JP7145642B2 - Smoked transpiration agent composition and smoked transpiration device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a smoke-type transpiration agent composition and a smoke-type transpiration device.

It is troublesome to clean mold that has grown in high places such as ceilings and upper walls using a chlorine-based mold remover or the like. Therefore, there is a demand for a cleaning method that can easily remove mold from every corner of a living space, such as high positions and narrow gaps, and maintain the living space in a clean state.

For example, Patent Literature 1 proposes an anti-mold smoke agent composition for indirect heating systems for bathrooms containing a chemical agent, azodicarbonamide, and a perfume. According to the invention of Patent Document 1, the chemical can be efficiently smoked and volatilized.
Further, Patent Document 2 discloses a transpiration device characterized by having an exothermic agent that generates heat when water is added and an activator for an aqueous solution of a chemical for transpiration, and containing the aqueous chemical solution for transpiration in a water container. Proposed. According to the invention of Patent Document 2, by breaking the film on the bottom surface of the water container, the chemical can evaporate together with the water vapor.

Japanese Patent No. 5891289 JP 2001-218826 A

However, the invention described in Patent Document 1 involves operations such as preparing water for heating the exothermic agent. The invention of Patent Document 2 does not consider the reaction rate between the exothermic agent and water. If the reaction rate between the exothermic agent and water is too fast, the time until the agent or the like begins to evaporate (transpiration start time) becomes too short, and it is not possible to secure time for the worker to evacuate. If the reaction rate between the exothermic agent and water is too fast, the time for the agent to evaporate (transpiration duration) becomes too short, so that the agent cannot evaporate sufficiently and the effect of the agent cannot be exhibited sufficiently.
Accordingly, an object of the present invention is to provide a fumigation-type transpiration agent composition that can sufficiently exhibit the effects of the agent with a simpler operation.

The present invention has the following aspects.
[1] independently having a water-containing liquid (A) and an exothermic solid (B),
The water-containing liquid (A) contains a water-soluble solvent (a1) having a boiling point of 150° C. or higher and water (a2),
The exothermic solid (B) contains an exothermic agent (b1) that generates heat by hydration reaction,
A fumigation-type transpiration agent composition, wherein the water-containing liquid (A) and the pyrogenic solid (B) are brought into contact with each other to transpire the water-containing liquid (A).
[2] The fumigation type transpiration agent composition according to [1], wherein the content of the water-soluble solvent (a1) is 30 to 60% by mass with respect to the total mass of the water-containing liquid (A).
[3] The content of the water-containing liquid (A) with respect to the total weight of the water-containing liquid (A) and the exothermic solid (B) is 40 to 90% by mass, according to [1] or [2]. fumigation-type transpiration agent composition.
[4] The smoke-type transpiration agent composition according to any one of [1] to [3], wherein the water-containing liquid (A) further contains a drug (a3).
[5] The smoking-type transpiration agent composition according to any one of [1] to [4], wherein the exothermic solid (B) further contains an organic blowing agent (b2).

[6] The fumigation type transpiration agent composition according to any one of [1] to [5] is housed in a housing,
In the housing, a liquid storage section containing the water-containing liquid (A), a heating section containing the exothermic solid (B), and the liquid storage section and the heat generating section are partitioned so as to communicate with each other. A fumigation type transpiration device provided with a partition member.

According to the fumigation-type transpiration agent composition of the present invention, the effect of the agent can be fully exhibited with a simpler operation.

1 is a cross-sectional view of a fumigation-type transpiration device according to an embodiment of the present invention; FIG. It is a schematic diagram explaining the evaluation method of the fungicidal effect.

(Smoke type transpiration agent composition)
The fumigation-type transpiration agent composition of the present invention comprises a water-containing liquid (A) and a pyrogenic solid (B). The water-containing liquid (A) and the exothermic solid (B) are independent of each other.

<Water-containing liquid (A)>
The water-containing liquid (A) is a liquid containing a water-soluble solvent (a1) (component (a1)) and water (a2) (component (a2)).
Component (a1) is a water-soluble solvent having a boiling point of 150° C. or higher. Since the water-containing liquid (A) contains the component (a1), the water-containing liquid (A) comes into contact with the exothermic solid (B) and evaporates in the form of white smoke. Compared to the case where only water is brought into contact with the heat-generating solid (B), when the water-containing liquid (A) containing the component (a1) is brought into contact with the heat-generating solid (B), the heat-generating solid (B ) slows down the exothermic reaction. Therefore, the water-containing liquid (A) can sufficiently transpire by delaying the transpiration start time and lengthening the transpiration duration.
The boiling point of component (a1) is preferably 150°C to 300°C, more preferably 150°C to 250°C. If the boiling point of the component (a1) is within the above range, the transpiration start time can be delayed and the transpiration duration can be lengthened.

