Method for suppressing mold-derived odors, and composition for suppressing mold-derived odors.

Abstract

It suppresses odors caused by mold. [Solution] A method for suppressing mold-derived odors, comprising the step of applying an antimicrobial compound to mold at a concentration below the minimum inhibitory concentration for mold growth.

Description

Technical Field

[0001] The present invention relates to a method for suppressing mold-derived odor and a composition for suppressing mold-derived odor.

Background Art

[0002] Molds are likely to occur and grow in places where there is appropriate moisture, temperature, and nutrients. In highly airtight houses such as condominiums, the indoor environment is prone to moisture accumulation, which provides an environment where molds are likely to occur. Particularly in houses, molds are likely to occur and grow on ceilings, walls, floors, such as in areas around air conditioners, under sinks, in closets, basements, storage rooms, shoe boxes, closets, bathrooms, as well as on washing machines, windows, wallpapers, curtains, mattresses, etc. Furthermore, the occurrence and growth of molds may generate mold-derived odors, which, even if they are faint odors, may become offensive odors that cause discomfort to the occupants. Therefore, attempts have been made to identify the causative substances of the offensive odors and eliminate the discomfort, but the causative substances of mold-derived odors in living spaces have not been fully identified (Patent Document 1). On the other hand, as a countermeasure against mold-derived odors, usually, masking the odor with a strongly scented fragrance is carried out. For example, products such as aromatic deodorants are widely known. However, these cannot eliminate the mold-derived odor components themselves. On the other hand, there are also means of spraying a large amount of fungicides to kill molds, which are the source of mold-derived odors, but there are problems from the perspective of safety, such as chemical residues and irritation to the human body. Under such circumstances, a simple means of eliminating unpleasant mold-derived odors is desired.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In view of the above situation, an object of the present invention is to provide a new technology having an effect of suppressing mold-derived odor.

Means for Solving the Problems

[0005] One aspect of the present invention provides a method for suppressing mold-derived odor, a composition for suppressing mold-derived odor, and an aerosol product containing the composition. As specific aspects, the following aspects [1] to

[12] are provided. [1] A method for suppressing mold-derived odor, comprising a step of applying an antimicrobial compound to mold at a concentration below the minimum growth inhibitory concentration of the mold. [2] The method for suppressing mold-derived odor according to [1], wherein the minimum growth inhibitory concentration is the minimum growth inhibitory volume concentration or the minimum growth inhibitory surface concentration. [3] The method for suppressing mold-derived odor according to [1] or [2], wherein the antimicrobial compound is used at a concentration of 95% or less of the minimum growth inhibitory concentration of the mold. [4] The method for suppressing mold-derived odor according to any one of [1] to [3], wherein the antimicrobial compound is used at a concentration of 0.2% or more of the minimum growth inhibitory concentration of the mold. [5] The method for suppressing mold-derived odor according to any one of [1] to [4], wherein the mold-derived odor is based on one or more selected from the group consisting of 3-methyl-1-butanol and phenylethyl alcohol. [6] The method for suppressing mold-derived odor according to any one of [1] to [5], wherein the mold is one or more selected from the group consisting of the genus Penicillium and the genus Cladosporium. [7] The method for suppressing mold-derived odor according to any one of [1] to [6], wherein the antimicrobial compound is isopropyl methylphenol, 1,4-bis[3,3´-(1-decylpyridinium)methyloxy]butane dibromide, silver ion, benzalkonium chloride, benzalkonium saccharinate, or enilconazole. [8] The aforementioned antimicrobial compound is isopropylmethylphenol, The aforementioned mold belongs to the genus Penicillium, A method for suppressing mold-derived odors according to any one of [1] to [7], wherein the minimum inhibitory volume concentration of isopropylmethylphenol against Penicillium molds is 280 ppm by mass. [9] The aforementioned antimicrobial compound is isopropylmethylphenol, The aforementioned mold belongs to the genus Cladosporium. A method for suppressing mold-derived odors according to any one of [1] to [7], wherein the minimum inhibitory volume concentration of isopropylmethylphenol against Cladosporium molds is 200 ppm by mass.

[10] The mold-derived odor suppression method according to any one of [1] to [9], wherein the mold is mold inside the air conditioner.

[11] A method for suppressing mold-derived odors according to any one of [1] to

[10] , comprising applying an antimicrobial compound to mold using an aerosol product.

[12] A composition for use in a method for suppressing mold-derived odors as described in any of [1] to

[11] . [Effects of the Invention]

[0006] The present invention provides a method for effectively suppressing mold-derived odors by applying an antimicrobial compound, such as a fungicide, at a concentration below the minimum inhibitory concentration for mold growth. A preferred embodiment of the present invention involves applying an antimicrobial compound at a concentration lower than the concentration that completely kills or inhibits the growth of mold, thereby suppressing mold growth and consequently preventing the generation of odors. A preferred embodiment of the present invention provides a novel odor suppression method for suppressing mold-derived odors, and because it can be used at lower concentrations than conventional methods, it can be used safely. [Brief explanation of the drawing]

[0007] [Figure 1] Schematic cross-sectional view of an aerosol product according to one embodiment. [Modes for carrying out the invention]

[0008] The numerical ranges described herein can be any combination of upper and lower limits. For example, if the numerical range is described as "preferably 30 to 100, more preferably 40 to 80," then the ranges of "30 to 80" and "40 to 100" are also included in the numerical range described herein. Similarly, if the numerical range is described as "preferably 30 or more, more preferably 40 or more, and also preferably 100 or less, more preferably 80 or less," then the ranges of "30 to 80" and "40 to 100" are also included in the numerical range described herein.

[0009] 1. Method for suppressing mold-derived odors One embodiment of the present invention is a method for suppressing mold-derived odors, comprising the step of applying an antimicrobial compound to mold at a concentration below the minimum inhibitory concentration for mold growth.

[0010] The molds that cause mold-derived odors and are suppressed by the method of the present invention are those that produce unpleasant odors through their growth and proliferation, and examples include molds belonging to the genera Cladosporium, Penicillium, and Aspergillus.

[0011] The antimicrobial compounds used in the method of the present invention are not particularly limited as long as they are compounds that can suppress mold-derived odors. Examples of antimicrobial compounds include phenolic compounds, cationic surfactant compounds, silver ion-containing compounds, carboxylic acid compounds, azole compounds, glycerol monofatty acid ester compounds, chlorhexidine compounds, silicon compounds, and the like. Examples of phenolic compounds include isopropylmethylphenol (IPMP), carvacrol, thymol, triclosan, methylparaben, ethylparaben, propylparaben, butylparaben, 4-chloro-3,5-dimethylphenol, orthophenylphenol, o-cresol, m-cresol, and p-cresol. Examples of cationic surfactant compounds include benzalkonium salts such as benzalkonium chloride, benzalkonium methosulfate, and benzalkonium organic acid salts (e.g., benzalkonium saccharate), benzethonium salts such as benzethonium chloride, benzethonium methosulfate, and benzethonium organic acid salts, cetylpyridinium salts such as cetylpyridinium chloride, cetylpyridinium methosulfate, and cetylpyridinium organic acid salts, didecyldimethylammonium salts such as didecyldimethylammonium chloride and decyldimethylammonium methosulfate, and dilauryldimethylammonium chloride. Examples of silver ion-containing compounds include dilauryldimethylammonium salts such as dilauryldimethylammonium methosulfate, distearyldimethylammonium salts such as distearyldimethylammonium chloride and distearyldimethylammonium methosulfate, 1,4-bis[3,3'-(1-decylpyridinium)methyloxy]butanedibromide (Hygenia), 1,4-bis[3,3'-(1-decylpyridinium)methyloxy]butanedichloride, and 1,4-bis[3,3'-(1-decylpyridinium)methyloxy]butanedimethosulfate. Examples of silver ion-containing compounds include silver oxide, silver-containing polymers, silver-supported zeolites, silver nanoparticles, silver ions, silver nitrate, and silver sulfide. Examples of carboxylic acid compounds include carboxylic acids such as benzoic acid, salicylic acid, sorbic acid, ethylenediaminetetraacetic acid (EDTA), glycine, alkyldiethylaminoglycine, and polylysine, or their salts.Other antimicrobial compounds include, for example, dehydroacetic acid, chloramine, 3-iodo-2-propyl-N-butylcarbamate (IPBC), phenoxyethanol, biguanide compounds, azole compounds such as tebuconazole and enilconazole (imazalil), glycerin monofatty acid ester compounds such as monolaurin, monocaprin, and monocaprylin, chlorhexidine compounds such as chlorhexidine salts like chlorhexidine gluconate and chlorhexidine hydrochloride, octadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride, dodecyldimethyl(3-triethoxysilylpropyl)ammonium chloride, dodecyldiisopropyl(3-triethoxysilylpropyl)ammonium chloride, tetradecyldimethyl(3-triethoxysilylpropyl)ammonium chloride, and tetradecyldiethyl(3-triethoxysilyl Examples of silicon-based compounds include propyl ammonium chloride, tetradecyl di-n-propyl(3-triethoxysilylpropyl)ammonium chloride, pentadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride, pentadecyl diethyl(3-triethoxysilylpropyl)ammonium chloride, pentadecyl di-n-propyl(3-triethoxysilylpropyl)ammonium chloride, hexadecyldimethyl(3-triethoxysilylpropyl)ammonium chloride, hexadecyl diethyl(3-triethoxysilylpropyl)ammonium chloride, hexadecyl di-n-propyl(3-triethoxysilylpropyl)ammonium chloride, octadecyl diethyl(3-triethoxysilylpropyl)ammonium chloride, and octadecyl di-n-propyl(3-triethoxysilylpropyl)ammonium chloride. These may be a single compound or a mixture of two or more compounds. Among these antimicrobial compounds, phenolic compounds, cationic surfactant compounds, silicon compounds, or combinations thereof are preferred, with isopropylmethylphenol (IPMP) being particularly preferred. Although the detailed mechanism is not fully understood, these components are more easily incorporated into the mold's body during its growth process, thereby suppressing mold-derived odors.

