JP2006006670A - Carrier of negative charge oxygen atom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the generator of a negative charge oxygen atom capable of generating the negative charge oxygen atom and applying it to the sterilization of highly durable fungi including the sterilization of the bacillus which forms a spore, and its carrier, especially the carrier of the negative charge oxygen atom using a carrying tube to be applied to a medical sterilization/disinfection device. <P>SOLUTION: In the carrier of the negative charge oxygen atom for disinfection/sterilization for irradiating a sample to be disinfected with the negative charge oxygen atom by forming a rare gas flow or a dry air flow to the irradiating direction of the negative charge oxygen atom from a negative charge oxygen atom generation part, the rare gas flow or the dry air flow is directed to the sample to be disinfected through a tube made of nylon or Teflon (R) of 3-5 mmϕ and the negative charge oxygen atom is irradiated. The sample to be disinfected is placed inside a medical disinfection/sterilization box and the flow velocity of the rare gas flow or the dry air flow inside the tube is 0-500 cm/s. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a device for transporting negatively charged oxygen atoms, in particular, stably producing negatively charged oxygen atoms under atmospheric pressure, and irradiating an object for sterilization and sterilization using a carrier gas. It is related with the conveying apparatus for doing.

Negatively charged oxygen atoms O ^- is represented by an oxidation treatment of the strong oxidation and various substances by utilizing the oxidizing power possessed by the negatively charged oxygen atoms, antifungal treatment of the food, the use of the sterilization and the like is expected Yes.
As a method for producing negatively charged oxygen atoms, a method for producing negatively charged oxygen atoms by attaching low energy electrons to oxygen atoms generated by discharge or the like is known. However, a high vacuum is required to cause discharge, and there are problems in terms of energy.

  The present inventor has disclosed a negative charge oxygen atom production method using a solid electrolyte having oxygen ion conductivity as a production method and production apparatus for efficiently producing negative charge oxygen atoms without requiring high vacuum or discharge energy. And the manufacturing apparatus is proposed (patent document 1).

However, an apparatus using a solid electrolyte having oxygen ion conductivity has a low generation efficiency of negatively charged oxygen atoms.
When using negatively charged oxygen atoms, the method of using a so-called vacuum atmosphere has limited the object of use. For example, plant substances and animal substances containing a large amount of water instantly change in quality, making it difficult to use them for sterilization.

  On the other hand, there is a method in which a carrier gas is flowed and sterilization is performed by negatively charged oxygen atoms accompanying the carrier gas. Although such a method can sterilize some harmful reproductive microorganisms, In the case of fungi (for example, Bacillus bacteria) covered with a durable substance as described above, a sufficient effect could not be obtained.

  Further, in view of the above circumstances, the same applicant stated that “in a negative charge oxygen atom production apparatus, a negative charge oxygen atom generating member formed of a calcium aluminum composite oxide having a calcium oxide: aluminum oxide molar ratio of 12: 7”. The oxygen chamber is separated from the normal pressure generation chamber by the heating means of the negative charge oxygen atom generation member, the cathode is disposed on the side of the oxygen chamber of the negative charge oxygen atom generation member, and the negative charge oxygen atoms are disposed on the side of the generation chamber. An anode is disposed at a distance from the generating member, a direct current power source is connected to the anode and the cathode, and a rare gas flow is formed from the negative charge oxygen atom generation unit to the irradiation direction of the negative charge oxygen atoms in the generation chamber, An apparatus or method for producing negatively charged oxygen atoms is proposed in which an accelerating voltage is applied by arranging an accelerating electrode for applying a voltage between the anode and the anode in the direction of irradiation of negatively charged oxygen atoms (special feature). Wish No. 003-164719).

The outline of the above-mentioned separately proposed apparatus or method for producing negatively charged oxygen atoms is as follows.
FIG. 2 is a view for explaining an embodiment of the separately proposed negative charge oxygen atom production apparatus. The negative charge oxygen atom production apparatus has a negative charge oxygen atom generation member 22 made of a fired body made of a calcium aluminum composite oxide, and a cathode 23 is formed on the bottom surface inside the cylindrical negative charge oxygen atom generation member 22. The heating means 24 such as an electric heater for heating the fired body and a halogen lamp is provided, and is separated into an oxygen 26 and a negative charge oxygen atom generation chamber 27 by a partition wall 25, and an oxygen chamber. 26 is supplied with normal-pressure oxygen through an oxygen supply port 28.

  On the other hand, the negative charge oxygen atom generation chamber 27 is provided with an anode 10 acting as an extraction electrode in the vicinity of the negative charge oxygen atom generation portion 29 of the negative charge oxygen atom generation member 22, and the generation voltage E1 is Applied. The irradiation unit 11 that irradiates negatively charged oxygen atoms is provided with an acceleration electrode 12 that accelerates the generated negatively charged oxygen atoms, and an acceleration voltage is applied from the acceleration power source E2. A sample 13 is placed on the front surface of the acceleration electrode.