Component (a1) includes so-called ethylene glycol-based solvents, propylene glycol-based solvents, ethylene glycol-based ethers, propylene glycol-based ethers, dialkyl glycol ether-based solvents, polyethylene glycol-based solvents, and the like.
Component (a1) is, for example, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl ethyl ether, tripropylene glycol dimethyl ether. , triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, propylene glycol, dipropylene glycol, tri Propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol and the like.
As the component (a1), propylene glycol, ethylene glycol, and glycerin are preferable from the viewpoints of delaying the transpiration start time, lengthening the transpiration duration, and further enhancing the visibility of white smoke vapor. Further, when the fumigation type transpiration agent composition of the present invention is required to have a sterilizing effect, the component (a1) is preferably propylene glycol, which has an excellent sterilizing effect.
The above component (a1) may be used alone or in combination of two or more.

The content of component (a1) is preferably 30 to 60% by mass, more preferably 45 to 55% by mass, relative to the total mass of the water-containing liquid (A). If the content of the component (a1) is at least the above lower limit, it is easy to ensure the time to start transpiration, the duration of transpiration is lengthened, and white smoke-like vapor can be visually recognized better. If the content of the component (a1) is equal to or less than the above upper limit, the exothermic temperature of the exothermic solid (B) can be further increased, and the water-containing liquid (A) can be sufficiently evaporated.

The (a2) component is water. The component (a2) is, for example, ion-exchanged water, distilled water, purified water such as pure water, or tap water.
The content of component (a2) is preferably 40 to 70% by mass, more preferably 45 to 55% by mass, relative to the total mass of the water-containing liquid (A). If the content of the component (a2) is at least the above lower limit, the exothermic temperature of the exothermic solid (B) can be further increased, and the water-containing liquid (A) can be sufficiently evaporated. If the content of the component (a2) is equal to or less than the above upper limit, it is easy to secure the transpiration start time, the transpiration duration is increased, and white smoke-like vapor can be visually recognized better.

The water-containing liquid (A) may contain the drug (a3) (component (a3)). By containing the (a3) component, the (a3) component can transpire together with the (a1) component and the (a2) component.

The component (a3) can be determined depending on the purpose. The (a3) component is, for example, an antibacterial agent, a bactericide, an antifungal agent, an antifungal agent, an insecticide, a fragrance, or the like.
Examples of antibacterial agents, bactericides, antifungal agents, antifungal agents, and insecticides include organic agents, silver-based inorganic antibacterial agents, and the like.
Organic agents include, for example, 3-methyl-4-isopropylphenol (IPMP), 3-iodo-2-propynylbutylcarbite (IPBC), O-phenylphenol (OPP), methoxadiazone, phenothrin, d・dT- Cyphenothrin and the like. Organic agents include cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, benzalkonium salts, benzethonium salts, pyridinium salts and imidazolium salts. Counter ions of salts of cationic surfactants are, for example, halogen ions such as iodine and chlorine.
Silver-based inorganic antibacterial agents are, for example, silver oxides, chlorides, nitrates, sulfates, silver supports, and the like. A silver carrier is a carrier in which silver itself is carried. Examples of carriers for silver supports include phosphates (zirconium phosphate, calcium phosphate, etc.), metal oxides (silicon oxide, aluminum oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, etc.), inorganic compounds (zeolite, clay minerals, silica gel, etc.). One carrier may be used alone, or two or more carriers may be used in combination.

The above-mentioned (a3) component may be used individually by 1 type, and 2 or more types may be combined and used.

The content of component (a3) is appropriately determined according to the type of component (a3). The content of component (a3) is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, relative to the total mass of the water-containing liquid (A). If the content of the component (a3) is within the above range, the effect of the component (a3) can be exhibited more satisfactorily.

Even if the water-containing liquid (A) does not contain the (a3) component, if the (a1) component has a medicinal effect (for example, propylene glycol), the water-containing liquid (A) contains the (a3) component. The fumigation-type transpiration agent composition of the present invention exhibits medicinal efficacy even without it.