[0012] In the method of the present invention, "minimum inhibitory concentration" refers to the minimum amount of antimicrobial compound required to inhibit the growth of a specific type of mold. A lower minimum inhibitory concentration indicates a stronger inhibitory effect on mold growth by the antimicrobial compound, while a higher minimum inhibitory concentration indicates that a larger amount of antimicrobial compound is required to inhibit mold growth. The minimum inhibitory concentration can be expressed as, for example, the minimum inhibitory volume concentration (mass ppm) and the minimum inhibitory surface concentration (μg / cm³). 2 ) includes. The minimum inhibitory volume concentration of growth in this invention is evaluated using PDA medium containing a predetermined amount of antimicrobial compound. The PDA medium is sterilized by autoclaving. Although the antimicrobial compound is added to the PDA medium after sterilization by autoclaving, it may be added to the PDA medium before sterilization by autoclaving if the antimicrobial compound does not decrease in content due to volatilization or thermal decomposition during sterilization by autoclaving. Using PDA medium sterilized by autoclaving, a dilution series is prepared with different concentrations of the antimicrobial compound, and spores of a specific mold (microorganism) cultured in each medium are collected. The spore count is reduced to 1.8-2.5 × 10⁶ in an aqueous solution of 0.05 w / v% polyoxyethylene (20) sorbitan monooleate (manufactured by Fujifilm Wako Pure Chemical Industries). 6 Prepare a spore solution to a concentration of 1 / mL, inoculate 2 μL of the spore solution into three locations on the culture medium, and incubate at 25°C for 5 days. Evaluate whether or not colony formation is observed on the medium. The concentration of the antimicrobial compound in the medium with the lowest amount of antimicrobial compound among the media in which colony formation was not observed is defined as the minimum inhibitory volume concentration. The minimum inhibitory surface concentration of the present invention is evaluated by the following procedure. First, sterilize the filter paper with ultraviolet light. Then, dilute the antimicrobial compound with a solvent as needed, and drop 2 μL of the diluted solution onto three locations on the filter paper. Allow the dropped filter paper to dry sufficiently, and then attach it to the PDA culture medium. Next, prepare a spore solution of a specific mold (microorganism). This spore solution is prepared using a 0.05 w / v% polyoxyethylene (20) sorbitan monooleate aqueous solution (manufactured by Fujifilm Wako Pure Chemical Industries) to obtain spores with a number of 1.8 to 2.5 × 10⁶. 6 Adjust the concentration to 1 spore / mL. Finally, inoculate 2 μL of this spore solution onto the area of ​​the filter paper where the antimicrobial compound has been dropped. After inoculation, incubate at 25°C for 5 days and visually evaluate whether or not colonies have formed on the filter paper. The lowest concentration of the antimicrobial compound at which no colonies were observed is defined as the minimum inhibitory surface concentration.

[0013] The minimum inhibitory volume concentration for growth according to the present invention is measured by the following procedure. (1) Measurement of the first growth inhibitory volume concentration Dilution series of antimicrobial compounds are prepared at concentrations of 10,000 ppm, 8,000 ppm, 6,000 ppm, 4,000 ppm, 2,000 ppm, 1,000 ppm, 800 ppm, 400 ppm, 200 ppm, and 100 ppm. The lowest concentration that inhibits the growth of the target microorganism (first inhibitory concentration) is then measured. When measuring the first inhibitory concentration, it is not necessary to prepare all of the above dilution series; the boundary between the concentration at which growth was inhibited and the concentration at which growth was not inhibited is identified, and the lowest concentration at which growth inhibition was confirmed is defined as the first inhibitory concentration. For example, if dilution series of 800 ppm by mass and 600 ppm by mass are prepared, and colony formation is not observed in the 800 ppm medium but is observed in the 600 ppm medium, then 800 ppm by mass is the first inhibitory concentration. In measuring the first inhibitory concentration, if the boundary between the concentration at which microbial growth inhibition was confirmed and the concentration at which growth was not confirmed (i.e., growth was confirmed), it is not necessary to prepare all dilution series from 10,000 ppm to 100 ppm. For example, if only 2,000 ppm and 1,000 ppm culture media are prepared, and colony formation is not confirmed in the 2,000 ppm medium but is confirmed in the 1,000 ppm medium, then it is not necessary to prepare culture media at other concentrations to check for colony formation (it is clear that colonies will not form in media above 2,000 ppm, but will form in media below 1,000 ppm). (2) Measurement of the second growth inhibitory volume concentration A dilution series is prepared by decreasing the concentration in 100 ppm increments from the first inhibitory concentration, and the lowest concentration that can inhibit the growth of the target microorganism (second inhibitory concentration) is measured. Specifically, a dilution series is prepared at the first inhibitory concentration, the first inhibitory concentration - 100 ppm, the first inhibitory concentration - 200 ppm, and the first inhibitory concentration - 300 ppm. Growth is observed starting from the highest concentration, and the lowest concentration at which growth inhibition is confirmed is defined as the second inhibitory concentration. For example, if the first inhibitory concentration is 800 ppm, a dilution series of 800 ppm, 700 ppm, and 600 ppm is prepared, and colony formation is not observed in the 800 ppm medium, but colony formation is observed in the 700 ppm medium, then 800 ppm is the second inhibitory concentration. (3) Measurement of minimum inhibitory volume concentration A dilution series is prepared by decreasing the concentration in 20 ppm by mass increments from the second inhibitory concentration, and the lowest concentration that can inhibit the growth of the target microorganism (minimum inhibitory volume concentration) is measured. Specifically, a dilution series is prepared with the second inhibitory concentration, the second inhibitory concentration - 20 ppm by mass, the second inhibitory concentration - 40 ppm by mass, the second inhibitory concentration - 60 ppm by mass, and the second inhibitory concentration - 80 ppm by mass. Growth is observed starting from the highest concentration, and the lowest concentration at which growth inhibition is observed is defined as the minimum inhibitory volume concentration.

