JP2015168670A - Room spray antibiotic agent and room spray device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a room spray antibiotic agent capable of improving hygienic condition while keeping antibiotic condition in a room for a long period and capable of being efficiently sprayed.SOLUTION: A room spray antibiotic agent of the present invention contains copper compound-carrying titanium oxide in which a copper compound is carried on titanium oxide particles containing 50 mol% or more of anatase type titanium oxide. The antibiotic agent further comprises 1 to 20 pts.mass of cationic surfactant relatively to 100 pts.mass of the copper compound-carrying titanium oxide, a solvent distributing the copper compound-carrying titanium oxide and the cationic surfactant, and liquid carbon dioxide. In addition, the titanium oxide particles have an average primary particle size of 10 nm to 50 nm, and the copper compound has an average particle size of 0.5 nm to 10 nm. Furthermore, copper ion is present in the copper compound at 4 to 10 pts.mass relatively to 100 pts.mass of the titanium oxide particles.

Description

  The present invention relates to a space spray antibacterial agent and a space spray apparatus using the same. More specifically, the present invention relates to a space spray antibacterial agent capable of performing an antibacterial treatment over a wide area, such as indoors, and a space spray device using the same.

  In a closed space such as indoors, bacteria are likely to propagate due to the influence of temperature, humidity, etc., and therefore, it is required to treat bacteria and sterilize them to prevent bacterial growth.

  Conventionally, as a method of sterilizing and antibacterial indoors, for example, there is a method of vaporizing and smoking a chemical such as an inorganic substance or an organic substance having a sterilizing effect. Patent Document 1 discloses a smoke agent composition containing an inorganic drug containing a transition metal, an organic foaming agent, and a calcium compound. Patent Document 2 discloses a method of fumigating 4-hydroxy-6-methyl-3- (4-methylpentanoyl) -2-pyrone in a closed space.

  Further, as a method for antibacterial indoors, there is a method of spraying an antibacterial component as an aerosol, for example. Patent Document 3 discloses an insect repellent / antibacterial aerosol agent that injects an aerosol solution containing a room temperature volatile pyrethroid insect repellent component into a space.

JP 2010-280577 A JP 2003-40712 A JP 2003-238321 A

  However, the antibacterial / bactericidal component comprising an organic component volatilizes and decomposes over time when sprayed indoors, so that there is a problem that the antibacterial action is difficult to last for a long time. Furthermore, in the case of an antibacterial material sprayed with an organic component, dust adheres to the organic component attached to the wall surface or the like, which may deteriorate the environment in terms of hygiene. In addition, when an active ingredient is vaporized by heating the medicine, it is difficult to vaporize when the medicine is an inorganic component, and it may be difficult to spray the medicine efficiently.

  The present invention has been made in view of such problems of the prior art. An object of the present invention is to provide a space spray antibacterial agent capable of improving hygiene while maintaining indoor antibacterial properties for a long period of time and efficiently spraying it, and a space spray device using the same. It is in.

  The space spray antibacterial agent which concerns on the 1st aspect of this invention contains the copper compound carrying | support titanium oxide formed by carrying | supporting a copper compound in the titanium oxide particle which contains 50 mol% or more of anatase type titanium oxides. Further, the antibacterial agent comprises 1 to 20 parts by mass of a cationic surfactant based on 100 parts by mass of the copper compound-carrying titanium oxide, a solvent in which the copper compound-carrying titanium oxide and the cationic surfactant are dispersed, and liquefied carbon dioxide. Contains carbon. And the average primary particle diameter of a titanium oxide particle is 10 nm-50 nm, and the average particle diameter of a copper compound is 0.5 nm-10 nm. Moreover, the copper ion in a copper compound is 4-10 mass parts with respect to 100 mass parts of titanium oxide particles.

  The space spray antibacterial agent according to the second aspect of the present invention is the antibacterial agent according to the first aspect, wherein 0.5 to 10% by mass of the copper compound-supported titanium oxide, 5 to 15% by mass of the solvent, and liquefied dioxide dioxide. It contains 70 to 90% by mass of carbon.

  The space spray antibacterial agent according to the third aspect of the present invention is the antibacterial agent according to the first or second aspect, wherein the cationic surfactant is an ammonium salt.

  A space spray device according to a fourth aspect of the present invention includes the space spray antibacterial agent according to any one of the first to third aspects, and a pressure-resistant container filled with the space spray antibacterial agent.

  Since the space spray antibacterial agent of the present invention is excellent in photocatalytic activity by visible light, it can exhibit high antibacterial properties. Furthermore, the antibacterial property can be maintained for a long time. Moreover, since it is a spraying type antibacterial agent, it can be efficiently sprayed. And the deposit | attachment obtained from the said antibacterial agent can suppress adhesion of dirt, such as dust, and can improve a hygiene surface.

