Smoking device for toilet and deodorizing method of toilet

Abstract

To provide a smoking device for toilets capable of excellently reducing odor of a toilet in a short time.SOLUTION: A toilet has an outer container and a contents container located inside the outer container, wherein the contents container houses a smoke agent composition (A), forming a smoke agent section, the outer container contains a heat-generating substance (B) that generates heat upon contact with water, forming a heating section. In this smoke generating device that heats the smoke agent composition (A) via the content container with hydration reaction heat of the heat-generating substance (B), the smoke generating agent composition (A) contains a drug and an organic foaming agent, and the heat-generating substance (B) has a specific range for the temperature measured at 30 seconds and the duration at 50°C according to a specific measurement method.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a fumigation device for a toilet and a method for deodorizing a toilet.

Background Art

[0002] The odor in a toilet can be caused not only by the odor in the toilet bowl but also by the growth of bacteria in the back of the floor, the ventilation fan, etc. Therefore, in order to deal with the odor in the toilet, disinfection of the entire toilet space is required. As a method of treating a closed space such as a toilet with insecticide, disinfection, etc., fumigation treatment can be mentioned. In the fumigation treatment, a drug or the like as an active ingredient is volatilized in smoke into the treatment target space, and the entire treatment target space is treated. Therefore, the fumigation treatment is effective as a means for easily treating even hard-to-reach places. A fumigation device is used for the fumigation treatment. For example, Patent Document 1 proposes a fumigation device including a housing, a heating unit in which a heating agent is accommodated in the housing, a metal inner container provided in the housing and located above the heating unit, and a fumigation agent composition containing a drug filled in the inner container. According to the invention of Patent Document 1, the drug can be volatilized into the space by the fumigation treatment.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, even when using a conventional fumigation device, the odor in the toilet cannot be sufficiently reduced. In addition, while the fumigation treatment is being performed and the treatment target space is filled with smoke, it is not possible to enter the toilet. Since the toilet is a space frequently used by residents, it is required to complete the fumigation treatment in a short time. When the time for the fumigation treatment is shortened, the diffusion of the active ingredient becomes insufficient, and the disinfection effect cannot be sufficiently enhanced.

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a fumigation device for a toilet that can better reduce the odor in the toilet in a short time.

Means for Solving the Problems

[0006] The present inventor has obtained the following findings. In the toilet space, Moraxella, Micrococcus, and Kocuria are widely present and metabolize dirt to produce odors. The above three bacterial species have high resistance to stress such as drying and high resistance to drugs, and cannot be sufficiently sterilized by conventional fumigation devices. As a result of intensive studies based on the above findings, the present inventor has found that by using an exothermic agent having specific characteristics, a high sterilization effect can be exhibited on the above three bacterial species in a short time, and the present invention has been completed. The present invention has the following aspects.

[0007] <1> It has an outer container and an inner container located inside the outer container. The inner container contains a fumigant composition (A) to form a fumigant part. The outer container contains an exothermic substance (B) that generates heat when it comes into contact with water to form a heating part. In a fumigation device that heats the fumigant composition (A) through the inner container by the heat of hydration reaction of the exothermic substance (B). The fumigant composition (A) contains a drug and an organic foaming agent. The exothermic substance (B) is a fumigation device for a toilet, the temperature measured by the following measurement method satisfies the following temperature conditions (i) and (ii). ≪Measurement Method≫ Mix 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C, and measure the water temperature while stirring. ≪Temperature Conditions≫ (i) The water temperature 30 seconds after mixing 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C is 50°C or higher. (ii) When 600 g of distilled water at 20°C and 100 g of exothermic substance (B) at 20°C are mixed, the duration at 50°C or higher is 30 seconds or more within 60 seconds from the start of mixing. <2> The toilet fumigation device according to <1>, wherein the fumigant composition (A) contains a nonionic surfactant (A3). <3> The toilet fumigation device according to <2>, wherein the fumigant composition (A) contains a water-insoluble silicon-containing inorganic compound (A4).

[0008] <4> Using the toilet fumigation device according to any one of <1> to <3>, A method for deodorizing a toilet, comprising contacting water with the exothermic substance (B) and heating the fumigant composition (A) by the heat of hydration of the exothermic substance (B) to volatilize the agent. <5> A method for deodorizing a toilet according to <4>, which sterilizes one or more selected from bacteria of the genus Moraxella, bacteria of the genus Micrococcus, and bacteria of the genus Kocuria.

Advantages of the Invention

[0009] According to the toilet fumigation device of the present invention, the odor of the toilet can be reduced better in a short time.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0011] (Toilet fumigation device) The toilet fumigation device of the present invention (hereinafter sometimes simply referred to as "fumigation device") has a fumigant part and a heating part. In this manuscript, the term "sterilization" includes, in addition to reducing or killing the number of bacteria, the effect of suppressing the growth of bacteria (bacteriostasis). In addition, the term "deodorization" includes, in addition to reducing the generated odor, the effect of suppressing the generation of odor.

[0012] The fumigation device of the present invention will be described below with reference to embodiments. The fumigation device 10 shown in FIG. 1 includes an outer container 12, a heating unit 20 provided inside the outer container 12, and a fumigant unit 32 provided inside the outer container 12. The outer container 12 has a substantially cylindrical main body 14, a bottom portion 16, and a lid portion 18 provided at the upper portion of the main body 14. An inner container 30 is located inside the outer container 12, and the inner container 30 is filled with a fumigant composition to form a fumigant unit 32. The bottom portion 31 of the inner container 30 is spaced apart from the bottom portion 16 of the outer container 12.

[0013] <Outer container> The main body 14 is, for example, a cylindrical or polygonal cylindrical molded body. Examples of the material of the main body 14 include metal, ceramic, plastic, paper, etc. Examples of the metal constituting the main body 14 include tin, aluminum, copper, stainless steel, etc. From the viewpoint of being easy to process and having excellent strength, the material of the main body 14 is preferably metal, and more preferably tin. The wall thickness of the main body 14 is, for example, 0.1 to 0.5 mm.