The water-containing liquid (A) may contain a surfactant (a4) (component (a4)) (excluding component (a3)).
Component (a4) is an anionic surfactant, nonionic surfactant, amphoteric surfactant, or the like.

Anionic surfactants include, for example, linear alkyl (8-18 carbon atoms) benzenesulfonates (LAS), linear or branched alkyl (8-18 carbon atoms) sulfates (AS), alkyl (carbon 8-18) Ether sulfate or alkenyl (8-18 carbon atoms) ether sulfate (AES), α-olefin sulfonate (AOS) (alkyl group with 8-18 carbon atoms), alkyl group (8-18 carbon atoms) 18), α-sulfo fatty acid (C 8-18) ester salt (α-SF salt) (alkyl group C 8-18), alkyl (C 8-18) ether carboxylic acid Carboxylic anions such as salts, polyoxyalkylene ether carboxylates, alkyl (C8-C18) amide ether carboxylates, alkenyl (C8-18) amide ether carboxylates, acylamino carboxylates, etc. Surfactant; Alkyl (8-18 carbon atoms) amide ether carboxylate, phosphate ester salt (alkyl group with 8-18 carbon atoms) amide ether carboxylate, polyoxyalkylene alkyl (8-18 carbon atoms) phosphorus and phosphate type anionic surfactants such as acid ester salts, polyoxyalkylene alkyl (C8-18) phenyl phosphate salts, glycerin fatty acid ester monophosphate salts, and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine salts, diethanolamine salts and triethanolamine salts, and ammonium salts. Among these, alkali metal salts are preferred.

Amphoteric surfactants include, for example, alkyl (8-18 carbon atoms) carboxybetaine, alkyl (8-18 carbon atoms) sulfobetaine, alkyl (8-18 carbon atoms) hydroxysulfobetaine, alkyl (8-18 carbon atoms) Amidobetaine, imidazolinium betaine and the like.

Nonionic surfactants include, for example, higher alcohols (8 to 22 carbon atoms), alkylphenols, higher fatty acids (8 to 22 carbon atoms), higher amines (8 to 22 carbon atoms), and alkylene oxides (2 to 4 carbon atoms). (average number of added moles 3-50) polyoxyalkylene type nonionic surfactant, polyoxyethylene polyoxypropylene block copolymer, fatty acid (8-18 carbon atoms) alkanolamide, polyhydric alcohol fatty acid (8-carbon atoms 22) Esters or their alkylene oxide adducts, fatty acid (8-22 carbon atoms) polyglycerin esters, sugar fatty acid (8-22 carbon atoms) esters, alkyl (or alkenyl) (8-22 carbon atoms) amine oxides, amide amine oxides , alkylene oxide adducts of hydrogenated castor oil, N-alkylpolyhydroxy fatty acid amides, alkylglycosides, alkylpolyglycosides, glyceryl ethers, and the like.
Among these, as the component (a4), nonionic surfactants are preferred, and polyoxyethylene alkyl ethers (alcohol ethoxylates) obtained by adding ethyleneoxy groups to higher alcohols are more preferred. Polyoxyethylene alkyl ethers having 12 to 28 moles of oxy groups are preferred. These polyoxyethylene alkylene ethers can enhance the sterilization effect.
The above-mentioned (a4) component may be used individually by 1 type, and 2 or more types may be combined and used.
The content of component (a4) is preferably 0.1 to 20% by mass, more preferably 0.1 to 5% by mass, relative to the total mass of the water-containing liquid (A). (a4) If the content of the component is within the above range, the sterilization effect is likely to be obtained.

The water-containing liquid (A) may contain optional components (water-containing liquid optional components) other than the components (a1) to (a4).
Optional components of the water-containing liquid include coloring agents and antioxidants.

The method for producing the water-containing liquid (A) is not particularly limited. The method for producing the water-containing liquid (A) is, for example, a method of adding the (a1) component to the (a2) component and mixing them. At this time, if necessary, the components (a3) to (a4) and the optional water-containing liquid component are dispersed in the component (a2).

<Pyrogenic solid (B)>
The exothermic solid (B) contains an exothermic agent (b1) (component (b1)) that generates heat by hydration reaction. Since the exothermic solid (B) contains the component (b1), the exothermic solid (B) reacts with the water-containing liquid (A) to generate heat and evaporate the water-containing liquid (A).