  The generation chamber 27 is provided with a noble gas inlet 14 and a noble gas discharge port 15, and the noble gas in the generation chamber 27 is directed from the negative charge oxygen atom generation unit 29 toward the negative charge oxygen atom irradiation unit 11. A stream 16 is formed.

  Further, a cooling means 17 is provided on the wall surface of the generation chamber 27 to circulate the refrigerant 18 to prevent the temperature of the generation chamber 27 from rising. Thereby, it is possible to prevent the radiant heat applied by the heating unit 24 and the heat transmitted from the generation unit of the negatively charged oxygen atoms by the rare gas flow from being transmitted to the irradiation unit.

  Further, it has been explained that the negative charge oxygen atom generating member of the present invention is a self-supportable member in which a calcium aluminum composite oxide is used as a cylindrical sintered body. A coating layer of calcium aluminum composite oxide may be formed thereon, or may be formed on the support by a film forming method that does not alter the composition of the raw material oxide such as plasma spraying or sputtering.

  Since the cathode is disposed in the oxygen chamber, it is preferable to use a conductive material such as a metal or a conductive oxide that does not cause alteration when heated in an oxygen atmosphere, such as platinum, gold, or a noble metal, nickel, stainless steel, etc. The material such as platinum is preferable, and platinum and gold are particularly preferable. The cathode can be formed by a coating method, a vacuum film forming method, or the like.

  The fired body can be heated by providing a heating means such as a heater in contact with the fired body or by disposing a halogen lamp. Examples of the anode functioning as an extraction electrode include gold-stable noble metals such as gold and platinum, metals such as nickel, and alloys such as stainless steel (SUS304, SUS430, etc.). Among these, platinum is preferable, and rod-like bodies, linear bodies, net-like bodies, or those coated on a substrate can be used. The distance between the generation part of the fired body and the anode is preferably 10 mm or less in order to generate negatively charged oxygen atoms at a low voltage. If it is possible to form an interval on the order of μm with an insulating member and hold the anode horizontally, the smaller the interval, the greater the electric field strength formed between the anode and the cathode. Operation with voltage becomes possible.

  The potential difference between the cathode and the anode is 1 to 2000 V / cm, preferably 10 to 1000 V / cm, and more preferably 50 to 500 V / cm. When it is lower than 1 V / cm, the production efficiency is low, and when it is higher than 2000 V / cm, the fired body or the electrode may be damaged.

  The fired body is preferably heated to 200 to 1000 ° C, more preferably 500 to 800 ° C. When the temperature is lower than 200 ° C, the generation efficiency is insufficient, and when the temperature is higher than 1000 ° C. Is not preferable because the influence of heat on the surroundings becomes large and countermeasures are required.

Further, in the negative charge oxygen atom production apparatus, it is possible to efficiently irradiate the irradiation part with negative charge oxygen atoms generated by forming a rare gas flow in the generation chamber.
The rare gas flow in the generation chamber has an action of transferring heat from the generation part of the heated negatively charged oxygen atoms. Therefore, since heat is transferred not only to negatively charged oxygen atoms but also to the irradiated part by the rare gas flow, the flow rate of the rare gas flow must be considered in consideration of the temperature rise of the irradiated part, and is altered by heating. It is preferable not to increase the flow rate of the rare gas flow.

  As the rare gas flow, one having a small molecular weight is preferable because the amount of disappearance of negatively charged oxygen atoms can be reduced, and helium, xenon, or the like can be used. In particular, helium is easier to obtain than xenon and has a large mean free path of negatively charged oxygen atoms, so that the amount of negatively charged oxygen atoms disappearing can be reduced.

In addition, it is preferable to consider the arrangement of the inlet of the rare gas flow into the production chamber so that the rare gas flow is stably formed from the negative charge oxygen atom generation part to the irradiation part.
Moreover, the speed of the negatively charged oxygen atoms irradiated to the sample placed on the irradiation unit is adjusted by adjusting the voltage applied between the anode acting as the extraction electrode and the acceleration electrode arranged in the irradiation unit. It is possible to do that.

  Thus, in the negatively charged oxygen atom production apparatus, not only the voltage applied to the anode, but also a rare gas flow is formed in the production chamber, and further, an acceleration voltage is applied between the anode and the irradiation part, Moreover, since they can be adjusted, negatively charged oxygen atoms having an energy level according to the purpose can be given to the sample of the irradiated portion.

For example, it is possible to sterilize substances that are altered under reduced pressure at normal pressure, and to adjust the negatively charged oxygen atoms to be irradiated according to the type of bacteria to be sterilized. Even in the case of bacterial cells having a large property, sterilization becomes possible by increasing the accelerating voltage and irradiating negatively charged oxygen atoms having a large effect.
International Publication No. 96/178034 Pamphlet

  The present invention provides a negatively charged oxygen negative atom generator capable of effectively utilizing the action of negatively charged oxygen atoms under atmospheric pressure, and generates negatively charged oxygen atoms having a large oxidizing action to form spores. Using negatively charged oxygen atom generator that can be applied to sterilization of highly durable fungi such as fungi, and its transport device, especially transport tube for medical sterilization and sterilization device It is an object of the present invention to provide a negative charge oxygen atom transfer device.