[0014] The lid portion 18 has a through hole (smoke passage hole), and examples thereof include mesh, punching metal, and a lattice-shaped frame body. Examples of the material of the lid portion 18 are the same as those of the main body 14. The material of the lid portion 18 and the material of the main body 14 may be the same or different.

[0015] The bottom portion 16 is, for example, a non-woven fabric or a metal mesh. By using a non-woven fabric or a metal mesh for the bottom portion 16, water can be introduced into the heating unit 20 from the bottom portion 16 to generate hydration reaction heat, and the fumigant composition can be heated.

[0016] The inner diameter R12 of the outer container 12 is, for example, 45 to 90 mm. When the outer container 12 is in the shape of a polygonal cylinder, the average of the diagonal lengths is taken as the inner diameter R12. The height H12 of the outer container 12 is, for example, 30 to 110 mm. The height H12 is the distance from the upper end of the main body 14 to the inner surface (upper surface) of the bottom 16.

[0017] <Inner container> The inner container 30 functions as a container for filling the fumigant part 32 and also functions as a heat transfer part for transmitting the heat energy generated in the heating part 20 to the fumigant part 32. The inner container 30 is cylindrical or polygonal cylindrical, and its lower end is closed by the bottom 31.

[0018] Examples of the material of the inner container 30 include tinplate, stainless steel, etc.

[0019] The wall thickness of the inner container 30 is, for example, 0.1 to 0.5 mm. When the wall thickness of the inner container 30 is equal to or greater than the above lower limit value, the rigidity of the container can be further enhanced. When the wall thickness of the inner container 30 is equal to or less than the above upper limit value, the heat energy generated in the heating part 20 can be transmitted to the fumigant part 32 faster and more efficiently.

[0020] The inner diameter R30 of the inner container 30 is, for example, 30 to 85 mm. When the outer container 12 is in the shape of a polygonal cylinder, the average of the diagonal lengths is taken as the inner diameter R30.

[0021] The distance D30 between the lower surface of the bottom 31 of the inner container 30 and the upper surface of the bottom 16 of the outer container 12 is, for example, 8 to 20 mm. When the distance D30 is equal to or greater than the above lower limit value, heat energy can be uniformly transmitted from the bottom 31 to the fumigant composition. When the distance D30 is equal to or less than the above upper limit value, the delay in the time (fumigation start time) until the organic foaming agent (A2) starts to decompose can be suppressed.

[0022] <Fumigant part> The fumigant part 32 is formed by containing the fumigant composition (A) in the inner container 30. The fumigant composition (A) contains the drug (A1) and the organic foaming agent (A2).

[0023] <<Agent>> The agent (A1) is a so-called disinfectant (or bactericide). Examples of the agent (A1) include insecticidal components such as methoxadiazone, d·d-T phenothrin, phenothrin, 3-phenoxybenzyl chrysanthemate (also referred to as phenothrin), permethrin, etc.; silver alone; silver compounds such as silver oxide, silver chloride, silver nitrate, etc.; those obtained by supporting silver alone or a silver compound on substances such as zeolite, silica gel, low molecular glass, calcium phosphate, silicate, titanium oxide (hereinafter sometimes referred to as a carrier) (hereinafter sometimes referred to as a supported body), etc.; 4-isopropyl-3-methylphenol (also referred to as "IPMP"); 3-iodo-2-propynyl butylcarbamate (also referred to as "IPBC"), etc. Among them, silver alone, silver compounds and their supported bodies (i.e., agents containing silver) are preferred because of their high disinfection effect and high bacteriostatic effect.

[0024] The content of the agent (A1) is preferably 2 to 40% by mass, more preferably 2 to 20% by mass, based on the total mass of the fumigant composition (A). When the agent (A1) is an agent containing silver, the content of the agent (A1) is preferably 0.001 to 0.5% by mass in terms of silver, more preferably 0.04 to 0.1% by mass, based on the total mass of the fumigant composition (A). When the content of the agent (A1) is at least the above lower limit value, the disinfection effect can be further enhanced and the deodorizing effect can be further enhanced. When the content of the agent (A1) is at most the above upper limit value, the agent (A1) can be volatilized more efficiently.

[0025] The content of the agent (A1) in the fumigant composition (A) is preferably 0.01 to 0.60 g / m 3 with respect to the volume of the treatment target space, more preferably 0.01 to 0.40 g / m 3 When the content of the agent (A1) is at least the above lower limit value, the disinfection effect can be further enhanced. When the content of the agent (A1) is at most the above upper limit value, the agent (A1) can be volatilized more efficiently.

[0026] <<Organic foaming agent>> Examples of the organic foaming agent (A2) include azodicarbonamide, p,p'-oxybis(benzenesulfonyl hydrazide), N,N'-dinitrosopentamethylenetetramine, azobisisobutyronitrile, and the like. Among the above, azodicarbonamide (ADCA) is preferred as the organic foaming agent (A2) because of its low decomposition temperature and large amount of generated foaming gas.

[0027] The content of the organic foaming agent (A2) can be determined in consideration of the types of the organic foaming agent and the chemicals. The content of the organic foaming agent (A2) is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, based on the total mass of the fumigant composition (A). When the content of the organic foaming agent (A2) is at least the above lower limit value, the chemical (A1) can be volatilized more efficiently. When the content of the organic foaming agent (A2) is at most the above upper limit value, the generation of decomposition products (white substances) of the fumigant composition (A) can be reduced.

[0028] ≪Nonionic surfactant≫ The fumigant composition (A) may contain a nonionic surfactant (A3). By containing the nonionic surfactant (A3) in the fumigant composition (A), the disinfection effect can be enhanced and the deodorization effect can be further enhanced.

