JP5845385B2 - Air purifier - Google Patents

Description

  The present invention relates to an air cleaning apparatus that can react with an object to be processed such as germs and organic substances in a remote place using an active substance.

  Conventionally, a photocatalytic reaction using titanium oxide is known for oxidative decomposition of this kind of organic matter. Titanium oxide is known to have a photocatalytic action, and deodorization or antibacterial action can be exhibited by irradiating light (ultraviolet rays) to titanium oxide. By irradiating the titanium oxide with ultraviolet rays, hydroxyl radicals known as active substances having high oxidizing power are generated on the titanium oxide, and the generated hydroxyl radicals are decomposed by oxidizing the odor components and microorganisms adsorbed on the filter. Because. Therefore, by processing the photocatalyst into a filter shape such as a honeycomb and venting the filter while irradiating with ultraviolet rays, the air can be deodorized or antibacterial.

  For example, as this type of deodorizing device, a device in which a photocatalyst 102 is kneaded into an adsorbent 101 to form a honeycomb as shown in FIG. 9 is known (see, for example, Patent Document 1).

  Air containing odor is passed through the honeycomb holes 103 and a lamp as the photocatalyst excitation source 104 is turned on to excite the photocatalyst 102 to decompose and deodorize the odor.

  Further, as shown in FIG. 10, the photocatalyst 201 is irradiated with ultraviolet rays 203 through an optical fiber 202, the active species 204 generated from the photocatalyst 201 is diffused into the gas phase, and the object 205 to be treated facing each other with an interval of 3 mm or less. In addition, a method of etching or modifying with a predetermined pattern has been known (for example, see Patent Document 2).

Japanese Patent No. 2574840 Japanese Patent No. 4088456

  The conventional deodorization apparatus described in Patent Document 1 is a honeycomb-shaped structure in which a photocatalyst 102 is kneaded, and can act on a substance adsorbed on the honeycomb structure by aeration. However, there is a problem that the effect cannot be obtained for those that are not adsorbed on the honeycomb structure or those that adhere to the surface of the object and do not scatter in the air. This is because the hydroxyl radical generated from the photocatalyst is unstable and has a very short life, so that it is hardly released from the honeycomb structure and the effect is limited to the vicinity of the honeycomb structure.

  The conventional method described in Patent Document 2 causes a non-contact oxidation reaction on the surface of an object to be processed existing at a distance of 3 mm or less from the photocatalyst. That is, since the hydroxyl radical generated on titanium oxide is unstable and has a very short life, there is a problem that a non-contact oxidation reaction cannot be caused at a distance of 3 mm or more.

  Therefore, the present invention solves the above-mentioned conventional problems, generates an active substance that is stable and has a long life and can be released from the photocatalyst into the gas phase, etc., and treats germs and organic substances in remote places. An object of the present invention is to provide an air cleaning device capable of reacting with an object.

In order to achieve this object, the present invention holds a photocatalyst on a base material that can pass air in a main body having a suction port and a blowout port, and releases an active substance by irradiating light. An air cleaning device comprising an active substance generating material, air purifying means, and air blowing means for blowing out at least part of the air sucked from the suction port from the outlet, wherein the active substance generating material is A first halogen-containing titanium oxide is prepared as the photocatalyst, supported on the substrate and dried, and then added with oxo acid and a second halogen , thereby achieving the intended purpose. It is.
Further, in the main body having a suction port and a blowout port, an active material generating material that holds a photocatalyst on a base material that can pass air and emits an active material by irradiating light, an air purification means, An air cleaning device comprising a blowing means for blowing out at least part of the air sucked from the suction port from the blow-out port, wherein the active substance generating material uses halogen-containing titanium oxide as an acidic binder as the photocatalyst. In this way, after being supported on a base material, an oxo acid and an additional halogen are attached, thereby achieving the intended purpose.

According to the present invention, at least an oxo acid and a photocatalyst are contained, a photocatalyst is held on a base material through which air can pass in a main body having a suction port and a blowout port, and an active substance is released by irradiation with light. An air cleaning device comprising an active substance generating material, an air purifying means, and an air blowing means for blowing out at least part of the air sucked from the suction port from the outlet, wherein the active substance generating material is After the first halogen-containing titanium oxide was prepared as the photocatalyst, supported on the substrate and dried, and then added with oxo acid and the second halogen, the photocatalyst to the gas phase etc. was stable and long in life. It is possible to provide an air purifying apparatus that can generate an active substance that can be released in the air and react with an object to be treated such as germs and organic substances in a remote place.
Further, in the main body having a suction port and a blowout port, an active material generating material that holds a photocatalyst on a base material that can pass air and emits an active material by irradiating light, an air purification means, An air cleaning device comprising a blowing means for blowing out at least part of the air sucked from the suction port from the blow-out port, wherein the active substance generating material uses halogen-containing titanium oxide as an acidic binder as the photocatalyst. By supporting oxo acid and additional halogen after loading on the substrate, the halogen-containing titanium oxide can be evenly supported on the substrate, and it is stable and has a long life and is released from the photocatalyst to the gas phase, etc. It is possible to provide an air cleaning device that can generate an active substance that can be reacted and react with an object to be processed such as germs and organic substances in a remote place.