  The negatively charged oxygen atom transport device for sterilization and sterilization of the present invention heats a member made of a calcium aluminate composite oxide or a composite oxide containing at least cerium to take out the negatively charged oxygen atoms, and the negatively charged oxygen atoms Device for transporting negatively charged oxygen atoms for sterilization and sterilization by irradiating negatively charged oxygen atoms toward the sample to be sterilized by forming a rare gas flow or a dry air flow in the direction of irradiation of the negatively charged oxygen atoms from the generator In the method, the rare gas flow or the dry air flow is irradiated with negatively charged oxygen atoms toward the sample to be sterilized through a 3-5 mmφ nylon or Teflon (registered trademark) tube.

  Further, the sample to be sterilized is placed in a medical sterilization / sterilization box, and a flow rate of a rare gas flow or a dry air flow in the tube is 0 to 500 cm / s.

  The complex oxide is formed as a thin film on a substrate made of an oxygen ion conductor, and a heater for heating the complex oxide is adjacent to or in contact with the thin film made of the complex oxide. It is formed integrally with the thin film.

Alternatively, the composite oxide is characterized in that a thin film is formed on a steatite ceramic heater substrate.
Furthermore, a cathode is disposed on the back side of the substrate on which the composite oxide is formed into a thin film, an anode is disposed on the side opposite to the surface on which the cathode is disposed, oxygen is supplied to the cathode side, and the cathode and anode A negative charge oxygen atom is taken out from the side where the anode is arranged by applying a voltage therebetween, and the anode is arranged with a space from the member formed of the complex oxide.

  Further, the oxygen chamber provided with the negative charge oxygen atom generating member and a normal pressure generation chamber are partitioned, a cathode is disposed on the side of the oxygen chamber of the negative charge oxygen atom generating member, and the negative charge is provided on the side of the generation chamber. An anode is disposed at a distance from the oxygen atom generating member, a direct current power source is connected to the anode and the cathode, and a rare gas flow from the negative charge oxygen atom generation unit to the irradiation direction of the negative charge oxygen atoms in the generation chamber. Alternatively, an accelerating electrode for forming a dry air flow and applying a voltage between the anode and the anode to be sterilized, which is the irradiation direction of the negatively charged oxygen atoms, is arranged, and an accelerating voltage is applied to the negatively charged oxygen further. The atomic flow is accelerated, and the sample to be sterilized is arranged on the anode side of the acceleration electrode for applying a voltage between the anode and the anode.

  In the sterilization apparatus of the present invention, the generated negatively charged oxygen atoms are accelerated by the rare gas flow and the acceleration voltage, so that the negatively charged oxygen atoms whose oxidation action is adjusted can be irradiated to the sample to be sterilized. Appropriate processing can be performed according to the target. That is, even a sample that is denatured under reduced pressure can exert an oxidizing action on negatively charged oxygen atoms, and even if the sample is covered with a shell or the like, a desired treatment can be performed.

  Further, the negative charge oxygen atom production apparatus of the present invention forms a rare gas flow under a normal pressure between the negative charge oxygen atom generation part and the irradiation part, and between the acceleration voltage provided in the irradiation part and the anode. Since an adjustable acceleration voltage was applied to the irradiated portion, negatively charged oxygen atoms corresponding to the sample can be given to the irradiated part, so that even a sample that is altered under reduced pressure can oxidize negatively charged oxygen atoms. Even if the sample is covered with a shell or the like, a desired treatment can be performed. In addition, since a tube made of nylon or Teflon (registered trademark) having a diameter adapted to the standard of a medical tube is used, it can be well adapted to a medical sterilization / sterilization box.

In addition, since the flow rate does not form an O ⁻ layer on the side wall in the tube, O ⁻ can be transported efficiently.

In the present invention, 12CaO · 7Al ₂ O ₃ (hereinafter referred to as calcium aluminate composite oxide or C12A7) that includes an active oxygen species, or a member made of a composite oxide containing at least cerium (CeO ₂ alone or CeO _2). And a composite obtained by mixing and firing CaO, CeO ₂ and CaO, Al ₂ O ₃ (hereinafter referred to as cerium composite oxide), and preferably by heating the composite oxide (sintered body). The electrode is placed on both sides of the electrode and heated to apply a voltage, take in oxygen from one surface, generate negatively charged oxygen atoms from the other, and generate the negatively charged oxygen atoms at normal pressure. It is possible to accelerate the generated negatively charged oxygen atoms by forming a noble gas flow or a dry air flow in the direction in which the negatively charged oxygen atoms are irradiated from the The irradiation direction of the luggage oxygen atom, it has been found that by applying an acceleration voltage is provided an acceleration electrode accelerating the negatively charged oxygen atoms it is possible to increase the energy.

