Fumigant composition and antifungal fumigation device

Abstract

To provide a composition for smoking agent capable of having an enhanced adhesion and stagnation effect for improving the anti-fungal effect particularly in a moist space, while a conventional composition for smoking agent containing a nonionic surfactant which is hardly volatilized by smoking has insufficient adhesion and stagnation effect due to insufficient amount of active ingredients adhering to the surface treated by smoking, and to provide an anti-fungal smoking unit.SOLUTION: A composition for smoking agent includes a component (A): organic foaming agent, a component (B): nonionic surfactant, a component (C): cationic polymer, and a component (D): microbial control agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fumigant composition and an antifungal fumigation device. [Background technology]

[0002] A humid space such as a bathroom is an environment where microorganisms such as bacteria and mold are likely to grow. In order to suppress the growth of bacteria, mold, and the like, it is common to treat the inside of a closed space with a fumigant composition containing an active ingredient such as a fungicide. In a bathroom or the like, water flows frequently, so that the active ingredient attached to the wall or floor surface is easily washed away by the water. For this reason, it is required that the fumigant composition has an effect of retaining the active ingredient on the treated surface such as the wall or floor surface (adhesion retention effect).

[0003] For example, Patent Document 1 proposes a fumigant composition containing a copolymerized nonionic surfactant of oxypropylene and oxyethylene. According to the invention of Patent Document 1, it is intended to improve the adhesion retention effect and the durability of the antifungal effect (antifungal sustained effect). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Republished WO2015 / 159816 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the copolymerized nonionic surfactant of oxypropylene and oxyethylene has a problem that it is difficult to volatilize by fumigation. Therefore, in the invention of Patent Document 1, the amount of the active ingredient attached to the treated surface is insufficient, and sufficient adhesion and retention effect is not obtained.

[0006] Therefore, an object of the present invention is to provide a fumigant composition and an anti-fungal fumigation device that can enhance the adhesion and retention effect and further improve the anti-fungal effect, particularly the sustained anti-fungal effect in humid spaces. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] (A) component: an organic foaming agent, (B) component: a nonionic surfactant; Component (C): a cationic polymer, (D) Component: A fumigant composition comprising a microbial control agent. [2] The fumigation composition described in [1], wherein the (B) component contains a copolymerized nonionic surfactant of oxypropylene and oxyethylene. [3] The fumigant composition according to [1] or [2], wherein the component (C) comprises a cationic polysaccharide. [4] The fumigant composition according to any one of [1] to [3], wherein the content of the component (C) is 3 to 20 mass% relative to the total mass. [5] The fumigant composition according to any one of [1] to [4], wherein the component (D) contains silver or a silver compound. [6] The fumigant composition according to any one of [1] to [5], wherein the mass ratio of the (B) component to the (C) component is 0.3 to 4.0.

[0008] [7] A housing having a cylindrical body, a bottom, and a lid; A heating unit in which a heat generating agent is accommodated in the housing; A metal fumigant container is provided in the housing and positioned above the heating unit, [1]-[6]. An antifungal fumigation device comprising a fumigation agent container filled with the fumigation agent composition according to any one of [1] to [6]. Effect of the Invention

[0009] The fumigant composition and anti-fungal fumigation device of the present invention can enhance the adhesion and retention effect, and can further improve the anti-fungal effect, particularly the sustained anti-fungal effect in humid spaces. [Brief description of the drawings]

[0010] [Figure 1] 1 is a cross-sectional view of an anti-mold fumigation device according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a perspective view of an evaluation chamber used in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] <Fumigant composition> The fumigant composition of the present invention is a composition containing component (A), component (B), component (C) and component (D). The fumigant composition of the present invention can exhibit microbial suppression effects such as antibacterial, disinfecting, bactericidal, antifungal, anti-mold, etc. In this specification, the term "microorganism" includes bacteria, fungi, molds, etc.

[0012] <Component (A)> Component (A) is an organic foaming agent that decomposes when heated to generate a large amount of heat and generate carbon dioxide gas, nitrogen gas, etc. (hereinafter collectively referred to as foaming gas), thereby turning the components contained in the fumigant composition into smoke and volatilizing them. Examples of the component (A) include azodicarbonamide, p,p'-oxybis(benzenesulfonylhydrazide), N,N'-dinitrosopentamethylenetetramine, azobisisobutyronitrile, etc. Among these, azodicarbonamide is preferred from the viewpoints of decomposition temperature, amount of foaming gas generated, etc. These components (A) may be used alone or in combination of two or more.

[0013] The content of the (A) component can be determined taking into consideration the type of the (A) component and the types of other components. The content of the (A) component is, for example, preferably 55 to 74 mass%, more preferably 60 to 74 mass%, based on the total mass of the fumigant composition. When the (A) component content is equal to or greater than the lower limit, the (B) component, which is difficult to turn into smoke, can be efficiently turned into smoke and easily evaporated. When the (A) component content is equal to or less than the upper limit, the amount of decomposition product of the (A) component scattered in the air is reduced, making it less likely to contaminate the target space.

[0014] <(B) component> Component (B) is a nonionic surfactant. By containing component (B), the fumigant composition can retain component (D) that has been volatilized by the fumigation on the treated surface, thereby enhancing the adhesion and retention effect. Examples of component (B) 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, etc. Examples of 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, copolymerized nonionic surfactants of oxypropylene and oxyethylene, etc. These components (B) may be used alone or in combination of two or more.