Schematic sectional view showing an air cleaning device according to Embodiment 1 of the present invention. Schematic sectional view showing an air cleaning device according to a second embodiment of the present invention. Schematic sectional view showing an air cleaning device according to a third embodiment of the present invention. Schematic sectional view showing an air cleaning device according to a fourth embodiment of the present invention. The graph which shows the hydrogen peroxide generation amount in the Example of this invention The graph which shows the effective chlorine generation amount in the Example of this invention The graph which shows the hydrogen peroxide generation amount in the Example of this invention The graph which shows the effective chlorine generation amount in the Example of this invention A perspective view showing a conventional deodorizing apparatus Schematic sectional view showing a conventional photocatalytic lithography method

The air purifying device according to claim 1 of the present invention contains at least an oxo acid and a photocatalyst, holds a photocatalyst on a base material that can pass air in a main body having a suction port and a blowout port, and irradiates light. An air purifying device comprising an active material generating material that releases an active material by performing, an air purifying unit, and an air blowing unit for blowing out at least a part of the air sucked from the suction port from the blowing port. The active material generating material is characterized in that a first halogen-containing titanium oxide is prepared as the photocatalyst, supported on the substrate and dried, and then an oxo acid and a second halogen are impregnated. It is. By containing at least oxo acid and photocatalyst as the active substance generator, radical components such as hydroxyl radicals generated on the surface of the photocatalyst by light irradiation are converted into active substances such as active oxygen species having a long life. be able to. Active substances released in a medium such as the gas phase have a long life, so they react with germs, molds, viruses, allergens, odorous components, organic substances, etc. located away from the active substance generating material, resulting in degradation or reduced activity The effect of making it possible can be obtained.
Further, the air purifier according to claim 2 is an active substance in which a photocatalyst is held on a base material capable of passing air in a main body having a suction port and a blowout port, and the active substance is released by irradiating light. An air purifier comprising: a generating material; an air purifying means; and an air blowing means for blowing out at least a part of the air sucked from the suction port from the blowing port, wherein the active substance generating material is the photocatalyst. After supporting halogen-containing titanium oxide on the base material with an acidic binder and then adding oxo acid and additional halogen, the halogen-containing titanium oxide can be uniformly supported on the base material and is stable. An air purifier that can generate active substances that can be released from the photocatalyst into the gas phase, etc., and has a long life, and can react with objects to be treated such as germs and organic substances in remote locations It can be provided.

In addition, by containing an active substance generating material Gaha androgenic, improve the activity of the photocatalyst, it is possible to increase the generation of the active substance. Moreover, chlorine compounds, such as hypochlorous acid and chlorine, can be produced | generated as an active substance.

In addition, after chemically bonding the halogen compound to the photocatalyst, the addition of oxo acid , the halogen and the photocatalyst are chemically bonded to increase the amount of hydroxyl radicals generated. By this action, it can be efficiently changed to active species having a long life such as hydrogen peroxide, hypochlorous acid, chlorine and the like.

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

(Embodiment 1)
As shown in FIG. 1, the air purifying apparatus of the present invention contains an ultraviolet lamp as a light source 4 for irradiating light, at least an oxo acid and a photocatalyst in a main body 3 having a suction port 1 and a blowout port 2. The active substance generating material 5 that releases the active substance by irradiating light, the dust collection filter 6 and the deodorizing filter 7 as air purification means, and at least part of the air sucked from the suction port is blown from the blowout port. And a fan 8 as a blowing means for taking out.

  The air containing the active substance generated from the active substance generating material 5 moves to a dust collecting filter 6 or a deodorizing filter 7 as a purifying means, and adhering or adsorbing to the purifying means, mold, virus, allergen, odor component, An effect of reacting with an organic substance or the like to reduce decomposition or activity can be obtained. In addition, the active substance is released into the room from the main body 3 of the air cleaning device, and reacts with germs, molds, viruses, allergens, odorous components, organic substances, etc. adhering to the air or on the wall surface, thereby decomposing / antibacterial or reducing the activity. The effect that can be obtained.

  Examples of the photocatalyst include titanium oxide, tungsten oxide, strontium titanate, niobium oxide, and tantalum oxide. Of these, titanium oxide is preferable from the viewpoint of the strength of activity.

  Examples of titanium oxide include anatase-type titanium oxide, rutile-type titanium oxide, and brookite-type titanium oxide. In addition to providing an antibacterial effect in the dark, high photocatalytic activity is obtained. preferable. In the present invention, “anatase-type titanium oxide” refers to titanium oxide in which a diffraction peak appears in the vicinity of a diffraction angle 2θ = 25.5 degrees in powder X-ray diffraction spectrum measurement (use electrode: copper electrode).

  Examples of titanium oxide include titanium dioxide, hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, oxygen-deficient titanium oxide, nitrogen-substituted titanium oxide, and sulfur-substituted titanium oxide. It is done. The crystal form is not particularly limited as long as it has photocatalytic activity, and any of amorphous, anatase, rutile, and brookite forms may be used. There is no problem even if components having different crystal forms such as a combination of rutile type and anatase type titanium oxide are combined.

  Although titanium oxide is often in a powder form, a titanium oxide thin film may be formed by oxidizing a metal surface such as a titanium plate. Alternatively, a titanium thin film may be formed by coating glass or the like with titanium alkoxide or the like and performing heat treatment. A titanium oxide film may be formed by spraying titanium powder on a metal surface or the like.

  Further, it is not limited at all to coat the surface of titanium oxide with a metal such as Pt, Pd, Rh, Ru, Au, Ag, Cu, Fe, or Ni. Further, there is no limitation to using a photocatalyst whose surface has an impurity metal such as Cr or V to increase the absorption wavelength of light.

Titanium oxide is preferably from a specific surface area of 200~350m ² / g, more preferably from 250 to 350 ² / g. Here, the specific surface area in the present invention is a surface area value per gram of titanium oxide powder measured by a BET method (nitrogen adsorption / desorption method). When the specific surface area is 200 m ² / g or more, the contact area with the object to be decomposed can be increased. Further, when anatase type titanium oxide is used, when the specific surface area is 350 m ² / g or less, a photocatalytic reaction can be performed with higher efficiency than when amorphous titanium oxide is used.

