ° C. for 2 hours to prepare a sterilization plate B.

  (3) As a metal, zinc powder having an average particle diameter of 50 μm, copper powder of 75 to 150 μm, and commercially available conductive carbon paint (conductive carbon and polyester resin dispersed in a solvent), zinc: copper : The weight ratio of carbon was well kneaded at a ratio of 10: 1: 5 to make a paste to prepare a treatment liquid. The prepared treatment liquid was spread on a PET film and dried at 60 ° C. for 2 hours to prepare a sterilization plate C.

  (4) A comparative plate A was prepared by spreading a paint containing 96% zinc and 4% acrylic resin on a PET film and drying at 60 ° C. for 2 hours.

  (5) A comparative plate B was prepared by spreading a paint containing 83% zinc, 5% aluminum, and 12% acrylic resin on a PET film and drying at 60 ° C. for 2 hours.

  (6) A comparative plate C was prepared without any processing.

  The iron plate prepared by the methods (1) to (6) was placed in a plastic petri dish so that the surface to which the sterilizing material was applied faced upward.

A bacterial solution was prepared by adding Escherichia coli (IFO 3972) to about 10 ⁵ (cfu / ml) in a normal bouillon medium diluted 400 times with purified water. 20 ml of each bacterial solution was placed in a plastic petri dish, and 0.1 ml of the solution was collected at regular intervals and cultured to compare changes in the number of bacteria. FIG. 6 shows the result of dividing the number of bacteria after the lapse of a predetermined time by the initial number of bacteria and normalizing the value as the residual ratio of the bacteria on the vertical axis and the elapsed time on the horizontal axis. In the sterilization plates A, B, and C, the number of bacteria decreased and it was found that the bacteria were sterilized. In the sterilization plates A and B, the sterilization rate was higher in A with Zn added. In the sterilization plate C to which copper and zinc were added, the decrease in the number of bacteria after 1 hour was particularly remarkable.

  A slight decrease in the number of bacteria was observed in the comparative plate A coated with a commercially available paint. In comparison plates B and C, the number of bacteria hardly changed, and it was found that the sterilization effect was not working.

  Table 2 shows the results of measuring the surface electrical resistance of the prepared sterilization plate and the comparison plate.

  It can be seen that the comparative plates A and B have very high surface resistance and do not have conductivity. On the other hand, the sterilization plates A, B, and C have low surface resistance and conductivity. Compared with the results of FIG. 6, the sterilization plates A, B, and C having conductivity have the sterilization performance, and the comparison plates A and B that have no conductivity and any treatment It was found that the comparative plate C that was not used had low sterilization performance.

Further, in other samples in which the type of resin was arbitrarily selected, when the surface resistance value was measured in the same manner, the values shown in Table 3 were obtained, and the surface electrical resistance of the sterilization treatment part was 10 ⁷ Ω. / □ or less is preferable.

The sterilization plate C prepared in Example 5 was placed on a slide glass and placed at a position that fits into the field of view of the microscope. Escherichia coli (IFO 3972) is added to a normal bouillon medium diluted 400 times with purified water, and about 10 ⁶ cfu / ml of bacterial solution is placed on a slide glass so that it touches the sterilization plate C. 2 ml was dropped. As soon as observed with a microscope, E. coli was unevenly distributed at a specific position on the sterilization plate C and aggregated. The sterilization plate C was a mixture of zinc, copper and conductive carbon, and it was not possible to confirm in which position each material was applied. Compared with the size of E. coli (about 2 μm), the size of zinc and copper is sufficiently large (50 to 150 μm), and when combined with the results of Example 4, the bacteria are probably located at a high concentration. Seemed to be agglomerated.

Zinc and copper powders whose particle sizes are arbitrarily selected from an average particle size of 0.3 μm to 150 μm, and commercially available conductive carbon paint (conductive carbon and polyester resin dispersed in a solvent), metal powder The carbon paint was kneaded well at a ratio of 11: 5 to make a paste, and seven types of treatment liquids were prepared. The prepared treatment liquid was spread on a PET film and dried at 100 ° C. for 1 hour to prepare a sterilization film. Each of these sterilizing films was cut into a circle having a diameter of 85 mm (about 57 cm ² ), and placed in a plastic petri dish so that the coating surface of the paint was directed upward.

A bacterial solution was prepared by adding Escherichia coli (IFO 3972) to 10 ⁵ (cfu / ml) in a normal bouillon medium diluted 400 times with purified water. 20 ml each of the bacterial solution was placed in a plastic petri dish, and after 3 hours, 0.1 ml of the solution was collected and cultured, and the change in the number of bacteria relative to the initial stage was compared as the sterilization speed. The sterilization speed here represents the decay rate of the number of bacteria in terms of the sterilization rate relative to the initial stage, and it can be said that the faster the sterilization speed, the better the sterilization performance. In order to prevent the sterilizing action of ultraviolet rays, the experiment was conducted with the petri dish shielded from light.