[0015] As component (B), a copolymer type nonionic surfactant of oxypropylene and oxyethylene is preferred because it has a superior adhesion retention effect. Examples of the copolymerized nonionic surfactant of oxypropylene and oxyethylene include a compound represented by the following formula (b1) and a compound represented by the following formula (b2). The compound represented by the following formula (b1) is an EO-PO-EO type nonionic surfactant in which PO (propylene oxide) is sandwiched between EO (ethylene oxide). The compound represented by the following formula (b2) is a PO-EO-PO type nonionic surfactant in which EO is sandwiched between PO. R 1 -O-(EO) a -(PO) b -(EO) c -R 2 (b1) R 1 -O-(PO) d -(EO) e-(PO) f -R 2 (b2)

[0016] In formula (b1) and formula (b2), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and it is preferable that both are a hydrogen atom.

[0017] In formula (b1), a represents the average number of repetitions of EO (average number of moles added), and is preferably a number from 5 to 150, and more preferably a number from 10 to 100. b represents the average repeat number of PO (average number of moles added), and is preferably a number from 5 to 250, and more preferably a number from 10 to 60. c represents the average number of repetitions of EO (average number of moles added), and is preferably a number from 5 to 150, and more preferably a number from 10 to 100. In addition, a+b+c is preferably a number from 20 to 500. Commercially available EO-PO-EO type nonionic surfactants include, for example, the product names "Pluronic (registered trademark) PE6400 (manufactured by BASF Japan Ltd.)" and "Pluronic (registered trademark) PE6800 (manufactured by BASF Japan Ltd.)".

[0018] In the formula (b2), d represents the average repeat number of PO (average number of moles added), and is preferably a number from 5 to 150, and more preferably a number from 10 to 30. e represents the average number of repetitions of EO (average number of moles added), and is preferably a number from 5 to 250, and more preferably a number from 5 to 30. f represents the average repeat number of PO (average number of moles added), and is preferably a number from 5 to 150, and more preferably a number from 10 to 30. Moreover, d+e+f is preferably a number from 20 to 500. Commercially available PO-EO-PO type nonionic surfactants include, for example, those sold under the trade names "Pluronic (registered trademark) RPE1740 (manufactured by BASF Japan Ltd.)," "Pluronic (registered trademark) RPE2525 (manufactured by BASF Japan Ltd.)," "ADEKA (registered trademark) Pluronic (registered trademark) 17R-3 (manufactured by ADEKA Corporation)," "ADEKA (registered trademark) Pluronic (registered trademark) 17R-4 (manufactured by ADEKA Corporation)," and "ADEKA (registered trademark) Pluronic (registered trademark) 31R-1 (manufactured by ADEKA Corporation)."

[0019] As the copolymer type nonionic surfactant of oxypropylene and oxyethylene, a PO-EO-PO type nonionic surfactant is more preferred because it has a superior antifungal effect and a sustained antifungal effect.

[0020] The content of component (B) is, for example, preferably 6 to 20 mass%, more preferably 6 to 18 mass%, and even more preferably 8 to 15 mass%, based on the total mass of the fumigant composition. When the content of component (B) is equal to or greater than the lower limit, the antifungal effect can be further enhanced. When the content of component (B) is equal to or less than the upper limit, the volatilization rate of the fumigant composition can be further enhanced.

[0021] <(C) component> The component (C) is a cationic polymer. In this specification, the term "cationic polymer" refers to a polymer compound (a compound having a molecular weight of 10,000 or more) that has cationic surface activity (cationicity). By including the (C) component in the fumigant composition, the volatilization rate of the fumigant composition can be further increased. By improving the volatilization rate of the fumigant composition, the amount of volatilization of the (B) component is increased, and the antifungal effect can be further improved. It is believed that the volatilization rate of the fumigant composition is improved by the fumigation process in which the (B) component, which is difficult to volatilize, is adsorbed on the (C) component, which is easily volatilized by the fumigation process. By improving the volatilization rate of the fumigant composition, the amount of volatilization of the (B) component increases, and the amount of the (B) component that adheres to the treated surface increases. This further enhances the adhesion and retention effect.

[0022] Examples of the component (C) include cationic polysaccharides such as cationic cellulose, cationic guar gum, cationic starch, polydiallyldimethylammonium chloride, cationic polyvinyl alcohol, etc. As the component (C), cationic polysaccharides are preferred because of their excellent adsorption ability for the component (B), and cationic cellulose is more preferred. As used herein, the term "polysaccharide" refers to a sugar that produces two or more monosaccharides upon hydrolysis. These components (C) may be used alone or in combination of two or more.

[0023] Examples of cationic cellulose include compounds in which one or two of glycidyl trimethyl ammonium chloride and glycidyl dimethyl dodecyl ammonium chloride are added to hydroxyethyl cellulose. Among these, from the viewpoint of improving the sustained antifungal effect by improving the volatilization rate of the (B) component, compounds having a constitutional unit represented by the following formula (c1) and compounds having a constitutional unit represented by the following formula (c2) are preferred.

[0024] [ka]

[0025] [ka]

[0026] In formula (c1), s and t are the average number of moles of oxyethylene groups added, and u is the average number of moles of glycidyltrimethylammonium chloride added. The mass average molecular weight of the compound having the constitutional unit represented by formula (c1) is 10,000 to 10 million.