  That is, if negatively charged oxygen atoms are used for sterilization or the like, treatment under normal pressure is indispensable. However, in the atmosphere, negatively charged oxygen atoms can react effectively with the atmosphere or moisture. The problem that the substance to be treated cannot be sufficiently treated with negatively charged oxygen atoms having a low energy level is that the flow velocity of a rare gas flow such as helium or dry air flow and the acceleration voltage applied to the acceleration electrode It is possible to use.

The present invention will be described below with reference to the drawings.
FIG. 1 shows an embodiment of a negative charge oxygen atom (O ⁻ ) transfer device for sterilization and sterilization according to the present invention. In FIG, 1 is O ^- a generator unit, the O ^- O generated by the generator ^- together with pulled to the right in FIG spatial electrode 6, rare gas fed from the cylinder 4 of the noble gas or dry air Or it is conveyed by dry air and is carried to the reaction part 3 through the nylon tube (or Teflon (registered trademark) tube) 7. The reaction unit 3 is, for example, a medical sterilization / sterilization box. The generation of O ⁻ can be confirmed by the ammeter 8 or the ion measuring instrument 9.

O ^- has a strong oxidizing power, that although minute sterilization force is also strong, that it is none other than that it is easy to return to the original O ₂ and immediately oxidation speaking in reverse. In particular, when it encounters moisture, it easily returns to the original O ₂ and disappears.

Therefore O ^- as the gas for transporting chemically stable noble gases used. However, since a rare gas such as He is expensive, dry air is used instead of the rare gas in the case of a medical sterilization / sterilization apparatus that dissipates in the air.
In particular, when the O ⁻ is transported with a rare gas or dry air using a transport tube, there are the following problems.

O ⁻ tends to diffuse in the radial direction of the tube within the tube, and when it hits the side wall of the tube, it accumulates at that location and forms an O ⁻ layer. As a result, the O ⁻ layer is negatively charged up, so that the O ⁻ floating in this vicinity repels the O ⁻ layer and consequently the flow of O ⁻ is inhibited. Further, the material is required not to be attacked by O ⁻ , and therefore, the tube is suitably made of nylon or Teflon (registered trademark). Further, a flow rate at which an O ⁻ layer near the side wall of the tube is difficult to be formed is preferable, and the size of the diameter needs to be appropriately selected. In addition, there is a standard for the diameter of the medical tube, and this embodiment is set to 4 mmφ in accordance with this standard. In the 4 mmφ tube, it was confirmed that the carrier gas flow rate in the tube is preferably 0 to 500 cm / s. Incidentally, the O ^- generation chamber (e.g., 1,6 between 27 and 1 in FIG. 2) the flow rate of the carrier gas is usually 0.1cm / s~30cm / s used, the transport gas in the tube The flow rate of the gas is approximately 10 times the flow rate of the carrier gas in the production chamber, although it depends on the cross-sectional area of the production chamber.

In addition, the said Example is based on the following structures similar to the said prior proposal.
In FIG. 2, the negative charge oxygen atom generation chamber 27 is provided with an anode 10 acting as an extraction electrode in the vicinity of the negative charge oxygen atom generation portion 29 of the negative charge oxygen atom generation member 22. E1 is applied. The irradiation unit 11 that irradiates negatively charged oxygen atoms is provided with an acceleration electrode 12 that accelerates the generated negatively charged oxygen atoms, and an acceleration voltage is applied from the acceleration power source E2. Further, the sample 13 is placed on the front surface or the rear surface of the acceleration electrode. When the sample is placed behind the accelerating electrode, the structure is such that O ⁻ such as a mesh can pass through.

  Although not shown, in the embodiment of the present invention, as shown in FIG. 1, the generation chamber 27 of FIG. 2 and the sample chamber (sterilization / sterilization box) in which the sample 13 is placed are separated, and both chambers are separated. The space is connected with the nylon tube or Teflon (registered trademark) tube. In this case, the acceleration electrode 12 is placed near the exit of the generation chamber or in the sample chamber.

  The generation chamber 27 is provided with a noble gas inlet 14 and a noble gas discharge port 15, and the noble gas in the generation chamber 27 is directed from the negative charge oxygen atom generation unit 29 toward the negative charge oxygen atom irradiation unit 11. A stream 16 is formed. As in the separately proposed embodiment, the fired body can be heated by providing a heating means such as a heater in contact with the fired body or by arranging a halogen lamp. Examples of the anode 10 that functions as an extraction electrode include gold-stable gold, noble metals such as platinum, metals such as nickel, and alloys such as stainless steel (SUS304, SUS430, etc.). Among these, platinum is preferable, and rod-like bodies, linear bodies, net-like bodies, or those coated on a substrate can be used. The distance between the generation part of the fired body and the anode is preferably 10 mm or less in order to generate negatively charged oxygen atoms at a low voltage. If it is possible to form an interval on the order of μm with an insulating member and hold the anode horizontally, the smaller the interval, the greater the electric field strength formed between the anode and the cathode. Operation with voltage becomes possible.