  The results are shown in FIG. When the particle sizes of zinc and copper are different, the zinc / copper size ratio on the horizontal axis of the graph moves away from 1, but the region where the zinc / copper size ratio is 0.1 or less, or 8 or more, that is, zinc and copper It was found that when the particle size ratio was 0.1 or less or 8 or more, the sterilization speed was slower than when the particle size difference was small, and the sterilization rate after 3 hours was less than 99%. That is, even when the same weight of metal powder is contained, the contact efficiency with the conductive material or other metal particles is poor when the particle size difference is large compared to the case where the particle size difference between the two types of metal is small. It is thought to be.

Thoroughly knead a zinc powder with an average particle size of 50 μm, a copper powder of 75 to 150 μm, and a commercially available conductive carbon paint (conductive carbon and polyester resin dispersed in a solvent), and the total amount of metal powder Four types of treatment liquids with varying amounts of carbon were prepared. The prepared treatment liquid was spread on a PET film and dried at 100 ° C. for 1 hour to prepare a sterilization film. Each of these sterilizing films was cut into a circle having a diameter of 85 mm (about 57 cm ² ), and placed in a plastic petri dish so that the coating surface of the paint was directed upward.

A bacterial solution was prepared by adding Escherichia coli (IFO 3972) to 10 ⁵ (cfu / ml) in a normal bouillon medium diluted 400 times with purified water. 20 ml of each bacterial solution was placed in a plastic petri dish, and the change in the number of bacteria relative to the initial value after 3 hours was compared as the sterilization speed. In order to prevent the sterilizing action of ultraviolet rays, the experiment was conducted with the petri dish shielded from light.

  The results are shown in FIG. When the amount of carbon relative to the total weight of the metal powder is 0.02% or more, the sterilization speed is almost the same value. That is, in order to produce a sufficient potential difference between the conductive carbon material and the metal to exhibit the sterilization performance, it is considered that a carbon amount of 0.02% is sufficient.

A zinc powder having an average particle diameter of 50 μm, a copper powder having a particle size of 75 to 150 μm, a carbon powder and an acrylic resin emulsion, the weight ratio of the metal powder and carbon being constant, and the amount of the acrylic resin being varied at an arbitrary ratio 6 Different types of treatment solutions were made. The prepared treatment liquid was spread on a PET film and dried at 100 ° C. for 1 hour to prepare a sterilization film. Each of these sterilizing films was cut into a circle having a diameter of 85 mm (about 57 cm ² ), and placed in a plastic petri dish so that the coating surface of the paint was directed upward.

A bacterial solution was prepared by adding Escherichia coli (IFO 3972) to 10 ⁵ (cfu / ml) in a normal bouillon medium diluted 400 times with purified water. 20 ml of each bacterial solution was placed in a plastic petri dish, and the change in the number of bacteria relative to the initial value after 3 hours was compared as the sterilization speed. In order to prevent the sterilizing action of ultraviolet rays, the experiment was conducted with the petri dish shielded from light.

  The results are shown in FIG. When the resin amount was within a range of 7% to 35% of the total solid content, the sterilization film exhibited good sterilization performance. When the resin is less than 7%, not only the sterilization performance is lowered, but also the adhesion between the metal or carbon and the film is lowered. Moreover, when the amount of the resin exceeds 35%, the adhesion is good and sufficient strength is obtained, but the sterilization performance deteriorates because conduction between the metal and the conductive material is inhibited. Examples of the resin include nylon, polyester, polyether, epoxy, polyurethane, polycarbonate and the like in addition to acrylic.

  A zinc powder with an average particle diameter of 50 μm, a copper powder with a particle size of 75 to 150 μm, and a commercially available conductive carbon paint (conductive carbon and polyester resin dispersed in a solvent), the weight ratio of zinc, copper and carbon. Was well kneaded at a ratio of 10: 1: 5 to make a paste to prepare a treatment liquid. The prepared treatment liquid was spread on a PET film and dried at 100 ° C. for 1 hour to prepare a sterilization film. Similarly, a sterilization filter was prepared by applying to a sponge-like filter and drying at 100 ° C. for 1 hour.

  The prepared sterilization film was placed in a commercially available humidifier, and water was put into a water supply tank. Then, water was collected from the periphery of the sterilization film and cultured to measure the number of bacteria in water. Operation of the humidifier was started and continued until drought occurred. The next morning, residual water was collected from the periphery of the sterilization film, cultured, and the number of bacteria in water was measured. Thereafter, water was put into the water supply tank and the operation was started, and the change in the number of bacteria in the water was measured for 14 days as a comparison between the one in which the sterilization filter was arranged in the same manner and the one without the sterilization member. . A similar experiment was performed under conditions with a sterilization filter.