[0029] As the nonionic surfactant (A3), a fatty acid ester of a polyhydric alcohol or its ethylene oxide adduct, or a copolymer type nonionic surfactant (EOPO nonionic) of an oxyethylene group (EO) and an oxypropylene group (PO) is preferred. As the fatty acid ester of a polyhydric alcohol or its ethylene oxide adduct, sorbitan fatty acid esters, POE-sorbitan fatty acid esters, and glycerin fatty acid esters are more preferred. Examples of the fatty acid ester of a polyhydric alcohol or its ethylene oxide adduct include monooleic acid ester, monolauric acid ester, glyceryl monocaprylate, and the like. As for the EOPO nonionic surfactants, examples include EO-PO-EO type nonionic surfactants in which the PO (propylene oxide) block represented by the following (1) is sandwiched by EO (ethylene oxide) blocks, PO-EO-PO type nonionic surfactants in which the EO block represented by the following (2) is sandwiched by PO blocks, and the like. R 1 -O-(EO) a -(PO) b -(EO) c -R 2 ···(1) R 1 -O-(PO) d -(EO) e -(PO) f -R 2 ···(2)

[0030] (In formulas (1) and (2), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a hydrogen atom is preferred in both cases.

[0031] (In formula (1), a represents the average repeating number (average added mole number) of EO, a number of 5 to 150 is preferred, and a number of 10 to 100 is more preferred. b represents the average repeating number (average added mole number) of PO, a number of 5 to 250 is preferred, and a number of 10 to 60 is more preferred. c represents the average repeating number (average added mole number) of EO, a number of 5 to 150 is preferred, and a number of 10 to 100 is more preferred. Also, a + b + c is preferably a number of 20 to 500. Examples of the nonionic surfactant represented by formula (1) include "Pluronic PE9200 (manufactured by BASF Japan Ltd.)", "Pluronic PE9400 (manufactured by BASF Japan Ltd.)", "Pluronic PE6400 (manufactured by BASF Japan Ltd.)", and the like.

[0032] (2) In the formula, d represents the average number of repetitions (average number of added moles) of PO, a number from 5 to 150 is preferred, and a number from 10 to 30 is more preferred. e represents the average number of repetitions (average number of added moles) of EO, a number from 5 to 250 is preferred, and a number from 5 to 30 is more preferred. f represents the average number of repetitions (average number of added moles) of PO, a number from 5 to 150 is preferred, and a number from 10 to 30 is more preferred. d + e + f is preferably a number from 20 to 500. Examples of the nonionic surfactant represented by formula (2) include "Pluronic RPE1740 (manufactured by BASF Japan Ltd.)", "Pluronic RPE2035 (manufactured by BASF Japan Ltd.)", "Pluronic RPE3110 (manufactured by BASF Japan Ltd.)", and the like.

[0033] As the EO-PO nonionic surfactant, a PO-EO-PO type nonionic surfactant represented by formula (2) is more preferred in terms of excellent persistence of the sterilization effect.

[0034] The content of the nonionic surfactant (A3) is preferably 5 to 25% by mass, more preferably 9 to 20% by mass, based on the total mass of the fumigant composition (A). When the content of the nonionic surfactant (A3) is at least the above lower limit value, the action of the component (A1) can be enhanced more. When the content of the nonionic surfactant (A3) is at most the above upper limit value, the odor derived from the nonionic surfactant (A3) can be suppressed better.

[0035] ≪Water-insoluble silicon-containing inorganic compound≫ The fumigant composition (A) may contain a water-insoluble silicon-containing inorganic compound (A4). Water-insoluble means a component having a solubility of 0.1 g or less in 100 mL of ion-exchanged water. When the fumigant composition (A) contains the water-insoluble silicon-containing inorganic compound (A4), the sterilization effect can be enhanced more and the deodorizing effect can be enhanced more.

[0036] Examples of the water-insoluble silicon-containing inorganic compound (A4) include clay, talc, zeolite, amorphous silica, diatomaceous earth, etc. Among them, as the water-insoluble silicon-containing inorganic compound (A4), amorphous silica and diatomaceous earth, which mainly contain amorphous silicon dioxide and have a high content thereof, are more preferable.

[0037] The water-insoluble silicon-containing inorganic compound (A4) is preferably a compound having an oil absorption of 30 to 400 mL / 100 g, and more preferably a compound having an oil absorption of 90 to 200 mL / 100 g. When the oil absorption is at least the above lower limit value, the sterilization performance can be further enhanced. When the oil absorption is at most the above upper limit value, the volatility of the nonionic surfactant (A3) can be further enhanced. The oil absorption is measured in accordance with JIS K5101-13-1 (refined linseed oil method). As a substitute for refined linseed oil, linseed oil manufactured by FUJIFILM Wako Pure Chemical Corporation is used.

[0038] The content of the water-insoluble silicon-containing inorganic compound (A4) is preferably 5 to 23% by mass, and more preferably 7 to 18% by mass with respect to the total mass of the fumigant composition (A). When the content of the water-insoluble silicon-containing inorganic compound (A4) is at least the above lower limit value, the sterilization effect can be further enhanced and the deodorizing effect can be further enhanced. When the content of the water-insoluble silicon-containing inorganic compound (A4) is at most the above upper limit value, the agent (A1) can be volatilized more efficiently.

[0039] In the fumigant composition (A), the ratio of the mass of the water-insoluble silicon-containing inorganic compound (A4) to the mass of the nonionic surfactant (A3) (A4 / A3 ratio) is preferably 0.5 to 0.9, and more preferably 0.6 to 0.8. When the A4 / A3 ratio is at least the above lower limit value, the decomposition of the component (A3) during heating is suppressed and the sterilization performance can be further enhanced. When the A4 / A3 ratio is at most the above upper limit value, the sterilization effect can be further enhanced and the deodorizing effect can be further enhanced.