  In the present invention, an “oxo acid” is a compound having a hydroxyl group (OH) and an oxo group (C═O). For example, phosphoric acid, phosphorous acid, sulfuric acid, sulfurous acid, carbonic acid, nitric acid, nitrous acid , Boric acid, silicic acid, arsenic acid, carboxylic acid, sulfonic acid, sulfinic acid, chromic acid, dichromic acid, permanganic acid and halogen oxoacids such as hypochlorous acid, chlorous acid, chloric acid, perchlorine Examples include acids, perbromic acid, iodic acid, and periodic acid. On the other hand, those that are not oxidatively decomposed by the photocatalyst are preferable, and phosphoric acid, sulfuric acid, carbonic acid, nitric acid, and boric acid are exemplified.

  For example, when phosphoric acid is used as the oxo acid, it can be used as an aqueous solution having an appropriate concentration using a phosphate or hydrogen phosphate. Moreover, phosphoric acid compounds, such as polyphosphoric acid and metaphosphoric acid, can be used similarly. All have a plurality of oxo groups in the structure.

  The mechanism by which oxo acid converts radical substances into stable compounds is not clear, but oxygen-rich structures like oxo acids coordinate with radicals to convert them into more stable active substances. It is thought that it is done.

  In the present invention, it is preferable that at least a part of the halogen is chemically bonded to the photocatalyst. When the chemical bond is an ionic bond, the halogen and titanium oxide are firmly bonded, for example, the amount of active substance generated is reduced. The effect that it can improve can be acquired. Halogen includes fluorine, iodine, bromine and chlorine. For example, when fluorine is used as the halogen, the fluorine content may be 1.25 wt% to 4.0 wt% from the viewpoint of enhancing the amount of active substance generated and antibacterial performance during light irradiation. preferable. The fluorine content in the fluorine-containing titanium oxide (IV) can be determined by a spectrophotometric analysis method (JIS K 0102).

  In the present invention, “at least a part of the halogen is chemically bonded to the photocatalyst” means that the photocatalyst, for example, titanium oxide and at least a part of the halogen are chemically bonded. Preferably, it refers to a state where titanium oxide and halogen are bonded at an atomic level, not supported or mixed, and more preferably that titanium oxide and halogen are ionically bonded. In the present invention, “chemically bonded halogen” refers to, for example, a halogen that is difficult to elute in water among the halogens contained in the halogen-containing titanium oxide. In addition, when two or more types of halogens are contained, the effect can be obtained as long as one or more of them are chemically bonded.

  The amount of halogen chemically bonded to titanium oxide is determined by dispersing the titanium oxide photocatalyst in water and maintaining the pH adjusting agent (for example, hydrochloric acid, aqueous ammonia) at pH = 3 or lower or pH = 10 or higher. It can be calculated by measuring the elution amount of halogen by colorimetric titration or the like and subtracting the elution amount from the total amount of halogen contained in the halogen-containing titanium oxide.

  The chemical bond is preferably an ionic bond. When the chemical bond is an ionic bond, the halogen and titanium oxide are strongly bonded, and for example, the antibacterial activity and the photocatalytic reaction can be improved. The ionic bond between titanium oxide and halogen is analyzed by a photoelectron spectrometer. it can. For example, when the halogen is fluorine, when the halogen-containing titanium oxide is analyzed with a photoelectron spectrometer, the peak of the fluorine 1s orbital (F1s) shows a spectrum in the range of 683 eV to 686 eV. This is because the value of the peak top of titanium fluoride in which fluorine and titanium are ion-bonded is within the above range.

  The light source for irradiating the light for exciting the photocatalyst preferably has an intensity from 370 nm to 400 nm. For example, when titanium oxide is used as a photocatalyst, the stronger the emission peak in the wavelength range, the more efficiently the titanium oxide can be excited with respect to the input power. For example, when a straight tube type fluorescent lamp type black light or a cold cathode tube is used, it is possible to irradiate a wide range with strong light, so that it is easy to fix a photocatalyst in a wide range and increase the amount of active substances generated. In addition to the above, sunlight, germicidal lamps, fluorescent lamps, xenon lamps and the like may be used as the light source.

  Further, there is a light source using a semiconductor element as a light source having a strong emission peak at the wavelength. For example, a light emitting diode or a semiconductor laser can be used. These are suitable for locally irradiating a small portion because the irradiation area is small and the size of the light source is small.

  The active substance generated from the active substance generating material of the invention is an oxidizing agent having an action of reacting with an organic substance to oxidize or an action of modifying a higher order structure of the organic substance, such as an active oxygen species or a halogen oxide. There is.

  Active oxygen species include hydroxyl radicals, superoxide radicals, singlet oxygen, hydrogen peroxide, and ozone. These include a C—C bond (bond energy of about 347 kJ / mol), a C—H bond (bond energy of about 415 kJ / mol), or a C═C bond π bond (bond energy of about 285 kJ). It is known that bonds such as / mol) are cleaved by an oxidation reaction.

  In order to break this bond, dissociation energy higher than the bond energy is required. For example, the hydroxyl radical, which is a strong active oxygen species, has an oxidation potential of about 2.8 V and a dissociation energy of about 504 kJ / mol, so that it can be oxidatively decomposed by breaking the C—C bond. Such an oxidizing agent has a property of being unstable and extremely short in life (about 1 millisecond or less) because of its large energy.

  On the other hand, in the case of hydrogen peroxide, the oxidation potential is 1.77 V and the dissociation energy is 319 kJ / mol. In this case, since it is lower than the energy for cutting the C—C bond, it cannot be cut, but the π bond of the C═C double bond can be cut. In addition, in the case of organic substances having a relatively large molecular weight such as proteins and enzymes, a three-dimensional higher order structure is important in order to perform the original function. The higher-order structure can be denatured, the original function can be lost, and a sterilizing action and an antiviral action can be obtained. And since hydrogen peroxide has a lower oxidation potential, its stability is higher than that of hydroxyl radicals, and thus has a property of extending its life (about 1 hour or more). Such a substance is suitable when the active substance is allowed to act on a remote position such as a gas phase or a liquid phase.