It is a schematic diagram for demonstrating the band gap of the copper compound carrying | support titanium oxide contained in the space spray antibacterial agent which concerns on embodiment of this invention. It is sectional drawing which shows the outline of the space spray apparatus which concerns on embodiment of this invention.

  Hereinafter, a space spray antibacterial agent and a space spray device according to an embodiment of the present invention will be described in detail with reference to the drawings. In addition, the dimension ratio of drawing quoted by the following embodiment is exaggerated on account of description, and may differ from an actual ratio.

[Space spray antibacterial agent]
The space spray antibacterial agent according to the embodiment of the present invention contains a copper compound-supported titanium oxide obtained by supporting a copper compound on titanium oxide particles containing 50 mol% or more of anatase-type titanium oxide, and a cationic surfactant. ing. Further, the space spray antibacterial agent contains a solvent for dispersing the copper compound-supported titanium oxide and the cationic surfactant, and liquefied carbon dioxide.

(Copper compound-supported titanium oxide)
The space spray antibacterial agent which concerns on this embodiment contains the copper compound carrying | support titanium oxide as an active particle which exhibits antibacterial property. And by spraying the said antibacterial agent on antibacterial objects, such as an indoor floor, a wall, and a ceiling, a copper compound carrying | support titanium oxide adheres to the surface of the said object, and high antibacterial property is expressed.

  The copper compound-supported titanium oxide in the present embodiment has titanium oxide particles containing 50 mol% or more of anatase-type titanium oxide and a copper compound supported on the surface of the titanium oxide particles. This copper compound-supported titanium oxide is excellent in photocatalytic activity by visible light because the copper compound is supported on the surface of the titanium oxide particles. The reason why the copper compound-supported titanium oxide is excellent in photocatalytic activity is considered as follows.

As shown in FIG. 1, the titanium oxide simple substance on which the copper compound is not supported generates electrons and holes by photoexcitation due to ultraviolet irradiation. The generated electrons reduce oxygen in the air or water adsorbed on the surface of titanium oxide by one electron to generate a superoxide anion (.O ₂ ⁻ ). Further, the holes oxidize water adsorbed on the surface of titanium oxide to generate hydroxy radicals (.OH). The resulting hydroxy radical can inactivate bacteria by denaturing and degrading them.

  In this way, holes and electrons generated by photoexcitation can be separated to prevent recombination of both, and bacteria can be oxidatively decomposed by the strong oxidizing power and high mobility of the holes. However, in order to generate electrons with titanium oxide and reduce oxygen by one electron in this way, from the valence band of 3.04 V (pH = 0) to its redox potential of -0.046 V (pH = 0). It is necessary to photoexcite electrons to a high position.

In contrast, with a copper compound-supported titanium oxide in which a copper compound is supported on the surface of titanium oxide, it is not necessary to photoexcite electrons in the titanium oxide up to the high position as described above. That is, as shown in FIG. 1, when photoexcitation is performed with visible light to +0.16 V, which is a redox potential of copper ions, the excited electrons are transferred to divalent copper (Cu (II)) and monovalent copper (Cu (I )), The oxygen is further reduced by two or four electrons to produce H ₂ O ₂ or H ₂ O. At this time, monovalent copper itself returns to divalent copper. On the other hand, the generated holes have the same strong oxidizing power and high mobility as conventional titanium oxide, so that organic substances, that is, bacteria can be oxidatively decomposed. Thus, the copper compound-supported titanium oxide can be suitably used indoors because it can be photoexcited by visible light while having an oxidizing power equivalent to that of a single titanium oxide.

  It is preferable that the titanium oxide particle which carries a copper compound on the surface contains 50 mol% or more of anatase type titanium oxide. Anatase-type titanium oxide has a higher band gap than rutile-type titanium oxide, and is superior in photocatalytic activity because of the high energy level at the bottom of the conduction band. Therefore, the titanium oxide particles preferably contain 50 mol% or more of anatase type titanium oxide, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

  Thus, in the space spray antibacterial agent of this embodiment, the copper compound carrying | support titanium oxide is used as active particle which exhibits antibacterial property. Therefore, it becomes possible to exhibit high antibacterial properties even under visible light in the room. As described above, when photoexcitation is performed with visible light up to +0.16 V, which is the oxidation-reduction potential of copper ions, excited electrons move to divalent copper, and recombination of electrons and holes can be prevented. Therefore, the copper compound supported on the titanium oxide particles is preferably a divalent copper compound. In addition, since the monovalent copper compound is superior in antibacterial activity, antiviral activity and antiallergen activity than the divalent copper compound, the copper compound supported on the titanium oxide particles is monovalent and monovalent. Both of the copper compounds are preferred.