[0027] In formula (c2), v and w are the average number of moles of oxyethylene groups added, x is the average number of moles of glycidyltrimethylammonium chloride added, and y is the average number of moles of glycidyldimethyldodecylammonium chloride added. The mass average molecular weight of the compound having the constitutional unit represented by formula (c2) is 10,000 to 10 million.

[0028] Commercially available compounds having a structural unit represented by formula (c1) include, for example, products under the trade name "SUPRACARE212 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Co.)", "SUPRACARE240 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Co.)", "SUPRACARE241 (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Co.)", "UCARE JR125 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Co.)", "UCARE JR400 (quaternary nitrogen content 1.9% by mass, manufactured by Dow Chemical Co.)", "UCARE Examples of such products include "LR30M (quaternary nitrogen content 1.0% by mass, manufactured by Dow Chemical Co.)", "Catinal HC-100 (quaternary nitrogen content 1.5% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", "Catinal HC-200 (quaternary nitrogen content 1.5% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", "Catinal LC-100 (quaternary nitrogen content 1.0% by mass, manufactured by Toho Chemical Industry Co., Ltd.)", and "Catinal LC-200 (quaternary nitrogen content 1.0% by mass, manufactured by Toho Chemical Industry Co., Ltd.)".

[0029] Commercially available compounds having a constitutional unit represented by formula (c2) include, for example, products under the trade name "SoftCAT SL-5 (quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co.)", "SoftCAT SL-30 (quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co.)", "SoftCAT SL-60 (quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co.)", "SoftCAT SL-100 (quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co.)", "SoftCAT SX-400X (quaternary nitrogen content 2.1 mass%, manufactured by Dow Chemical Co.)", "SoftCAT SX-1300X (quaternary nitrogen content 2.1 mass%, manufactured by Dow Chemical Co.)", "SoftCAT SX-400H (quaternary nitrogen content: 2.1% by mass, manufactured by The Dow Chemical Company) and the like.

[0030] Among these, from the viewpoint of improving the sustained antifungal effect, "SUPRACARE212", "SUPRACARE241" and "SoftCAT SL-100" are preferred, and "SUPRACARE212" and "SUPRACARE241" are more preferred.

[0031] Cationic cellulose improves the volatilization rate of the fumigant composition by volatilizing the component (B) together with the component (B) in an adsorbed state. However, if the component (B) is excessively adsorbed to the cationic cellulose, the cationic cellulose becomes too heavy, and the volatilization rate decreases. It is believed that by adsorbing an appropriate amount of the component (B), the cationic cellulose can efficiently volatilize the fumigant composition without the cationic cellulose becoming excessively heavy.

[0032] The degree of cationization of the compound having the constitutional unit represented by formula (c1) is preferably 1.9 mass% or less, and more preferably 1.0 mass% or less. When the degree of cationization is equal to or less than the upper limit, the volatilization rate of the (B) component is increased. The "degree of cationization" herein refers to the content (mass %) of nitrogen atoms derived from the cationizing agent in the molecules of component (C), i.e., the content of nitrogen atoms relative to the total mass of component (C). The degree of cationization of component (C) is calculated based on the specified chemical structure. When the chemical structure of component (C) is not specified, such as when the ratio of any monomer in component (C) is unknown, the degree of cationization of component (C) is calculated from the experimentally determined nitrogen content. The nitrogen content in component (C) can be measured, for example, by the Kjeldahl method.

[0033] An example of the cationic guar gum is O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride. Commercially available cationized guar gum products include, for example, trade names "JAGUAR EXCEL (manufactured by Sansho Co., Ltd.)", "JAGUAR C-14S (manufactured by Sansho Co., Ltd.)", "JAGUAR C-500 (manufactured by Sansho Co., Ltd.)", "Catinal CG-100 (manufactured by Toho Chemical Industry Co., Ltd.)", "Catinal CG-100S (manufactured by Toho Chemical Industry Co., Ltd.)", "Catinal CG-100LD (manufactured by Toho Chemical Industry Co., Ltd.)", and "Guarsafe JK140 (manufactured by JINGKIN CHEMISTRY COMPANY)".

[0034] An example of the cationic starch is hydroxypropyltrimonium starch chloride. Commercially available cationic starch products include, for example, trade names "Sensomer CI-50 (manufactured by Lubrizol Nippon Co., Ltd.)", "DOCSTARCH CP (manufactured by DOC JAPAN Co., Ltd.)", and "DOCSTARCH CP Plus (manufactured by DOC JAPAN Co., Ltd.)".

[0035] The content of component (C) is, for example, preferably 3 to 20 mass%, more preferably 5 to 20 mass%, and even more preferably 8 to 20 mass%, based on the total mass of the fumigant composition. When the content of component (C) is equal to or greater than the lower limit, the sustained antifungal effect can be further improved. When the content of component (C) is equal to or less than the upper limit, the volatilization rate of the fumigant composition can be further improved.

[0036] The mass ratio of component (B) to component (C) (hereinafter also referred to as "B / C ratio") is preferably 0.3 to 4.0, more preferably 0.3 to 2.6, and even more preferably 0.5 to 1.5. When the B / C ratio is within the above numerical range, the antifungal effect can be further improved.