[0014] Regarding the minimum growth inhibitory volume concentration, specifically, the minimum growth inhibitory volume concentration of IPMP against Penicillium mold is 280 ppm by mass, and the minimum growth inhibitory volume concentration of IPMP against Cladosporium mold is 200 ppm by mass. The minimum growth inhibitory volume concentrations of 1,4-bis[3,3´-(1-decylpyridinium)methyloxy]butane dibromide (registered trademark "Hygenia", manufactured by Tama Chemical Industry Co., Ltd.), silver ions, benzalkonium chloride, benzalkonium saccharinate, and enilconazole (imazalil) against Penicillium mold and Cladosporium mold are as shown in Table 1. [Table 1]

[0015] The minimum growth inhibitory surface concentration of the present invention is measured by the following procedure. (1) Measurement of the first growth inhibitory surface concentration Dilution series with concentrations of 400 μg / cm 2 , 320 μg / cm 2 , 240 μg / cm 2 , 160 μg / cm 2 , 80 μg / cm 2 , 40 μg / cm 2 , 20 μg / cm 2 , 10 μg / cm 2 are prepared, and the first growth inhibitory surface concentration, which is the lowest concentration capable of inhibiting the growth of the target microorganism, is measured. In the measurement of the first growth inhibitory surface concentration, the boundary between the concentration at which growth was inhibited and the concentration at which growth was not inhibited (growth was confirmed) is confirmed, and the minimum concentration at which growth inhibition was confirmed is taken as the first growth inhibitory surface concentration. For example, when dilution series of 40 μg / cm 2 and 20 μg / cm 2 are prepared, and colony formation could not be confirmed in the medium of 40 μg / cm 2 but colony formation could be confirmed in the medium of 20 μg / cm 2 , the first growth inhibitory surface concentration is 40 μg / cm 2Therefore, if the boundary between the concentration at which microbial growth is inhibited and the concentration at which growth is observed is known, it is not necessary to prepare all dilution series. For example, 40 and 20 μg / cm³. 2 Prepare only the culture medium and add 40 μg / cm³. 2 Colony formation was not observed in the culture medium at 20 μg / cm³. 2 If colonies are formed in the culture medium, there is no need to prepare culture media of other concentrations to confirm colony formation.

[0016] (2) Measurement of the second growth inhibitory surface concentration The first growth-inhibiting surface concentration was 4 μg / cm³. 2 A dilution series is prepared with progressively lower concentrations, and the lowest concentration that inhibits the growth of the target microorganism, known as the second inhibitory surface concentration, is measured. Specifically, the first inhibitory surface concentration and the first inhibitory surface concentration -4 μg / cm³ are measured. 2 , 1st growth inhibition surface concentration -8 μg / cm³ 2 , and the first growth inhibition surface concentration -12 μg / cm³ 2 A dilution series is prepared, and growth is observed starting from the highest concentration. The lowest concentration at which growth inhibition is confirmed is defined as the second growth-inhibiting surface concentration. For example, if the first growth-inhibiting surface concentration is 40 μg / cm³ 2 In this case, 36 μg / cm³ 2 , 32 μg / cm³ 2 , 28 μg / cm³ 2 Prepare a dilution series of 36 μg / cm³. 2 Colony formation was not observed in the culture medium, but at 32 μg / cm³ 2 If colony formation is observed in the culture medium, use 36 μg / cm³. 2 This becomes the second growth-inhibiting surface concentration.

[0017] (3) Measurement of the minimum inhibitory surface concentration: 0.8 μg / cm³ from the second inhibitory surface concentration. 2 A dilution series is prepared with progressively lower concentrations, and the minimum inhibitory surface concentration (MST), which is the lowest concentration that can inhibit the growth of the target microorganism, is measured. Specifically, the second inhibitory surface concentration and the second inhibitory surface concentration -0.8 μg / cm³ are measured. 2 Second growth inhibition surface concentration -1.6 μg / cm³ 2Second growth inhibition surface concentration -2.4 μg / cm³ 2 , and the second growth inhibition surface concentration was -3.2 μg / cm³. 2 A dilution series was prepared, and growth was observed starting from the highest concentration. The lowest concentration at which growth inhibition was confirmed was defined as the minimum surface concentration for growth inhibition.

[0018] The minimum surface concentrations of IPMP, Hygenia, silver ions, benzalkonium chloride, benzalkonium saccharate, and imazalil that inhibit growth of Penicillium and Cladosporium fungi are shown in Table 2. [Table 2]

[0019] In one embodiment of the mold-derived odor suppression method of the present invention, the concentration at which the antimicrobial compound is applied is less than or equal to the minimum inhibitory concentration for mold growth, but may be less than the minimum inhibitory concentration, and may also be 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 48% or less, 46% or less, 44% or less, 42% or less, 40% or less, 38% or less, 36% or less, 34% or less, 32% or less, 30% or less, 28% or less, 26% or less, 24% or less, 22% or less, 20% or less, 18% or less, 16% or less, 14% or less, 13% or less, 12% or less, 10% or less, 8% or less, 6% or less, or 4% or less of the minimum inhibitory concentration.

[0020] Even a faint odor from mold can be unpleasant for consumers. Examples include 3-methyl-1-butanol, phenylethyl alcohol, geosmin, 2-methylisoborneol, 2,4,6-trichloroanisole, 6-methyl-5-hepten-2-one, and 1-octen-3-ol.

[0021] The inventors of this invention have discovered that mold-derived odors can be suppressed even when antimicrobial compounds, such as fungicides, are applied to mold at a concentration that inhibits the growth of mold, which is one of the causes of these odors. Specifically, based on the finding that mold-derived odors can be suppressed even when antimicrobial compounds are applied at a concentration lower than the concentration that completely kills or inhibits the growth of mold, the inventors provide an odor suppression method and the like, which includes the step of applying antimicrobial compounds, such as fungicides, to mold at a concentration below the minimum inhibitory concentration for the growth of mold, which is one of the causes of these odors.

[0022] In one embodiment of the mold-derived odor suppression method of the present invention, the concentration at which the antimicrobial compound is applied is less than or equal to the minimum inhibitory concentration for mold growth. However, from the viewpoint of effectively suppressing odor, the concentration is 0.2% or more, 0.4% or more, 0.6% or more, 0.8% or more, 1% or more, 1.5% or more, 2% or more, 4% or more, 6% or more, 8% or more, 10% or more, 12% or more, 14% or more, and 1% or more of the minimum inhibitory concentration for mold growth. It may also be 6% or more, 18% or more, 20% or more, 22% or more, 24% or more, 26% or more, 28% or more, 30% or more, 32% or more, 34% or more, 36% or more, 38% or more, 40% or more, 42% or more, 44% or more, 46% or more, 48% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more.

[0023] While there are no particular limitations on where mold can grow, examples include air conditioners, bathrooms, changing rooms, toilets, ventilation fans, washing machines, closets, storage spaces, windows, exterior walls, wallpaper, curtains, mattresses, and drainpipes. Air conditioners, washing machines, closets, and storage spaces tend to trap mold-derived odors, which can be unpleasant for users. Furthermore, because air conditioners, ventilation fans, and washing machines have complex structures, it is difficult to completely eliminate all mold that has grown. Air conditioners, in particular, spread trapped mold-derived odors, and since it is difficult to eliminate the mold, odor suppression is especially necessary.

[0024] Antimicrobial compounds may be applied to mold in the form of wet wipes, heat vaporization products, aerosol products, spray products, gel products, paste products, or products that automatically dispense the agent. A product that automatically dispenses the agent is, for example, one that is installed on top of a toilet's water tank and dispenses the antimicrobial compound into the water periodically or each time the toilet is flushed, and can be applied to mold in the water tank or the water in the toilet. Among these, aerosol products are preferred because they can easily treat even complex structures.

[0025] 2. Composition for use in a method for suppressing mold-derived odors. The composition used in the method for suppressing mold-derived odors contains an antimicrobial compound. The composition of the present invention may contain compounds other than antimicrobial compounds. For example, the composition of the present invention may contain a solvent for purposes such as viscosity adjustment or improving the penetration of the antimicrobial compound into mold. Examples of such solvents include glycol ether solvents, hydrocarbon solvents, alcohol solvents, aromatic solvents, ester solvents, and water. Examples of glycol ether solvents include propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. Examples of hydrocarbon solvents include aliphatic hydrocarbons such as paraffinic hydrocarbons and naphthenic hydrocarbons, as well as alicyclic hydrocarbons, with kerosene such as No. 1 kerosene being preferred. Specifically, examples include normal paraffins and isoparaffins. Typical normal paraffins have 8 to 16 carbon atoms, such as Neothiosol manufactured by Chuo Kasei Co., Ltd. and Normal Paraffin MA manufactured by JXTG Energy Corporation. Typical isoparaffins have 8 to 16 carbon atoms, such as IP Clean LX and Supersol FP25 manufactured by Idemitsu Kosan Co., Ltd. Examples of alcohol-based solvents include lower alcohols such as ethanol and propanol, and polyhydric alcohols such as glycerin and propylene glycol. Examples of aromatic solvents include toluene and xylene. Examples of ester-based solvents include isopropyl myristate, hexyl laurate, and isopropyl palmitate.

[0026] Furthermore, the composition of the present invention may contain other components, to the extent that they do not impair the effects of the present invention. Examples of other components include pH adjusters, ultraviolet absorbers, inorganic substances, surfactants other than cationic surfactant compounds, solubilizers, and fragrances.

