Self-spouting spatial treatment agent composition and self-jetting type space treatment apparatus

Abstract

To further enhance the persistence of the control effect of a self-spouting spatial treatment agent composition in view of the following circumstances that when the content of the nonionic surfactant is simply increased in order to enhance the durability of the control effect, the elution of the active ingredient (silver or the like) of the inorganic chemical as a carrier is inhibited, the control effect is lowered, and the control effect cannot be enhanced.SOLUTION: Provided is a self-spouting spatial treatment agent composition that contains a component (A) which is a metal support including a support (A1) having a supported amount of at least one metal selected from silver and copper of 4 mass% or more, and a component (B) which is a nonionic surfactant, wherein the content of the component (B) is 7 to 16 mass% based on the total mass of the self-spouting spatial treatment agent composition, the ratio of the content of the component (B) to the content of the component (A), and the mass ratio of the component (B) to the component (A) is 4 to 12.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a self-spraying space treatment agent composition and a self-spraying space treatment device.

Background Art

[0002] Water is indispensable for the growth of microorganisms such as bacteria and mold. Among living environments, bathrooms, toilets, washbasins, kitchens, air conditioners, window sills, etc. are environments where water can be abundantly present. Therefore, in such environments, microbial contamination has become a problem. In particular, places that are difficult to reach by hand, such as ceilings and high parts of walls, are areas where cleaning is not thorough and microbial growth is likely to occur. As a preventive measure against the growth of microorganisms, there is a control treatment using a self-spraying space treatment agent composition. The self-spraying space treatment agent composition contains active ingredients such as fungicides and volatilizes the active ingredients in a sealed space in a short time to perform a control treatment. As the self-spraying space treatment agent composition, a jet-type fumigant (fumigation agent) composition, a full-dose injection aerosol agent composition, etc. are known.

[0003] Active ingredients against microorganisms include inorganic agents and organic agents. Among them, inorganic agents are stable and can maintain a control effect for a long time. For example, Patent Document 1 proposes a self-spraying space treatment agent composition containing silver, a silver compound or a carrier thereof, and a specific nonionic surfactant. According to the invention of Patent Document 1, an improvement in the persistence of the antifungal effect is intended.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Due to the improvement of airtightness of living equipment and the rise of temperature, contamination by fast-growing microorganisms (e.g., pink stain) becomes prominent throughout the year. Therefore, further improvement in the persistence of the control effect is required. As a result of the study by the present inventors, in order to enhance the persistence of the control effect, simply increasing the content of the nonionic surfactant inhibits the elution of the active ingredient (such as silver) of the inorganic-based agent serving as the carrier, resulting in a decrease in the control effect and the inability to enhance the control effect. The present invention has been made in view of the above circumstances, and aims at a self-spraying type space treatment agent composition capable of further enhancing the persistence of the control effect.

Means for Solving the Problems

[0006] The present inventors have obtained the finding that increasing the amount of the nonionic surfactant covers the carrier and shields the elution of the active ingredient such as silver, reducing the control effect, and have thus completed the present invention.

[0007] <1> (Component (A): A metal carrier containing a carrier (A1) in which the supported amount of at least one metal of silver and copper is 4% by mass or more, and Component (B): A nonionic surfactant, a self-spraying type space treatment agent composition, The content of the Component (B) is 7 to 16% by mass with respect to the total mass of the self-spraying type space treatment agent composition, The self-spraying type space treatment agent composition, which is the ratio of the content of the Component (B) to the content of the Component (A), and the mass ratio represented by the Component (B) / the Component (A) is 4 to 12. <2> The Component (B) is a copolymer type nonionic surfactant of oxyethylene and oxypropylene, and the self-spraying type space treatment agent composition according to <1>. <3> (Component (C1): Further containing an organic foaming agent, the self-spraying type space treatment agent composition according to <1> or <2>. <4> (Component (C2): Further containing a propellant, the self-spraying type space treatment agent composition according to <1> or <2>.

[0008] <5> An aerosol-type space treatment device having the aerosol-type space treatment agent composition according to any one of <1> to <4>.

Advantages of the Invention

[0009] According to the aerosol-type space treatment agent composition of the present invention, the persistence of the control effect can be further enhanced.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0011] (Aerosol-type space treatment agent composition) The aerosol-type space treatment agent composition of the present invention contains (A) component: a metal carrier and (B) component: a nonionic surfactant. In this specification, the numerical range represented by "~" means a numerical range having the numerical values before and after ~ as the lower limit value and the upper limit value.

[0012] ((A) component) (A) component is a metal carrier containing a carrier (hereinafter sometimes referred to as "(A1) component") containing at least one metal of silver and copper (hereinafter sometimes referred to as "(a1) component"). By containing the (A) component, a control effect is exhibited, and by containing the (A1) component, the control effect is enhanced and the persistence of the control effect is enhanced. Note that both the (A) component and the (A1) component are blended in the aerosol-type space treatment agent composition as a particle group.

[0013] (a1) The form of the component may be a simple metal or a metal compound. (a1) As the silver of the component, it is at least one selected from simple silver and silver compounds. Examples of silver compounds include silver oxide, silver chloride, silver nitrate, silver sulfate, silver carbonate, silver sulfonate salts, inorganic silver salts, etc. Among them, as silver, simple silver, silver oxide, and silver nitrate are preferable.

[0014] (a1) As the copper of the component, it is at least one selected from simple copper and copper compounds. As the copper compound, either an inorganic metal compound or an organic metal compound may be used. Examples of inorganic metal compounds include copper chloride (CuCl2, CuCl), copper sulfate (CuSO4), copper iodide (CuI2), copper nitrate, copper sulfide, copper phosphate, ammonium chloride copper, copper hydroxide, copper oxide, etc. When the copper compound undergoes a neutralization process, etc., a copper hydroxide or oxide is supported on the surface of the carrier as a part of the copper compound. Examples of organic metal compounds include copper oxalate. The above-mentioned (a1) component may be used alone or in combination of two or more.

