JP6614961B2 - Smoke agent and smoke device - Google Patents

Description

  The present invention relates to a smoke agent and a smoke device.

With the growing awareness of hygiene awareness and food safety, the need for measures against microorganisms such as fungi, viruses and molds is increasing. Among microorganisms, there is a high demand for measures against mold that is particularly noticeable (mold killing, mold prevention, etc.). Therefore, as a method for controlling microorganisms in a bathroom where microorganisms such as mold are likely to propagate, there is a method in which a smoke agent containing a sterilizing effect and a combustion agent is heated to smoke in the bathroom. Proposed.
For example, Patent Document 1 discloses a smoke agent containing a silver-containing agent, an organic foaming agent (combustion agent) such as azodicarbonamide, and a surfactant.

JP 2013-249262 A

In recent years, in addition to bathrooms, it has been desired that microorganisms such as molds can be controlled even in a narrow space (hereinafter also referred to as “small space”) such as a closet or a shoe box with a relatively low ceiling.
However, conventional smoke agents place importance on the ability of the smoke containing the medicine to reach the ceiling vigorously in a short time. Therefore, when a conventional smoke agent is applied to a small space, the smoke is ejected vigorously upward (vertical direction) of the small space, and the diffusion of the medicine to the surroundings (lateral direction) tends to be insufficient, thus preventing the smoke. Unevenness is likely to occur in the effect.
In addition, when using a smoke agent, contamination of white sediment or the like due to generated smoke may be a problem, but when a conventional smoke agent is applied to a small space, the problem of contamination is significant. Become.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a smoke agent and a smoke device that are less likely to cause unevenness in the control effect when used in a space with a low ceiling, and that are low in pollution. To do.

  As a result of intensive studies, the present inventors have found that smoke smoke using an organic foaming agent such as azodicarbonamide as a combustion agent is used in combination with a specific amount of a tetrazole-type gas generating agent, so that mild smoke can be produced over several minutes. It has been found that the diffusion of the drug to the surroundings can be improved and contamination can be reduced, and the present invention has been completed.

That is, this invention has the following aspects.
[1] Component (A): an organic foaming agent and component (B): a chemical agent, wherein the component (A) includes a tetrazole type gas generant, and is a tetrazole type gas generant / (A) component. The smoke agent whose mass ratio represented is 0.05-0.8.
[2] The bag according to [1], wherein the tetrazole-type gas generating agent is at least one selected from 5-amino-1H-tetrazole and 5,5′-bi-1H-tetrazole diammonium salt. Smoke agent.
[3] The component (B) is an inorganic drug containing silver, or at least one organic drug selected from 3-methyl-4-isopropylphenol and 3-iodo-2-propynylbutylcarbamate. [1] or [2].
[4] The smoke agent according to any one of [1] to [3], wherein the content of the tetrazole-type gas generating agent is 4 to 79% by mass with respect to the total mass of the smoke agent.
[5] The content of the organic foaming agent other than the tetrazole-type gas generating agent is 20 to 95% by mass with respect to the total mass of the smoke agent, according to any one of [1] to [4]. Smoke agent.
[6] The smoke agent according to any one of [1] to [5], wherein the content of the component (A) is 24 to 99% by mass with respect to the total mass of the smoke agent.
[7] The component (B) is the inorganic agent, and the content thereof is 0.001 to 1% by mass in terms of silver concentration with respect to the total mass of the smoke agent, [3] to [6] The smoke agent as described in any one of these.
[8] In any one of [3] to [6], the component (B) is the organic agent, and the content thereof is 1 to 30% by mass with respect to the total mass of the smoke agent. The smoke agent described.
[9] A smoke device in which the smoke agent according to any one of [1] to [8] is accommodated and includes a heating unit that heats the smoke agent.

  ADVANTAGE OF THE INVENTION According to this invention, the smoke control agent and smoke generator which are hard to produce a nonuniformity in the control effect in use in the space where a ceiling is low, and are low-contamination can be provided.

It is a schematic sectional drawing which shows one example of embodiment of the soot device concerning this invention. It is the schematic explaining the evaluation method of the microorganisms control effect in [Example].

[Fumigant]
The smoke agent of the present invention contains the following components (A) and (B).
In the present invention, the term “control” refers to sterilizing microorganisms such as bacteria, viruses, and molds, or suppressing the growth of microorganisms, such as so-called sterilization, antibacterial, mold prevention, antifungal, and sterilization. Including concept.

<(A) component>
(A) A component is an organic foaming agent. The component (A) is a component (combustion agent) that generates pyrolysis gas by heating or combustion and smokes the component (B) by the action of the generated pyrolysis gas.

As the component (A), a tetrazole type gas generating agent (hereinafter also referred to as “(A1) component”) and an organic foaming agent other than the tetrazole type gas generating agent (hereinafter also referred to as “(A2) component”). And both.
By having both the component (A1) and the component (A2), it is possible to suppress smoke from being ejected vigorously and to generate gradual smoke continuously. As a result, smoke is sufficiently diffused not only upward (vertical direction) but also around (horizontal direction), so that a uniform control effect can be obtained. In addition, it is possible to suppress pollution in the space due to smoke.