[0027] 3. Aerosol Products In one embodiment of the method of the present invention, an antimicrobial compound can be applied to mold using an aerosol product. In this embodiment, the aerosol product that can be used comprises an aerosol container equipped with a spray valve and a spray button equipped with a nozzle connected to the spray valve. The aerosol container is filled with an aerosol composition consisting of an antimicrobial compound-containing composition (aerosol concentrate) and a propellant.

[0028] (1) Composition containing antimicrobial compound The antimicrobial compound-containing composition (aerosol stock solution) used in the aerosol product that can be used in the odor suppression method of the present invention contains an antimicrobial compound. The content of the antimicrobial compound is preferably 0.01 to 70% by mass / volume in the stock solution. A sufficient odor suppression effect can be obtained when the antimicrobial compound is 0.01% by mass / volume or more in the stock solution, and the uniform diffusion of spray particles is improved when it is 70% by mass / volume or less. The lower limit of the antimicrobial compound content is more preferably 0.1% by mass / volume or more, even more preferably 0.3% by mass / volume or more, and particularly preferably 0.5% by mass / volume or more, and the upper limit is more preferably 65% ​​by mass / volume or less, even more preferably 50% by mass / volume or less, and particularly preferably 25% by mass / volume or less.

[0029] The aerosol concentrate may contain a solvent for purposes such as adjusting the viscosity of the concentrate, improving production suitability, and enhancing the penetration of antimicrobial compounds into mold. Examples of such solvents include the glycol ethers mentioned above, hydrocarbon solvents, alcohol solvents, aromatic solvents, ester solvents, and water.

[0030] The solvent content is preferably 30 to 99.99% by mass / volume in the stock solution. A solvent content of 30% by mass / volume or more in the stock solution increases the solubility of the antimicrobial compound, making mixing and filling in the manufacturing process easier and thus improving production suitability. A content of 99.99% by mass / volume or less is preferable because it ensures a sufficient odor suppression effect. The lower limit of the solvent content is more preferably 35% by mass / volume or more, even more preferably 50% by mass / volume or more, and the upper limit is more preferably 99.9% by mass / volume or less, and even more preferably 99.5% by mass / volume or less.

[0031] The aerosol concentrate may contain other components as long as they do not impair the effects of the present invention. Examples include pH adjusters, UV absorbers, inorganic substances, surfactants other than cationic surfactant compounds, solubilizers, and fragrances.

[0032] The amount of undiluted liquid in the aerosol composition can be appropriately changed depending on the intended use and the combination with the propellant, and is not particularly limited, but for example it can be 1 to 50% by volume in the aerosol composition. If the amount of undiluted liquid in the aerosol composition is 1% by volume or more, a sufficient odor suppression effect can be obtained, and if it is 50% by volume or less, the undiluted liquid can be sprayed as atomized particles, so it can be applied over a wide area to the surface to be treated. The lower limit of the amount of undiluted liquid in the aerosol composition is more preferably 3% by volume or more, even more preferably 5% by volume or more, and the upper limit is more preferably 40% by volume or less, and even more preferably 30% by volume or less.

[0033] (2) Propellant The propellant contained in the aerosol composition of the aerosol product that can be used in the odor suppression method of the present invention is a medium for spraying the aerosol concentrate and is pressurized and filled into a pressure-resistant aerosol container together with the aerosol concentrate. As propellants, one or more types of liquefied petroleum gases (LPG) such as propane, propylene, n-butane, and isobutane, liquefied gases such as dimethyl ether (DME), compressed gases such as carbon dioxide, nitrogen gas, and compressed air, and halogenated carbon gases such as HFC-152a, HFC-134a, HFO-1234yf, and HFO-1234ze can be used. The propellant used should be appropriately selected in accordance with its compatibility with the aerosol concentrate and the container components such as the spray valve.

[0034] The propellant content in the aerosol composition can be appropriately changed depending on the intended use and combination with the stock solution, and is not particularly limited, but for example, it can be 50 to 99% by volume in the aerosol composition under 25°C conditions. When the propellant content in the aerosol composition is 50% by volume or more, the stock solution can be sprayed as atomized particles, which makes it easier for the antimicrobial compound to diffuse and efficiently obtain an odor suppression effect. Also, when the propellant content is 99% by volume or less, a sufficient antimicrobial effect can be obtained. The propellant content in the aerosol composition is more preferably 60% by volume or more at the lower limit, even more preferably 70% by volume or more, and more preferably 97% by volume or less at the upper limit, and even more preferably 95% by volume or less.

[0035] The volume ratio of the stock solution to the propellant in the aerosol composition at 25°C is preferably 1:99 to 50:50, more preferably 3:97 to 40:60, and even more preferably 5:95 to 30:70. By using such a volume ratio, the balance between the adhesion and diffusion of the antimicrobial compound is optimized, thereby obtaining a sufficient odor suppression effect.

[0036] (3) Injection valve The spray valve for an aerosol product usable in the odor suppression method of the present invention comprises an opening / closing member for switching communication between the inside and outside of the aerosol container and blocking it when the spray member is operated by the user, a housing to which the opening / closing member is attached, and a mounting member for holding the housing in a predetermined position on the aerosol container. The opening / closing member also includes a stem that slides up and down in conjunction with the spray member. The sliding of the stem switches between communication (spray state) and blocking (non-spray state) of the aerosol composition. The spray valve has a housing hole for taking in the aerosol composition from the aerosol container and a stem hole for sending the taken-in aerosol composition to the spray member. The housing has a housing hole for taking in the aerosol composition from the aerosol container. The stem has a stem hole for sending the aerosol composition taken into the housing to the spray member. The path from the housing hole to the stem hole constitutes an internal passage through which the aerosol composition passes.

[0037] In the present invention, the injection valve is preferably a quantitative injection valve that dispenses a fixed amount by operating the injection member once, or a continuous injection valve that dispenses continuously.

[0038] (4) Injection member The spray button for an aerosol product that can be used in the odor suppression method of the present invention is a component attached to the aerosol container via a spray valve. The spray button has an internal passage for the aerosol composition taken in from the aerosol container via the stem hole of the spray valve, and a nozzle through which the aerosol composition is sprayed.

[0039] From the viewpoint of setting the spray duration within a desired range, the inner diameter (nozzle hole diameter) of the spray button's nozzle is preferably Φ 0.4 to 3 mm, more preferably Φ 0.5 to 2 mm, and even more preferably Φ 0.6 to 1.6 mm. Furthermore, having multiple nozzles with areas equal to these is also acceptable.

[0040] (5) Injection pressure The aerosol product that can be used in the odor suppression method of the present invention is filled with a stock liquid and a propellant, i.e., an aerosol composition, in an aerosol container as described above, and a fixed amount of the aerosol composition is sprayed with a single press of the spray button. Under conditions of 25°C, the spray pressure of the aerosol composition at a distance of 15 cm from the nozzle is preferably 1 to 50 gf, and more preferably 5 to 30 gf. By having the spray pressure within the above range, the spraying time can be set within a desired range. The aforementioned spray pressure can be measured as the maximum value of the spray pressure when the aerosol composition is sprayed towards the center of a 60 mm diameter circular plate attached to a digital force gauge (for example, a DST-2N manufactured by Imada Co., Ltd.) which is placed on its side 15 cm away from the nozzle of the aerosol product, under conditions of 25°C.

[0041] (6) Aerosol products The spray valve of the aerosol product that can be used in the odor suppression method of the present invention may be a metered spray valve. The single spray volume of the metered spray valve is not particularly limited, but is preferably 0.08 to 5 mL, more preferably 0.1 to 1 mL, and even more preferably 0.4 to 1 mL. If the spray volume per use is within the above range, the antimicrobial compound contained in the spray particles can be sufficiently and uniformly attached to the predetermined location by simply operating the spray member a predetermined number of times according to the size of the space, thereby effectively suppressing odors. The aerosol product that can be used in the odor suppression method of the present invention may be a continuous-spray type aerosol product equipped with a conventional valve instead of a metering-type spray valve. In the case of a continuous-spray type aerosol product, the spray volume is not particularly limited, but is preferably 0.1 to 3 mL / second, more preferably 0.2 to 2 mL / second, and even more preferably 0.3 to 1.5 mL / second. [Examples]

[0042] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0043] 1.1 Method for measuring the minimum inhibitory volume concentration (1) Test bacteria ·Penicillium citrinum(NBRC6352)(Penicillium genus) Cladosporium sphaerospermum (NBRC6348) (Genus Cladosporium)

[0044] (2) Antimicrobial compounds IPMP (Isopropylmethylphenol)

[0045] (3) Preparation of culture medium <Preparation of culture medium for pre-culture> The PDA medium was sterilized by autoclaving. A PDA slant medium was prepared by dispensing 10 ml of PDA medium into a glass test tube (φ18 mm × 180 mm) and tilting it at a 10° angle. <Preparation of culture medium for measuring minimum inhibitory volume concentration> PDA medium containing a predetermined amount of IPMP was sterilized by autoclaving. In a 60 mm petri dish, 10 ml of a mixture of PDA medium and IPMP-containing PDA medium in a predetermined ratio was dispensed to prepare PDA medium with a predetermined concentration containing IPMP.