As shown in FIG. 10, the number of bacteria increased in several days without a sterilizing film, and a high number of bacteria of 10 ⁶ (cfu / ml) or more was continuously shown from the fourth day. On the other hand, when the sterilization film was inserted, the increase in the number of bacteria was clearly reduced as compared with the case without sterilization, and the sterilization action was confirmed. The reason why the number of bacteria did not become 10 or less seems to be that the area of the sterilization film was small and the ability was insufficient, and that floating microorganisms were continuously mixed from the air. In addition, no bacteria were detected even when the filter equipped with the sterilization filter was operated for 14 days.

  The sterilization apparatus of the present invention can provide a sterilization apparatus for water that does not use electric power and can cope with the case where the water depth of the aquarium is deep or the fluctuation of the water level is large, using the sterilization apparatus. , Humidifiers, dehumidifiers, recirculating bathtubs, water tanks such as rivers and lakes In addition, it can be expected to be used for disinfection devices.

1 is a schematic perspective view of a best mode 1 for carrying out the invention of the present invention. Schematic perspective view of the best mode 2 for carrying out the invention of the present invention Schematic perspective view of the best mode 3 for carrying out the invention of the present invention The figure which shows the microbe elimination effect of Example 1 of this invention The figure which shows the relationship between the material which comprises the film of Example 3 of this invention, and the disinfection effect The figure which shows the relationship between the combination of the metal of Example 4 of this invention, and disinfection effect The figure which shows the relationship between the particle diameter of the metal of Example 6 of this invention, and the disinfection speed. The figure which shows the relationship between the carbon content of Example 7 of this invention, and the disinfection speed. The figure which shows the relationship between the resin mixing amount of Example 8 of this invention, and the disinfection speed. The figure which shows the change of the number of bacteria in the humidification apparatus of Example 9 of this invention. Schematic perspective view of conventional humidifier The schematic perspective view for demonstrating the internal structure of the humidification apparatus of a prior art example The schematic perspective view for demonstrating the internal structure of the humidification apparatus of a prior art example

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Disinfection apparatus 2 Zinc plate 3 Copper plate 4 Spacer 5 Short-circuit part 11 Disinfection apparatus 12 Frame
DESCRIPTION OF SYMBOLS 13 Hollow ball 21 Sanitization apparatus 22 Foaming body 23 Resin net 24 Connecting rod 100a Intake port 100b Outlet 101 Water supply tank 102 Water tank 103 Heating cylinder 104 Water absorption body 105 Blower 106 Electrode

Claims (15)

A sterilization apparatus characterized in that two or more kinds of conductive materials having different oxidation-reduction potentials are conducted and floated on water. The sterilizing apparatus according to claim 1, wherein the conductive material is metal and / or carbon. The sterilization apparatus according to claim 1 or 2, wherein the conductive material contains a bactericidal metal. 4. The removal according to claim 1, comprising two or more kinds of metal materials having different redox potentials arranged at intervals and a short-circuit portion for short-circuiting the metal materials. Bacteria device. The sterilization apparatus according to claim 4, wherein the short-circuit portion is located above the water surface. 6. The sterilizing apparatus according to claim 4 or 5, wherein the metal materials are opposed to each other via an insulating spacer. The sterilization apparatus according to claim 6, wherein metal materials and insulating spacers are alternately laminated. The sterilizing apparatus according to claim 6 or 7, wherein the bulk specific gravity of the insulating spacer is lighter than water. The sterilization apparatus according to any one of claims 1 to 3, wherein the conductive material is powder and / or fibrous. The sterilization apparatus according to claim 9, wherein the treatment liquid in which the conductive material is dispersed or dissolved is applied to a base material having a bulk specific gravity lighter than water. The sterilizing apparatus according to claim 10, wherein the surface electrical resistance of the surface-treated portion where the treatment liquid in which the conductive material is dispersed or dissolved is applied is 10 ⁷ Ω / □ or less. The sterilizing apparatus according to claim 10 or 11, wherein the treatment liquid is applied to a place located below the surface of the base material having a bulk specific gravity lighter than water. The sterilization apparatus according to any one of claims 10 to 12, wherein the substrate having a bulk specific gravity lighter than water is porous. A water treatment method, wherein the sterilization apparatus according to claim 1 is floated on water. A water treatment method comprising: a connection unit that connects the sterilization apparatus according to claim 1, wherein the sterilization apparatus communicated by the connection unit is floated on water.

Images