  Examples of such monovalent copper compounds include copper (I) oxide, copper (I) sulfide, copper (I) iodide, copper (I) chloride, and copper (I) hydroxide. In addition, as the divalent copper compound, copper hydroxide (II), copper oxide (II), copper chloride (II), copper acetate (II), copper sulfate (II), copper nitrate (II), copper fluoride ( II), copper (II) iodide, copper (II) bromide and the like. In addition, these copper compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

  The average primary particle diameter of the titanium oxide particles in the copper compound-supported titanium oxide is preferably 10 nm to 50 nm. When the average primary particle diameter of the copper compound-supported titanium oxide is within this range, it is sprayed as ultrafine particles as the liquefied carbon dioxide is vaporized, so that it can reach every corner of the entire room by self-diffusion. In addition, the average primary particle diameter of the titanium oxide particles can be measured by a dynamic light scattering method.

  Moreover, in a copper compound carrying | support titanium oxide, it is preferable that the average particle diameter of the copper compound carry | supported on the surface of a titanium oxide particle is 0.5 nm-10 nm. Furthermore, it is preferable that the copper ion in a copper compound is 4-10 mass parts with respect to 100 mass parts of titanium oxide particles. When the average particle diameter and the supported amount of the copper compound are within this range, it becomes easy to reduce oxygen by two electrons or four electrons as described above. As a result, holes and electrons generated by photoexcitation can be easily separated to prevent recombination of both, and bacteria can be oxidatively decomposed by the strong oxidizing power of the holes. In addition, the average particle diameter of a copper compound can be measured by observing using a transmission electron microscope etc.

  The titanium oxide particles supporting the copper compound on the surface are preferably photo-semiconductor titanium oxide particles having a valence band potential of 3 V (vs. SHE, pH = 0) or more. When the upper end potential of the valence band in the titanium oxide particles is 3 V or more, the generated holes can exhibit a strong oxidizing power.

  Thus, since the copper compound carrying | support titanium oxide which concerns on this embodiment has carry | supported the copper compound in the titanium oxide particle which contains 50 mol% or more of anatase type titanium oxides, it is excellent in antibacterial activity also under visible light irradiation. In particular, since the copper compound-supported titanium oxide contains a divalent copper compound necessary for the photocatalytic activity by visible light, the photocatalytic activity by visible light is excellent. In addition, the said copper compound carrying | support titanium oxide exhibits the said photocatalytic activity also with the ultraviolet light whose energy is higher than visible light.

  It is preferable that the space spray antibacterial agent of this embodiment contains 0.5-10 mass% of copper compound carrying | support titanium oxide, and it is more preferable to contain 5-10 mass%. By setting the copper compound-supported titanium oxide to 0.5% by mass or more, sufficient antibacterial properties can be imparted to the surface of the antibacterial object. Moreover, it can suppress that an antibacterial target object colors or generate | occur | produces dust by making a copper compound carrying | support titanium oxide into 10 mass% or less.

(Cationic surfactant)
When spraying the above-described copper compound-supported titanium oxide into the space, if the atomization is insufficient, the appearance of the antibacterial object may be impaired. Therefore, the space spray antibacterial agent of this embodiment adds a cationic surfactant as a dispersant. By adding a cationic surfactant, it is possible to maintain a state in which the copper compound-supported titanium oxide is highly dispersed in the solvent. Furthermore, by adding a cationic surfactant, it becomes possible to impart spreadability to the antibacterial object to the space spray antibacterial agent. As a result, the copper compound-carrying titanium oxide strongly adheres to the antibacterial object, so that the durability of the antibacterial action can be increased.

  In addition, by containing a cationic surfactant together with copper compound-supported titanium oxide, copper ions that have been reduced to monovalent by the photocatalytic action of titanium oxide are divalently oxidized by the atmosphere, preventing a decrease in antibacterial activity. Has the effect of On the other hand, with a nonionic surfactant, copper ions are stabilized bivalently, so that antibacterial properties are difficult to develop.

  The cationic surfactant according to this embodiment preferably has a molecular weight Mw of 500 to 100,000, and more preferably 1,000 to 10,000. By addition of the cationic surfactant, the surfactant is adsorbed on the surface of the copper compound-supported titanium oxide to form an adsorption layer. And the copper compound carrying | support titanium oxide can be highly dispersed in a solvent by the steric hindrance effect of the said adsorption layer. Therefore, when the molecular weight of the cationic surfactant is 500 or more, the steric hindrance effect is sufficiently exhibited, and the dispersion stability of the copper compound-supported titanium oxide can be improved. Moreover, when the molecular weight of a cationic surfactant is 100,000 or less, it can cover the surface of a copper compound carrying | support titanium oxide, and can suppress that a catalyst activity falls.