  Halogen oxides include chlorine oxides (for example, hypochlorous acid, chlorous acid, perchloric acid, chlorine dioxide, etc.) and bromide oxides (for example, bromic acid, hypobromous acid, perbrominated acid, etc.) ), Iodine oxide (for example, iodic acid, periodic acid, etc.) can be used. These have oxidizing power. For example, the oxidation potential of hypochlorous acid is 1.5 V, and the dissociation energy is about 268 kJ / mol. Although it is lower than the C—C bond cleavage energy, it breaks hydrogen bonds and van der Waals bonds, denatures higher-order structures of relatively high molecular weight organic substances such as proteins and enzymes, and loses its original function. It is possible to obtain a sterilizing action, an antifungal action and an antiviral action. Further, it can affect the light absorption structure such as a dye, and can obtain a decoloring action.

  These active substances react with environmental chemical substances such as odorous substances and VOCs, microorganisms such as bacteria, fungi, or protozoa, and coloring substances such as dyes, and oxidize all or part of them. Deodorizing, antifungal, antiviral, decolorizing or antibacterial effects.

  In the present invention, “antibacterial” means sterilization and / or decomposition of gas phase bacteria, and preferably means reduction of gas phase bacteria concentration and / or inhibition of bacterial growth. Specifically, it means that when the active substance is in contact with the bacterium for 24 hours or more, the contacted bacterium concentration can be reduced by two orders of magnitude or more from the initial concentration. In the present invention, the target of antibacterial activity is not particularly limited, and examples thereof include bacteria, molds, viruses, and the like, and bacteria are preferred from the viewpoint of antibacterial activity. Examples of bacteria include Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, MRSA, Bacillus cereus, and Klebsiella pneumoniae.

  In the present invention, the type of active substance to be generated can be selectively generated according to the type and amount of oxo acid and halogen contained. For example, when phosphate is used as an oxo acid, it has been confirmed that hydrogen peroxide is generated as an active substance. It has also been confirmed that hypochlorous acid is generated when fluorine and chlorine are used as the halogen. Note that the halogen content is not uniform, and when halogen is chemically bonded to titanium oxide, the amount of active oxygen generated can be improved. It is considered that the substance is released in the form of a highly antibacterial active substance such as a system active substance. What is necessary is just to control the halogen containing state and ratio by the target substance to generate | occur | produce. In addition, it is not preferable to obtain the same effect with a halogen oxo acid generated from a halogen without containing an oxo acid because the amount of halogen oxo acid generated is small.

  By supporting the photocatalyst on the base material, it is possible to effectively perform irradiation of light and prevention of scattering of the photocatalyst. In the case of supporting on a base material, the halogen-containing titanium oxide is prepared first, and then supported on the base material, and then added with oxo acid and additional halogen. Although it does not specifically limit as a base material, A general filter base material can be used, A metal, a plastic, a synthetic resin fiber, a natural fiber, wood, paper, glass, a ceramic etc. are mentioned, Preferably a metal, a ceramic, and glass It is. When plastic or paper is used as the base material, titanium oxide may be supported by coating the surface of the base material with silicone, fluororesin, silica, or the like.

  The shape of the substrate is not particularly limited, but a plate shape, a net shape, a honeycomb shape, a fiber shape, a bead shape, a slit shape, a foam shape, a filter shape, and the like can be used. It can be done efficiently. A plate-like filter is preferably provided with an opening such as a punching shape in which holes are formed in a plate, a knitted shape in which fibers are knitted, and a non-woven shape in which fibers are bonded. If it is plate-shaped, pressure loss may be reduced by expanding the surface area of the filter by folding the plate into a pleat shape.

When a binder is used to immobilize the photocatalyst on the substrate, alkali silicates composed of silicates such as Na ₂ O, K ₂ O, LiO ₂ , inorganic colloids such as silica sol, alumina sol, zirconia sol, silica, silicon And alkoxides such as titanium and hydrolysates thereof. In addition, since alkali components, such as Na, reduce the crystallinity of titanium oxide (IV) and may deteriorate the performance, it is preferable that the main component is SiO ₂ as a binder. A hydrolyzate of alkoxides is preferable.

  Examples of silicon alkoxides include tetraethoxysilane and polymers thereof such as methoxypolysiloxane, ethoxypolysiloxane, butoxypolysiloxane, and lithium silicate. Examples of titanium alkoxides include tetrapropoxytitanium and polymers thereof. Is mentioned. These metal alkoxides are hydrolyzed with water and acid and can be used as a binder.

  The binder is preferably acidic, and examples thereof include a product obtained by hydrolyzing silicon, titanium and the like with an acid, acidic silica sol, alumina sol and the like. When hydrolyzing silicon, titanium or the like with an acid, the pH may be adjusted to 1 to 5 using hydrochloric acid, sulfuric acid or the like. When silica sol is used, one having a pH of 2 to 4 and a particle size of about 10 to 50 nm is preferable. When a neutral or alkaline silica sol having a pH is used, gelation is often caused when a halogen-containing titanium oxide is added, and it is often difficult to uniformly support the substrate.

When a cationic component such as Na, K, NH ₄ is contained in the binder, the antibacterial performance may be lowered due to the progress of the reaction with the halogen and the adsorption to the titanium (IV) oxide surface. The cation component should be as low as possible. For example, when Na is contained in the binder solution, the Na concentration is preferably greater than 0 wt% and not more than 0.05 wt% as Na ₂ O.