[0046] (4) Preculture The test bacteria were cultured at 25°C for 1 week using pre-culture medium.

[0047] (5) Measurement of the minimum inhibitory volume concentration (IPMP) The culture medium was prepared and colony formation was confirmed as follows. (i) Using pre-cultured Penicillium citrinum (NBRC6352) and Cladosporium sphaerospermum (NBRC6348), spores were collected using a dry cotton swab (Mentip Φ 3×152mm, manufactured by Nippon Menbao), and the spore count was reduced to 1.8-2.5×10 in an aqueous solution of 0.05 w / v% polyoxyethylene (20) sorbitan monooleate (manufactured by Fujifilm Wako Pure Chemical Industries). 6Spore solution was prepared to a concentration of 1.8 to 2.5 × 10¹⁴ spores / ml. The number of spores was measured using a microscope after placing the collected spore solution into a cell counter plate (WATSON). 6 I confirmed that the value is per ml. (ii) Two μL of spore extract was inoculated at three locations on the prepared medium for measuring the minimum inhibitory volume concentration. (iii) After inoculation, the cells were incubated for 5 days in an incubator set to 25°C. (iv) After culturing, the petri dish was visually inspected to evaluate whether colony formation had been confirmed.

[0048] The minimum inhibitory volume concentration of IPMP against Penicillium citrinum was measured as follows. (i) Culture media with IPMP concentrations of 400 ppm by mass, 200 ppm by mass, 100 ppm by mass, and 0 ppm by mass were prepared, and colony formation was observed. Colony formation was not observed in the medium with an IPMP concentration of 400 ppm by mass, but colony formation was observed in the medium with an IPMP concentration of 200 ppm by mass or less. Therefore, the first inhibitory volume concentration was 400 ppm by mass. (ii) A culture medium with an IPMP concentration of 300 ppm by mass was prepared, and colony formation was observed. Colony formation was not observed in the medium with 300 ppm by mass of IPMP. Therefore, the second inhibitory volume concentration was 300 ppm by mass. (iii) Culture media with IPMP concentrations of 280 ppm, 260 ppm, 240 ppm, and 220 ppm were prepared, and colony formation was observed. Colony formation was not observed in the medium with an IPMP concentration of 280 ppm, but colony formation was observed in the media with concentrations of 260 ppm, 240 ppm, and 220 ppm. From the results above, the minimum inhibitory volume concentration of IPMP against Penicillium citrinum was 280 ppm by mass.

[0049] The minimum inhibitory volume concentration for Cladosporium sphaerospermum was measured as follows. (i) Culture media with IPMP concentrations of 200 ppm by mass, 100 ppm by mass, and 0 ppm by mass were prepared, and colony formation was observed. Colony formation was not observed in the medium with an IPMP concentration of 200 ppm by mass, but colony formation was observed in the medium with an IPMP concentration of 100 ppm by mass. Therefore, the first inhibitory volume concentration was 200 ppm by mass. (ii) Colony formation was observed in a medium containing 100 ppm by mass of IPMP (200 ppm by mass - 100 ppm by mass), so the second inhibitory volume concentration was 200 ppm by mass. (iii) Culture media with IPMP concentrations of 180 ppm, 160 ppm, 140 ppm, and 120 ppm were prepared, and colony formation was confirmed. Colony formation was confirmed in the media with concentrations of 180 ppm, 160 ppm, 140 ppm, and 120 ppm. Based on the above results, the minimum inhibitory volume concentration of IPMP against Cladosporium sphaerospermum was 200 ppm by mass. These results are shown in Table 3.

[0050] [Table 3]

[0051] (6) Minimum inhibitory volume concentration of antimicrobial compounds other than IPMP Similar to the IPMP study, the minimum inhibitory volume concentrations (MLLs) of hygienic agents, silver ions, benzalkonium chloride, and benzalkonium saccharate against Penicillium citrinum, and against Cladosporium sphaerospermum, were measured. The results are shown in Table 1.

[0052] 1.2 Method for measuring the minimum surface concentration of growth inhibitory agents (1) Test bacteria, antimicrobial compounds, and pre-culture The test bacteria, antimicrobial compounds, and pre-cultures were prepared in the same manner as the minimum inhibitory volume concentration (MDL) measurements.

[0053] (2) Preparation of culture medium <Preparation of culture medium for pre-culture> The PDA medium was sterilized by autoclaving. A PDA slant medium was prepared by dispensing 10 ml of PDA medium into a glass test tube (φ18 mm × 180 mm) and tilting it at a 10° angle. <Preparation of culture medium for measuring minimum inhibitory surface concentration> The culture medium used in this study was prepared by adding PDA medium powder and agar powder to water at concentrations of 19.5 g / L, and then sterilized by autoclaving. Diluted PDA medium was prepared by dispensing 10 ml of autoclaved culture medium into a 60 mm petri dish.

[0054] (3) Measurement of minimum inhibitory surface concentration (IPMP) (i) Using pre-cultured Penicillium citrinum (NBRC6352) and Cladosporium sphaerospermum (NBRC6348), spores were collected using a dry cotton swab (Mentip Φ 3×152mm, manufactured by Nippon Menbao), and the spore count was reduced to 1.8-2.5×10 in an aqueous solution of 0.05 w / v% polyoxyethylene (20) sorbitan monooleate (manufactured by Fujifilm Wako Pure Chemical Industries). 6 Spore solution was prepared to a concentration of 1.8 to 2.5 × 10¹⁴ spores / ml. The number of spores was measured using a microscope after placing the collected spore solution into a cell counter plate (WATSON). 6 I confirmed that the value is per ml. (ii) Three locations on a sterilized filter paper (5.0 cm × 5.0 cm) using ultraviolet light were inoculated with 2 μL of IPMP solution at a predetermined concentration. (iii) The filter paper was dried and attached to the culture medium. (iv) 2 μL of spore solution was inoculated at three points on the attached filter paper where the IPMP solution was dropped. (v) Subsequently, the cells were cultured for 5 days in an incubator set to 25°C. (vi) Colony formation was confirmed after culturing. In this way, the boundary between IPMP concentrations at which colony formation was not observed and those at which it was observed was identified, and the minimum inhibitory surface concentration of IPMP for Penicillium citrinum and Cladosporium sphaerospermum was measured. As a result, the minimum inhibitory surface concentration of IPMP for Penicillium citrinum was 8.0 μg / cm³. 2 Therefore, the minimum surface concentration of IPMP that inhibits growth of Cladosporium sphaerospermum is 33.6 μg / cm³. 2 That was the case.

[0055] (4) Minimum inhibitory surface concentration of antimicrobial compounds other than IPMP Similar to the IPMP study, the minimum inhibitory surface concentrations of hygienic agents, silver ions, benzalkonium chloride, and benzalkonium saccharate for Penicillium citrinum, and for Cladosporium sphaerospermum, were measured. The results are shown in Table 2.

[0056] 2. Suppression of mold-derived odors (minimum inhibitory volume concentration) (Examples 1-8, Comparative Examples 1, 2) (1) Test bacteria ·Penicillium citrinum(NBRC6352)(Penicillium genus)

[0057] (2) Antimicrobial compounds IPMP (Isopropylmethylphenol) 1,4-Bis[3,3'-(1-decylpyridinium)methyloxy]butanedibromide (Hygenia, manufactured by Tama Chemical Industry Co., Ltd.)