  In the space spray antibacterial agent of this embodiment, the content of the cationic surfactant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the copper compound-supported titanium oxide. When the content of the cationic surfactant is less than 1 part by mass, sufficient dispersion stability of the copper compound-supported titanium oxide cannot be maintained, and aggregation or sedimentation may occur in the pressure vessel. Moreover, when content of a cationic surfactant exceeds 20 mass parts, adhesiveness is provided with respect to an antibacterial target object and there exists a possibility of becoming the cause of adhesion, such as dust.

  Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, and triethanolamine / difatty acid ester quaternary salts. Further, fatty acid monoester monoamide salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, polyethylene polyamines, benzethonium chloride, and the like of N-hydroxyethyl-N-methyl-propanediamine are also included. In addition, these cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

From the viewpoint of availability and stability, the cationic surfactant is preferably an ammonium salt type surfactant. Examples of such surfactants include alkyl (C _12-18 ) trimethylammonium chloride, methyl polyoxyethylene alkyl (C _12-18 ) ammonium chloride, alkyl N-methylpyridium bromide (C _12-18). ). Also, mono or dialkyl (C _12-18 ) methylated ammonium chloride and alkyl (C _12-18 ) pentamethylpropylenediamine dichloride can be mentioned.

(solvent)
The space spray antibacterial agent of this embodiment contains a solvent for dispersing the copper compound-supported titanium oxide and the cationic surfactant. Although it does not specifically limit as the said solvent, The thing which volatilizes easily after spraying can be selected suitably.

  Examples of the solvent include aromatic hydrocarbons (such as toluene and xylene), alcohols (such as methanol, ethanol, and isopropyl alcohol), ketones (such as acetone, methyl ethyl ketone, and methyl isobutyl ketone). Examples of the solvent include aliphatic hydrocarbons (such as hexane and heptane), ethers (such as tetrahydrofuran), amide solvents (such as DMF and DMAc), and the like. In addition, these solvents may be used individually by 1 type, and may be used in combination of 2 or more types. These solvents increase the adhesion rate of the copper compound-supported titanium oxide to antibacterial objects such as floor surfaces, wall surfaces, and ceiling surfaces, and increase the antibacterial effect. In view of safety, easy availability, and drying properties, ethanol is particularly suitable as the solvent.

  The space spray antibacterial agent of this embodiment preferably contains 5 to 15% by mass of a solvent for dispersing the copper compound-supported titanium oxide and the cationic surfactant. Although content of a solvent is not specifically limited, By being this range, a copper compound carrying | support titanium oxide and a cationic surfactant can fully be disperse | distributed, and also the drying property after spraying can be improved.

(Liquefied carbon dioxide)
The space spray antibacterial agent of this embodiment contains a dispersion obtained by mixing the above-described copper compound-supported titanium oxide, a cationic surfactant and a solvent, and liquefied carbon dioxide. And this space spray antibacterial agent is filled in the pressure vessel mentioned later. Therefore, when the liquefied carbon dioxide expands inside the pressure vessel, the space spray antibacterial agent can be sprayed to the outside of the vessel through the nozzle provided in the pressure vessel.

  The content of liquefied carbon dioxide in the space spray antibacterial agent is not particularly limited as long as an expansion pressure capable of spraying the space spray antibacterial agent to the outside of the pressure resistant container is obtained. However, the content of liquefied carbon dioxide in the space spray antibacterial agent is preferably 70 to 90% by mass.

  The space spray antibacterial agent of this embodiment may contain components other than those described above as long as the effects of the present invention are not impaired. Examples of the other components include plant essential oils, synthetic fragrances, and antioxidants.

  Examples of plant essential oils and synthetic flavors include fragrances such as peppermint oil, peppermint oil, cypress oil, hiba oil, pine oil, lavender oil, eucalyptus oil, citronella oil, lime oil, hyssop oil, rosemary oil and tea tree oil. The plant essential oil which has is mentioned. In addition, plant essential oils such as rose oil, ylang-ylang oil, clove oil, bay oil, geranium oil, sage oil, patchouli oil, winter grease oil and the like can also be mentioned. Further, methyl salicylate, ionone, phenoxyethanol, linalool, dihydrolinalool, cineol, citronole, eugenol, menthol, menthone, and the like can also be mentioned.

  Examples of the antioxidant include vitamin E such as α, β, γ, and δ-tocopherol, γ-oryzanol, dibutylhydroxyanisole (BHA), and dibutylhydroxytoluene (BHT).