[0037] <(D) component> Component (D) is a microorganism control agent. Component (D) is an active ingredient that exhibits disinfecting, antibacterial, and antifungal effects. Examples of the component (D) include silver-containing compounds and organic chemicals. As component (D), a compound containing silver is preferred because it has a superior sustained antifungal effect. These components (D) may be used alone or in combination of two or more.

[0038] Examples of compounds containing silver include silver compounds having disinfecting, germicidal, antibacterial, antifungal, antifungal and deodorizing effects as an active ingredient, such as silver oxide; inorganic silver salts such as silver chloride, silver nitrate, silver sulfate, silver carbonate and silver sulfonate; and organic silver salts such as silver formate and silver acetate. As the compound containing silver, a support in which the above-mentioned silver compound is supported on a substance (hereinafter also referred to as a "support") such as zeolite, silica gel, low molecular weight glass, calcium phosphate, silicate, titanium oxide, etc., may be used. Examples of the support include zeolite-based antibacterial agents, silica gel-based antibacterial agents, titanium oxide-based antibacterial agents, and silicate-based antibacterial agents, each supporting a silver compound such as simple silver, silver oxide, inorganic silver salt, or organic silver salt. Among these, the silver-containing compound is preferably simple silver, inorganic silver salts such as silver oxide and silver nitrate, or a support in which these are supported on a carrier, and more preferably a zeolite-based antibacterial agent. The silver-containing compound may be used alone or in combination of two or more kinds.

[0039] Examples of organic agents include 3-methyl-4-isopropylphenol (IPMP), 3-iodo-2-propynyl butylcarbamate (IPBC), o-phenylphenol (OPP), sodium benzoate, glutaraldehyde, polyhexamethylene biguanidine hydrochloride, and the like.

[0040] The content of the (D) component is, for example, preferably 1.5 to 8 mass%, more preferably 1.5 to 5 mass%, and even more preferably 3 to 5 mass%, based on the total mass of the fumigant composition. When the content of the (D) component is equal to or more than the above lower limit, the antifungal effect and the antifungal sustaining effect can be further improved. When the content of the (D) component is equal to or less than the above upper limit, the antifungal sustaining effect can be further improved.

[0041] <Optional ingredients> The fumigant composition of the present embodiment may contain other components (optional components) in addition to the components (A), (B), (C) and (D). Optional components include additives that can be used in conventionally known fumigant compositions, such as binders, excipients, heat generating assistants, stabilizers, efficacy enhancers, antioxidants, fragrances, and solvents. These optional components may be used alone or in combination of two or more.

[0042] Examples of binders include cellulose-based compounds, starch-based compounds, natural product-based compounds, and synthetic polymer-based compounds. Examples of the cellulose compounds include methyl cellulose, ethyl cellulose, carboxymethyl cellulose and its calcium salts and sodium salts, hydroxymethyl cellulose, hydroxypropyl methyl cellulose (HPMC), hydroxypropyl cellulose, and the like. Examples of starch-based compounds include starch, pregelatinized starch, dextrin, hydroxypropyl starch, and carboxymethyl starch sodium salt. Examples of natural compounds include gum arabic, sodium alginate, tragacanth, and gelatin. Examples of synthetic polymer compounds include polyvinyl alcohol, polyvinylpyrrolidone, and sodium polyacrylate.

[0043] Examples of excipients include inorganic minerals, etc. Examples of inorganic minerals include clay, kaolin, talc, quartz, and rock crystal. Examples of the heat generating assistant include zinc oxide, calcium phosphate, and melamine. Examples of the stabilizer include butylhydroxyanisole, propyl gallate (propyl-3,4,5-trihydroxybenzoate), epoxy compounds, etc. Examples of the epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, etc. Examples of potency enhancers include piperonyl butoxide (5-[2-(2-butoxyethoxy)ethoxymethyl]-6-propyl-1,3-benzodioxole), S-421 (di(2,3,3,3-tetrachloropropyl)ether), and the like. Examples of the antioxidant include dibutylhydroxytoluene (BHT) and tocopherol. The flavoring agent includes various flavors and the like. Examples of the solvent include water and monohydric alcohols. Examples of the monohydric alcohols include ethanol, propanol, and butanol.

[0044] When the fumigant composition contains an optional component, the content of the optional component is, for example, preferably 5 to 19 mass%, more preferably 5 to 17 mass%, and even more preferably 5 to 14 mass%, relative to the total mass of the fumigant composition. When the content of the optional component is equal to or greater than the above lower limit, the fumigant composition can be imparted with physical properties based on the additive. When the content of the optional component is equal to or less than the above upper limit, the sustained antifungal effect can be further improved. The combined amount of components (A), (B), (C) and (D) and these optional components does not exceed 100% by mass, with the total mass of the fumigant composition being 100% by mass.

[0045] <Method for producing fumigant composition> The fumigant composition of the present embodiment can be obtained by mixing component (A), component (B), component (C), component (D), and, if necessary, optional components. The fumigant composition of the present embodiment is prepared as a solid preparation such as a powder, granules, tablet or the like. As a method for producing the fumigant composition, a known method is used depending on the desired formulation. For example, when a granular preparation is produced, a known method for producing granulated material, such as extrusion granulation, compression granulation, stirring granulation, rolling granulation, fluidized bed granulation, etc., is used.

[0046] A specific example of a manufacturing method using extrusion granulation is a method in which the components of the fumigant composition are mixed in a kneader or the like, an appropriate amount of water is added as necessary, and the resulting mixture is granulated in a forward extrusion or horizontal extrusion granulator using a die having a desired opening size. The resulting granules may be further cut into a desired size using a cutter or the like, and dried to remove moisture.