[0058] (3) Preparation of culture medium <Preparation of culture media for analysis and quantitative testing of odor components> PDA medium and IPMP were mixed in predetermined amounts, and the PDA medium was sterilized in an autoclave. A dilution series of IPMP-containing PDA slant medium was prepared by dispensing 40 ml of a mixture of PDA medium and IPMP-containing PDA medium in any ratio into a 100 ml vial (Φ 37 mm × 120 mm) and tilting the vial by 10°. Specifically, the dilution series was prepared so that the IPMP concentrations were 200 ppm by mass, 100 ppm by mass, 50 ppm by mass, 25 ppm by mass, 12.5 ppm by mass, and 0 ppm by mass. Similarly, PDA medium mixed with hygienic acid in predetermined amounts was sterilized in an autoclave, and a dilution series was prepared so that the hygienic acid concentration was 200 ppm by mass, 100 ppm by mass, 50 ppm by mass, 25 ppm by mass, 12.5 ppm by mass, and 0 ppm by mass. <Preparation of culture media for sensory evaluation> PDA medium mixed with IPMP or Hygenia in specified amounts was sterilized by autoclaving. A dilution series of IPMP-containing PDA slant medium was prepared by dispensing 40 ml of a mixture of PDA medium and IPMP-containing PDA medium in a predetermined ratio into a glass test tube (φ18 mm × 180 mm) and tilting it by 10°. Specifically, a dilution series was prepared so that the IPMP concentrations were 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, and 0 ppm. Similarly, a dilution series of hygienic-containing PDA slant medium was prepared so that the hygienic-containing concentrations were 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, and 0 ppm. <Preparation of culture medium for colony count measurement> PDA medium and IPMP were mixed in predetermined amounts, and the PDA medium was sterilized in an autoclave. A dilution series of IPMP-containing PDA medium was prepared by dispensing 10 ml of a mixture of PDA medium and IPMP-containing PDA medium in a predetermined ratio into a Φ 90 mm petri dish. Specifically, the dilution series was prepared so that the IPMP concentrations were 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, and 0 ppm. Similarly, the dilution series was prepared so that the hygienic concentration was 200 ppm, 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, and 0 ppm.

[0059] (4) Preculture The test bacteria were cultured at 25°C for 1 week using pre-culture medium.

[0060] (5) Analysis and quantitative determination of odor components The odor components 3-methyl-1-butanol and phenylethyl alcohol, derived from Penicillium citrinum cultured in a culture medium for odor component analysis and quantification, were analyzed and quantified using the following procedure. Hereinafter, phenylethyl alcohol will also be referred to as phenethyl alcohol. (i) Using pre-cultured Penicillium citrinum (NBRC 6352), spores were collected using a dry cotton swab (Mentip Φ 3 × 152 mm, manufactured by Nippon Menbao), and the spore count was reduced to 1.8-2.5 × 10⁶ in a 0.05 w / v% polyoxyethylene (20) sorbitan monooleate (manufactured by Fujifilm Wako Pure Chemical Industries) aqueous solution. 6 Spore solution was prepared to have a concentration of spores / ml. (ii) The number of spores is determined by placing the spore solution prepared in (i) into a cell counter plate (WATSON) and counting the number of spores using a microscope, resulting in a count of 1.8 to 2.5 × 10⁻⁶. 6 I confirmed that the value is per ml. (iii) After confirmation, 30 μL of spore solution was inoculated into a culture medium for the analysis and quantification of odor components and spread with a platinum loop. *A control group was prepared separately, which did not use spore solution inoculation. (iv) A φ1 mm hole was made in the lid of the vial, a wire was passed through the hole, and a MonoTrap RGPS TD (manufactured by GL Sciences Co., Ltd.), which serves as an odor collector, was attached to the end of the wire. At this time, the distance between the culture medium and the collector was fixed at approximately 10 mm. (v) After the procedure in (iv), the cells were immediately incubated in an incubator set to 25°C for 3 days. (vi) Three days later, GC-MS analysis was performed on the adsorbent adsorbing the odor. The control group and the treated group were compared, and the compounds and peak area values ​​were calculated for the peaks detected only in the treated group. Compound identification was performed by library search from the mass spectra of the compound peaks to select candidate compounds. Subsequently, the reagents of the candidate compounds were subjected to the same analytical conditions as standards, and identification was confirmed by confirming that the peak retention time and mass spectrum were identical. <Analysis conditions> Thermal desorbing device: Portable thermal desorber TD265 (manufactured by GL Sciences Co., Ltd.) Pressure: 100kPa Holding temperature: 250℃ Holding time: 2.0 minutes Analytical instrument: GCMS-QP2010Ultra (manufactured by Shimadzu Corporation) Column: InterCap Pure-WAX (Inner diameter 0.25 mm x Length 30 m x Film thickness 0.25 μm) (Manufactured by GL Sciences Co., Ltd.) Column temperature: 50°C (5 min) - (10°C / min) - 250°C (10 min) Carrier gas: Helium 120kPa Inlet temperature: 250℃ Detector temperature: 200℃ Gas flow rate: 1.0 mL / min Analysis mode: SIM (Selective Ion Detection) Target ingredients: m / z 55.00 (3-methyl-1-butanol), m / z 91.00 (phenylethyl alcohol) <Analysis method> Peak areas were determined from the mass chromatograms of m / z 55.00 (3-methyl-1-butanol) and m / z 91.00 (phenylethyl alcohol).

[0061] (6) Estimated number of colonies The number of colonies in the culture medium in the vial was estimated using the following procedure. (i) In the culture medium prepared for counting colonies, if the number of spores is 1.8-2.5 × 10 6 A spore solution prepared to a concentration of spores / mL was diluted 1000-fold and 30 μL was applied using a convex stick. (ii) The cells were immediately incubated in an incubator set to 25°C for 3 days. (iii) After culturing, the number of colonies formed was counted. After counting, the estimated number of colonies that would be formed from 30 μL of spore solution used in the odor component analysis and quantification test was calculated using formula (1). Equation (1): Estimated number of colonies = Number of colonies counted × 1000

[0062] (7) Amount of odor components generated per colony The amount of odor components generated per colony was calculated using equation (2). Equation (2): Amount of odor component generated per colony = Peak area / Estimated number of colonies

[0063] (8) Suppression rate of odor component generation The reduction rate of odor component generation was calculated using equation (3). Equation (3): Odor component generation suppression rate = (1 - amount of odor component generated per colony / amount of odor component generated per colony in a culture medium with an antimicrobial compound concentration of 0 ppm by mass) × 100

[0064] (9) Sensory evaluation (i) In the sensory evaluation medium, the number of spores is 1.8 to 2.5 × 10 6 30 μL of spore solution, prepared to have a concentration of spores / mL, was inoculated and spread using a platinum loop. (ii) The cells were immediately incubated in an incubator set to 25°C for 3 days. (iii) Five expert panelists conducted a sensory evaluation of the odor in the glass test tube and the degree of pleasantness or unpleasantness of the odor, and the average value was calculated. The evaluation criteria were as follows: Odor evaluation criteria 5: Strong smell 4: Strong smell 3: Easily detectable odors 2: A faint smell that can be identified as a specific scent. 1: A smell that can finally be detected 0: Odorless Criteria for evaluating the degree of pleasure or displeasure 4: Extremely pleasant 3: Very pleasant 2: Pleasure 1: Slightly comfortable 0: Neither pleasant nor unpleasant -1: Slightly unpleasant -2: Unpleasant -3: Very unpleasant -4: Extremely unpleasant

[0065] (10) Odor suppression rate The odor suppression rate in the glass test tube was calculated using equation (4). Equation (4): Odor suppression rate (%) = (1 - Odor evaluation score / Odor evaluation score in culture medium with zero antimicrobial compound concentration) × 100

[0066] In this test, a success rate was defined as a reduction in odor component generation of 20% or higher. This is because, with a reduction in odor component generation of 20% or higher, the sensory evaluation showed an improvement of 0.5 or more compared to the odor evaluation with an antimicrobial compound concentration (IPMP concentration, hygienic compound concentration) of 0 ppm by mass, and the pleasantness / unpleasantness evaluation also showed an improvement of 0.5 or more compared to the pleasantness / unpleasantness evaluation with an antimicrobial compound concentration of 0 ppm by mass. The data above was summarized in Table 4. [Table 4]