[0040] ≪Optional Component≫ The fumigant composition (A) may contain components other than (A1) to (A4) (optional components). Examples of optional components include binders, excipients, exothermic aids, stabilizers, potency enhancers, antioxidants, flavoring agents, and the like. The optional components may be used alone or in combination of two or more. Note that the total of (A1) to (A4) and the optional components does not exceed 100% by mass.

[0041] Examples of binders include cellulose-based compounds (such as methylcellulose, ethylcellulose, carboxymethylcellulose and its calcium and sodium salts, hydroxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, etc.), starch-based compounds (such as starch, pregelatinized starch, dextrin, hydroxypropyl starch, sodium carboxymethyl starch, etc.), natural product-based compounds (such as gum arabic, sodium alginate, tragacanth, gelatin, etc.), synthetic polymer-based compounds (such as polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, etc.).

[0042] Examples of excipients include sugars (such as sucrose, glucose) and sugar alcohols (such as maltitol, sorbitol, xylitol).

[0043] Examples of exothermic aids include zinc oxide, calcium phosphate, melamine, etc.

[0044] Examples of stabilizers include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate (propyl-3,4,5-trihydroxybenzoate), epoxy compounds (such as epoxidized soybean oil, epoxidized linseed oil, etc.).

[0045] 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), etc.

[0046] Examples of antioxidants include dibutylhydroxytoluene (BHT), tocopherol, and the like.

[0047] Examples of flavoring agents include various fragrances. The fragrance can impart a scent when the smoke agent composition is used and mask the odor of the smoke agent. The fragrance components are not particularly limited, and lists of fragrance raw materials that can be used are described in various documents. For example, fragrances described in the following documents can be mentioned. 「Perfume and Flavor Chemicals」, Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994), 「Synthetic Fragrance Chemistry and Product Knowledge」, written by Motokazu Indoh, Chemical Industry Daily Co., Ltd. (1996); 「Perfume and Flavor Materials of Natural Origin」, Steffen Arctander, Allured Pub. Co. (1994); 「Encyclopedia of Scents」, edited by the Japan Flavor Association, Asakura Shoten (1989); 「Perfumery Material Performance V.3.3」, Boelens Aroma Chemical Information Service (1996); 「Floweroils and Floral Compounds In Perfumery」, Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc.

[0048] Examples of solvents include water and monohydric alcohols (such as ethanol, propanol, butanol, etc.).

[0049] These optional components may be used alone or in combination of two or more.

[0050] ≪Physical Properties of Smoke Agent Composition (A)≫ The particle size of the smoke agent composition (A) is preferably 1 to 15 mm, more preferably 1 to 10 mm. When the particle size of the smoke agent composition (A) is equal to or greater than the above lower limit value, leakage of the smoke agent composition (A) from the smoke passage holes can be more reliably suppressed. When the particle size of the smoke agent composition (A) is equal to or less than the above upper limit value, the smoke agent composition (A) can be quickly heated, and it is easy to increase the smoke efficiency. In this specification, the particle size of the smoke agent composition (A) is determined by the following measurement method. Ten sieves with mesh openings of 5600 μm, 4000 μm, 3350 μm, 2800 μm, 2360 μm, 2000 μm, 1400 μm, 1180 μm, 1000 μm, and 100 μm are provided in this order from the top, and a classification operation is performed using a sieve shaker provided with a tray at the bottom. Next, the masses of the granules collected from each sieve and the tray are measured. For the granules collected in the tray, the mass frequencies are added and integrated in order from the granules remaining on the sieve with the smallest mesh opening, and the mesh opening of the first sieve at which the integrated mass frequency becomes 50% or more is defined as "a μm", and the mesh opening of the sieve with a mesh opening one step larger than a μm is defined as "b μm". Also, the integrated value of the mass frequency from the tray to the sieve with a mesh opening of a μm is defined as "c%", and the mass frequency of the granules on the sieve with a mesh opening of a μm is defined as "d%". Using these values of a to d, D M50 (mass 50% diameter) is taken as the average particle size.

[0051]

Equation

[0052] ≪Manufacturing method of the smoke agent composition (A)≫ As the manufacturing method of the smoke agent composition (A), a known manufacturing method is used according to the target dosage form. For example, when making a granular preparation, it can be manufactured by a known manufacturing method for granulated products such as an extrusion granulation method, a compression granulation method, a stirring granulation method, a rolling granulation method, a fluidized bed granulation method, etc. As a specific example of the production method by the extrusion granulation method, each component of the fumigant composition (A) is mixed by a kneader or the like, and an appropriate amount of water is added and mixed as necessary. Then, the obtained mixture is granulated using a die having an arbitrary aperture diameter with a forward extrusion or lateral extrusion granulator. The granulated product may be further cut into an arbitrary size with a cutter or the like, and dried for moisture removal. Examples of the drying method include a heat drying method using a conventionally well-known dryer. The drying temperature is not particularly limited, but from the viewpoint of suppressing volatilization of fragrances and the like, 50 to 80 °C is preferable. The drying time is appropriately determined according to the drying temperature. The water content of the fumigant composition (A) after drying is not particularly limited, but preferably 5% by mass or less, more preferably 2% by mass or less, and may even be 0% by mass. When the water content is below the above upper limit value, the volatilization rate of the agent can be further increased. The water content can be measured with a moisture meter, for example, by grinding the fumigant composition (A) after drying and measuring it under the conditions of 105 °C for 20 minutes. Examples of the moisture meter include the moisture meter "MOC-120H" manufactured by Shimadzu Corporation.

[0053] <Heating section> The heating section 20 is formed of an exothermic substance (B) that generates heat upon contact with water. The exothermic substance (B) is in the form of granules and forms the heating section 20 in a state having fluidity.