[0047] The drying method may be, for example, a heat drying method using a conventionally known dryer. The drying temperature is not particularly limited, but is preferably 50 to 80° C. When the drying temperature is equal to or higher than the lower limit, the moisture content in the fumigant composition can be suppressed. When the drying temperature is equal to or lower than the upper limit, decomposition of the components in the fumigant composition can be suppressed. The drying time is appropriately determined depending on the drying temperature. The moisture content of the fumigant composition after drying is not particularly limited, but is, for example, preferably 5% by mass or less, more preferably 2% by mass or less, and may be 0% by mass, relative to the total mass of the fumigant composition. When the moisture content of the fumigant composition is equal to or less than the above upper limit, the volatilization rate of the fumigant composition can be further increased. The moisture content can be measured, for example, by grinding the dried fumigant composition and measuring it with a moisture meter at 105° C. for 20 minutes. An example of the moisture meter is the moisture meter “MOC-120H” manufactured by Shimadzu Corporation.

[0048] <<Method of using the fumigant composition (fumigation method)>> When the fumigant composition of the present embodiment is heated, the component (A) is thermally decomposed, generating white smoke and scattering each component. The fumigant composition can be smoked at a heating temperature of 200 to 700°C, and preferably 250 to 450°C. The smoking method of this embodiment includes a direct heating method and an indirect heating method. The direct heating method is a method in which an ignition device or the like is used to directly burn the fumigant composition and smoke it. The indirect heating method is a method of fumigation in which the temperature (thermal energy) required for the thermal decomposition of component (A) is supplied via a heat transfer part (e.g., the wall (side wall or bottom wall) of a container containing the fumigant composition, the space within the container, etc.) without burning the fumigant composition. As a smoking method, smoking by indirect heating is preferred because it is simple and has an excellent anti-contamination effect.

[0049] The indirect heating method may be any method capable of supplying heat energy to the fumigant composition up to a temperature at which the (A) component can be thermally decomposed, and may be any known heating method commonly used in indirect heating fumigation methods. For example, a method of contacting a substance (heat generating agent) that generates heat when in contact with water with water and utilizing the reaction heat, a method of mixing a metal with a metal oxide or an oxidizing agent that has a lower ionization tendency than the metal (for example, mixing iron powder with an oxidizing agent (ammonium chlorate, etc.)) and utilizing the heat generated by the oxidation reaction, a method of utilizing the heat generated by an electric force such as a heating wire (for example, a hot plate, etc.), etc. Among these, from the viewpoint of practicality, a method of contacting a heat generating agent with water and utilizing the reaction heat is preferred. Examples of the heat generating agent include calcium oxide, magnesium chloride, aluminum chloride, calcium chloride, iron chloride, etc. Among them, calcium oxide is preferred as the heat generating agent from the viewpoint of practicality.

[0050] <Anti-mold fumigation device> The fumigant composition of the present invention can be filled into a smoking device and used in a known smoking method. The antifungal smoking device is one embodiment of a smoking device that includes a full-volume injection type container that contains a fumigant composition. Hereinafter, an anti-fungal fumigation device according to one embodiment of the present invention will be described with reference to FIG.

[0051] As shown in Fig. 1, anti-fungal smoking device 10 comprises housing 12, heating section 20 provided inside housing 12, and fumigating agent section 32 provided inside housing 12. Housing 12 is composed of a substantially cylindrical main body 14, a bottom section 16, and a lid section 18 provided on the upper part of main body 14. A fumigating agent container 30 is provided within housing 12, and a fumigating agent composition is filled in fumigating agent container 30 to form fumigating agent section 32. Fumigating agent container 30 is located above heating section 20. Anti-fungal smoking device 10 is an example of an indirect heating type smoking device.

[0052] The lid portion 18 has through holes, and examples of the material include a mesh, a punched metal, a lattice-shaped frame, etc. Examples of the material of the lid portion 18 include metal, ceramic, etc. The material of the main body 14 is the same as that of the lid portion 18 .

[0053] The fumigant container 30 functions as a container for filling the fumigant section 32, and also functions as a heat transfer section for transferring thermal energy generated in the heating section 20 to the fumigant section 32. The fumigant container 30 may be, for example, a metal container.

[0054] Heating section 20 is not particularly limited, and can be appropriately determined in consideration of the amount of heat required to smoke fumigation agent section 32. Heating section 20 is preferably formed by filling it with a heat generating agent, and particularly preferably filled with calcium oxide. Heating section 20 may also be formed by filling it with iron powder and an oxidizing agent separated by a partition material, or may be formed by filling it with a metal and a metal oxide or an oxidizing agent having a smaller ionization tendency than the metal, separated by a partition material.

[0055] The bottom 16 may be appropriately determined depending on the mechanism of the heating unit 20. For example, when the heating unit 20 is composed of a heat generating agent (calcium oxide, etc.), a nonwoven fabric, a metal mesh, etc. may be used for the bottom 16. By making the bottom 16 from a nonwoven fabric or a metal mesh, water can be allowed to permeate the heating unit 20 from the bottom 16 to generate reaction heat and heat the fumigant composition.