[0015] Examples of the carrier constituting the (A1) component include zeolite, silica gel, low molecular glass, calcium phosphate, silicate, and titanium oxide. Among them, as the carrier, calcium phosphate and zeolite are preferable. (A1) The specific surface area of the carrier constituting the component is, for example, 100 - 600 m 2 / g.

[0016] (A1) The content (loading amount) of the (a1) component in the (A1) component is preferably 4% by mass or more, more preferably 5 - 10% by mass, based on the total mass of the (A1) component. When the loading amount of the (a1) component is at least the above lower limit value, the content of the (a1) component can be increased to increase the bonding points with the (B) component. By increasing the bonding points between the (A) component and the (B) component, after adhering to the walls, ceilings, floors, facilities, etc. (hereinafter sometimes referred to as "treatment target surfaces") that make up the treatment target space, it becomes difficult to flow out due to moisture, and the persistence of the control effect can be enhanced. When the loading amount of the (a1) component is at most the above upper limit value, the (a1) component is uniformly dispersed in the treatment target space, and a higher control effect is exhibited at every corner of the treatment target space. (a1) The loading amount of the component, and the metal loading amount of each metal-supported antibacterial agent, are determined from the elemental ratio of the metal and the carrier using a fluorescent X-ray analyzer. Also, the amount of the supported metal is measured by extracting the metal into a solution and using an atomic absorption photometer or an ICP emission spectroscopic analyzer.

[0017] (A1) The particle size of the component can be determined, for example, considering the size of the target space, etc. The finer the particles of the (A1) component, the higher the volatilization rate, the higher the effect of the (A1) component, and the wider the spread. If the particle size of the (A1) component is too small, it becomes difficult to fall after diffusion, and it takes time for the effect of the (A1) component to appear in the lower part of the treatment target space. (A1) The volume average particle size of the component is preferably, for example, 0.1 - 7 μm, more preferably 1 - 4 μm. The volume average particle size refers to the value obtained by a laser diffraction / scattering particle size distribution measuring device and can be measured as follows. The (A1) component is dispersed in distilled water so that the solid content is 1% by mass to make a sample. This sample is put into a laser diffraction / scattering particle size distribution measuring device, dispersed by ultrasonic waves in the device, and then irradiated with a laser to measure the particle size distribution. The diameter at which the cumulative volume frequency is 50% (volume) is taken as the average particle size.

[0018] (A) The component may contain a metal support ((A2) component) other than the (A1) component. (Component (A2)) Examples of the metal support include a metal support containing a metal other than component (a1) (component (a2)) and a metal support having a content of component (a1) outside the range of the content of component (a1) in component (A1). Examples of component (a2) include nickel, zinc, iron, aluminum, and the like.

[0019] The volume average particle diameter of component (A2) is the same as that of component (A1).

[0020] The content of component (A) is preferably 0.1 to 3% by mass, more preferably 0.5 to 2.5% by mass, based on the total mass of the self-spraying space treatment agent composition. When the content of component (A) is at least the above lower limit value, the control effect can be further enhanced. When the content of component (A) is at most the above upper limit value, it volatilizes more uniformly and the initial control effect can be further enhanced.

[0021] The content of component (A1) in component (A) is preferably 50% by mass or more, more preferably 65% by mass or more, and may be 100% by mass, based on the total mass of component (A). When the content of component (A1) is at least the above lower limit value, the control effect can be further enhanced and the persistence of the control effect can be further enhanced. When the content of component (A1) is at most the above upper limit value, component (a1) is uniformly dispersed in the treatment target space and a higher control effect is exhibited at every corner of the treatment target space.

[0022] The particle diameter of component (A) can be determined, for example, considering the size of the target space and the like. The finer the particles of component (A), the higher the volatilization rate, the higher the effect of component (A), and the wider the spread. If the particle diameter of component (A) is too small, it is difficult to fall after diffusion, and it takes time for the effect of component (A) to appear below the treatment target space. The volume average particle diameter of component (A) is preferably 0.1 to 7 μm, more preferably 1 to 4 μm, for example.

[0023] <(Component (B))> (B) component is a nonionic surfactant. The (B) component has the effect of attaching the (A) component to the surface to be treated and keeping it in place (spreading effect). Therefore, by containing the (B) component, the space treatment agent makes it difficult for the (A) component attached to the surface to be treated to be washed away by water (excellent water resistance) even in places where water frequently flows, such as on the walls of a bathroom, thus enhancing the sustainability of the control effect. In addition, the combined use of the (B) component and the (A) component further enhances the sterilization effect.

[0024] Examples of the (B) component include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acids, sucrose fatty acid esters, propylene glycol fatty acid esters, glycerin alkyl ethers, polyoxyethylene (POE) - added nonionic surfactants, and the like. Examples of the POE - added nonionic surfactants include POE - sorbitan fatty acid esters, POE - glycerin fatty acid esters, POE - propylene glycol fatty acid esters, POE - alkyl ethers, POE·polyoxypropylene (POP) - alkyl ethers, alkanolamides, and copolymer - type nonionic surfactants of oxypropylene and oxyethylene. These (B) components may be used alone or in combination of two or more.

[0025] As the (B) component, a compound represented by the following general formula (I) is preferable because of its excellent spreading property on the treatment surface.

[0026] R 1 -O-(AO) x -R 2 ···(I) (In the formula (I), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and AO represents an oxyalkylene group. (AO) x includes an oxyethylene group (EO) and at least one of an oxypropylene (PO) group and an oxybutylene group, and x is a number from 20 to 500.)