[0054] Examples of the exothermic substance (B) include calcium oxide, magnesium chloride, aluminum chloride, calcium chloride, iron chloride, alum, zinc sulfide, magnesium sulfate, nickel chloride, and the like. From the viewpoints of ease of handling and the amount of heat, calcium oxide is preferable as the exothermic substance (B).

[0055] The particle size of the exothermic substance (B) is preferably 1 to 7 mm, more preferably 1 to 5 mm. When the particle size of the exothermic substance (B) is at least the above lower limit value, the persistence of the thermal energy generated from the exothermic substance (B) can be further enhanced. When the particle size of the exothermic substance (B) is at most the above upper limit value, the exothermic substance (B) can be accommodated at a higher density between the content 30 and the outer container 12. Therefore, thermal energy can be efficiently supplied by the fumigant part 32. The particle size of the exothermic substance (B) is the mass 50% diameter, which is measured by the same method as the fumigant composition (A).

[0056] The bulk density of the exothermic substance (B) is preferably 0.65 to 0.90 g / mL, more preferably 0.70 to 0.85 mL. When the bulk density of the exothermic substance (B) is at least the above lower limit value, the exothermic substance (B) can be accommodated at a higher density between the content 30 and the outer container 12, and thermal energy can be efficiently supplied by the fumigant part 32. When the bulk density of the exothermic substance (B) is at most the above upper limit value, the heating time does not become longer than necessary, so the usability is improved. The method for measuring the bulk density will be described. Calcium oxide is gently filled into a cylindrical container with a volume of 100 mL at a constant rate, the mass after trituration is weighed, and the bulk specific gravity (g / mL) is calculated from the mass (g) of calcium oxide / volume (mL).

[0057] The temperature measured by the following measurement method of the exothermic substance (B) satisfies the following temperature conditions (i) and (ii).

[0058] ≪Measurement method≫ 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C are mixed, and the water temperature is measured while stirring. The water temperature measuring device used for the method of measuring the water temperature will be described. The water temperature measuring device 100 in Fig. 1 has a container 102, a stirrer 120, and a thermometer 130.

[0059] Examples of the container 102 include a Dewar flask (D-1000, manufactured by Taiyo Nippon Sanso Corporation), etc. Examples of the stirrer 120 include a three-one motor (BL1200, manufactured by Shin-Tong Science Co., Ltd.). Examples of the thermometer 130 include a thermocouple thermometer (thermometer: AP-310E, manufactured by Anritsu Meter Co., Ltd.) and a temperature sensor: BS-21E-020-TC2-ASP, manufactured by Anritsu Meter Co., Ltd.).

[0060] A method for measuring the water temperature using the water temperature measuring device 100 will be described. For example, 600 mL of distilled water 110 at 20°C is poured into the container 102, and the stirring blade 122 of the stirrer 120 is placed in the distilled water 110. The position of the stirring blade 122 is 10 mm above the bottom of the container 102. The sensor part 132 of the thermometer 130 is placed in the distilled water 110. The distance D132 from the upper end of the stirring blade 122 to the lower end of the sensor part 132 is 20 mm. While stirring the distilled water 110 with the stirrer 120 (300 rpm), 100 g of calcium oxide is added to the distilled water 110, and the container 102 is covered with a cork stopper. The water temperature is measured for 60 seconds from the time when calcium oxide is added (when the hydration reaction starts). The water temperature 30 seconds after the start of the hydration reaction is defined as the water temperature at 30 seconds. The time during which the water temperature remains at 50°C or higher within 60 seconds from the start of the hydration reaction is defined as the 50°C duration. The water temperature at 30 seconds and the 50°C duration can be adjusted by combinations such as the type, particle size, and bulk density of the exothermic substance (B).

[0061] ≪Temperature Conditions≫ (i) The water temperature 30 seconds after mixing 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C is 50°C or higher. That is, the water temperature at 30 seconds is 50°C or higher. (ii) The duration during which the temperature is 50°C or higher is 30 seconds or more within 60 seconds after mixing 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C. That is, the 50°C duration is 30 seconds or more.

[0062] The water temperature at 30 seconds is 50°C or higher. When the water temperature at 30 seconds is at or above the above lower limit value, the volatilization of the chemical agent (A1) starts promptly, and the time for the fumigation treatment can be shortened. The upper limit of the water temperature at 30 seconds is 100°C or lower, and substantially 60°C or lower.

[0063] The duration at 50°C is 20 seconds or more, preferably 30 seconds or more, and more preferably 40 seconds or more. When the duration at 50°C is at least the above lower limit, the volatilization amount of the agent (A1) can be increased, and the disinfection effect can be enhanced. The upper limit of the duration at 50°C is substantially 50 seconds.

[0064] In the method for measuring the water temperature, the time until 20°C distilled water reaches 50°C (50°C arrival time) is preferably 30 seconds or less, and more preferably 10 seconds or less. When the 50°C arrival time is at or below the above upper limit, the fumigation treatment time can be further shortened. The lower limit of the 50°C arrival time is not particularly limited.

[0065] The ratio of the mass of the exothermic substance (B) to the mass of the fumigant composition (A) (B / A ratio) is preferably 1 to 20, and more preferably 5 to 15. When the B / A ratio is at least the above lower limit, poor smoke generation of the fumigant composition (A) can be suppressed and the disinfection performance can be further enhanced. When the B / A ratio is at or below the above upper limit, the heating time does not become longer than necessary, so the usability is improved.

[0066] (Method for manufacturing a fumigation device) The fumigation device 10 is obtained by accommodating the fumigant composition (A) in the inner container 30 and accommodating the exothermic substance (B) in the space formed between the inner container 30 and the outer container 12. The method for accommodating the fumigant composition (A) in the inner container 30 and the method for accommodating the exothermic substance (B) in the space formed between the inner container 30 and the outer container 12 are not particularly limited, and can be accommodated by known methods. The filling amount of the fumigant composition (A) can be appropriately determined in consideration of the volume of the treatment target space (tray) and the content of the component (A1) in the fumigant composition (A). The filling amount of the exothermic substance (B) can be appropriately determined in consideration of the filling amount of the fumigant composition (A).