[0056] A fumigation method using the anti-fungal fumigation device 10 will be described. First, the anti-mold fumigation device 10 is installed in the target space. Next, the heating unit 20 is made to generate heat according to the mechanism of the heating unit 20. For example, when the heating unit 20 is filled with calcium oxide, the bottom 16 is immersed in water. As a result, the water seeping in from the bottom 16 reacts with the calcium oxide in the heating unit 20, generating heat of about 200 to 450°C. The heat generated by the reaction of the water seeping in from bottom 16 with calcium oxide in heating section 20 is transferred to fumigant section 32 via the side and bottom walls of fumigant container 30, causing the temperature of fumigant section 32 to rise, causing component (A) to thermally decompose and generate carbon dioxide, which in turn generates steam of components (B) to (D) and the carbon dioxide generated by thermal decomposition of component (A). Components (B) to (D) pass through the through-holes of lid section 18 together with the generated steam with great force, and components (B), (C) and (D) are diffused into the target space, thereby achieving a microbial suppression effect. In this way, fumigation can be easily performed by using antifungal fumigation device 10.

[0057] The target space is not particularly limited, and examples thereof include a bathroom, a living room, a closet, a toilet, etc.

[0058] The amount of the fumigant composition of the present embodiment to be used may be appropriately determined according to the volume of the space in which the fumigation treatment is to be carried out. 3 The amount of the fumigant composition used is preferably 0.1 to 2.4 g, and more preferably 0.4 to 2.0 g per unit area. When the amount of the fumigant composition used is equal to or more than the lower limit, a sufficient antifungal effect is easily obtained. When the amount of the fumigant composition used is equal to or less than the upper limit, costs can be reduced and the dispersion rate of the active ingredient can be easily maintained. The fumigation treatment time (the time from the start of fumigation to the release of the sealing of the target space) is not particularly limited, but is preferably 30 to 120 minutes, more preferably 60 to 90 minutes. When the fumigation treatment time is equal to or more than the above lower limit, the antifungal effect is likely to be sufficiently obtained. When the fumigation treatment time is equal to or less than the above upper limit, the efficiency of the fumigation treatment is likely to be improved. EXAMPLES

[0059] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. The raw materials used in this example are as follows:

[0060] [Raw materials used] <Component (A)> A-1: Azodicarbonamide, trade name "Daiblo (registered trademark) AC.2040 (C)", manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

[0061] <(B) component> B-1: PO-EO-PO type nonionic surfactant 1, product name "Pluronic (registered trademark) RPE1740", manufactured by BASF Japan Ltd. B-2: PO-EO-PO type nonionic surfactant 2, product name "Pluronic (registered trademark) RPE2525", manufactured by BASF Japan Ltd. B-3: EO-PO-EO type nonionic surfactant 1, product name "Pluronic (registered trademark) PE6400", manufactured by BASF Japan Ltd. B-4: EO-PO-EO type nonionic surfactant 2, product name "Pluronic (registered trademark) PE6800", manufactured by BASF Japan Ltd. B-5: Sorbitan fatty acid ester, product name "Emazol (registered trademark) O-10V", manufactured by Kao Corporation. B-6: Glycerin fatty acid ester, product name "Poem (registered trademark) DL-100", manufactured by Riken Vitamin Co., Ltd.

[0062] <(C) component> C-1: Cationic cellulose 1, product name "SUPRACARE241", quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co. C-2: Cationic cellulose 2, product name "SUPRACARE212", quaternary nitrogen content 1.9 mass%, manufactured by The Dow Chemical Company. C-3: Cationic cellulose 3, product name "SoftCAT SL-5", quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co. C-4: Cationic cellulose 4, product name "SoftCAT SL-30", quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co. C-5: Cationic cellulose 5, product name "SoftCAT SL-100", quaternary nitrogen content 1.0 mass%, manufactured by Dow Chemical Co. C-6: Cationic guar gum, product name "JAGUAR C-14S", manufactured by Sansho Co., Ltd. C-7: Polydiallyldimethylammonium chloride, trade name "Sharol (registered trademark) DC-902P", manufactured by Daiichi Kogyo Seiyaku Co., Ltd. C-8: Cationic polyvinyl alcohol, trade name "GOHSENEX (registered trademark) K-434", manufactured by Mitsubishi Chemical Corporation.

[0063] <(D) component> D-1: Silver-supported zeolite-based inorganic antibacterial agent, product name "Zeomic (registered trademark) AJ10N", silver content 2.5 mass%, average particle size approximately 2.5 μm, manufactured by Sinanen Zeomic Co., Ltd. D-2: 3-Methyl-4-isopropylphenol (IPMP), product name "4-Isopropyl-3-methylphenol", manufactured by Tokyo Chemical Industry Co., Ltd.

[0064] <Optional ingredients> HPMC: Hydroxypropyl methylcellulose, trade name "Metolose (registered trademark) 60SH-50", manufactured by Shin-Etsu Chemical Co., Ltd. ZnO: Zinc oxide, product name "Japanese Pharmacopoeia Zinc Oxide", average particle size 0.6 μm, true specific gravity 5.6 g / cm 3 (20℃), manufactured by Sakai Chemical Industry Co., Ltd. Clay: Clay, product name "NK-300", SiO2: 75% by mass, Al2O3·2SiO2·2H2O: 25% by mass, manufactured by Showa KDE Co., Ltd. (Other ingredients) Calcium oxide, trade name "CAg", rotary kiln fired product (produced by Kudzu), bulk density 0.80g / cm 3 (20℃), manufactured by Yoshizawa Lime Industry Co., Ltd.