[0027] R in formula (I) 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group include an alkyl group and an alkenyl group. R 1 and R 2 Examples of the hydrocarbon group include linear or branched hydrocarbon groups. R 1 and R 2 are preferably hydrocarbon groups having 1 to 3 carbon atoms and hydrogen, and more preferably hydrogen.

[0028] (AO) x Preferably contains EO and PO in terms of excellent persistence of the control effect, more preferably a copolymer type nonionic surfactant composed of EO and PO (that is, a block adduct or random adduct of EO and PO), and even more preferably a block adduct of EO and PO.

[0029] (AO) x Examples of the component (B) in which (AO) is a block adduct of EO and PO include compounds represented by the following (i) to (iii).

[0030] R 1 -O-(EO) a -(PO) b -R 2 ···(i) R 1 -O-(EO) c -(PO) d -(EO) e -R 2 ···(ii) R 1 -O-(PO) f -(EO) g -(PO) h -R 2 ···(iii)

[0031] In the case of formula (i), (AO) in formula (I) x is a diblock type composed of EO and PO. (In formula (i), a represents the average number of repetitions (average number of added moles) of EO, a number from 10 to 300 is preferred, and a number from 10 to 200 is more preferred. b represents the average number of repetitions (average number of added moles) of PO, a number from 5 to 250 is preferred, and a number from 10 to 60 is more preferred. However, the sum of a and b is the value of x in formula (I).

[0032] (In the case of formula (ii), (AO) in formula (I) x is of a triblock type with PO sandwiched by EO. (In formula (ii), c represents the average number of repetitions (average number of added moles) of EO, a number from 5 to 150 is preferred, and a number from 10 to 100 is more preferred. d represents the average number of repetitions (average number of added moles) of PO, a number from 5 to 250 is preferred, and a number from 10 to 60 is more preferred. e represents the average number of repetitions (average number of added moles) of EO, a number from 5 to 150 is preferred, and a number from 10 to 100 is more preferred. However, the sum of c, d, and e is the value of x in formula (I).

[0033] (In the case of (iii), (AO) in formula (I) x is of a triblock type with EO sandwiched by PO. In formula (iii), f represents the average number of repetitions (average number of added moles) of PO, a number from 5 to 150 is preferred, and a number from 10 to 30 is more preferred. g represents the average number of repetitions (average number of added moles) of EO, a number from 5 to 250 is preferred, and a number from 5 to 30 is more preferred. h represents the average number of repetitions (average number of added moles) of PO, a number from 5 to 150 is preferred, and a number from 10 to 30 is more preferred. However, the sum of f, g, and h is the value of x in formula (I).

[0034] Among those described above, as the component (B), from the viewpoint of excellent spreading property on the surface to be treated and further enhancing the persistence of the control effect, the compound represented by formula (iii) is preferred.

[0035] The component (B) is easily available in the market. (ii) Examples of commercially available products of the compound represented by the formula include "Pluronic PE6400" manufactured by BASF Japan Ltd., "Pluronic PE9200" manufactured by BASF Japan Ltd., and the like. (iii) Examples of commercially available products of the compound represented by the formula include "Pluronic RPE1740", "Pluronic RPE2525" manufactured by BASF Japan Ltd., "ADEKA Pluronic 17R-3", "ADEKA Pluronic 17R-4", and "ADEKA Pluronic 31R-1" with the trade names of ADEKA Corporation, and the like. In addition, as the component (B), those synthesized by the methods described in various publications and the like may be used.

[0036] The mass average molecular weight of the component (B) is preferably 1500 to 8000. If the mass average molecular weight of the component (B) is within the above range, the spreading property is excellent and the persistence of the control effect can be further enhanced. The mass average molecular weight of the component (B) is a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent and converted using PEG (polyethylene glycol) as a calibration curve.

[0037] The content of the component (B) is preferably 7 to 16% by mass, more preferably 8 to 14% by mass. When the content of the component (B) is not less than the above upper limit value, the water resistance can be further enhanced. When the content of the component (B) is not more than the above upper limit value, the elution of the component (a1) of the component (A) is not shielded, the control effect is further enhanced, the injection force of the self-spraying space treatment agent composition is increased, and the component (a1) adheres to the treatment target surface more uniformly. As a result, the control effect is enhanced and the persistence of the control effect can be further enhanced.

[0038] The ratio of the content of the component (B) to the content of the component (A), that is, the mass ratio (B / A ratio) represented by the component (B) / (A) component is preferably 4 to 12, more preferably 5 to 10. When the B / A ratio is not less than the above lower limit value, the spreading property and water resistance of the component (A) are enhanced, and the control effect and the persistence of the control effect can be further enhanced. When the B / A ratio is not more than the above upper limit value, the elution of the component (a1) is not shielded, and the control effect can be further enhanced.

[0039] <Any component> The self-spraying space treatment agent composition may contain optional components other than the component (A) and the component (B). The optional components are appropriately determined according to the dosage form and the like of the self-spraying space treatment agent composition. When the self-spraying space treatment agent composition is a fumigant composition or a fuming agent composition (collectively referred to as "fumigant composition"), the self-spraying space treatment agent composition may contain an organic foaming agent, a combustion aid, a stabilizer, an excipient, a fragrance, etc. When the self-spraying space treatment agent composition is a total amount injection aerosol agent composition, the self-spraying space treatment agent composition may contain a propellant, a solvent, a fragrance, etc.