  The potential difference between the cathode and the anode is 1 to 2000 V / cm, preferably 10 to 1000 V / cm, and more preferably 50 to 500 V / cm. When it is lower than 1 V / cm, the production efficiency is low, and when it is higher than 2000 V / cm, the fired body or the electrode may be damaged.

The fired body is preferably heated to 200 to 1000 ° C, more preferably 500 to 800 ° C. When the temperature is lower than 200 ° C, the generation efficiency is insufficient, and when the temperature is higher than 1000 ° C. Is not preferable because the influence of heat on the surroundings becomes large and countermeasures are required.
Moreover, in the negative charge oxygen atom production apparatus of the present invention, it is possible to efficiently irradiate the irradiation part with negative charge oxygen atoms generated by forming a rare gas flow in the generation chamber.

  The rare gas flow in the generation chamber has an action of transferring heat from the generation part of the heated negatively charged oxygen atoms. Therefore, since heat is transferred not only to negatively charged oxygen atoms but also to the irradiated part by the rare gas flow, the flow rate of the rare gas flow must be considered in consideration of the temperature rise of the irradiated part, and is altered by heating. It is preferable not to increase the flow rate of the rare gas flow. It is desirable that the transfer nylon tube and the like have a cooling structure like the generation chamber. As the rare gas flow, one having a small molecular weight is preferable because the amount of disappearance of negatively charged oxygen atoms can be reduced, and helium, xenon, or the like can be used. In particular, helium is easier to obtain than xenon and has a large mean free path of negatively charged oxygen atoms, so that the amount of negatively charged oxygen atoms disappearing can be reduced. In addition, since rare gas is expensive, dry air may be used when it is difficult to collect the rare gas for general-purpose use such as medical purposes.

  In the present invention, negatively charged oxygen atoms irradiated to the sample placed on the irradiation unit are adjusted by adjusting the voltage applied between the anode acting as the extraction electrode and the acceleration electrode arranged on the irradiation unit. It is possible to adjust the speed.

  Thus, in the negatively charged oxygen atom production apparatus of the present invention, not only the voltage applied to the anode, but also a rare gas flow is formed in the production chamber, and further an acceleration voltage is applied between the anode and the irradiation part. In addition, since they can be adjusted, negatively charged oxygen atoms having an energy level according to the purpose can be given to the sample of the irradiated portion.

For example, it is possible to sterilize substances that are altered under reduced pressure at normal pressure, and to adjust the negatively charged oxygen atoms to be irradiated according to the type of bacteria to be sterilized. Even in the case of bacterial cells having a large property, sterilization becomes possible by increasing the accelerating voltage and irradiating negatively charged oxygen atoms having a large effect.
Hereinafter, the present invention will be described with reference to examples of the present invention.

O ^- Example of the present invention relates to transportation method (Example 1)
Using a self-heating device coated with C12A7, heating to 650 ° C. under the flow rate of He in the tube of 0.1 cm / s, and then applying a voltage of 100 V / cm to the spatial mesh electrode, current 10 μA can be observed. It was. When the ion current was measured with a microammeter at the tip of a 100 mm nylon 4 mmΦ tube fixed to the body with an air joint behind the electrode, a current of 10 nA was observed.

(Example 2)
Using a self-heating type vessel coated with C12A7, heating to 650 ° C. under a flow rate of He in the tube of 10 cm / s, and then applying a voltage of 100 V / cm to the spatial mesh electrode, a current of 10 μA could be observed. . When the ion current was measured with a microammeter at the tip of a 4 mmφ tube made of 100 cm Teflon (registered trademark) fixed to the main body with an air joint behind the electrode, a current of 1 nA was observed.

Example 3
Using a self-heating type device coated with C12A7, heating to 650 ° C. under a flow rate of He in the tube of 500 cm / s, and then applying a voltage of 100 V / cm to the air mesh electrode, a current of 10 μA can be observed. It was. A current of 50 nA was observed when the ionic current was measured with a reduced current meter at the tip of a 100 mm nylon 4 mmΦ tube fixed to the main body by an air joint behind the electrode.

Example 4
O ^- stop He supply after filled with He into the generator (flow rate 0). When a self-heating type vessel coated with C12A7 was used and ripened to 650 ° C., and then a voltage of 100 V / cm was applied to the spatial mesh electrode, a current of 10 μA could be observed. When the ion current was measured with a microammeter at the tip of a 100 mm nylon 4 mmΦ tube fixed to the main body by an air joint behind the electrode, a current of 5 nA was observed.