  Examples of the method for supporting the photocatalyst on the substrate include dip coating and spraying, but any means may be used as long as the photocatalyst can be immobilized on the substrate. If the carrying amount is not enough in one treatment, a plurality of treatment steps may be repeated. Moreover, after carrying | supporting, a binder may be shrink | contracted by heating at about 50-700 degreeC with a dryer for about 0.01-5 hours, and it may fix to a base material firmly, 90-150 degreeC is 0.00. 1 hour heating is more preferred. In the case of performing such heat drying treatment, it is desirable that the main component of the base material is composed of glass or ceramics.

  When attaching an oxo acid and an additional halogen to the halogen-containing titanium oxide, the halogen-containing titanium oxide prepared in the first step is brought into contact with an aqueous solution containing an oxo acid or a halogen of a type different from the halogen. Can be produced. Although it does not specifically limit as an oxo acid, A general oxo acid compound can be used. For example, when the oxo acid is a phosphate compound, zinc phosphate, aluminum phosphate, potassium phosphate, calcium phosphate, silver (I) phosphate, chromium (III) phosphate, cobalt phosphate, ferric phosphate, Titanium phosphate, iron phosphate (III), copper phosphate (II), lead phosphate (II), magnesium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium monohydrogen phosphate, diphosphoric acid phosphate Sodium hydrogen, lithium dihydrogen phosphate, triammonium phosphate, tripotassium phosphate, tricalcium phosphate, trisodium phosphate, trilithium phosphate, sodium ammonium hydrogen phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate, Diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, polyphosphoric acid, ammonium polyphosphate Arm, potassium polyphosphate, sodium polyphosphate, metaphosphate, aluminum metaphosphate, potassium metaphosphate, sodium metaphosphate, sodium hexametaphosphate, adenosine triphosphate, adenosine diphosphate, nucleic acid compounds, and the like.

  Further, when the oxo acid is a carbonate compound, ammonium carbonate, potassium carbonate, calcium carbonate, sodium carbonate, lead carbonate, barium carbonate, manganese carbonate, lithium carbonate, magnesium carbonate, ammonium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, Examples include strontium carbonate, cesium carbonate, cerium carbonate, iron carbonate, and copper carbonate.

  When the oxo acid is a sulfuric acid compound, sulfuric acid, zinc sulfate, aluminum sulfate, ammonium sulfate, potassium sulfate, calcium sulfate, ammonium hydrogen sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, tin (II) sulfate, strontium sulfate, cesium sulfate , Ferrous sulfate, ferrous sulfate, ferric sulfate, ferric sulfate, titanium sulfate, copper (II) sulfate, sodium sulfate, magnesium sulfate, manganese sulfate, lithium sulfate and the like.

  When the oxo acid is a nitrate compound, nitric acid, zinc nitrate, ammonium nitrate, potassium nitrate, chromium nitrate (III), cobalt nitrate (II), cesium nitrate, iron (II) nitrate, copper (II) nitrate, nickel nitrate, Examples thereof include barium nitrate, magnesium nitrate, manganese nitrate, and lithium nitrate.

  When the oxo acid is a boric acid compound, boric acid, zinc borate, ammonium borate, potassium borate, calcium borate, barium borate, magnesium borate, manganese (II) borate and the like can be mentioned.

  The oxo acid is used for the addition after mixing at a concentration capable of being dissolved in a suitable solvent. For example, it is used by dissolving in purified water to a concentration of about 0.01% to 10% by weight.

  Examples of the method for attaching oxo acid to the photocatalyst include dip coating and spraying. When using titanium oxide as a photocatalyst, after contacting titanium oxide with an oxo acid solution, if powdered, it is centrifuged or filtered, and if fixed to a substrate, it is pulled up and then 100 ° C or lower. Dry at low temperature to eliminate liquid residue. It is presumed that the oxo acid and halogen adsorbed in this manner are not chemically bonded to titanium oxide, but are adsorbed randomly on the pores or surface of titanium oxide.

  In addition, a halogen compound of a type different from the halogen to be chemically bonded can be mixed and simultaneously added to the solution. Examples of the halogen at this time include chlorides such as sodium chloride, potassium chloride, and magnesium chloride in the case of chlorine compounds. Moreover, in an iodine compound, potassium iodide etc. are mentioned. Examples of bromine compounds include bromides such as potassium bromide, calcium bromide, ammonium bromide, and sodium bromide. These are also used by mixing and dissolving a soluble amount in an oxoacid solution. For example, it can be dissolved and used at a concentration of about 0.01% to 10% by weight.

  When a straight tube type light source such as a black light, a germicidal lamp, or a cold cathode tube is used as the light source, if the photocatalyst is disposed so as to surround the light source, the light from the light source can be efficiently irradiated onto the photocatalyst. Further, when the thickness of the photocatalyst surrounding the light source is increased to prevent light from being transmitted, peripheral members can be prevented from being deteriorated by light such as ultraviolet rays. In addition, by using a reflecting plate whose surface is formed of metal or glass around the photocatalyst, the reflecting plate reflects the light from the light source, and the surface of the photocatalyst can be efficiently irradiated with light.

  It is desirable that at least a part of the ventilation path, the purifying means, and the air blowing means constituting the main body are made of a material that is inert to the active substance. Thereby, the main body, the purifying means, and the air blowing means are not deteriorated by the active substance, and a highly reliable air cleaner can be obtained. As a material inert to the active substance, metals such as stainless steel and aluminum, glass, alumina, mica and the like can be used. A resin may be used as long as the influence of deterioration is small. Moreover, you may form the ventilation path itself with a photocatalyst, such as coating the metal surface with a photocatalyst.

  A blower, a fan, a pump, etc. can be used as a ventilation means. By using a fan, an air volume, a wind speed, etc. can be set easily. Furthermore, a louver that changes the direction of the wind may be used.

  There are no particular problems with the dust collection filter as long as dust, fungi, mold, etc. in the air can be collected, and general filter materials such as nets, knitted fabrics / woven fabrics, nonwoven fabrics, and glass fibers can be used. it can.