The (b1) component is, for example, a metal, metal oxide, or the like. The component (b1) is, for example, alkali metals such as sodium, alkaline earth metals such as magnesium and calcium, oxides thereof, and the like. Among them, as the component (b1), calcium and calcium oxide are preferable, and calcium oxide is more preferable.

Calcium oxide preferably has a temperature of 70° C. or higher 60 seconds after the start of the reaction and a duration of 98° C. or higher for 40 seconds or longer in the following tests, for example.
[Test method]
Put 600 mL of deionized water at 20 ° C. in a stainless steel Dewar bottle, and use a three-one motor set with stirring blades (blade shape: 4 pitch paddle blades, 75 mm diameter, 10 mm thickness, 2 blades, 30 mm blade spacing). Stir at 300 rpm. Next, 100 g of calcium oxide is put into the Dewar bottle. Immediately cover the Dewar bottle with a cork stopper and measure the water temperature at 20 mm above the stirring blade (water temperature at the start of the reaction).

The component (b1) is preferably a particle group. If it is a particle group, the contact area with the water-containing liquid (A) is increased, and the exothermic solid (B) can generate heat more efficiently.
The average particle size of component (b1) is preferably 0.5 to 10 mm, more preferably 0.9 to 7 mm. When the average particle size is at least the above lower limit, the gaps between the particles are large, and the water-containing liquid (A) is more likely to permeate. If the average particle size is equal to or less than the above upper limit, the surface area per unit volume of component (b1) is increased, and heat can be generated more efficiently.
The average particle size of component (b1) is a value determined by the following formula (s) after sieving.
Average particle size (mm) = Σ (Vi (%) + di (mm)) / Σ (Vi (%)) (s)
(s) In the formula, Vi is the abundance ratio of particles having a particle diameter di (mm), and the particle diameter di is represented by the median value between the meshes of each sieve.
Normally, the formula (s) calculates the arithmetic mean particle size as Σ(Vi(%)+di(mm))/Σ(100(%)).

The content of component (b1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and more preferably 80 to 100% by mass, relative to the total mass of the exothermic solid (B).

The exothermic solid (B) may contain an organic blowing agent (b2). By containing the organic blowing agent (b2), the exothermic solid (B) can evaporate the water-containing liquid (A) more satisfactorily. In addition, the heat-generating solid (B) contains the organic foaming agent (b2), so that white smoke-like steam can be more easily visually recognized when the water-containing liquid (A) is evaporated.

The component (b2) is thermally decomposed by heating to generate a large amount of heat, and also generates carbon dioxide gas, nitrogen gas, etc. (hereinafter collectively referred to as foaming gas). Component (b2) is, for example, azodicarbonamide, p,p'-oxybis(benzenesulfonylhydrazide), N,N'-dinitrosopentamethylenetetramine, azobisisobutyronitrile and the like.
Among them, azodicarbonamide is preferable as the component (b2) from the viewpoint of raising the decomposition temperature and increasing the amount of foaming gas generated.
The content of component (b2) is preferably 0 to 20% by mass, more preferably 1 to 20% by mass, even more preferably 5 to 10% by mass, relative to the total mass of the exothermic solid (B). If the content of the component (b2) is within the above range, the hydrous liquid (A) can evaporate more satisfactorily. In addition, if the content of the component (b2) is within the above range, the white smoky vapor can be made more visible.

The exothermic solid (B) may contain optional components (solid optional components) other than components (b1) and (b2).

Examples of the method for producing the exothermic solid (B) include a method of mixing the component (b1) and, if necessary, optional components such as the component (b2).

The ratio of the exothermic solid (B) to the total mass of the water-containing liquid (A) and the exothermic solid (B) (B/(A+B) percentage) is preferably 40 to 90% by mass. If the B/(A+B) percentage is within the above range, it is easy to sufficiently generate heat while securing the time until the start of heat generation.

The method for using the fumigation type transpiration agent composition will be described below.
For example, the container is placed on the floor of the space to be treated. The container to be used may be any container that has an open top, and examples thereof include flat plates, deep plates, cups, and the like. The material of the container is preferably one having heat resistance, and examples thereof include metal, glass, ceramics, and the like.

Place pyrogenic solid (B) in a container.
The water-containing liquid (A) is brought into contact with the exothermic solid (B) in the container. The contacting method is not limited, and includes a method of pouring the water-containing liquid (A) into a container containing the exothermic solid (B).