[0065] [Examples 1 to 30, Comparative Examples 1 to 4] <Production of fumigant composition> At room temperature (20°C), the components were mixed in a kneader (S5-2G type, manufactured by Moriyama Co., Ltd.) according to the compositions (mixing ratios) shown in Tables 1 to 6, and then 10 parts by mass of water was added to make a mixture, with the total amount of the composition being 100 parts by mass, and mixed. The mixture obtained was granulated using a pre-extrusion granulator (EXK-1, manufactured by Fuji Paudal Co., Ltd.) with a die having an opening of 3 mm in diameter, to obtain a granulated product. The granulated product obtained was cut into lengths of 2 to 5 mm using a flash mill (FL300, manufactured by Fuji Paudal Co., Ltd.) and dried for 2 hours using a dryer (RT-120HL, manufactured by Alp Co., Ltd.) set at 70°C, to obtain a granular fumigant composition.

[0066] <Preparation of anti-mold smoke device> A fumigation device having the same configuration as the antifungal fumigation device 10 shown in FIG. 1 was produced by the following procedure. The heating part 20 of a tin can (diameter 52 mm x height 67 mm) used in "Look Plus Bath Anti-Mold Fumigation Agent" manufactured by Lion Corporation was filled with 56 g of calcium oxide (product name "CAg", manufactured by Yoshizawa Lime Industry Co., Ltd.) as a heating agent, a dedicated bottom 16 was attached, 5 g of each example of fumigation agent composition was placed in the inner container (fumigation agent container 30), and then the lid 18 was attached to produce the anti-mold fumigation device 10.

[0067] Using the obtained antifungal fumigation device 10, the following evaluations of antifungal effect, antifungal sustaining effect, and adhesion retention effect were carried out. The results are shown in Tables 1 to 6. In the tables, the unit of "mixing ratio" is "mass %" and indicates the amount converted into pure content. In the tables, "-" indicates that the component is not contained. In the tables, "balance" refers to the mixing ratio of clay added so that the total of all components contained in the fumigant composition is 100 mass %.

[0068] <Evaluation of anti-mold effect and evaluation of sustained anti-mold effect> (1) Preparation of samples for evaluating antifungal effect Six 5 cm square plastic plates 120 were attached in a line in one corner of the floor 102 of the sealable evaluation room 100 (L1 = L2 = 1.6 m, H1 = 2.0 m, height from floor surface to ceiling surface: about 2 m) shown in Figure 2. A plastic water supply container 110 containing 23 mL of water was placed in the center of the floor of the evaluation room 100, and the mold-proofing fumigation device 10 prepared according to each example was placed in the plastic water supply container 110, smoking was started, and the evaluation room 100 was sealed. 90 minutes after the start of smoking, the air in the evaluation room 100 was exhausted, and the six 5 cm square plastic plates 120 were collected. Three of the collected 5 cm square plastic plates 120 were placed in a 1 L beaker containing about 1 L of tap water (enough to completely immerse the 5 cm square plastic plates 120) and a stirrer, and after 90 seconds of water treatment while stirring at 500 rpm, the plates were removed and dried at room temperature (20° C.). This was done to simulate the situation in a real home bathroom where water is splashed on the treated surfaces of the floor and walls after the fumigation treatment. Of the six 5 cm square plastic boards 120 collected, the 5 cm square plastic boards 120 after water treatment were designated "Board 1, Board 2, Board 3," and the 5 cm square plastic boards 120 that had not been water treated (before water treatment) were designated "Board 4, Board 5, Board 6."

[0069] (2) Evaluation method Cladosporium cladosporioides HMC1064 (bathroom isolate) cultured on a potato dextrose agar (Difco) slant medium at 25°C for 7 days and potato dextrose liquid medium diluted 50% and sterilized were used to measure the number of bacteria in the bath. 2 Spore solutions of CFU / mL were prepared. 0.1 mL of the spore liquid was inoculated onto plates 1, 2, 3, 4, 5, and 6 prepared in (1), as well as three 5 cm square plastic plates that had not been smoked (hereinafter referred to as plates 7, 8, and 9). Each of plates 1, 2, 3, 4, 5, 6, 7, 8, and 9 inoculated with the spore liquid was covered with a film cut to 40 mm x 40 mm (film described in JIS Z2801:2010 (antibacterial products - antibacterial test method, antibacterial effect)) and cultured for 5 days at 25°C and a relative humidity of 98% or more. After the cultivation, all bacteria were collected from plates 1, 2, 3, 4, 5, 6, 7, 8, and 9, appropriately diluted with physiological saline to a measurable concentration, and inoculated onto potato dextrose agar medium and cultivated at 25° C. for 5 days. The number of colonies formed was then visually counted. From the number of colonies counted and the dilution rate of the spore liquid, the viable bacterial count (CFU / plate) was calculated for each of plates 1, 2, 3, 4, 5, 6, 7, 8, and 9. Under these conditions, the number of viable bacteria recovered from each plate after incubation was 1 x 10 4 ~9×10 5 CFU / plate. The antifungal effect of the plates when exposed to water was evaluated based on the average viable bacterial counts of plates 1, 2, and 3 and the average viable bacterial counts of plates 4, 5, and 6.