  The deodorizing filter is not particularly limited as long as it can adsorb odorous substances in the air, and an adsorbent such as activated carbon, zeolite, silica gel, or sepiolite immobilized on fiber or paper can be used. . Those that are less likely to deteriorate with respect to the active substance are preferred.

(Embodiment 2)
As shown in FIG. 2, the air purifier of the present invention contains a light emitting diode as a light source 4 for irradiating light, at least an oxo acid and a photocatalyst in a main body 3 having an inlet 1 and an outlet 2. , An active substance generating material 5 that releases an active substance by irradiating light, a dust collecting filter 6 and deodorizing filter 7 as air purifying means, and a fan 8 as an air blowing means. The active material generating material 5 containing at least an oxo acid and a photocatalyst and the zeolite as an adsorbent for deodorization are held and integrated on a base material having an opening so that air can pass therethrough. Here, the integrated active substance generating material 5 and the adsorbent are mixed so that the blending ratio of the active substance generating material 5 is higher as the distance from the light emitting diode as the light source 4 is closer to the base material. Is retained.

  According to such a configuration, the air containing the active substance generated from the active substance generating material 5 passes through the dust collecting filter 6 or the deodorizing filter 7 as the purifying means, and is attached to or adsorbed on the purifying means. It reacts with viruses, allergens, odorous components, organic substances, etc., and has the effect of degrading or reducing the activity. Since the active substance generating material 5 has a higher blending ratio as the distance from the light emitting diode as the light source 4 is closer, more active substances can be generated. Moreover, since the active material generating material 5 and the adsorbent are mixed, the odor component adsorbed on the adsorbent and the active material can be reacted in a shorter time.

  In the upper part of the main body 3, a bypass as a ventilation path composed of glass as the light transmissive member 9 and a thin film of the active material generating material 5 ′ coated on the inner surface of the glass as the light transmissive member 9. A ventilation path 10 is provided. The room light that has passed through the glass serving as the light transmissive member 9 is irradiated onto the active substance generating material 5 ′ to release the active substance and to the room from the outlet 2 of the main body 3 by the action of the fan 8 as a blowing means. Released. The active substance released into the room from the main body 3 of the air cleaning device reacts with germs, molds, viruses, allergens, odor components, organic substances, etc. adhering to the air or on the wall surface, and has the effect of decomposing or reducing the activity. be able to.

(Embodiment 3)
As shown in FIG. 3, the air purifier of the present invention contains a light emitting diode as a light source 4 for irradiating light, at least an oxo acid and a photocatalyst in a main body 3 having a suction port 1 and a blowout port 2. , An active substance generating material 5 that releases an active substance by irradiating light, a dust collecting filter 6 and deodorizing filter 7 as air purifying means, and a fan 8 as an air blowing means.

  The active substance generating material 5 is held on the surface of a fluororesin film as the light transmissive member 9, and transmits light from a room such as a fluorescent lamp (not shown) and light from a light emitting diode as the light source 4 from the front and back surfaces. It can receive light and generate a large amount of active substance. The bypass ventilation path 10 is provided with a damper 11 that opens and closes the bypass ventilation path 10. By opening and closing the damper 11 and switching the air flow rate of the bypass ventilation path 10, the air containing the active substance can be supplied to the dust collection filter 6 and the deodorization filter 7 in an arbitrary amount.

  The generated air containing the active substance passes through a dust collection filter 6 or a deodorizing filter 7 as a purification means by a fan 8, and is attached to or adsorbed to the purification means such as germs, molds, viruses, allergens, odor components, organic substances, etc. The effect of reacting and degrading or reducing the activity can be obtained. Moreover, it reacts with various germs, molds, viruses, allergens, odorous components, organic substances, etc. released in the room and attached to the air or on the wall surface, thereby obtaining the effect of decomposing / antibacterial or reducing the activity.

(Embodiment 4)
As shown in FIG. 4, the air purifier of the present invention contains a black light as a light source 24 for irradiating light, at least an oxo acid and a photocatalyst in a main body 23 having a suction port 21 and a blowout port 22. , An active substance generating material 25 that releases an active substance by irradiating light, a humidifying filter 26 as a humidifying means for humidifying air and supplying moisture to the active substance generating material, and a heating means for heating the humidifying means And a fan 28 as a blowing means.

  The active material generating material 25 is fixed on the surface of a heat transfer plate 29 as a heating means for heating the active material generating material 25, and the heat transfer plate 29 generates heat using the heat of the heater 27, and is activated. The temperature of the substance generating material 25 can be raised.

  The humidifying filter 26 is wetted by being supplied with water 31 from a water tank 30 as a water supply means, and water can be supplied to the active substance generating material 25 by passing air through the humidified humidifying filter 26. The active substance generating material 25 can be generated from the active substance generating material 25 by controlling the active substance generating material 25 to an appropriate temperature by the heat transfer plate 29 and irradiating light from the light source 24 while supplying moisture. .

  In addition, the active substance can be generated more efficiently by reflecting the light generated from the light source 24 by the reflecting plate 32. The air containing the generated active substance is released into the room by the fan 28 and reacts with germs, molds, viruses, allergens, odorous components, organic substances, etc. adhering to the air or on the wall surface, thereby decomposing / antibacterial or reducing the activity. An effect can be obtained.

  As the humidifying means for humidifying the air and supplying moisture to the active substance generating material, those capable of containing a large amount of water vapor in the air are preferable. For example, in addition to a method in which moisture is attached to the humidifying filter shown in FIG. 4 and aerating, a method in which fine water droplets with pressure applied from a nozzle are sprayed, or a method in which a water tank is provided and water is refined by an ultrasonic vibrator However, it is not limited as long as it can contain a large amount of water vapor in the air. Adsorption of moisture in the air is indispensable for the photocatalytic reaction, but when the humidity is extremely low, the photocatalytic reaction may hardly occur. Therefore, by providing a humidifying means in front of the air supplied to the photocatalyst and supplying moisture, the photocatalytic reaction can be performed stably and the active substance can be generated stably.