[0040] The dosage form of the fumigant composition is, for example, a solid preparation such as a powder, a granule, a tablet, etc. The organic foaming agent ((C1) component) contained in the fumigant composition is a substance that generates a large amount of heat by thermal decomposition upon heating or combustion and generates carbon dioxide gas, nitrogen gas, etc. By containing the organic foaming agent, the fumigant composition ejects the component (A) and the component (B) in a short time and volatilizes the component (A) and the component (B). Examples of the (C1) component include azodicarbonamide (ADCA), nitrocellulose, p,p'-oxybis(benzenesulfonylhydrazide), N,N'-dinitrosopentamethylenetetramine, azobisisobutyronitrile, etc. These (C1) components may be used alone or in combination of two or more. Among the (C1) components, azodicarbonamide and nitrocellulose are preferable in that they have a low decomposition temperature and a large amount of generated foaming gas. The content of the (C1) component is preferably 55 to 85% by mass, more preferably 65 to 85% by mass, based on the total mass of the self-spraying space treatment agent composition. When the content of the (C1) component is at least the above lower limit value, the component (A) and the component (B) can be volatilized more quickly and in a larger amount, and the persistence of the control effect can be further enhanced. When the content of the (C1) component is at most the above upper limit value, the volatilization amount of the component (A) and the component (B) can be increased, and the persistence of the control effect can be further enhanced.

[0041] Examples of the combustion aids include zinc oxide, magnesium oxide, urea, melamine, melamine derivatives (such as industrial melamine, melamine nitrate, and melamine formaldehyde resin), and the like. The ratio of the mass of the combustion aid to the total mass of the self-spraying space treatment agent composition is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass.

[0042] Examples of the stabilizers include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, epoxy compounds (such as epoxidized soybean oil and epoxidized linseed oil), and the like. The content of the stabilizer with respect to the total mass of the self-spraying space treatment agent composition is preferably 0.01 to 15% by mass, more preferably 1 to 10% by mass.

[0043] Examples of the binders include cellulose-based compounds (such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose and its Ca salt and Na salt, hydroxypropyl methyl cellulose, and hydroxypropyl cellulose), starch-based compounds (such as starch, pregelatinized starch, dextrin, hydroxypropyl starch, and sodium carboxymethyl starch), natural product-based compounds (such as gum arabic, sodium alginate, tragacanth, and gelatin), synthetic polymer-based compounds (such as polyvinyl alcohol, polyvinyl pyrrolidone, and sodium polyacrylate), and the like. The content of the binder with respect to the total mass of the self-spraying space treatment agent composition is preferably 0.1 to 10% by mass, more preferably 2 to 6% by mass.

[0044] Examples of the excipients include clay, talc, diatomaceous earth, kaolin, bentonite, white carbon, calcium carbonate, and the like. Clay is a white powdery product industrially refined from clay minerals such as pyrophyllite (including pyrophyllite) containing aluminum silicate and quartz, and contains fine particles. The volume average particle diameter of the clay is preferably 0.1 to 100 μm, more preferably 1 to 30 μm. The volume average particle diameter is a value determined by a laser diffraction / scattering particle size distribution measuring device. Examples of the clay include those containing silicon oxide and aluminum silicate. The content of the excipient is preferably from 2 to 50% by mass, more preferably from 10 to 30% by mass, based on the total mass of the self-spouting spatial treatment composition.

[0045] The fragrance is not particularly limited, but lists of usable fragrance raw materials are described in various documents. For example, the fragrances described in the following documents can be mentioned. "Perfume and Flavor Chemicals", Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994), "Synthetic fragrance chemistry and product knowledge", Genichi Indo, Kagaku Kogyo Nipposha (1996), "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub.Co. (1994), "Encyclopedia of Fragrance", edited by the Japan Fragrance Association, Asakura Publishing (1989), "Perfumery Material Performance V.3.3", Boelens AromaChemical Information Service (1996), "Floweroils and Floral Compounds In Perfumery", Danute Lajaujis Anonis, Allured Pub.Co. (1993), etc.

[0046] The dosage form of the direct-acting aerosol composition is a liquid. Dimethyl ether is preferred as the propellant (component (C2)) contained in the total-spray aerosol composition. When the space treatment agent contains dimethyl ether as component (C2), the dispersibility and spray force of components (A) and (B) are improved, and when the self-spraying space treatment agent composition of the present invention is used in a bathroom or the like, more components (A) and (B) can reach the surface to be treated. Examples of components (other propellants) other than dimethyl ether as component (C2) include liquefied gases other than dimethyl ether (liquefied petroleum gas, chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroolefin, etc.), compressed gases (carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc.), and the like. Among these, from the viewpoint of injection force (momentum of injection), liquefied gas is preferred. The above-mentioned propellants may be used alone or in combination of two or more. When dimethyl ether and other propellants are used in combination, liquefied gas is preferred as the other propellant.

[0047] When dimethyl ether is used as component (C2), the content of dimethyl ether is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 100% by mass with respect to the total mass of component (C2). When the content of dimethyl ether is at least the above lower limit, the injection force can be further increased.

[0048] The content of component (C2) is preferably 50 to 90% by mass, more preferably 60 to 80% by mass with respect to the total mass of the self-spraying space treatment agent composition. When the content of component (C2) is at least the above lower limit, components (A) and (B) can be volatilized more quickly and in a larger amount, and the persistence of the control effect can be further enhanced. When the content of component (C2) is at most the above upper limit, the volatilization amount of components (A) and (B) can be increased, and the persistence of the control effect can be further enhanced.

[0049] The total amount injection type aerosol composition may contain a solvent as necessary. By containing a solvent, the compatibility between the self-spraying space treatment agent composition and the propellant can be enhanced, and the effect of the self-spraying space treatment agent composition can be further enhanced. Examples of the solvent include ethanol, methanol, acetone, glycol ethers (ethylene glycol or its derivatives, diethylene glycol or its derivatives, other alkylene glycols or their derivatives, etc.), propylene carbonate, dimethyl carbonate, N-methylpyrrolidone, N-ethylpyrrolidone, γ-butyrolactone, methyl lactate, ethyl lactate, dibutyl lactate, kerosene, water, etc. The solvent may be used alone or in combination of two or more.