[0067] (Method for using a fumigation device) The method for using the fumigation device of the present invention (i.e., the method for deodorizing a toilet) uses the fumigation device 10 of the present invention. In the smoking method using the smoking device 10, first, the smoking device 10 is installed in the space to be treated (toilet). Next, water is brought into contact with the heating unit 20. As a method of bringing water into contact with the heating unit 20, there is a method of putting water in a container and immersing the bottom 16 of the outer container 12 in the water of the container. When the bottom 16 is immersed in water, the water penetrates from the bottom 16 into the heating unit 20, and the water comes into contact with the exothermic substance (B). When the water comes into contact with the exothermic substance (B), heat is generated by the hydration reaction. The thermal energy generated by the hydration reaction is propagated to the fumigant part 32 through the inner container 30 to heat the fumigant part 32. The fumigant composition (A) of the heated fumigant part 32 generates gas by thermal decomposition of the organic blowing agent (A2), and the agent (A1) is smoked (smokes) together with the generated gas and ejects through the smoke passage hole of the lid part 18. Thereby, the agent (A1) volatilizes into the target space. The volatilized agent (A1) diffuses to the details in the space to be treated. The diffused agent (A1) acts on the bacteria attached to the floor surface, wall surface, outer surface of the toilet bowl, etc. of the space to be treated, reducing or killing the bacteria. In addition, the diffused agent (A1) adheres to the floor surface, wall surface, outer surface of the toilet bowl, etc., and suppresses the growth of bacteria (bacteriostasis).

[0068] The time (smoking start time) from when water is brought into contact with the heating unit 20 until the organic blowing agent (A2) starts to decompose is preferably, for example, 20 to 50 seconds, and more preferably 20 to 40 seconds. When the smoking start time is at least the above lower limit value, it is possible to secure the time until the user evacuates from the space where the fumigant is used. When the smoking start time is at most the above upper limit value, it is possible to prevent the user from misrecognizing poor smoking.

[0069] The time (smoking time) from when water is brought into contact with the heating unit 20 until the decomposition of the organic blowing agent (A2) is completed and the smoking treatment ends is preferably, for example, 3 to 15 minutes, and more preferably 5 to 10 minutes. When the smoking time is at least the above lower limit value, it becomes easier for the smoke to spread to every corner of the space. When the smoking time is at most the above upper limit value, leakage of the smoke from the space where it is used can be suppressed.

[0070] The time from the start of smoke generation to the replacement of the air in the target space (treatment time) by the smoke generating device 10 is preferably, for example, 15 to 30 minutes, more preferably 20 to 30 minutes. When the treatment time is at least the above lower limit value, the disinfection performance can be further enhanced. When the treatment time is at most the above upper limit value, the burden on the user that the target space cannot be used can be reduced.

[0071] Bacteria of the genus Moraxella, genus Micrococcus, and genus Kocuria are highly resistant to drugs. However, since the smoke generating device of the present invention has a specific exothermic substance (B), it starts heating the fumigant composition (A) in a short time and continues to heat the fumigant composition (A) for an arbitrary time. For this reason, a sufficient amount of the drug (A1) capable of disinfecting bacteria of the genus Moraxella, genus Micrococcus, and genus Kocuria is volatilized in a short time, and the odor in the toilet can be reduced better in a short time. For example, in the method of using the smoke generating device of the present invention, bacteria of the genus Moraxella, genus Micrococcus, and genus Kocuria are set to 1 / 1,000,000 to 1 / 1,000.

[0072] The bacteria to be disinfected are mainly bacteria of the genus Moraxella, genus Micrococcus, and genus Kocuria, as well as bacteria that cause odors. Among them, the smoke generating device of the present invention can more effectively reduce the odor in the toilet and prevent the generation of the odor in the toilet by disinfecting Moraxella osloensis, Moraxella sp., Micrococcus luteus, Kocuria marina, and Kocuria indica. That is, the method of using the smoke generating device of the present invention is also a method for disinfecting bacteria that cause the odor in the toilet.

Examples

[0073] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following description.

[0074] (Raw materials used) <Component (A1): Medicament> · A1-1: Silver-supported zeolite-based inorganic antibacterial agent (trade name: Zeomic AJ10N, manufactured by Sinanen Zeomic Co., Ltd., silver content 2.5% by mass, average particle diameter about 2.5 μm). · A1-2: 4-Isopropyl-3-methylphenol (IPMP) (trade name: 4-Isopropyl-3-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0075] <Component (A2): Exothermic substance> · A2-1: Azodicarbonamide (trade name: Diblow AC.2040(C), manufactured by Dainichi Seika Chemicals Co., Ltd.).

[0076] <Component (A3): Nonionic surfactant> · A3-1: PO-EO-PO type nonionic surfactant (trade name: Pluronic RPE1740, manufactured by BASF Japan Ltd.). · A3-2: EO-PO-EO type nonionic surfactant 1 (trade name: Pluronic PE6400, manufactured by BASF Japan Ltd.). · A3-3: Sorbitan fatty acid ester (trade name: Emalzol O-10V, manufactured by Kao Corporation).