  Although it does not specifically limit as an antibacterial target object to which the space spray antibacterial agent of this embodiment adheres, Building materials, such as a ceiling material, tile, glass, wallpaper, a wall material, a floor, and a construction material, etc. are preferable. In addition, as antibacterial objects, automobile interior materials (instrument panels, sheets, ceiling materials), home appliances such as refrigerators and air conditioners, textile products such as clothes and curtains, industrial facilities, and medical facilities are also preferable. Furthermore, as antibacterial objects, doors, door handles, pullers, handrails, interior counters, furniture, kitchens, toilets, baths, lighting fixtures, touch panels, switches, and sheets used for these purposes are also preferable. Since the deposit made of the space spray antibacterial agent of this embodiment has high antibacterial and antiviral properties, it is particularly effective for a surface that is frequently contacted by such a human body.

  In addition, the space spray antibacterial agent according to the present embodiment is used not only in houses but also in various rooms requiring cleanliness, such as hospitals, food factories, offices, cafeterias, houses, hotel accommodations, museums, etc. It is possible to antibacterial effectively and efficiently.

  The space spray antibacterial agent of this embodiment contains copper compound-supported titanium oxide formed by supporting a copper compound on titanium oxide particles containing 50 mol% or more of anatase-type titanium oxide. Further, the antibacterial agent comprises 1 to 20 parts by mass of a cationic surfactant based on 100 parts by mass of the copper compound-carrying titanium oxide, a solvent in which the copper compound-carrying titanium oxide and the cationic surfactant are dispersed, and liquefied carbon dioxide. Contains carbon. And the average primary particle diameter of a titanium oxide particle is 10 nm-50 nm, and the average particle diameter of a copper compound is 0.5 nm-10 nm. Moreover, the copper ion in a copper compound is 4-10 mass parts with respect to 100 mass parts of titanium oxide particles.

  Since the said space spray antibacterial agent contains the copper compound carrying | support titanium oxide, the deposit | attachment obtained by spraying is excellent in the photocatalytic activity by visible light, and can exhibit high antibacterial property and antiviral property. Furthermore, the antibacterial and antiviral properties can be maintained for a long time. In addition, by adding a predetermined amount of a cationic surfactant, the spatial spray antibacterial agent is imparted with spreading properties to antibacterial objects, while suppressing the adhesion of dirt such as dust and improving hygiene. Is possible.

[Method for producing space spray antibacterial agent]
Next, a method for producing the space spray antibacterial agent will be described. The space spray antibacterial agent prepares a copper compound-supported titanium oxide dispersion by mixing the above-described copper compound-supported titanium oxide, a cationic surfactant and a solvent, and highly dispersing the copper compound-supported titanium oxide in the solvent. . Then, the space spray antibacterial agent can be obtained by mixing the obtained dispersion and liquefied carbon dioxide.

  The copper compound-supported titanium oxide dispersion contains the above-described copper compound-supported titanium oxide, a cationic surfactant, and a solvent. And the said dispersion liquid can be prepared by mixing the above-mentioned copper compound carrying | support titanium oxide, a cationic surfactant, and a solvent, and highly dispersing copper compound carrying | support titanium oxide in a solvent. Therefore, as a method for producing the dispersion, any method can be used as long as the method can highly disperse the copper compound-supported titanium oxide.

  However, from the viewpoint of making the copper compound-supported titanium oxide into fine particles and improving the dispersibility, the copper compound-supported titanium oxide is preferably dispersed in a pre-dispersion process and a main dispersion process. As a result, the surface of the copper compound-carrying titanium oxide is wetted and the air layer on the surface is replaced with the solvent, so that the dispersion proceeds promptly in the subsequent main dispersion treatment. If this pre-dispersion treatment is insufficient, the progress of the dispersion is slow, and there is a possibility that a useless mechanical impact is given to the copper compound-supported titanium oxide. As a result, the crystal structure itself of the copper compound-carrying titanium oxide may be destroyed, resulting in a dispersion with reduced stability.

  The pre-dispersion treatment can be performed by stirring using a general dissolver. However, it is preferable to stir with a high-speed stirrer from the viewpoint of making the surface of the copper compound-supported titanium oxide easy to wet. As a high-speed stirrer, for example, T.M. K. Homomixer, T.W. K. Robomix and T. K. Fillmix (trade name, manufactured by Primix Co., Ltd.) can be used. In addition, Claremix (registered trademark) (trade name, manufactured by M Technique Co., Ltd.) and Ultra Disper (trade name, manufactured by Asada Tekko Co., Ltd.) can also be used.