In the above embodiment, the one using C12A7 as the O ⁻ generator is shown. However, the O ⁻ generator is not limited to that of C12A7, and the same applicant proposes “at least cerium. The composite oxide containing "may be used (Japanese Patent Application No. 2004-160374).

The oxygen radical generator using the “complex oxide containing at least cerium” heats a fired composite oxide containing oxygen radicals and containing at least cerium to extract oxygen radicals. Further, the composite oxide fired body is made of cerium alone, and the pellet of the composite oxide fired body is CeO ₂ at 1200 to 1500 ° C. under a gas flow mixed with 2 to 5% oxygen in normal pressure He. It is manufactured by baking for 5 to 7 hours.

Alternatively, the composite oxide fired body is made of cerium and aluminum, and the pellet of the composite oxide fired body has a composition of CeO ₂ : AL ₂ O ₃ = 1: 5 (molar ratio) of 1200 to 1500 ° C. It is produced by firing for 5 to 7 hours in a gas flow mixed with 2 to 5% oxygen in normal pressure He.

Alternatively, the fired composite oxide is made of cerium, calcium, and aluminum, and the pellet of the fired composite oxide is CeO ₂ : AL ₂ O ₃ : CaO = 2.1: 4.9: 12 ( The mixture composition is characterized by being manufactured by firing at 1200 to 1500 ° C. in normal pressure He for 5 to 7 hours under a gas flow mixed with 2 to 5% oxygen.

  Furthermore, the composite oxide fired body is formed as a thin film on an oxygen ion conductor substrate, and the oxygen ion conductor is a zirconia plate or yttria-stabilized zirconia.

In the case of using a composite oxide containing at least cerium, a conventional material made of C12A7 requires a high temperature of 700 ° C. or higher in order to generate O ⁻ (negatively charged oxygen atoms). The greatest effect is that O ⁻ (negatively charged oxygen atoms) can be generated at a temperature as low as 600 ° C.

In addition, the self-heating type | mold apparatus in the said Example is as follows which the same applicant proposes separately (refer Japanese Patent Application No. 2003-41661, Japanese Patent Application No. 2004-160374). However, embodiments of the present invention, O due to self-heating of the negatively charged oxygen atom generator ^- is used a generator, but using the nylon tube or Teflon tube, which is a feature of the present invention if, other O of Tammann tube type or the like have been separately proposed ^- may be a generator.

  FIG. 3 shows the basic structure of a self-heating type (heater integrated type) negative charge oxygen generator. In FIG. 3, 32 and 34 are strong solid electrolyte (hereinafter referred to as YSZ) substrates such as zirconia or yttria stable zirconia, and 31 is a thin film “C12A7” or “oxygen radical” formed on the substrate. A composite oxide fired body containing at least cerium (cerium composite oxide) ”. Reference numeral 35 denotes a porous electrode, which corresponds to the cathode 3 in FIG. 33 is a heater.

As shown in FIG. 3, the C12A7 or cerium composite oxide is a thin film having a thickness of 5 to 10 μm, and there is almost no temperature difference between the back surface and the front surface. Therefore, no temperature gradient is generated in the composite oxide, so that even when heated from the back surface, the efficiency of releasing from the surface to O ⁻ is not hindered.

  In addition, since the heater 33 is built in the YSZ 32 and 34 compared to the conventional structure in which heating is performed from the back side of the substrate, the heating efficiency to the cerium composite oxide is good and the power consumption is small. Is also unnecessary, and the apparatus can be miniaturized.

Further, since the YSZ 34 is interposed between the heater 33 and the temperature on the back side (35 side), the surface temperature is lowered, and the oxygen on the back side is lower than that of a conventional device provided with a heater on the back side. Fully inhaled. FIG. 4 shows another basic structure of the heater-integrated negative charge oxygen generator according to the present invention. The difference between FIG. 4 and FIG. 3 is that the heater 41 is formed outside the cerium composite oxide 42 formed with a thin film. Is a point. In this case, the heater 41 has a network structure so as not to hinder the release of negatively charged oxygen (O ⁻ ). In FIG. 4, 42 is a cerium composite oxide of a thin film formed on the substrate, 43 is a YSZ substrate, and 44 is a porous electrode. As in the case of FIG. 3, since the YSZ 43 is interposed between the temperature on the back surface side (44 side) and the heater 41, the surface temperature is low, compared to the conventional one in which a heater is provided on the back surface side, Inhalation of oxygen on the back side is sufficiently performed.

FIG. 5 shows another basic structure of the heater-integrated negative charge oxygen generator of the present invention. The basic structure is the same as that of FIG. 3, and shows a case where it is used without the external electric field of FIGS. .
The difference between FIG. 3 and FIG. 5 is that FIG. 3 forcibly extracts O ⁻ by an electric field, whereas FIG. 5 generates O ⁻ by thermal desorption from the surface of the complex oxide. Is a point. The former is used for applications such as the semiconductor manufacturing apparatus, and the latter is a structure suitable for purposes such as sterilization and deodorization, for example, toilets, kitchen tiles, and air conditioners.