[0077] <Component (A4): Water-insoluble silicon-containing inorganic compound> · A4-1: Amorphous silica 1 (trade name: Silicia 740, manufactured by Fuji Silysia Chemical Ltd., oil absorption 95 mL / 100 g, bulk density 0.34 g / mL). · A4-2: Diatomaceous earth (trade name: Radiolite #200, manufactured by Showa Chemical Industry Co., Ltd., oil absorption 140 mL / 100 g, bulk density 0.30 g / mL). · A4-3: Talc (trade name: Talc FH01, manufactured by Fukuoka Talc Kogyosho Co., Ltd., oil absorption 40 mL / 100 g, bulk density 0.10 g / mL). · A4-4: Clay (Product Name: NK-300, manufactured by Showa KDE Co., Ltd., oil absorption 35 mL / 100 g, bulk density 0.74 g / mL). · A4-5: Amorphous silica 2 (Product Name: Silicia 350, manufactured by Fuji Silysia Chemical Ltd., oil absorption 320 mL / 100 g, bulk density 0.09 g / mL).

[0078] <(B) component: Exothermic substance> · B-1: Calcium oxide 1 (Product Name: CAg, manufactured by Yoshizawa Lime Industry Co., Ltd., water temperature at 30 seconds: 53°C, duration at 50°C: 50 seconds, bulk density: 0.72 g / mL). · B-2: Calcium oxide 2 (Product Name: CAg, manufactured by Yoshizawa Lime Industry Co., Ltd., water temperature at 30 seconds: 51°C, duration at 50°C: 30 seconds, bulk density: 0.79 g / mL). · B-3: Calcium oxide 3 (Product Name: CAg, manufactured by Yoshizawa Lime Industry Co., Ltd., water temperature at 30 seconds: 50°C, duration at 50°C: 20 seconds, bulk density: 0.81 g / mL).

[0079] <(B’) component: Comparative product of (B) component> · B’-1: Calcium oxide 4 (Product Name: CAg (left to stand and absorb moisture at 20°C and 70% relative humidity), manufactured by Yoshizawa Lime Industry Co., Ltd., water temperature at 30 seconds: 48°C, duration at 50°C: 20 seconds, bulk density: 0.63 g / mL). · B’-2: Calcium oxide 5 (Product Name: CAg (left to stand and absorb moisture at 20°C and 70% relative humidity), manufactured by Yoshizawa Lime Industry Co., Ltd., water temperature at 30 seconds: 40°C, duration at 50°C: 0 seconds, bulk density: 0.60 g / mL). · B’-3: Calcium oxide 6 (Product Name: CAg (left to stand and absorb moisture at 20°C and 70% relative humidity), manufactured by Yoshizawa Lime Industry Co., Ltd., water temperature at 30 seconds: 50°C, duration at 50°C: 10 seconds, bulk density: 0.91 g / mL).

[0080] Regarding the (B) component and (B’) component, the water temperature at 30 seconds and the duration at 50°C were measured, and the results are shown in Table 1.

[0081]

Table 1

[0082] <Any component> · Zinc oxide: ZnO (trade name: Japanese Pharmacopoeia Zinc Oxide, manufactured by Sakai Chemical Industry Co., Ltd.). · Hydroxypropyl methylcellulose: HPMC (trade name: Methocel 60SH-50, manufactured by Shin-Etsu Chemical Co., Ltd.). · Fragrance: The fragrance composition described in Table 1 of JP 2018-64480 A.

[0083] (Examples 1 to 21, Comparative Examples 1 to 3) <Production of the fumigant composition> The fumigant composition (A) was produced by the following procedure. In Tables 2 to 4, the unit of the blending amount of each component of the fumigant composition (A) is mass%. Under room temperature (25°C) conditions, according to Tables 2 to 4, each component of the fumigant composition (A) was stirred and mixed with a kneader (manufactured by Moriya Co., Ltd., "S5-2G type"), and then 1 to 20 parts by mass of water was added and mixed with the total amount of the composition as 100 parts by mass to obtain a mixture. The obtained mixture was granulated using a pre-extrusion granulator (manufactured by Fuji Paudal Co., Ltd., "EXK-1") with a die having an opening diameter of 3 mm to obtain a granulated product. The obtained granulated product was cut into lengths of 2 to 5 mm by a flash mill (manufactured by Fuji Paudal Co., Ltd., "FL300") and dried for 2 hours by a blowing low-temperature dryer (manufactured by Tokyo Rika Kikai Co., Ltd., "WFO-520W") set at 70°C to obtain a granular fumigant composition (A).

[0084] <Fabrication of the fumigation device> A fumigation device having the same configuration as the fumigation device 10 shown in FIG. 1 was fabricated by the following procedure. A tin can (diameter 52 mm × height 67 mm) used in "Look Plus Bathroom Antifungal Fumigant" manufactured by Lion Corporation was filled with 55 g of calcium oxide (component (B) and component (B') described in the raw materials used) to form a heating part. A dedicated bottom was attached to the tin can, and after accommodating 5.0 g of the fumigant composition of each example in the inner container, a lid was attached to obtain the fumigation device of each example.

[0085] (Evaluation method) <Evaluation of Bactericidal Effect> Moraxella osloensis (NBRC 113899), Micrococcus luteus (NBRC 111528), and Kocuria marina (NBRC 113594), each cultured on SCD agar medium (manufactured by Kanto Chemical Co., Inc.) at 25°C for 3 days, were each suspended in a sterilized 0.05% Tween 80 (manufactured by Kanto Chemical Co., Inc.) aqueous solution to prepare a bacterial dispersion of 10 7 ~10 8 CFU / mL. A plastic plate (FRP plate, 50 mm × 50 mm) was inoculated with the bacterial dispersion of one bacterial species and fixed at room temperature for 3 hours to prepare a plastic plate for bactericidal test of each bacterium (the number of bacteria was approximately 10 7 CFU).