When the water-containing liquid (A) comes into contact with the exothermic solid (B) (that is, becomes a mixture of the water-containing liquid (A) and the exothermic solid (B)), the water of the components (a2) and (b1) The sum reaction causes the component (b1) to generate heat. At this time, the (a1) component slows down the reaction rate between the (b1) component and the (a2) component, thereby delaying the transpiration start time of the (b1) component.
When the mixture of the water-containing liquid (A) and the exothermic solid (B) reaches a specific temperature, the water-containing liquid (A) turns into white smoke-like steam and evaporates vigorously. At this time, the active ingredients contained in the water-containing liquid (A) (for example, propylene glycol contained as component (a1), component (a3), etc.) transpire and diffuse into the space to be treated. The diffused active ingredient exhibits antibacterial, bactericidal, insecticidal, and other effects depending on the type of active ingredient. The temperature reached by the mixture of the hydrous (A) and the exothermic solid (B) is preferably 100 to 350°C, for example.
The water-containing liquid (A) is injected while the mixture of the water-containing liquid (A) and the exothermic solid (B) is above a specific temperature. Since the water-containing liquid (A) contains the (a1) component, the reaction rate between the (b1) component and the (a2) component is slowed down, and the evaporation duration is lengthened. Therefore, the entire amount of the active ingredient in the water-containing liquid (A) can be transpired and diffused into the space to be treated.

The fumigation-type transpiration agent composition of the present embodiment vigorously transpires the water-containing liquid (A) by bringing the water-containing liquid (A) into contact with the pyrogenic solid (B). Therefore, the active ingredient can be diffused to every corner of the space to be processed.
In the fumigation-type transpiration agent composition of the present embodiment, since the water-containing liquid (A) contains (a1), the transpiration start time of component (b1) is slow and the transpiration duration of component (b1) is long. Therefore, most of the water-containing liquid (A) can be evaporated.

(Smoke type transpiration device)
The fumigation type transpiration device of the present invention comprises the fumigation type transpiration agent composition of the present invention and a housing containing it.
A smoking type transpiration device of the present invention will be described with reference to one embodiment.

The smoke-type transpiration device 1 of FIG.
The housing 10 has a bottom wall portion 12 , a side wall portion 14 rising from the peripheral edge of the bottom wall portion 12 , and a top wall portion 16 located at the upper end of the side wall portion 14 . An opening 18 is formed in the central portion of the ceiling wall portion 16 .

A heat-generating portion 30 is formed near the bottom wall portion 12 in the housing 10 by accommodating the heat-generating solid (B).
A liquid container 21 is provided above the heat generating portion 30 . The liquid container 21 includes a main body with open upper and lower ends, and a partition member 22 closing the lower end of the main body. The upper end of the liquid container 21 is in contact with the ceiling wall portion 16 . The partition member 22 is separated from the heat generating portion 30 . The liquid container 21 contains a water-containing liquid (A) to form a liquid reservoir 20 . Thus, the liquid storage part 20 and the heat generating part 30 are separated by the partition material 22 .

A breaker 24 is provided in the vicinity of the partition member 22 inside the liquid container 21 . A pushing tool 26 extending upward and protruding from the opening 18 is connected to the upper surface of the breaking tool 24 .

The shape of the housing 10 is not particularly limited, and examples thereof include a container having a hollow columnar shape, a hollow prismatic shape, or the like.
The material of the housing 10 is preferably one that is resistant to deformation due to the heat generated by the exothermic solid (B). Examples of materials for the housing 10 include metals and ceramics.

The shape of the liquid container 21 is not particularly limited, and can be appropriately determined according to the shape of the housing 10 . The liquid container 21 of the present embodiment preferably has a cylindrical or square tube with a partition member 22 at the lower end.
The material of the liquid container 21 may be any material that does not leak the water-containing liquid (A).
The partition member 22 of the liquid container 21 may partition the liquid storage portion 20 (that is, inside the liquid container 21) and the heat generating portion 30 (that is, inside the housing 10) so that they can communicate with each other. The partition material 22 is preferably a film that can be broken by a physical external force, such as a plastic film such as a polyethylene film or a polypropylene film, or a metal foil such as an aluminum foil.