  Examples of a dispersion apparatus that performs this dispersion processing include a kneader, a two-roll, a three-roll, SS5 (trade name, M Technique Co., Ltd.), and Miracle KCK (registered trademark) (trade name, manufactured by Asada Tekko Co., Ltd.). Such a kneader can be used. Moreover, an ultrasonic disperser, a microfluidizer (trade name, manufactured by Mizuho Kogyo Co., Ltd.) that is a high-pressure homogenizer, and NanoVita (registered trademark) (trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.) are also included. Furthermore, Starburst (registered trademark) (trade name, Sugino Machine Co., Ltd.), G-smasher (trade name, Rix Co., Ltd.) and the like are also included. For those using bead media such as glass and zircon, ball mills, bead mills, sand mills, horizontal media mill dispersers, colloid mills and the like can be used. As a medium used in the bead mill, a bead medium having a diameter of 1 mm or less is preferable, and a bead medium having a diameter of 0.5 mm or less is more preferable. The dispersion time of the pre-dispersion treatment and the main dispersion treatment may be appropriately adjusted depending on each dispersion apparatus and media so that the copper compound-supported titanium oxide is highly dispersed in the solvent together with the cationic surfactant.

  In addition, when supplying the pre-dispersed treatment liquid to the dispersing device, it is possible to process in a shorter time by supplying it with sufficient stirring using a high-speed stirrer or the like. .

  A space spray antibacterial agent can be obtained by encapsulating the thus obtained copper compound-supported titanium oxide dispersion together with liquefied carbon dioxide in a pressure vessel, for example.

[Space spraying equipment]
Next, the space spray device of this embodiment will be described. The space spray device of this embodiment includes the above-described space spray antibacterial agent and a pressure-resistant container filled with the space spray antibacterial agent.

  The pressure vessel is not particularly limited as long as it can stably hold the space spray antibacterial agent. Examples of the material of the pressure vessel include iron, stainless steel, and aluminum. Moreover, as a shape of a pressure vessel, what is used in the normal high-pressure gas container for carbon dioxide etc. can be used, for example.

  As a specific example of the space spray device of this embodiment, the one shown in FIG. 2 can be exemplified. In the space spray device 10, the pressure vessel includes a pressure vessel main body 1 and a siphon tube 2. Examples of the material of the siphon tube include copper, copper alloy, and stainless steel, and the siphon tube 2 is a single tube that reaches the bottom of the pressure vessel main body. The pressure vessel main body 1 includes a nozzle 3 so that the space spray antibacterial agent can be ejected upward. And the space spray antibacterial agent 4 is filled in the inside of a pressure-resistant container.

In the space spray device 10 of the present embodiment, first, the above-described copper compound-supported titanium oxide dispersion is placed in a pressure-resistant vessel body, and a valve with a siphon tube is attached. Thereafter, the space spray device 10 can be obtained by pressurizing and filling a predetermined amount of liquefied carbon dioxide. In the space spray device 10, the space spray antibacterial agent is filled in a pressure-resistant container with a siphon tube, and is normally in a pressurized state of about 65 to 75 kg / cm ² at 20 ° C. Under such pressure, carbon dioxide is liquefied. The space spray antibacterial agent is dissolved and dispersed in liquefied carbon dioxide.

Here, as a method of performing antibacterial treatment using the space spray device of the present embodiment, for example, by installing a space spray device on the floor surface and spraying the space spray antibacterial agent toward the space and the object to be antibacterial, The whole can be antibacterial. The antibacterial treatment is particularly effective for bacteria, fungi and the like. Spraying amount of space spraying antimicrobial agent is not particularly limited as long as the antimicrobial action is obtained, preferably in a 1 to 50 g / ^{m 3,} and particularly preferably to 3 to 20 g / ^{m 3.}

  When the space spray antibacterial agent of this embodiment is sprayed toward the indoor upper space, the liquefied carbon dioxide is vaporized when released into the atmosphere. The copper compound-carrying titanium oxide dispersion, along with vaporized carbon dioxide, floats in the space in the form of fine particles having a particle size of several hundred nm to several tens of μm, and adheres to the walls of the entire room. And since a cationic surfactant becomes a spreading | diffusion component and a copper compound carrying | support titanium oxide adheres to a wall surface etc. strongly, the sustainability of an antibacterial action can be improved.

  The space spray device of this embodiment sprays copper compound carrying titanium oxide carrying copper ions having a wide antibacterial action range and strong antibacterial activity against many types of bacteria. And since the said copper compound carrying | support titanium oxide is sprayed as an ultrafine particle with the pressure of liquefied carbon dioxide, it can spread to every corner of the whole space by self-diffusion. Moreover, a specific space can also be processed efficiently and effectively, for example, by processing a part where a medicine is difficult to enter, such as a gap between an object and a wall, under a desk, for example, with a spray gun attached to a pressure vessel.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.