[0086] As shown in FIG. 3, plastic plates 210 for bactericidal test were installed at the ceiling corners and floor corners of the sealable evaluation chamber 200 with a width W = 1.6 m, a depth L = 1.6 m, and a height H = 2.0 m, such that the surface inoculated with bacteria faced outward. A plastic container 220 for water supply containing 23 mL of water was installed at the center of the floor of the evaluation chamber 200. The fumigation device of each example was placed in the plastic container 220 for water supply, and fumigation treatment was started, and the evaluation chamber 200 was sealed. After 30 minutes from the start of smoke generation, the air was exhausted (treatment time: 30 minutes), and the plastic plates 210 for bactericidal test were collected. 10 mL of SCDLP liquid medium (manufactured by Shiotani MS Co., Ltd.) was added to the plastic plates 210 for bactericidal test to wash out the bacteria, and the solution was smear-inoculated onto SCD agar medium (manufactured by Kanto Chemical Co., Inc.). After culturing at 25°C for 5 days, the number of colonies was counted to calculate the viable bacteria count. Bacteria were collected from the plastic plates 210 for bactericidal test without fumigation treatment, smear-inoculated onto SCD agar medium, and the colonies after culturing at 25°C for 5 days were counted. The bactericidal activity value was calculated from the following formula. The obtained bactericidal activity values were classified and evaluated according to the following evaluation criteria.

[0087] Bactericidal activity value = Log10(viable bacteria count before treatment) - Log10(viable bacteria count after treatment)

[0088] ≪Evaluation Criteria≫ 〇〇〇〇: The sterilization activity value is 4 or more. 〇〇〇: The sterilization activity value is 3 or more and less than 4. 〇〇: The sterilization activity value is 2 or more and less than 3. 〇: The sterilization activity value is 1.5 or more and less than 2. ×: The sterilization activity value is less than 1.5.

[0089] <Evaluation of Deodorizing Effect> Moraxella osloensis (NBRC 113899), Micrococcus luteus (NBRC 111528), and Kocuria marina (NBRC 113594), each cultured on SCD agar medium (manufactured by Kanto Chemical Co., Inc.) at 25°C for 3 days, were each suspended in a sterilized 0.05% Tween 80 (manufactured by Kanto Chemical Co., Inc.) aqueous solution to prepare a bacterial dispersion of 10 7 ~10 8 CFU / mL. One glass petri dish (50 mm in diameter, manufactured by AS ONE Corporation) was inoculated with the bacterial dispersion of one bacterial species and fixed at room temperature for 3 hours to prepare a glass petri dish for odor evaluation of each bacterium (the number of bacteria was approximately 10 7 CFU).

[0090] Smoke treatment was performed in the same manner as in the "Evaluation of Sterilization Effect", except that the petri dish for odor evaluation was placed in the corner of the floor of the evaluation room 200 with the surface inoculated with bacteria facing upward. Sterilized urine (urine from 10 males blended and filter-sterilized) and 0.1 g of dust from a real household (collected from 10 households' toilets and UV-sterilized) were added to the recovered glass petri dish for odor evaluation. The glass petri dish for odor evaluation with dust and urine added was sealed in an airtight container and cultured at 25°C for 1 day. The odor after culture was subjected to sensory evaluation by 5 professional panelists based on the following evaluation points, and the average score of the 5 evaluation results was calculated. The obtained average score was classified according to the following evaluation criteria and evaluated.

[0091] ≪Evaluation Points≫ 4 points: No odor from bacteria is felt at all. 3 points: Little odor from bacteria is felt. 2 points: Slight smell from the bacteria can be felt. 1 point: Smell from the bacteria can be felt. 0 point: Strong smell from the bacteria can be felt.

[0092] ◎◎◎◎: Average score of 3.5 or more (with particularly excellent odor suppression effect). ◎◎◎: Average score of 2.5 or more and less than 3.5 (with excellent odor suppression effect). ◎◎: Average score of 1.5 or more and less than 2.5 (with odor suppression effect). ◎: Average score of 1.0 or more and less than 1.5 (with small odor suppression effect). ×: Average score less than 1.0 (no odor suppression effect is recognized).

[0093]

Table 2

[0094]

Table 3

[0095]

Table 4

[0096] As shown in Tables 2 to 4, Examples 1 to 21 were excellent in the antibacterial effect and the deodorizing effect. In Comparative Examples 1 to 3 using B’-1 to B’-3 as the heat-generating substance (B), there was an "×" evaluation in at least part of the antibacterial effect and the deodorizing effect. From the above results, it was confirmed that by applying the present invention, the deodorizing effect of the toilet can be obtained in a short time.

Claims

1. It has an outer container and an inner container located inside the outer container, The inner container contains a fumigant composition (A) to form a fumigant part, The outer container contains an exothermic substance (B) that generates heat upon contact with water to form a heating part, In a fumigation device that heats the fumigant composition (A) through the inner container by the heat of hydration of the exothermic substance (B), The fumigant composition (A) contains a drug and an organic foaming agent, The exothermic substance (B) is a fumigation device for a toilet, the temperature measured by the following measurement method satisfying the following temperature conditions (i) and (ii). <<Measurement method>> Mix 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C, and measure the water temperature while stirring. <<Temperature condition>> (i) The water temperature 30 seconds after mixing 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C is 50°C or higher. (ii) The duration at 50°C or higher is 30 seconds or more within 60 seconds after mixing 600 g of distilled water at 20°C and 100 g of the exothermic substance (B) at 20°C.

2. The fumigation device for a toilet according to claim 1, wherein the fumigant composition (A) contains a nonionic surfactant (A3).

3. The fumigation device for a toilet according to claim 2, wherein the fumigant composition (A) contains a water-insoluble silicon-containing inorganic compound (A4).

4. Using the fumigation device for a toilet according to any one of claims 1 to 3, A deodorizing method for a toilet, wherein water is brought into contact with the exothermic substance (B), and the fumigant composition (A) is heated by the heat of hydration of the exothermic substance (B) to volatilize the drug.

5. The method for deodorizing a toilet according to claim 4, which sterilizes one or more selected from bacteria of the genus Moraxella, bacteria of the genus Micrococcus, and bacteria of the genus Kocuria.

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