  In addition, a heater may be provided as a heating means for heating the air supplied to the photocatalyst. It is known that the activity of the photocatalytic reaction increases as the temperature increases, and the amount of active substance generated increases. As the heating means for heating the active substance generating material 25, one that can control the temperature by the amount of electricity or hot water is preferable, for example, nichrome wire, PTC heater, infrared lamp, refrigeration cycle, hot water coil, or recovering waste heat. Coil, heat transfer plate, etc. can be used. The heating temperature is preferably in a range not exceeding 100 ° C. at which water is completely vaporized, preferably 10 ° C. or more and 100 ° C. or less, preferably 20 ° C. or more and 80 ° C. or less, more preferably It is 40 degreeC or more and 60 degrees C or less. When a light-emitting diode is used as a light source, it is preferable to use the light-emitting diode at a temperature of 80 ° C. or lower because the element begins to deteriorate due to heat and its life is shortened.

  As the heating means for heating the active substance generating material, it is sufficient that the heating means can be heated to an appropriate temperature, such as a nichrome wire, a PTC heater, an infrared lamp, a refrigeration cycle, a hot water coil, a coil that collects waste heat, a heat transfer A board etc. can be used. Heated air may be sprayed onto the active substance generating material.

  The reflecting plate 32 is not particularly limited as long as it reflects light, and aluminum, glass, stainless steel, or the like can be used. In FIG. 4, the reflector is arranged on the side surface of the lamp. However, a plurality of reflectors or the entire vicinity of the ventilation path where the active substance generating material is fixed may be made of a material having a light reflecting action.

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

(Example 1)
<1>. The concentration of titanium oxide (trade name: SSP-25, manufactured by Sakai Chemical Industry Co., Ltd., anatase type, particle size: 5 to 10 nm, specific surface area: 270 m ² / g or more) as a photocatalyst for adjusting halogen-containing titanium oxide is 150 g / Pure water was added to titanium oxide so as to be L, and this was stirred to prepare a titanium oxide dispersion. To this titanium oxide dispersion, hydrofluoric acid (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) corresponding to 3% by weight in terms of fluorine (element) with respect to titanium oxide was added and kept at pH 3 at 25 ° C. For 60 minutes. The resulting reaction product was washed with water. The washing with water was performed until the electric conductivity of the filtrate collected by filtering the reaction product was 1 mS / cm or less. And this was dried in air at 130 degreeC for 5 hours, and the fluorine-containing titanium oxide was prepared.

<2>. Preparation of Glass Fiber Fabric Carrying Halogen-Containing Titanium Oxide Obtained Halogen-Containing Titanium Oxide and Silica-Based Binder (Silica Sol with Na Component of 0.05 wt% or Less as Na ₂ O Concentration, pH = 3, SiO ₂ Concentration of 20 wt% ) And purified water were mixed and dispersed and mixed in a ball mill for 24 hours to prepare a slurry. The finished slurry is dipped in a glass fiber fabric having an aperture ratio of 15% as a base material, impregnated with halogen-containing titanium oxide, air blown to remove excess liquid, and then dried in a 120 ° C. dryer for 30 minutes. A glass fiber fabric containing titanium oxide was prepared. The same dipping operation was repeated, so that the supported amount of the halogen-containing titanium oxide and the binder was 500 g / m ² . As the glass fiber fabric, a fabric having a basis weight of 354 g / m ² , a yarn density of 11 × 3/25 mm (same as vertical and horizontal), and a thickness of 0.42 mm was used. The opening ratio of the glass fiber fabric was about 15%.

<3>. Production of Active Material Generating Material Containing Oxo Acid and Halogen-Containing Titanium Oxide The obtained halogen-containing titanium oxide was impregnated in 50 mM phosphate buffered saline, which is a source of oxo acid and halogen, and then pulled up to 50 ° C. The active material generating material containing oxo acid and halogen-containing titanium oxide was left to stand for 2 hours in a drying oven and dried.

<4>. Measurement of amount of active substance generated The produced active substance generating material was cut into a strip having a length of 30 cm and a width of 1 cm, and inserted into a quartz glass tube having a diameter of 3 cm. Pipes were arranged at both ends of the glass tube so as not to leak gas, and air (temperature of about 25 ° C., relative humidity of about 50 ° C.) was supplied from the upstream side at a flow rate of 0.5 L / min. A glass-made gas sampling tube (impinger) was connected to the downstream side, and 20 ml of distilled water as a collection liquid was placed inside. The black light was irradiated so as to be 5 mW / cm ² so as to sandwich the quartz tube, and the gas was circulated for 24 hours to recover the active substance generated from the active substance generating material. The distance from the end face of the glass tube to the gas sampling container was 400 mm.

After 24 hours, distilled water remaining in the gas collection tube was collected, and hydrogen peroxide and hypochlorous acid as active substances were quantified. Hydrogen peroxide was measured using a chromogenic substrate for hydrogen peroxide quantification (trade name: H ₂ O ₂ Detection Kit Colorimetric, manufactured by Assay Designs), and 582 nm color development was measured with an ultraviolet-visible absorbance meter. The result is shown in FIG. Moreover, the measurement of hypochlorous acid used the free chlorine measuring reagent (made by HACH) by DPD method, and measured the effective chlorine concentration with the direct-reading water quality analyzer. The result is shown in FIG.

(Example 2)
As Example 2 , instead of halogen-containing titanium oxide, anatase-type titanium oxide (trade name: SSP-25, manufactured by Sakai Chemical Industry Co., Ltd.) that does not contain halogen and has photocatalytic activity was used. Then, an active material generating material containing oxo acid and titanium oxide was prepared, and the amount of active material generated was measured. The results are shown in FIG. 5 and FIG.