The breaking tool 24 may be any tool as long as it can break the partition material 22, and examples thereof include a plate having a cutting edge or the like formed on the lower surface.
The pushing tool 26 may be any tool as long as it can push the breaking tool 24 downward to break the partition material 22 when the upper end is pushed downward. The pushing tool 26 may be, for example, a rigid rod made of metal or resin.

The ratio of the water-containing liquid (A) and the pyrogenic solid (B) is the same as the B/(A+B) percentage in the fumigation type transpiration agent composition described above.

An example of a method for manufacturing the smoking type transpiration device 1 will be described.
A heat-generating portion 30 is formed by filling a heat-generating solid (B) in the housing 10 that does not have the top wall portion 16 . A liquid container 21 is provided in the housing 10 . A pushing tool 26 is attached to the breaking tool 24 and placed in these liquid containers 21 . The liquid container 21 is filled with the water-containing liquid (A). The fumigation type transpiration device 1 is obtained by providing the ceiling wall part 16 in the housing 10. - 特許庁
Furthermore, a cover that closes the opening 18 may be provided. A resin film or the like can be used as the cover.

A method of using the smoking type transpiration device 1 will be described.
A fumigation type transpiration device 1 is placed in a space to be treated. The upper end of the pushing tool 26 is pushed downward to break the partition member 22 . When the partition member 22 is broken, the water-containing liquid (A) in the liquid container 21 drops to the heat generating section 30 . When the water-containing liquid (A) drops into the heat-generating portion 30, it flows between the (b1) components, and the (a2) component comes into contact with the (b1) component. When the component (a2) comes into contact with the component (b1), the component (b1) generates heat due to the hydration reaction.
When the component (b1) generates heat and reaches a specific temperature, the water-containing liquid (A) turns into white smoke-like steam and evaporates vigorously. The steam then jets upward from the opening 18 . At this time, the active ingredient is diffused into the target space by the momentum of the jetted steam.
In this way, the entire amount of the water-containing liquid (A) is transpired into the target space to obtain the desired effect.

In the above-described embodiments, the liquid container is provided with the partition material provided at the lower end of the cylindrical molded body, but the liquid container is not limited to this. The liquid container may partition the water-containing liquid (A) and the exothermic solid (B), and may be, for example, a bag made of resin film or metal foil.

In the above-described embodiments, the liquid storage section is formed above the heat generating section, but the present invention is not limited to this. For example, a heat generating portion may be formed above the liquid storage portion.

Although the embodiment described above includes a breaking tool and a pushing tool, the present invention is not limited to this. For example, the partition material may be broken by a sharp member without the breaking tool and the pushing tool.

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(a1) component>
· a1-1: Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.).
· a1-2: Ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.).
· a1-3: glycerin.
<Component (a1′): Comparative product of component (a1)>
· a1′-1: anhydrous ethanol (manufactured by Junsei Chemical Co., Ltd.).

<(a2) component>
· a2-1: ion-exchanged water.

<(b1) component>
· b1-1: Calcium oxide (CaH, manufactured by Yoshizawa Lime Co., Ltd., average particle size 4 mm).

<(a3) component>
· a3-1: 2-isopropyl-5-methylphenol (IPMP) (Biosol, manufactured by Osaka Kasei Co., Ltd.).
a3-2: 3-iodo-2-propynylbutylcarbamate (IPBC) (GLYCACIL, manufactured by Lonza Japan Co., Ltd.).
· a3-3: phenothrin (Sumitrin, manufactured by Sumitomo Chemical Co., Ltd.).
· a3-4: Silver-supported zeolite-based inorganic antibacterial agent (Zeomic AJ10N, manufactured by Sinanen Zeomic Co., Ltd., silver content: 2.7% by mass).
· a3-5: Antibacterial fragrance (ANTI-MOLD LAVENDER, manufactured by Takasago International Corporation).

<(a4) component>
a4-1: alcohol ethoxylate (hydrocarbon group with 12 to 14 carbon atoms, added mole number of ethyleneoxy group: 8) (Rheox CL-80-90, manufactured by Lion Chemical Co., Ltd.).
a4-2: alcohol ethoxylate (hydrocarbon group with 18 carbon atoms, added mole number of ethyleneoxy group: 20) (EMALEX620 manufactured by Nippon Nyukazai Co., Ltd.).
a4-3: alcohol ethoxylate (hydrocarbon group with 16 carbon atoms, ethyleneoxy group with 12) (EMALEX112 manufactured by Nippon Nyukazai Co., Ltd.).