It should be noted that the use in the toilet or the air conditioner can be used without worrying about burns by covering the upper part with some protective material. In the case of FIG. 5, O ⁻ on the surface of the composite oxide is used. In addition, the structure of FIG. 3 may be used as long as an electric field is applied in the case of sterilization, and in the case of deodorization, it is preferable to use the honeycomb structure with the structure of FIGS. 3 and 5 described above. Note that the structure of FIG. 4 can also be used without an electric field. Also in the present invention, a negatively charged oxygen atom generator that generates O ⁻ without applying an electric field may be used.

The present invention can also be used in air. In the air, O ⁻ existing in the vicinity of the space away from the complex oxide diffuses into the air and reacts with water to form negative ion clusters of water, so that the oxidation reaction proceeds sufficiently. For the deodorization and sterilization in the air, an atmospheric circulation method (for example, an air conditioner) may be used in addition to the above atmospheric release method. Regarding sterilization and sterilization, in the case of a specific container (such as a plastic bottle or a surgical tool), it is preferable to install the specific container between the counter electrodes of the complex oxide.

Hereinafter, the present invention will be described by showing an experimental example of the sterilization / sterilization apparatus of FIG. In the present invention, the rare gas flow or the dry air flow of the conventional example flows into the sterilization / sterilization box through the nylon tube or the Teflon (registered trademark) tube as described above. Even if there is a difference, the present invention can be expected to have the same bactericidal effect.

(Experimental example 1)
A bacterial cell sample was prepared by applying 0.1 cm ³ of E. coli at a concentration of 107 cells / cm ³ on a copper plate covered with a polypropylene sheet.
The obtained bacterial cell sample was placed in the negative charge oxygen atom generator shown in FIG. 2 with a space between the cylindrical negative charge oxygen atom generator having a diameter of 20 mm and a length of 50 mm and the bacterial cell sample being 50 mm. It was made to flow at a flow rate of 0.5 cm / sec from the charged oxygen atom generation part toward the cell sample.
Further, a voltage with an electric field strength of 50 V / cm is applied to the extraction electrode that acts as an anode made of a platinum wire mesh with a spacing of 0.1 mm between lines provided at a position 10 mm from the negative charge oxygen atom generation portion. The acceleration electrode made of platinum provided in the irradiation part of the 500 mm bacterial cell sample from the oxygen atom generation part was irradiated with negatively charged oxygen atoms while applying a voltage of 200 V to the anode and energizing.
Irradiation was performed by changing the irradiation time to 30, 60, 90, and 120 seconds. The obtained sample was applied to a bacterial count measuring medium consisting of a trypticase soy agar medium, cultured at 40 ° C. for a whole day and night, colonies were counted, and the results are shown in Table 1.
(Table 1)
Irradiation time (seconds)
30 60 90 120
Number of colonies 50 20 10 0

(Experimental example 2)
Except for the point that the acceleration voltage applied between the extraction electrode and the irradiation part electrode was 10 V, negative charge oxygen atoms were irradiated in the same manner as in Experimental Example 1, and the results are shown in Table 2.
(Table 2)
Irradiation time (seconds)
30 60 90 120
Number of colonies 80 50 10 0

(Experimental example 3)
A cell sample was prepared by applying 0.1 cm ³ of Bacillus subtilis at a concentration of 107 cells / cm ³ on a copper plate covered with a polypropylene sheet.
The obtained bacterial cell sample is placed in the negative charge oxygen atom generator shown in FIG. 2 with an interval of 500 mm between the negative charge oxygen atom generator and the bacterial sample, and helium is transferred from the negative charge oxygen atom generator to the bacterial sample. The flow was directed at a flow rate of 0.5 cm / sec.
In addition, a voltage with an electric field strength of 50 V / cm was applied to the extraction electrode provided at a position 10 mm from the negative charge oxygen atom generation unit, and the extraction electrode was provided to the irradiation part of the bacterial cell sample 500 mm from the negative charge oxygen atom generation unit. The acceleration electrode was irradiated with negatively charged oxygen atoms while a voltage of 200 V was applied to the extraction electrode and energized.
Irradiation was performed by changing the irradiation time to 30, 60, 90, and 120 seconds. The obtained sample was applied to a medium for measuring the number of bacteria consisting of trypticase soy agar medium. After culturing at 40 ° C. all day and night, colonies were counted and the results are shown in Table 3.
(Table 3)
Irradiation time (seconds)
30 60 90 120
Number of colonies 200 150 100 50

(Experimental example 4)
Table 4 shows the results of irradiation with negatively charged oxygen atoms in the same manner as in Experimental Example 3 except that the acceleration voltage applied between the extraction electrode and the irradiation part electrode is 10V.
(Table 4)
Irradiation time (seconds)
30 60 90 120
Number of colonies 500 300 200 100