[Preparation of copper compound-supported titanium oxide]
First, 50 g of anatase type titanium oxide (product name: FP-6, manufactured by Showa Titanium Co., Ltd., average primary particle size: 15 nm) was suspended in 1000 ml of distilled water. Next, 1.5 g of copper chloride (II) dihydrate (CuCl ₂ .2H ₂ O, manufactured by Kanto Chemical Co., Ltd.) so that the copper ion is 1.0 part by mass with respect to 100 parts by mass of titanium oxide. ) Was added to the suspension. The suspension was heated to 90 ° C. and heat-treated for 1 hour with stirring.

Next, an aqueous sodium hydroxide solution and an aqueous glucose solution so that the molar ratio of CuCl ₂ .2H ₂ O: C ₆ H ₁₂ O ₆ : NaOH is 1: 4: 8 with respect to the heat-treated suspension. Was added. And after heat-processing a mixture for 1 hour at 70 degreeC and filtering a slurry, the obtained powder was wash | cleaned with a pure water, and it dried at 80 degreeC, and obtained a copper compound carrying | support titanium oxide by a mixer. It was. The aqueous sodium hydroxide solution was added with 13.75 ml of an aqueous solution having a concentration of 1 mol / L, and the aqueous glucose solution was added with 7 ml of an aqueous solution having a concentration of 1 mol / L. Sodium hydroxide and glucose manufactured by Kanto Chemical Co., Ltd. were used.

  1 part by mass of the obtained copper compound-supported titanium oxide was suspended in 99 parts by mass of ion-exchanged water, and dispersed for 5 minutes using a 150 W ultrasonic disperser. And the test piece for observation was obtained by casting the obtained solution to a 2 cm square slide glass base material. As a result of observing the obtained test piece with a transmission electron microscope, the average primary particle diameter of the titanium oxide particles was 15 nm, and the average particle diameter of the copper compound was 4 nm.

[Example 1]
First, 10 parts by mass of the copper compound-supported titanium oxide prepared as described above, 1.92 parts by mass of a cationic surfactant, and 80 parts by mass of ethanol were mixed. At this time, DISPERBYK (registered trademark) -140 manufactured by BYK-chemie was used as the cationic surfactant. DISPERBYK-140 is a cationic surfactant made of an alkyl ammonium salt of an acidic polymer. Since DISPERBYK-140 has a non-volatile content of 52.0%, the content of the surfactant itself (non-volatile content) in 1.92 parts by mass is 1.00 parts by mass.

  Next, the obtained mixture was subjected to a dispersion treatment for 2 hours together with zirconia beads φ0.1 mm as a medium using a dyno mill to obtain a copper compound-supported titanium oxide dispersion. In addition, the dyno mill made from Shinmaru Enterprises Co., Ltd. was used.

  Further, the obtained copper compound-supported titanium oxide dispersion was filled into a pressure-resistant vessel with a valve having an internal volume of 1 liter. This pressure vessel is made of Cr-Mo steel, and a siphon tube that is connected to a valve and reaches the lower part of the vessel is provided inside. And the antibacterial agent of this example was prepared by pressurizing and filling 0.5 kg of liquefied carbon dioxide gas into a pressure vessel.

[Example 2]
The antibacterial agent of this example was prepared in the same manner as in Example 1 except that the amount of the cationic surfactant mixed was 3.46 parts by mass. Since DISPERBYK-140 has a nonvolatile content of 52.0%, the content of the surfactant itself (nonvolatile content) in 3.46 parts by mass is 1.80 parts by mass.

[Example 3]
An antibacterial agent of this example was prepared in the same manner as in Example 1 except that the amount of the cationic surfactant mixed was 0.38 parts by mass. Since DISPERBYK-140 has a non-volatile content of 52.0%, the content of the surfactant itself (non-volatile content) in 0.38 parts by mass is 0.20 parts by mass.

[Comparative Example 1]
The antibacterial agent of this example was prepared in the same manner as in Example 1 except that DISPERBYK-108 manufactured by BYK-chemie was used as the surfactant and the mixing amount was 1.0 part by mass. DISPERBYK-108 is an anionic surfactant made of a hydroxyl group-containing carboxylic acid ester and has a nonvolatile content of 100%.

[Comparative Example 2]
The antibacterial agent of this example was prepared in the same manner as in Example 1 except that BYK-220S manufactured by BYK-chemie was used as the surfactant and the mixing amount was 1.9 parts by mass. BYK-220S is an anionic surfactant made of unsaturated acidic polycarboxylic acid polyester and polysiloxane. Moreover, since BYK-220S has a non-volatile content of 52.0%, the content of the surfactant itself (non-volatile content) in 1.9 parts by mass is 0.99 parts by mass.