<(b2) component>
· b2-1: Azodicarbonamide (Daiblo AC, 2040 (C), manufactured by Dainichiseika Kogyo Co., Ltd.).

(Evaluation method)
<Transpiration start time>
A heat-generating portion was formed by housing the exothermic solid (B) of each example in a cylindrical container made of a steel plate having a diameter of 70 mm and a height of 70 mm. Into this container, the water-containing liquid (A) of each example was added. The time from the addition of the water-containing liquid (A) to the vigorous jetting of steam was defined as "transpiration start time (seconds)". The transpiration start time (seconds) of each example was classified according to the evaluation criteria in Table 1 and evaluated. The masses of the water-containing liquid (A) and the exothermic solid (B) in each example are the masses described in the column of "transpiration apparatus" in Tables 2-4.

<Transpiration state>
A heat-generating portion was formed by housing the exothermic solid (B) of each example in a cylindrical container made of a steel plate having a diameter of 70 mm and a height of 70 mm. Into this container, the water-containing liquid (A) of each example was added. After the water-containing liquid (A) was added, the time during which the steam was vigorously jetted (transpiration duration) and the reaching height of the steam (reaching point) were measured and evaluated according to the following criteria.

≪Evaluation Criteria≫
A: The arrival point is 50 cm or more, and white smoke-like vapor continues for a uniform transpiration duration of 1 minute or more.
◯: The reaching point is 50 cm or more, and white smoke-like vapor is slightly uneven, but the transpiration duration continues for 1 minute or longer.
Δ: The reaching point is 50 cm or more, and the white smoke-like vapor is considerably non-uniform, but the transpiration duration is 1 minute or more.
x: The arrival point is less than 50 cm or the transpiration duration is less than 1 minute.

<Moldicidal effect>
Reference numeral 100 in FIG. 2 denotes an evaluation chamber used for evaluating the fungicidal effect. The evaluation room 100 has width W×depth D×height H=1.8 m×1.8 m×2.0 m.
A slide glass for test (FRP for test, FRP inoculated with bacteria) prepared by the following method 1 was attached to the position of the center P1 of the top surface 101 of the evaluation chamber 100 . The surface of the test slide glass inoculated with bacteria was directed to the bottom surface 102 .

<<Method 1: How to prepare a sample slide glass>>
Cladosporium cladosporioides HMC1064 (bathroom isolate) was prepared by culturing at 25° C. for 1 week on a potato dextrose agar slant medium (manufactured by Difco). Sterilized 0.05% Tween 80 (manufactured by Kanto Kagaku Co., Ltd.) was used as an aqueous solution of bacteria isolated in the bathroom. Colony-forming units of bathroom isolates yielded about 1.0×10 ⁶ CFU/mL of spore fluid. Next, 0.4 mL of this spore solution was inoculated into FRP20 for test, left standing overnight at room temperature, and dried and fixed.
The colony forming unit (CFU) means the number of colonies formed when a certain amount of microorganisms (such as bacteria) is spread on a solid medium on which they grow.
Next, the water-containing liquid (A) was allowed to evaporate in the same manner as in "<transpiration start time>" for the obtained fumigation-type transpiration agent composition of each example. The position where the container was placed was the center P2 of the bottom surface 102 of the evaluation chamber 100 . Ninety minutes after the water-containing liquid (A) and the exothermic solid (B) were brought into contact with each other, the air in the evaluation chamber 100 was exhausted and the test FRP was collected. A bacterial solution was recovered from the test FRP by Method 2 below. The recovered bacterial solution was appropriately diluted with physiological saline to a measurable concentration and smeared on a potato dextrose agar medium. After culturing this at 25° C. for 5 days, the number of formed colonies was visually counted.