[0067] From the results above, it was found that when antimicrobial compounds such as IPMP and Hygenia are used to suppress odors originating from Penicillium molds, the odor can be effectively suppressed even without completely killing the mold. Specifically, while the minimum inhibitory volume concentration of IPMP against Penicillium molds is 280 ppm by mass, in Example 4, where the IPMP concentration was 12.5 ppm by mass (approximately 0.04 times that amount), the odor was suppressed and the level of pleasantness / unpleasantness improved, even though the estimated number of colonies was equal to or greater than that of Comparative Example 1. In particular, in Example 4, the amount of phenethyl alcohol, a component of unpleasant odors, was suppressed to below the detection limit, and in Example 1, the amount of 3-methyl-1-butanol, a component of unpleasant odors, was suppressed to below the detection limit. Furthermore, in Example 3, where the IPMP concentration was 25 ppm by mass, which is 0.08 times the minimum inhibitory volume concentration, the estimated number of colonies decreased only slightly compared to Comparative Example 1. However, the amount of 3-methyl-1-butanol, a component of the unpleasant odor, was suppressed by more than 50%, and the amount of phenethyl alcohol was suppressed to below the detection limit, significantly improving the level of pleasantness or unpleasantness. In addition, while the minimum inhibitory volume concentration of Hygenia for Penicillium molds is 200 ppm by mass, in Example 8, where the Hygenia concentration was 12.5 ppm by mass, the estimated number of colonies was equal to or greater than that of Comparative Example 2, yet the odor was suppressed and the level of pleasantness or unpleasantness improved. In particular, in Example 8, the amount of phenethyl alcohol, a component of the unpleasant odor, was suppressed to below the detection limit. Furthermore, in Example 6, where the hygienic concentration was 50 ppm by mass, the estimated number of colonies was only slightly lower than in Comparative Example 2. However, the amount of 3-methyl-1-butanol, a component of the unpleasant odor, was suppressed to about 1 / 3, and the amount of phenethyl alcohol was suppressed to below the detection limit, significantly improving the level of pleasantness or unpleasantness.

[0068] 3. Suppression of mold-derived odors (minimum surface concentration for inhibiting growth) (Examples 9-16, Comparative Example 3) (1) Test bacteria ·Penicillium citrinum(NBRC6352)(Penicillium genus)

[0069] (2) Antimicrobial compounds IPMP (Isopropylmethylphenol) 1,4-Bis[3,3'-(1-decylpyridinium)methyloxy]butanedibromide (Hygenia, manufactured by Tama Chemical Industry Co., Ltd.) Silver ions (AG Alpha CF-01, manufactured by MGC Woodchem Co., Ltd.)

[0070] (3) Preparation of culture medium <Preparation of culture media for analysis and quantitative testing of odor components> The culture medium was prepared by adding PDA medium powder and agar powder to water to a concentration of 19.5 g / L. The resulting medium was sterilized by autoclaving. Diluted PDA slant medium was prepared by dispensing 40 ml into a 100 ml vial (Φ 37 mm × 120 mm) and tilting it at a 10° angle. <Preparation of culture media for sensory evaluation> The culture medium for this study was prepared by adding 19.5 g / L of PDA medium powder and 19.5 g / L of agar powder to water. The resulting medium was sterilized by autoclaving. Diluted PDA slant medium was prepared by dispensing 10 ml into a glass test tube (φ18 mm × 180 mm) and tilting it at a 10° angle.

[0071] (4) Preculture The test bacteria were cultured at 25°C for 1 week using pre-culture medium.

[0072] (5) Analysis and quantitative determination of odor components The odor components 3-methyl-1-butanol and phenylethyl alcohol, derived from Penicillium citrinum cultured in a culture medium for odor component analysis and quantification, were analyzed and quantified using the following procedure. (i) Using pre-cultured Penicillium citrinum (NBRC 6352), spores were collected using a dry cotton swab (Mentip Φ 3 × 152 mm, manufactured by Nippon Menbao), and the spore count was reduced to 1.8-2.5 × 10⁶ in a 0.05 w / v% polyoxyethylene (20) sorbitan monooleate (manufactured by Fujifilm Wako Pure Chemical Industries) aqueous solution. 6 Spore solution was prepared to have a concentration of spores / ml. (ii) The number of spores is determined by placing the spore solution prepared in (i) into a cell counter plate (WATSON) and counting the number of spores using a microscope, resulting in a count of 1.8 to 2.5 × 10⁻⁶. 6 I confirmed that the value is per ml. (iii) 2.80 × 8.94 cm (25 cm) 2 The filter paper, cut into strips, was sterilized by ultraviolet irradiation. (iv) The antimicrobial compound was appropriately diluted with 99.5% ethanol (only the silver ions were diluted with sterile deionized water), and 10 μL each was dropped onto three locations on the filter paper. The dropping procedure was as follows: first, a drop was placed in the center of the filter paper, and then one drop was placed on each side of the central drop at equal intervals from the central drop. (v) The filter paper was dried and attached to the slant culture medium. (vi) Three locations on the attached filter paper where the antimicrobial compound was applied were inoculated with 30 μL each of spore solution. (vii) A φ1 mm hole was made in the lid of the vial, a wire was passed through the hole in the lid, and a MonoTrap RGPS TD (manufactured by GL Sciences), which serves as an odor collector, was attached to the end of the wire. At this time, the distance between the culture medium and the collector was fixed at approximately 10 mm. After the procedures in (viii)(vii), the cells were immediately incubated in an incubator set to 25°C for 3 days. (ix) Three days later, the adsorbed odor trap was subjected to GC-MS analysis. The control group and the treated group were compared, and the compounds and peak area values ​​were calculated for the peaks detected only in the treated group. Compound identification was performed in the same manner as in Example 1. <Analysis conditions> Thermal desorbing device: Portable thermal desorber TD265 (manufactured by GL Sciences Co., Ltd.) Pressure: 100kPa Holding temperature: 250℃ Holding time: 2.0 minutes Analytical instrument: GCMS-QP2010Ultra (manufactured by Shimadzu Corporation) Column: InterCap Pure-WAX (Inner diameter 0.25 mm x Length 30 m x Film thickness 0.25 μm) (Manufactured by GL Sciences Co., Ltd.) Column temperature: 50°C (5 min) - (10°C / min) - 250°C (10 min) Carrier gas: Helium 120kPa Inlet temperature: 250℃ Detector temperature: 200℃ Gas flow rate: 1.0 mL / min Analysis mode: SIM (Selective Ion Detection) Target ingredient: m / z 55.00 (3-methyl-1-butanol) m / z <Analysis method> The peak area was determined from the mass chromatogram of m / z 55.00 (3-methyl-1-butanol).

[0073] (6) Amount of odor components generated The amount of odor components generated was calculated from the peak area of ​​3-methyl-1-butanol.

[0074] (7) Suppression rate of odor component generation The reduction rate of odor component generation was calculated using equation (3). Equation (3): Odor component generation suppression rate = (1 - Amount of odor components generated in culture medium containing antimicrobial compounds / Amount of odor components generated in culture medium without antimicrobial compounds)

[0075] (8) Sensory evaluation (i) Using pre-cultured Penicillium citrinum (NBRC 6352), spores were collected using a dry cotton swab (Mentip φ3 × 152 mm, manufactured by Nippon Menbao), and the spore count was reduced to 1.8-2.5 × 10⁶ in a 0.05 w / v% polyoxyethylene (20) sorbitan monooleate (manufactured by Fujifilm Wako Pure Chemical Industries) aqueous solution. 6 It was prepared to have a concentration of particles / ml. (ii) The number of spores is determined by placing the spore solution collected in (i) into a cell counter plate (WATSON Corporation) and counting the number of spores using a microscope, resulting in a count of 1.8 to 2.5 × 10⁻⁶. 6 I confirmed that the value is per ml. (iii) 1.00 × 8.00 cm (8 cm 2 The filter paper, cut into strips, was sterilized with ultraviolet light. (iv) The antimicrobial compound was appropriately diluted with 99.5% ethanol (only the silver ions were diluted with sterile deionized water), and 10 μL each was dropped onto three locations on the filter paper. The dropping procedure was as follows: first, a drop was placed in the center of the filter paper, and then one drop was placed on each side of the central drop at equal intervals from the central drop. (v) The filter paper was dried to a suitable temperature and attached to the slant culture medium. (vi) Three locations on the attached filter paper where the antimicrobial compound was applied were inoculated with 30 μL of spore solution each. (vii) The cells were immediately incubated in an incubator set to 25°C for 3 days. (viii) Five expert panelists conducted a sensory evaluation of the odor in the glass test tube and the degree of pleasantness or unpleasantness of the odor, and the average value was calculated. The evaluation criteria were the same as in Example 1. Furthermore, the percentage improvement in odor was calculated using formula (4). Equation (4): Odor suppression rate = (1 - Odor evaluation score in culture medium containing antimicrobial compounds / Odor evaluation score in culture medium without antimicrobial compounds) × 100