[Comparative Example 3]
The antibacterial agent of this example was prepared in the same manner as in Example 1 except that the amount of the cationic surfactant mixed was 5.8 parts by mass. Since DISPERBYK-140 has a nonvolatile content of 52.0%, the content of the surfactant itself (nonvolatile content) in 5.8 parts by mass is 3.0 parts by mass.

[Comparative Example 4]
The antibacterial agent of this example was prepared in the same manner as in Example 1 except that the mixing amount of the cationic surfactant was 0.02 part by mass. Since DISPERBYK-140 has a nonvolatile content ratio of 52.0%, the content of the surfactant itself (nonvolatile content) in 0.02 parts by mass is 0.01 parts by mass.

[Antimicrobial test]
E. coli was uniformly sprayed with a small spray in a 1.8 m square peat gradient chamber. Escherichia coli was used as a bacterial solution obtained by culturing plates in a normal agar medium at 35 ° C. for 8 hours and suspending the bacteria in 50 ml of sterilized physiological saline.

Next, 60 g of the antibacterial agent of each example was uniformly sprayed at a rate of 10 g / m ³ in the chamber sprayed with E. coli and kept for 4 hours, and then the number of viable bacteria was confirmed. The collection of viable bacteria was performed on an arbitrary 10 cm square wall surface and floor surface in the chamber using Pro Media ST-25 manufactured by Elmex Corporation.

  The reduction rate was calculated from the following formula from the number of bacteria in the chamber not sprayed with the antibacterial agent and the number of bacteria in the chamber sprayed with the antibacterial agent. And the case where the reduction rate was 50% or more was set as the pass.

  Further, in order to evaluate the persistence of the antibacterial agent, after 24 hours, E. coli was sprayed uniformly again into the peat gradient chamber and kept for 4 hours, and then the number of viable bacteria was confirmed. And the reduction rate was calculated | required similarly to the above-mentioned.

[Dust adhesion test]
First, a predetermined amount of antibacterial agent was sprayed on a 10 cm square glass substrate to obtain samples of each example. Next, 2 g of pseudo dust was sprinkled uniformly over the obtained sample, and the excess was removed by air spray. The pseudo dust used was a cotton wool yarn cut to 1 mm length and sufficiently loosened.

  Next, using a color difference meter, the color difference ΔE of the sample of each example was measured before and after adhering pseudo dust. That is, as the amount of dust attached increases, the color difference ΔE increases. In this test, a color difference ΔE of 3 or less was accepted.

  Table 1 shows the mixed amount of the copper compound-supported titanium oxide, the surfactant and the solvent, the viable cell reduction rate, and the result of the dust adhesion test.

  As shown in Table 1, Examples 1 to 3 gave good results with respect to the reduction rate of viable bacteria and dust adhesion. Further, the reduction rate after 28 hours was 50% or more, and it was confirmed that antibacterial properties were maintained for a long time.

  On the other hand, in Comparative Examples 1 and 2 where the surfactant is not a cationic surfactant, the reduction rate of viable bacteria was rejected. In Comparative Example 3 in which the amount of the cationic surfactant was excessive, dust adhesion was deteriorated. Further, in Comparative Example 4 in which the mixing amount of the cationic surfactant was too small, the copper compound-supported titanium oxide was agglomerated, resulting in a failure to spray.

  Although the present invention has been described with reference to the examples and comparative examples, the present invention is not limited to these, and various modifications can be made within the scope of the gist of the present invention.

4 Spatial spray antibacterial agent 10 Spatial spray device

Claims (4)

A copper compound-supported titanium oxide formed by supporting a copper compound on titanium oxide particles containing 50 mol% or more of anatase-type titanium oxide;
A cationic surfactant that is 1 to 20 parts by mass with respect to 100 parts by mass of the copper compound-supported titanium oxide;
A solvent for dispersing the copper compound-supported titanium oxide and the cationic surfactant;
Liquefied carbon dioxide,
Containing
The titanium oxide particles have an average primary particle size of 10 nm to 50 nm, the copper compound has an average particle size of 0.5 nm to 10 nm,
The space spray antibacterial agent whose copper ion in the said copper compound is 4-10 mass parts with respect to 100 mass parts of said titanium oxide particles.   The space spray antibacterial agent of Claim 1 which contains the said copper compound carrying | support titanium oxide 0.5-10 mass%, the said solvent 5-15 mass%, and liquefied carbon dioxide 70-90 mass%.   The space spray antibacterial agent according to claim 1 or 2, wherein the cationic surfactant is an ammonium salt. The space spray antibacterial agent according to any one of claims 1 to 3,
A pressure-resistant container filled with the space spray antibacterial agent;
A space spray device comprising:

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