[0050] The content of the solvent is preferably 1 to 30% by mass, more preferably 10 to 20% by mass, based on the total mass of the self-spraying space treatment agent composition.

[0051] (Manufacturing method) <Fumigant composition> The fumigant composition of the present invention is prepared as a solid preparation such as powder, granule, tablet, etc. As a manufacturing method of the fumigant composition, a known manufacturing method is used according to the target dosage form. For example, in the case of a granular preparation, known granulation methods such as extrusion granulation method, compression granulation method, stirring granulation method, rolling granulation method, fluidized bed granulation method, etc. are used. The fumigant composition of the present invention is obtained by mixing the component (A), component (B), component (C1) and optional components as required. An example of the extrusion granulation method will be described. Each component of the fumigant composition is mixed by a kneader or the like, and an appropriate amount of water is added and mixed as required to obtain a mixture. Using a die having an arbitrary aperture diameter, the obtained mixture is granulated by a forward extrusion or lateral extrusion granulator. The obtained granulated product may be further cut into an arbitrary size by a cutter or the like and dried for moisture removal. Examples of the drying method include a heat drying method using a conventionally known dryer. The drying temperature is not particularly limited, but is preferably 50 to 80°C from the viewpoint of suppressing the volatilization of fragrances and the like. The drying time is appropriately determined according to the drying temperature. The water content of the smoked agent composition after drying is not particularly limited, but is preferably 5% by mass or less, more preferably 2% by mass or less, and may even be 0% by mass. When the water content is 5% by mass or less, the volatilization rate of the smoked agent composition is good.

[0052] <Total amount injection type aerosol agent composition> A method for producing a total amount injection type aerosol agent composition will be described. A chemical solution is prepared by mixing component (A), component (B), and optional components as required. The obtained chemical solution is put into an aerosol container, and further filled with component (C2) to obtain a total amount injection type aerosol agent composition. For example, when dimethyl ether is used as the propellant, it is preferably filled so that the internal pressure of the container at 25°C is 0.3 to 0.6 MPa, and more preferably filled so that it is 0.4 to 0.5 MPa.

[0053] (Self-spraying type space treatment device) The self-spraying type space treatment device contains the self-spraying type space treatment agent composition of the present invention. Examples of the self-spraying type space treatment device include a smoked device, a total amount injection type aerosol device, etc. Examples of the smoked device include an indirectly heated smoked device, a directly heated smoked device, etc.

[0054] <Smoked device> Hereinafter, the smoked device will be described. The smoked device houses the self-spraying type space treatment agent composition in an arbitrary container such as a metal container or a ceramic container, and indirectly heats (indirect heating type) or directly heats (direct heating type) the self-spraying type space treatment agent composition to volatilize component (A) and component (B).

[0055] The indirectly heated smoked device (indirectly heated smoked device) has, for example, an outer container having a water passage hole at the bottom and a smoke passage hole at the top, and an inner container located inside the outer container. A heating part is formed by a heating agent filled in the outer container, and a smoked agent part is formed by a smoked agent composition filled in the inner container. In this indirectly heated smoked device, the heating part and the smoked agent part are adjacent to each other via the inner container.

[0056] An embodiment of an indirect heating type smoking device will be described with reference to the drawings. The indirect heating type smoking device 210 in Fig. 1 includes a housing 212, a heating unit 220 provided inside the housing (outer container) 212, and a smoking agent unit 232 provided inside the housing 212. The housing 212 has a substantially cylindrical main body 214, a bottom portion 216, and a lid portion 218 provided on the upper portion of the main body 214. An inner container 230 is provided in the housing 212, and the inner container 230 is filled with a smoking agent composition to form the smoking agent unit 232. The inner container 230 is located above the heating unit 220.

[0057] The lid portion 218 has a through hole, and examples include a mesh, punching metal, a lattice-shaped frame, etc. The material of the lid portion 218 is, for example, metal, ceramic, etc. The material of the main body 214 is the same as that of the lid portion 218.

[0058] The inner container 230 is a container filled with a smoking agent composition and functions as a heat transfer portion that transmits the heat energy generated by the heating unit 220 to the smoking agent unit 232. The inner container 230 is, for example, a metal container, etc.

[0059] The heating unit 220 is not particularly limited and can be appropriately determined in consideration of the amount of heat required for the smoking of the smoking agent unit 232.

[0060] The bottom portion 216 can be appropriately determined according to the mechanism of the heating unit 220. For example, when the heating unit 220 is composed of a heating agent (such as calcium oxide), the bottom portion 216 is a non-woven fabric, a metal mesh, etc. By using a non-woven fabric or a metal mesh for the bottom portion 216, water is sucked up from the bottom portion 216.

[0061] The filling amount of the smoking agent composition is appropriately determined according to the processing target space and is, for example, 1 to 50 g. The filling amount of the heating agent is appropriately determined in consideration of the type of the heating agent, the filling amount of the smoking agent composition, etc., and is, for example, 10 to 80 g.

[0062] A direct heating type smoking device (direct heating type smoking device) has, for example, a container, a smoking agent composition filled in the container, and an igniter that ignites the smoking agent composition. As the igniter, a heating element having match head medicine can be exemplified.