(Comparative Example 1)
As Comparative Example 1, the step of impregnating phosphate buffered saline was omitted, and a glass fiber fabric containing only halogen-containing titanium oxide was used, and the amount of active substance generated was measured in the same manner as in Example 1. It was. The results are shown in FIG. 5 and FIG.

(Comparative Example 2)
As Comparative Example 2, in the same manner as in Example 1, the amount of active substance generated was measured in the dark without irradiating with ultraviolet light using black light. The results are shown in FIG. 5 and FIG.

  Table 1 shows a list of conditions for Examples 1 and 2 and Comparative Examples 1 and 2.

  As shown in FIG. 5, in the active substance generating material of Example 1, about 153 nmol of hydrogen peroxide was detected after 24 hours. In the active material generating material of Example 2, 0.14 nmol of hydrogen peroxide was detected. On the other hand, the glass fiber fabrics of Comparative Example 1 and Comparative Example 2 were below the lower limit of detection (less than 0.1 nmol). In the case of containing an oxo acid and a photocatalyst, it was confirmed that hydrogen peroxide as an active substance was released from the active substance generating material by light irradiation. Moreover, it was confirmed that the amount of generation increased by 1000 times or more by using halogen-containing titanium oxide.

On the other hand, as shown in FIG. 6, 23.6 μg / m ^{3 of} hypochlorous acid, which is effective chlorine as an active substance, was detected from the active substance generating material of Example 1. In Example 2, 1.3 μg / m ^{3 was} detected. In Comparative Example 1 and Comparative Example 2, it was below the lower limit of detection (0.1 μg / m ³ or less). Similar to hydrogen peroxide, it was confirmed that hypochlorous acid was released by irradiation with light containing oxoacid and photocatalyst. In addition, it was confirmed that the generation amount increased about 20 times by using halogen-containing titanium oxide.

(Example 3)
An active material generating material containing oxo acid and halogen-containing titanium oxide, produced in the same manner as in Example 1, was prepared by using an ultraviolet light emitting diode (center wavelength of about 370 nm) and a circuit as an excitation light source, and distilled water for trapping the active material. It was enclosed in a 6.7 L resin box together with a petri dish containing 20 mL. With the light emitting diode, the titanium oxide filter was irradiated with ultraviolet rays so as to be about 0.85 mW / cm ² . The box produced in the same manner was allowed to stand at 15 ° C., 30 ° C., and 40 ° C. After 15 hours, distilled water was taken out, and dissolved hydrogen peroxide and effective chloric acid concentration were measured. The measurement was performed in the same manner as in Example 1.

  The results are shown in FIGS. The concentration of hydrogen peroxide trapped in distilled water was relatively low at 0.05 μM at 15 ° C., but was 0.18 μM at 30 ° C., a threefold increase. Furthermore, when it reached 40 ° C., it became 0.75 μM, an increase of 15 times compared with 15 ° C. On the other hand, the concentration of hypochlorous acid, which is available chlorine, also tended to increase as the temperature increased. There is a possibility that a suitable temperature may be slightly different depending on the type of the active substance to be generated. However, it has been clarified that the amount of the active substance generated is increased by increasing the temperature.

Example 4
Example except that an active material generating material containing oxo acid and halogen-containing titanium oxide prepared in the same manner as in Example 1 was used, and dry air (temperature of about 25 ° C., relative humidity of 0%) was supplied from the upstream side. In the same procedure as in No. 1, the amount of active substance generated was measured. In air with a humidity of 0%, the amount of hydrogen peroxide generated was below the detection limit (less than 0.1 nmol) even after 24 hours. From the test of Example 1, it is known that the active substance generating material can generate about 153 nmol of hydrogen peroxide after 24 hours in air of 50% humidity, and the presence of water is necessary for the generation of the active substance. I understood it.

  The air purifying apparatus according to the present invention can generate an active substance that is stable and has a long life and can be released from the photocatalyst into the gas phase and the like, and can react with an object to be treated such as germs and organic substances in a remote place. Since it is possible to provide an air purifier, it is useful for applications such as air purifiers, humidifiers, air conditioners, air conditioners, and vacuum cleaners.

DESCRIPTION OF SYMBOLS 1 Inlet 2 Outlet 3 Main body 4 Light source 5 Active substance generating material 6 Dust collection filter 7 Deodorizing filter 8 Fan 9 Light transmissive member 10 Bypass ventilation path 11 Damper 21 Inlet 22 Outlet 23 Main body 24 Light source 25 Active substance generating material 26 Humidification filter 27 Heater 28 Fan 29 Heat transfer plate 30 Water tank 31 Water 32 Reflector 101 Adsorbent 102 Photocatalyst 103 Honeycomb hole 104 Photocatalyst excitation source 201 Photocatalyst 202 Optical fiber 203 Ultraviolet ray 204 Active species 205 Processed object

Claims (2)

An active substance generating material that holds a photocatalyst on a base material that can pass air and releases an active substance by irradiating light, an air purifying means, and a suction opening in a main body having a suction opening and a blowout opening And an air purifier for blowing out at least a part of the air sucked from the blow-out port, wherein the active substance generating material produces a first halogen-containing titanium oxide as the photocatalyst. An air cleaning apparatus comprising an oxo acid and a second halogen attached after being supported on the substrate and dried . An active substance generating material that holds a photocatalyst on a base material that can pass air and releases an active substance by irradiating light, an air purifying means, and a suction opening in a main body having a suction opening and a blowout opening And an air purifier for blowing out at least a part of the air sucked from the blow-out port, wherein the active material generating material is based on halogen-containing titanium oxide as the photocatalyst by an acidic binder. An air cleaning device characterized in that oxo acid and additional halogen are attached after being supported on a material .

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