[0070] (3) Evaluation formula The mold prevention rate (%) was calculated using the following formulas (i) and (ii) from the average number of live bacteria on boards 1, 2, and 3 (plastic boards after water treatment) (the number of live bacteria on boards 1 to 3), the average number of live bacteria on boards 4, 5, and 6 (plastic boards before water treatment) (the number of live bacteria on boards 4 to 6), and the average number of live bacteria on unsmoked boards 7, 8, and 9 (the number of live bacteria on boards 7 to 9) using the following formulas (i) and (ii). The mold prevention effect was evaluated based on the value of the mold prevention effect persistence rate (%) according to the following criteria. The higher the mold prevention effect persistence rate (%), the better the mold prevention effect is, as it is not reduced even when treated with water (tap water). Antifungal rate after water treatment (%) = {1 - (viable bacteria count on plates 1-3) / (viable bacteria count on plates 7-9)} × 100 (i) Antifungal rate before water treatment (%) = {1 - (viable bacteria count on plates 4-6) / (viable bacteria count on plates 7-9)} × 100 (ii) Duration of antifungal effect (%) = (antifungal rate after water treatment (%)) / (antifungal rate before water treatment (%)) × 100 (iii)

[0071] (4) Judgment criteria ○○○: Anti-mold effect lasts for 80% or more. ○○: The anti-mold effect lasts for more than 65% but less than 80%. ○: The anti-mold effect lasts for 50% or more but less than 65%. ×: The anti-mold effect persists for less than 50%.

[0072] <Evaluation of adhesion retention effect> (1) Evaluation formula <Evaluation of antifungal effect and evaluation of antifungal durability> (1) The antifungal fumigation device 10 used was collected, and 12 hours or more after the start of fumigation, the lid 18 was opened and the residue of the fumigant composition (fumigation residue) was removed. The mass (g) of the removed fumigation residue was measured, and the mass (g) lost was calculated from the mass (g) of the filled fumigant composition. The volatilization rate (%) was calculated from the lost mass (g) and the mass (g) of the filled fumigant composition using the following formula (iv). A higher volatilization rate (%) indicates a more excellent adhesion and retention effect. Volatilization rate (%)={(mass disappeared (g)) / (mass of filled fumigant composition (g))}×100={((mass of filled fumigant composition (g))-(mass of smoke residue (g))) / (mass of filled fumigant composition (g))}×100 (iv)

[0073] (2) Judgment criteria ○○○: Evaporation rate is 70% or more. ○○: Evaporation rate is 65% or more but less than 70%. ○: Evaporation rate is 62% or more but less than 65%. ×: Evaporation rate is less than 62%.

[0074] [Table 1]

[0075] [Table 2]

[0076] [Table 3]

[0077] [Table 4]

[0078] [Table 5]

[0079] [Table 6]

[0080] As shown in Tables 1 to 5, Examples 1 to 30 in which the present invention was applied were evaluated for adhesion and retention effect as "○○○", "○○", or "○", and for anti-mold sustained effect as "○○○", "○○", or "○", confirming that they had excellent adhesion and retention effect and anti-mold sustained effect. In contrast, Comparative Example 1, which did not contain the (C) component, was evaluated as "x" in the adhesion retention effect and the antifungal sustaining effect. Comparative Example 2, which did not contain the (C) component and had an increased content of the (A) component, showed an improved volatilization rate, but was evaluated as "x" in the antifungal sustaining effect. Comparative Example 3, which did not contain the (C) component and had an increased content of the (B) component, showed a decreased volatilization rate and a decreased antifungal sustaining effect. Comparative Example 4, in which a non-cationized polysaccharide (HPMC) was added instead of the (C) component, showed a low volatilization rate and was evaluated as "x" in the antifungal sustaining effect.

[0081] From these results, it was found that according to the present invention, the adhesion and retention effect can be enhanced, and the mold prevention effect, particularly the mold prevention effect in a humid space, can be further improved. [Explanation of symbols]

[0082] 10. Anti-mold fumigation device 12. Chassis 14 Main unit 16 Bottom 18 Lid 20 Heating section 30 Fumigant container 32 Smoke Agents Department 100 Evaluation Room 102 Beds 110 Plastic water container 120 5cm square plastic plate

Claims

1. Component (A): an organic foaming agent; (B) component: a nonionic surfactant; Component (C): a cationic polymer, (D) component: a microbial control agent; The component (C) is at least one selected from the group consisting of cationic polysaccharides, polydiallyldimethylammonium chloride, and cationic polyvinyl alcohol, A fumigant composition, wherein the cationic polysaccharide is cationic cellulose or cationic guar gum.

2. 2. The fumigation composition according to claim 1, wherein the component (B) comprises a copolymerized nonionic surfactant of oxypropylene and oxyethylene.

3. The fumigation composition according to claim 1 or 2, wherein the component (C) comprises the cationic polysaccharide.

4. The fumigant composition according to any one of claims 1 to 3, wherein the content of the (C) component is 3 to 20 mass% relative to the total mass.

5. The fumigant composition according to any one of claims 1 to 4, wherein the component (D) comprises silver or a silver compound.

6. A housing including a cylindrical main body, a bottom and a lid; A heating unit in which a heat generating agent is accommodated in the housing; A metal fumigant container is provided in the housing and positioned above the heating unit, An anti-fungal fumigation device comprising a fumigant container filled with the fumigant composition according to any one of claims 1 to 5.

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