[0063] ≪Usage method≫ The usage method of the smoking device will be described by taking an indirect heating type smoking device as an example. Install the indirect heating type smoking device 210 in the space to be treated. Next, heat the heating unit 220 according to the mechanism of the heating unit 220. For example, when the heating unit 220 filled with calcium oxide is provided, immerse the bottom 216 in water. Thereby, the water that has entered from the bottom 216 reacts with calcium oxide in the heating unit 220, generating heat of about 200 to 450 °C. Then, the heat generated by the reaction of the water that has entered from the bottom 216 with calcium oxide in the heating unit 220 is transmitted to the smoking agent part 232 through the side wall and bottom wall of the inner container 230, and the temperature of the smoking agent part 232 rises. When the temperature of the smoking agent part 232 increases, the component (C1) thermally decomposes to generate gas. Together with the generated gas, the components (A) and (B) vigorously pass through the through holes of the lid part 218 and volatilize into the space to be treated. The volatilized components (A) and (B) diffuse in the space to be treated and adhere to the surface to be treated. In this way, the microorganisms in the space to be treated are controlled by the component (A), and the component (A) adheres to the surface to be treated together with the component (B), thereby enhancing the persistence of the control effect. After the completion of the smoking treatment (after the ejection from the smoking device has ended), ventilate the space to be treated after a predetermined time.

[0064] <Total amount injection type aerosol device> The total amount injection type aerosol device has a pressure-resistant container (total amount injection type aerosol container) having an ejection mechanism and a total amount injection type aerosol agent composition filled in the total amount injection type aerosol container. The filling amount of the total amount injection type aerosol agent composition is appropriately determined according to the space to be treated, and is, for example, 50 to 150 mL.

[0065] An embodiment of a full - volume spray aerosol device and its method of use will be described with reference to the drawings. The full - volume spray aerosol container of the present invention may be any container that can spray almost the entire amount of the contents outside the full - volume spray aerosol container by any spraying means (such as opening a valve) in one operation, and is not limited to the containers described below. The full - volume spray aerosol containers 20 in FIGS. 2 and 3 include a spray can 21 for containing the contents, and a nozzle cap 22 attached to the spray can 21 for spraying almost the entire amount of the contents contained in the spray can 21. The spray can 21 has a stem 23 provided to protrude from the center of its upper part and supported so as to be movable in the vertical direction while being biased upward, and a valve mechanism (not shown) that is opened by pressing the stem 23 downward. The nozzle cap 22 has a cap body 24 attached to the upper part of the spray can 21, a push button 25 for pressing the stem 23 of the spray can 21, and an injection nozzle 26 for injecting the contents ejected from the stem 23 of the spray can 21 by pressing the stem 23 of the spray can 21. The cap body 24 is a plastic cover member that covers the upper part of the spray can 21. The push button 25 can press the stem 23 of the spray can 21 by pressing the operation part 27. Further, the push button 25 is provided with a fitting part 28 arranged at the center of the lower surface of the push button 25 and fitted with the stem 23 of the spray can, and a flow path 29 that communicates with the fitting part 28 and guides the contents ejected from the stem 23 to the injection nozzle 26. An injection nozzle 26, which is a nozzle member, is provided at one end side of the push button 25. The injection nozzle 26 communicates with the flow path 29 of the push button 25 and injects the contents ejected from the stem 23 through an injection port 26a provided at its tip. Incidentally, the nozzle cap 22 is provided with a lock mechanism 30 for fixing the push button 25 in a fixed position when the push button 25 is pressed. Specifically, this lock mechanism 30 includes a locking portion 31 disposed on the cap body 24 side for locking the push button 25 in a fixed position, and a locked portion 32 disposed on the push button 25 side and locked to the locking portion 31 on the cap body 24 side. In this lock mechanism 30, when the push button 25 is pushed down against the biasing force of the stem 23 biased upward, the locked portion (protrusion) 32 rides over the locking portion (ridge) 31 of the shoulder cover 33 while slidingly contacting it. At this time, when the pressing of the push button 25 is released, although the stem 23 biased upward presses the push button 25 upward, the locked portion 32 of the push button 25 is locked to the locking portion 31 of the shoulder cover 33 without riding over it. As a result, the push button 25 can be fixed in a fixed position, that is, by pressing this push button 25, the stem 23 is pressed, and the content ejected from this stem 23 can be fixed at the ejection position where it is ejected from the ejection port 26a of the ejection nozzle 26. In this way, since the push button 25 is fixed in a fixed position by the lock mechanism 30, the pressing state of the stem 23 is maintained. As a result, with the valve mechanism of the spray can 21 in an open state, spraying continues until the content contained in this spray can 21 is exhausted, and spraying ends when the gas pressure by the propellant disappears. The total amount of the sprayed aerosol composition diffuses in the treatment target space, and the components (A) and (B) adhere to the treatment target surface. In this way, the microorganisms in the treatment target space are controlled by the component (A), and the component (A) adheres to the treatment target surface together with the component (B), thereby enhancing the persistence of the control effect. After the spraying of the content is completed, the treatment target space is ventilated after a predetermined time.

[0066] According to the present invention, since it contains the component (A) and the component (B) and the B / A ratio is within a specific range, it is excellent in the control effect and excellent in the persistence of the control effect. Therefore, the self-spraying type space treatment agent composition of the present invention is suitable for microbial control treatment in bathrooms, toilets, washrooms, kitchens, air conditioners, window frames, living rooms, closets, etc. Among them, the self-spraying type space treatment agent composition of the present invention is particularly suitable for microbial control treatment in bathrooms, toilets, washrooms, kitchens, air conditioners, and window frames.

Examples

[0067] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following description.