[0076] In this test, a test was considered successful if the reduction rate of odor component generation was 20% or higher. The data above has been summarized in Table 5. [Table 5]

[0077] The results above indicate that when using antimicrobial compounds such as IPMP, Hygenia, and silver ions to suppress odors originating from Penicillium molds, the odor can be effectively suppressed even without completely killing the mold. Specifically, the minimum surface concentration of silver ions that inhibits growth of Penicillium molds was 6 μg / cm³. 2 However, the silver ion concentration is lower, at 0.4-4 μg / cm³. 2 In Examples 13-16, the amount of 3-methyl-1-butanol, a component of unpleasant odor, was suppressed. The lowest silver ion concentration was 0.4 μg / cm³. 2In Example 16, compared to Comparative Example 3, which did not use an antimicrobial compound, the rate of suppression of odor component generation was improved, and improvements were confirmed in both the pleasantness / unpleasantness evaluation and the odor evaluation. Since the amount of 3-methyl-1-butanol generated in Examples 13 to 15 was suppressed more than in Example 16, it can be said that the pleasantness / unpleasantness evaluation and odor evaluation were also improved compared to Example 16. Furthermore, the minimum surface concentration at which IPMP inhibits growth of Penicillium fungi is 33.6 μg / cm³. 2 However, the IPMP concentration is lower at 24 μg / cm³. 2 In Example 9, the amount of 3-methyl-1-butanol generated was suppressed. Furthermore, the minimum inhibitory surface concentration of Hygenia against Penicillium fungi was 24.8 μg / cm³. 2 However, the hygienic concentration is lower, at 6-24 μg / cm³. 2 In Examples 10-12, the amount of 3-methyl-1-butanol generated was suppressed. Since the amount of 3-methyl-1-butanol generated in Examples 9-12 was suppressed compared to Example 16, it can be said that the pleasantness / unpleasantness evaluation and odor evaluation were improved compared to Example 16.

[0078] 4. Odor suppression using aerosol products (Examples 17-19) (1) Test bacteria Penicillium citrinum(NBRC6352)(Penicillium spp.)

[0079] (2) Antimicrobial compounds IPMP (Isopropylmethylphenol) 1,4-Bis[3,3'-(1-decylpyridinium)methyloxy]butanedibromide (Hygenia, manufactured by Tama Chemical Industry Co., Ltd.)

[0080] (3) Preparation of aerosol composition Stock solutions 1-3 were prepared with the compositions listed in Table 6. [Table 6]

[0081] Aerosol products were manufactured by filling aerosol cans with stock solutions 1-3 and liquefied gas as propellant as shown in Table 7 (Examples 17-19). Aluminum cans with an outer diameter of Φ45 mm and a height of 100 mm were used for the aerosol products. A valve with a discharge volume of 0.4 cc manufactured by Mitani Valve Co., Ltd. was used for the valve of the aerosol product, and the spray button used for the aerosol product had the cross-sectional structure shown in Figure 1, with a nozzle diameter of 1.0 mm. In Figure 1, 111 is the spray button and 112 is the nozzle.

[0082] (4) Surface concentration measurement 2.80 x 8.94 cm (25 cm) 2 A filter paper was attached to the inner wall of the air conditioner enclosure, 30 mm away from the air vent. The aerosol sample was placed with the nozzle 15 cm away from the air conditioner outlet and sprayed. The filter paper was collected, finely chopped, immersed in ethanol, and extracted using ultrasound for 15 minutes to extract the active ingredient, IPMP. LC quantitative analysis was performed using amyl benzoate as an internal standard, and the results were obtained at 25 cm. 2 From the amount of IPMP deposited per unit area, the surface concentration (μg / cm³) can be calculated. 2 ) was calculated.

[0083] (5) Preparation of culture medium <Preparation of culture media for analysis and quantitative testing of odor components> The culture medium for this study was prepared by adding 19.5 g / L of PDA medium powder and 19.5 g / L of agar powder to water. The resulting medium was sterilized by autoclaving. Diluted PDA slant medium was prepared by dispensing 40 mL into a 100 mL vial (φ37 mm × 120 mm) and tilting it at a 10° angle.

[0084] (6) Preculture The test bacteria were cultured at 25°C for 1 week using pre-culture medium.

[0085] (7) Analysis and quantitative determination of odor components (i) Using pre-cultured Penicillium citrinum (NBRC6352), spores were collected using a dry cotton swab (Mentip φ3×152mm, manufactured by Nippon Cotton Swab Co., Ltd.), and the spore count was reduced to 1.8-2.5×10 in an aqueous solution of 0.05 w / v% polyoxyethylene (20) sorbitan monooleate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). 6 It was prepared to have a concentration of particles / ml. (ii) The number of spores is determined by placing the spore solution collected in (i) into a cell counter plate (WATSON Corporation) and counting the number of spores using a microscope, resulting in a count of 1.8 to 2.5 × 10⁻⁶. 6 I confirmed that the value is per ml. (iii) 2.80 × 8.94 cm (25 cm) 2 The filter paper was sterilized by ultraviolet irradiation. (iv) The filter paper was attached to the inner wall of the housing 30 mm away from the air vent of the air conditioner. The aerosol sample was placed so that the nozzle was 15 cm away from the air outlet of the air conditioner and sprayed. (v) The filter paper was dried to a suitable temperature and attached to the slant culture medium. (vi) Three 30 μL doses of spore solution were inoculated onto the attached filter paper. The inoculation procedure involved first dropping the solution into the center of the filter paper, and then dropping it into two more locations on either side of the center, at equal intervals. (vii) A φ1 mm hole was made in the lid of the vial, a wire was passed through the hole in the lid, and a MonoTrap RGPS TD (manufactured by GL Sciences), which serves as an odor collector, was attached to the end of the wire. At this time, the distance between the culture medium and the collector was fixed at approximately 10 mm. After the procedures in (viii)(vii), the cells were immediately incubated in an incubator set to 25°C for 3 days. (ix) Subsequently, the adsorbed odor agent was subjected to GC-MS analysis, and the control group and the treated group were compared. For peaks detected only in the treated group, the compounds were identified and their peak area values ​​were calculated. Compound identification was performed in the same manner as in Example 1. <Analysis conditions, analysis method, amount of odor component generation, and odor component generation suppression rate> The analytical conditions, analytical method, amount of odor component (3-methyl-1-butanol) generated, and the odor component generation suppression rate were the same as in Example 9. When this data was organized, it was as shown in Table 7. [Table 7]

[0086] As shown in Table 7, when an antimicrobial compound was actually sprayed into the air conditioner using an aerosol product at the expected spray distance, the surface concentration of the antimicrobial compound (IPMP, Hygenia) adhering to the inside of the air conditioner was lower than the minimum growth inhibition surface concentration, but it was confirmed that the amount of 3-methyl-1-butanol, an odor component, was suppressed. In one aspect of the present invention, it was confirmed that mold odor caused by mold inside an air conditioner can be suppressed using an aerosol product. [Explanation of Symbols]

[0087] 111: Spray button, 112: Nozzle

Claims

1. A method for suppressing mold-derived odors, comprising the step of applying an antimicrobial compound to mold at a concentration below the minimum inhibitory concentration for mold growth.

2. The method for suppressing mold-derived odors according to claim 1, wherein the minimum growth inhibitory concentration is the minimum growth inhibitory volume concentration or the minimum growth inhibitory surface concentration.

3. The method for suppressing mold-derived odors according to claim 1, wherein an antimicrobial compound is used at a concentration of 95% or less of the minimum inhibitory concentration for mold growth.

4. A method for suppressing mold-derived odors according to claim 1, wherein the mold-derived odor is based on one or more selected from the group consisting of 3-methyl-1-butanol and phenylethyl alcohol.

5. The method for suppressing mold-derived odors according to claim 1, wherein the mold is one or more species selected from the group consisting of the genera Penicillium and Cladosporium.

6. The method for suppressing mold-derived odors according to claim 1, wherein the antimicrobial compound is isopropylmethylphenol, 1,4-bis[3,3'-(1-decylpyridinium)methyloxy]butanedibromide, silver ions, benzalkonium chloride, benzalkonium saccharate, or enilconazole.

7. The method for suppressing mold-derived odors according to any one of claims 1 to 6, wherein the mold is mold inside the air conditioner.

8. A method for suppressing mold-derived odors according to any one of claims 1 to 6, wherein an antimicrobial compound is applied to the mold using an aerosol product.

9. A composition for use in a method for suppressing mold-derived odors according to any one of claims 1 to 6.

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