<<Method 2: Method for collecting bacteria from test FRP>>
The test FRP inoculated with the bacteria and 10 mL of SCDLP medium (manufactured by Nihon Pharmaceutical Co., Ltd.) were placed in a sterilized plastic petri dish (manufactured by AS ONE) and stirred with a conlage rod (manufactured by Nissui Pharmaceutical Co., Ltd.) to extract the bacteria from the test FRP. .
The number of viable bacteria was obtained from the counted number of colonies and the dilution ratio of the bacterial solution, and the obtained value was defined as the "number of bacteria after treatment". Separately, the bacterial solution recovered from the test FRP in the untreated area was appropriately diluted with physiological saline to a measurable concentration, and smeared on a potato dextrose agar medium. After culturing this bacterial solution at 25° C. for 5 days, the number of formed colonies was visually counted. The number of viable bacteria was obtained from the counted number of colonies and the dilution ratio of the bacterial solution, and the obtained value was defined as the "number of untreated bacteria".
The number of bacteria obtained as "number of bacteria after treatment" and "number of untreated bacteria" is converted to common logarithm (log), and the value obtained by subtracting "number of bacteria after treatment" from "number of untreated bacteria" (Δlog = log (number of untreated bacteria) - log (number of bacteria after treatment)) was determined, and the value was taken as the fungicidal efficacy. Based on the value of the fungicidal efficacy, the fungicidal efficacy was evaluated based on the following evaluation criteria.

[Evaluation criteria]
◎◎: Δlog is 4.0 or more.
A: Δlog is 3.0 or more and less than 4.0.
○: Δlog is 2.0 or more and less than 3.0.
Δ: Δlog is 1.0 or more and less than 2.0.
x: Δlog is less than 1.0.

(Examples 1 to 26, Comparative Examples 1 to 3)
According to the composition of the water-containing liquid (A) shown in Tables 2 to 4, the (a1) component (or (a1') component) and the (a2) component were mixed. Components (a3) and (a4) were added to this and mixed to prepare a water-containing liquid (A) of each example.
According to the composition of the exothermic solid (B) shown in Tables 2 to 4, an exothermic solid consisting of the component (b1) or a mixture of the components (b1) and (b2) was prepared.
In this way, a fumigation-type transpiration agent composition was obtained which independently contained the water-containing liquid (A) and the pyrogenic solid (B).
The obtained fumigation type transpiration agent composition was evaluated for transpiration start time, transpiration state, and fungicidal effect, and the results are shown in the table.
In addition, the compounding quantity in a table|surface is a pure part conversion value. Ingredients whose blending amounts are not listed in the table are not blended.

As shown in Tables 2 to 4, in Examples 1 to 26, the evaluation of the transpiration start time is "△" to "◎ ◎", the evaluation of the transpiration state is "△" to "◎", and the fungicidal effect is "△ ” to “◎”.
Comparative Example 1 containing the component (a1′) instead of the component (a1), Comparative Example 2 containing no component (a1), and Comparative Example 3 containing no component (a2) are all transpiration start time, transpiration The evaluation of the state and the fungicidal effect was "x".

1 smoking type transpiration device 10 housing 20 liquid storage part 22 partition material 30 heat generating part

Claims (6)

independently having a water-containing liquid (A) and an exothermic solid (B),
The water-containing liquid (A) contains a water-soluble solvent (a1) having a boiling point of 150° C. or higher and water (a2),
The exothermic solid (B) comprises an exothermic agent (b1) that generates heat by hydration reaction , azodicarbonamide, p,p'-oxybis(benzenesulfonylhydrazide), N,N'-dinitrosopentamethylenetetramine, and containing one or more organic blowing agents (b2) selected from azobisisobutyronitrile ,
The content of the organic blowing agent (b2) is 1 to 20% by mass with respect to the total mass of the exothermic solid (B),
A fumigation-type transpiration agent composition, wherein the water-containing liquid (A) and the pyrogenic solid (B) are brought into contact with each other to transpire the water-containing liquid (A). 2. The fumigation type transpiration agent composition according to claim 1, wherein the organic blowing agent (b2) is azodicarbonamide. The fumigation type transpiration agent composition according to claim 1 or 2 , wherein the content of said water-soluble solvent (a1) is 30 to 60% by mass with respect to the total mass of said water-containing liquid (A). 4. The content of the water-containing liquid (A) with respect to the total weight of the water-containing liquid (A) and the exothermic solid (B) is 40 to 90% by mass, according to any one of claims 1 to 3. fumigation type transpiration agent composition. The fumigation type transpiration agent composition according to any one of claims 1 to 4 , wherein the water-containing liquid (A) further contains a drug (a3). The fumigation type transpiration agent composition according to any one of claims 1 to 5 is housed in a housing,
In the housing, a liquid storage section containing the water-containing liquid (A), a heating section containing the exothermic solid (B), and the liquid storage section and the heat generating section are partitioned so as to communicate with each other. A fumigation type transpiration device provided with a partition member.

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