[0068] (Raw materials used) <Component (A): Metal carrier> · A1-1: Silver-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) AK10N", silver loading 5.0% by mass, average particle diameter about 2.5 μm, manufactured by Shinanen Zeomic Co., Ltd. · A1-2: Silver-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) AL10N", silver loading 10% by mass, average particle diameter about 2.5 μm, manufactured by Shinanen Zeomic Co., Ltd. · A1-3: Silver-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) LGK10T", silver loading 5.0% by mass, average particle diameter about 7.0 μm, manufactured by Shinanen Zeomic Co., Ltd. · A1-4: Silver-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) AL85N", silver loading 10% by mass, average particle diameter about 1.9 μm, manufactured by Shinanen Zeomic Co., Ltd. · A1-5: Copper-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) CA10N", copper loading 10% by mass, average particle diameter about 2.5 μm, manufactured by Shinanen Zeomic Co., Ltd. · A1-6: Silver·copper-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) AC10N", silver loading 3.5% by mass, copper loading 6.5% by mass, average particle diameter about 2.5 μm, manufactured by Shinanen Zeomic Co., Ltd. · A2-1: Silver-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) AW10N", silver loading 0.5% by mass, average particle diameter about 2.5 μm, manufactured by Shinanen Zeomic Co., Ltd. · A2-2: Silver-supported zeolite-based inorganic antibacterial agent, trade name "Zeomic (registered trademark) AJ10N", silver loading 2.5% by mass, average particle size approximately 2.5 μm, manufactured by Shinanen Zeomic Co., Ltd. · A2-3: Silver-supported calcium phosphate-based inorganic antibacterial agent, trade name: Apasidar AW, silver loading 2.3% by mass, average particle size approximately 2.0 μm, manufactured by Sangi Co., Ltd.

[0069] <(Component (B): Nonionic surfactant)> · B-1: PO-EO-PO type nonionic surfactant 1 (POEOPO1), trade name "Pluronic RPE1740", manufactured by BASF Japan Ltd. · B-2: PO-EO-PO type nonionic surfactant 2 (POEOPO2), trade name "Pluronc RPE2525, manufactured by BASF Japan Ltd. · B-3: EO-PO-EO type nonionic surfactant 1 (EOPOEO1), trade name "Pluronic PE6400", manufactured by BASF Japan Ltd. · B-4: EO-PO-EO type nonionic surfactant 2 (EOPOEO2), trade name "Pluronic PE9200, manufactured by BASF Japan Ltd. · B-5: Sorbitan fatty acid ester (SMO), trade name "Emazol O-10V, manufactured by Kao Corporation.

[0070] <(Component (B): Comparative product of component (B))> · B’―1: Amphoteric surfactant, lauryldimethylaminoacetic acid betaine (35% solution), trade name "SWANOL (registered trademark) AM-301", manufactured by Nippon Surfactant Industry Co., Ltd.

[0071] <(Component (C1): Organic foaming agent)> · C1-1: Azodicarbonamide (ADCA), trade name "Diblow AC.2040(C)", manufactured by Dainichi Seika Kogyo Co., Ltd.

[0072] <(Component (C2): Propellant)> · C2-1: Dimethyl ether (DME), manufactured by Mitsubishi Gas Chemical Company, Inc.

[0073] <Any component> ·EtOH: Ethanol, special grade reagent, manufactured by Junsei Chemical Co., Ltd. ·ZnO: Zinc oxide, Japanese Pharmacopoeia zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.6 μm. ·HPMC: Hydroxypropylmethylcellulose, trade name "Methocel 60SH-50", manufactured by Shin-Etsu Chemical Co., Ltd. · Clay: SiO2 = 75% by mass, Al2O3·2SiO2·2H2O = 25% by mass, "NK-300", manufactured by Showa KDE Co., Ltd., average particle size = approximately 10 μm.

[0074] <Heating agent> · Calcium oxide: Trade name "CAg", rotary kiln fired product (Katsuki production), bulk density = 0.80 g / cm 3 (20 °C), manufactured by Yoshizawa Lime Industry Co., Ltd.

[0075] (Evaluation method) <Preparation of test pieces> As shown in Fig. 4, two FRP plates (SL-EC, 5 cm × 5 cm, manufactured by Nitto Shinko Co., Ltd.) 120 were arranged and attached to the floor corner of an airtight evaluation chamber (height H2 from the floor to the ceiling: approximately 2 m, width L4: 1.6 m, depth L3 = 1.6 m) 102 with approximately the same volume as an 1818-type (for meter module) bathroom. Each example's self-spraying space treatment agent device (smoke device or total amount injection aerosol device) 130 was placed on the floor of the evaluation chamber 102, and the contents were sprayed (spray treatment). For 90 minutes from the start of the injection of the contents, the evaluation chamber 102 was sealed, then exhausted for 30 minutes, and the FRP plate 120 was recovered and used as a test piece.

[0076] <Initial control effect> To each of one of the prepared test pieces and an untreated FRP plate that had not been subjected to the spray treatment, a Rhodotorula dispersion (10 20.4 mL of (cfu / mL) was inoculated and cultured at 25°C and 90% RH for 4 days. The number of colonies after culture was counted and the viable cell count was measured. The inhibition rate of viable cell count was determined by the following formula (s1). The obtained inhibition rate was classified according to the following evaluation criteria and evaluated. The higher the inhibition rate, the better the initial control effect.

[0077] Inhibition rate of viable cell count (%) = {1 - (viable cell count of test piece) / (viable cell count of untreated FRP plate)} × 100 ···(s1)

[0078] ≪Evaluation criteria≫ ○○: Inhibition rate of viable cell count is 50% or more. ○: Inhibition rate of viable cell count is 30 or more and less than 50%. ×: Inhibition rate of viable cell count is less than 30%.