(Experimental example 5)
Table 5 shows the results of irradiation with negatively charged oxygen atoms in the same manner as in Experiment 3 except that the acceleration voltage applied between the extraction electrode and the irradiation portion electrode was 1V.
(Table 5)
Irradiation time (seconds)
30 60 90 120
Number of colonies 10 5 5 × 10 4 10 4 3 × 10 3

  Thus, in the negative charge oxygen atom transport device for sterilization and sterilization, the rare gas flow or the dry air flow is directed to the sample to be sterilized through a 3-5 mmφ nylon or Teflon (registered trademark) tube. By irradiating negatively charged oxygen atoms, it is possible to efficiently sterilize and sterilize, especially when the sample to be sterilized is placed in a medical sterilization / sterilization box. .

It is a figure explaining the conveyance apparatus of the negative charge oxygen atom of this invention. It is a figure explaining the generator of the negative charge oxygen atom using the conventional noble gas flow. It is a figure which shows the structure of the conventional self-heating type negative charge oxygen generator. It is a figure which shows the structure of the other conventional self-heating type negative charge oxygen generator. It is a figure which shows the structure of the further another conventional self-heating type negative charge oxygen generator.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 O ^- generation part 2 O ^- conveyance part 3 Reaction part 4 Gas cylinder 5 Negative-charge oxygen generator 6 Space electrode 7 Tube 8 Ammeter 9 Ion measuring device 11 Irradiation part 12 Acceleration electrode 13 Sample 14 Noble gas inlet 15 Noble Gas outlet 16 Noble gas flow 17 Cooling means 18 Refrigerant 20 Anode 22 Negative charge oxygen atom generating member 23 Cathode 24 Heating means 25 Partition 26 Oxygen chamber 27 Generation chamber 28 Oxygen supply port 29 Generating part

Claims (9)

A member composed of a calcium aluminate composite oxide or a composite oxide containing at least cerium is heated to extract negatively charged oxygen atoms, and a rare gas flow from the negatively charged oxygen atom generating portion to the irradiation direction of the negatively charged oxygen atoms. Or in a negative charge oxygen atom transport device for sterilization and sterilization that irradiates negatively charged oxygen atoms toward the sample to be sterilized by forming a dry air flow,
A negative charge for sterilization and sterilization is characterized by irradiating a sample to be sterilized with negative charge oxygen atoms through a 3-5 mmφ nylon or Teflon (registered trademark) tube with the rare gas flow or dry air flow. Charge oxygen atom transport device.   The negatively charged oxygen atom transport apparatus according to claim 1, wherein the sample to be sterilized is placed in a medical sterilization / sterilization box.   3. The negative charge oxygen atom transfer device according to claim 1, wherein a flow rate of the rare gas flow or the dry air flow in the tube is 0 to 500 cm / s.   The composite oxide is formed as a thin film on a substrate made of an oxygen ion conductor, and a heater for heating the composite oxide is in proximity to or in contact with the thin film made of the composite oxide. The negatively charged oxygen atom transport device according to any one of claims 1 to 3, wherein the negatively charged oxygen atom transport device is formed integrally with the negative charge oxygen atom.   4. The negative charge oxygen atom transport device according to claim 1, wherein the composite oxide is formed as a thin film on a steatite ceramic heater substrate.   A cathode is disposed on the back side of the substrate on which the complex oxide is formed, an anode is disposed on the side opposite to the surface on which the cathode is disposed, oxygen is supplied to the cathode side, and a voltage is applied between the cathode and the anode. The negative charge oxygen atom transport apparatus according to any one of claims 1 to 5, wherein negative charge oxygen atoms are taken out from the side on which the anode is arranged by applying a negative electrode.   7. The negative charge oxygen atom transport device according to claim 6, wherein the anode is disposed with a space provided from a member formed of the complex oxide.   The oxygen chamber provided with the negative charge oxygen atom generation member and a generation chamber at normal pressure are partitioned, a cathode is disposed on the side of the oxygen chamber of the negative charge oxygen atom generation member, and the negative charge oxygen atoms are formed on the side of the generation chamber. An anode is disposed at a distance from the generating member, a DC power source is connected to the anode and the cathode, and a rare gas flow or drying is performed with respect to the irradiation direction of the negatively charged oxygen atoms in the generating chamber from the negatively charged oxygen atom generating unit An accelerating electrode that forms an air flow and applies a voltage between the anode and the sample to be sterilized, which is the irradiation direction of the negatively charged oxygen atoms, is disposed, The apparatus for transporting negatively charged oxygen atoms according to claim 6 or 7, wherein   9. The negative charge oxygen atom transport device according to claim 8, wherein the sample to be sterilized is disposed on the anode side of the acceleration electrode for applying a voltage between the anode and the anode.

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