[0079] <Durability> The other of the prepared test pieces was placed in a 1 L beaker. Next, 500 mL of tap water (an amount sufficient to immerse the entire test piece) and a stir bar were placed in the 1 L beaker, and the stir bar was stirred at 500 rpm (water treatment). Each test piece with water treatment times of 1 minute, 2 minutes, 3 minutes, 4 minutes, and 5 minutes was dried at room temperature to obtain a test piece after water treatment. Next, 0.4 mL of Rhodotorula dispersion (10 2 cfu / mL) was inoculated onto the test piece after water treatment and cultured at 25°C and 90% RH for 4 days. The number of colonies after culture was counted and the viable cell count was measured. The persistence rate of the control effect was determined by the following formula (s2), and among the test pieces after water treatment with a persistence rate of 50% or more, the longest water treatment time (persistence time) was evaluated according to the following evaluation criteria. For example, if the persistence rate is 50% or more for the test pieces after water treatment with water treatment times of 1 to 4 minutes and less than 50% for the test piece after water treatment with a water treatment time of 5 minutes, the persistence time is 4 minutes. If the persistence rate is less than 50% for all test pieces with water treatment times of 1 to 5 minutes, the persistence time is less than 1 minute. The longer the 50% water treatment time, the better the durability. Note that the "viable cell count of the test piece without water treatment" in formula (s2) is the viable cell count of the test piece in the evaluation of the "initial control effect".

[0080] Persistence rate of control effect (%) = {1 - (number of viable bacteria on the test piece after water treatment) / (number of viable bacteria on the test piece without water treatment)} × 100 ···(s2)

[0081] ≪Evaluation Criteria≫ ○○○: The duration was 5 minutes. ○○: The duration was 4 minutes. ○: The duration was 2 or 3 minutes. ×: The duration was 1 minute or less.

[0082] (Examples 1 to 32, Comparative Examples 1 to 9) According to the compositions shown in Tables 1 to 5, the fumigant compositions of each example were prepared. In the table, "-" for the blending amount indicates that it was not blended. The "balance" of clay is the amount such that the total mass of the fumigant composition is 100% by mass. Under the condition of 25°C, according to the compositions shown in the table, after stirring and mixing each component with a kneader (manufactured by Moriya Co., Ltd., "S5-2G type"), 10 to 20 parts by mass of water was added to make the total amount of the composition 100 parts by mass and mixed to obtain a mixture. The obtained mixture was granulated using a pre-extrusion granulator (manufactured by Fuji Paudal Co., Ltd., "EXK-1") with a die having an opening diameter of 3 mm to obtain a granulated product. The obtained granulated product was cut to a length of 2 to 5 mm by a flash mill (manufactured by Fuji Paudal Co., Ltd., "FL300") and dried for 2 hours by a dryer (manufactured by Alp Co., Ltd., "RT-120HL") set at 70°C to obtain a granular fumigant composition. A fumigation device having the same configuration as the indirect heating type fumigation device 210 shown in Fig. 1 was manufactured by the following procedure. Calcium oxide (trade name: CAg, manufactured by Yoshizawa Lime Industry Co., Ltd.) as a heating agent was filled in an amount of 56 g in the heating part of a tin can (diameter 52 mm × height 67 mm) used for "Look Plus Bathtub Mildew Prevention Smoke Agent" manufactured by Lion Corporation, a dedicated bottom cover was attached, and after accommodating 5.0 g of the fumigant composition of each example in the inner container, the lid was attached to obtain a fumigation device for each example. Using the fumigation device of each example, the initial control effect and persistence were evaluated, and the results are shown in the table.

[0083] (Example 33, Comparative Examples 10 to 11) According to the composition shown in the table, a total amount injection aerosol composition was prepared. In the table, the "balance" of ethanol is the amount such that the total mass of the total amount injection aerosol composition is 100% by mass. (A) component, (B) component, and ethanol were mixed according to the composition in the table to prepare a chemical solution. The obtained chemical solution was placed in a total amount injection aerosol container, and then the (C2) component was filled into the total amount injection aerosol container and sealed. Thereafter, a nozzle cap was attached to produce a total amount injection aerosol device. The total amount of the contents used for filling the total amount injection aerosol container was set to 15 g. Using the total amount injection aerosol devices of each example, the initial control effect and persistence were evaluated, and the results are shown in the table.

[0084]

Table 1

[0085]

Table 2

[0086]

Table 3

[0087]

Table 4

[0088]

Table 5

[0089] As shown in the table, in Examples 1 to 33, the evaluation of persistence was "○" to "○○○", and the evaluation of the initial control effect was "○" or "○○". In Comparative Examples 1 to 4 containing only the (A2) component as the (A) component, the evaluation of persistence or the evaluation of the initial control effect was "×". In Comparative Example 5 where the B / A ratio is 3.50, Comparative Example 10, and Comparative Example 9 containing component (B') instead of component (B), the evaluation of persistence was "×". In Comparative Example 6 where the B / A ratio is 12.31 and Comparative Example 11, the evaluation of the initial control effect was "×". In Comparative Example 7 where the blending amount of component (B) is 5%, the evaluation of persistence was "×". In Comparative Example 8 where the blending amount of component (B) is 18.6%, the evaluation of the initial control effect was "×". From the above results, it was confirmed that by applying the present invention, excellent control effects and excellent persistence can be achieved.

Explanation of Signs

[0090] 20 Total amount injection type aerosol container 210 Indirect heating type fumigation device

Claims

1. A self-spraying space treatment agent composition comprising: Component (A): a metal support (A1) in which the supported amount of at least one metal of silver and copper is 4% by mass or more; and Component (B): a nonionic surfactant. The content of the component (B) is 7 to 16% by mass based on the total mass of the self-spraying space treatment agent composition. A self-spraying space treatment agent composition, which is the ratio of the content of the component (B) to the content of the component (A), and the mass ratio represented by the component (B) / the component (A) is 4 to 12.

2. The self-spraying space treatment agent composition according to claim 1, wherein the component (B) is a copolymer type nonionic surfactant of oxyethylene and oxypropylene.

3. The self-spraying space treatment agent composition according to claim 1, further comprising Component (C1): an organic foaming agent.

4. The self-spraying space treatment agent composition according to claim 1, further comprising Component (C2): a propellant.

5. A self-spraying space treatment device having the self-spraying space treatment agent composition according to any one of claims 1 to 4.

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