The component (A1) is not particularly limited as long as it is a foaming agent having a tetrazole ring in the molecule. For example, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1- (2-dimethylaminoethyl) -5-mercapto-1H-tetrazole, 1H-tetrazol-5-yl- Guanidine, 5,5′-bi-1H-tetrazole diammonium salt, 5,5′-bi-1H-tetrazole piperazine salt, 1,5′-bi-1H-tetrazole guanidine salt, 5-acetylamino- 1H-tetrazole, 5-octanoylamino-1H-tetrazole, 5,5′-azobis-1H-tetrazo Such as, Jiguanijin salts. These may be used alone or in combination of two or more.
Among these, 5-amino-1H-tetrazole and 5,5′-bi-1H-tetrazole / diammonium salt are preferable from the viewpoint of excellent gas generation.

As the component (A2), one that generates a large amount of heat by pyrolysis by heating and generates carbon dioxide gas, nitrogen gas or the like (hereinafter generally referred to as “foaming gas”) is used. Examples include amide, nitrocellulose, 4,4′-oxybis (benzenesulfonylhydrazide), N, N′-dinitrosopentamethylenetetramine, azobisisobutyronitrile and the like. These may be used alone or in combination of two or more.
Among these, azodicarbonamide is preferable from the viewpoint of gas generation from the viewpoint of low decomposition temperature and generation of a large amount of foaming gas.

  The content of the component (A1) is preferably 4 to 79% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 40% by mass with respect to the total mass of the smoke smoke agent. If content of (A1) component is in the said range, the diffusion effect of (B) component will be fully acquired.

  20-95 mass% is preferable with respect to the total mass of a smoke agent, as for content of (A2) component, 30-80 mass% is more preferable, and 40-60 mass% is further more preferable. If content of (A2) component is 20 mass% or more, (B) component will disperse | distribute efficiently, and if it is 95 mass% or less, contamination can be suppressed more.

  The mass ratio represented by (A1) component / (A) component (that is, (A1) component) / {(A1) component + (A2) component}) is 0.05 to 0.8. 1-0.65 are preferable and 0.2-0.4 are more preferable. If mass ratio is in the said range, the diffusibility of smoke will improve and the control effect will increase.

  The content of the component (A) is preferably 24 to 99% by mass, more preferably 50 to 90% by mass, and still more preferably 60 to 80% by mass with respect to the total mass of the smoke smoke agent. If content of (A) component is 24 mass% or more, (B) component will disperse | distribute efficiently, and if it is 99 mass% or less, contamination can be suppressed more.

<(B) component>
(B) A component is a chemical | medical agent. (B) A component is a component which controls microorganisms.
Examples of the component (B) include antibacterial agents, bactericides, fungicides, antifungal agents, deodorants, insecticides, repellents, and mixed agents thereof. Just choose. Specific examples include inorganic chemicals and organic chemicals that are widely used for smoke agents.

As an inorganic chemical | medical agent, the thing containing silver is mentioned, Specifically, silver or a silver compound is mentioned.
Silver is silver alone.
On the other hand, examples of the silver compound include inorganic silver salts such as silver oxides, chloride salts, nitrates, sulfates, sulfonates, and carbonates; organic silver salts such as silver formate and acetate. It is done.
In addition, as an inorganic chemical, silver or a silver compound supported on a substance (hereinafter also referred to as “carrier”) such as zeolite, silica gel, low molecular glass, calcium phosphate, silicate, titanium oxide (hereinafter referred to as “carrier”). May also be used. Specific examples of the support include zeolite-based inorganic antibacterial agent supporting silica alone or silver compound, silica / alumina-based inorganic antibacterial agent, silica gel-based inorganic antibacterial agent, titanium oxide-based inorganic antibacterial agent, silicate-based inorganic antibacterial agent Etc.
These inorganic chemical agents may be used alone or in combination of two or more.
Among these, silver oxides and zeolite antibacterial agents carrying silver compounds are preferable.

Examples of the organic drug include 3-methyl-4-isopropylphenol (IPMP), 3-iodo-2-propynylbutyl carbamate (IPBC), o-phenylphenol (OPP), methoxadiazone, and the like. These may be used alone or in combination of two or more.
Among these, IPMP and IPBC are preferable, and it is more preferable to use IPMP and IPBC in combination.

When the component (B) is an inorganic chemical, the content is preferably such that the silver concentration in the smoke agent is 0.001 to 1% by mass relative to the total mass of the smoke agent, An amount of 0.5% by mass is more preferable. If the content of the inorganic drug is less than 0.001% by mass, the effect of the inorganic drug may be reduced, and even if the content exceeds 1% by mass, the effect of the inorganic drug is saturated and further improvement of the effect cannot be achieved. There is a fear. In particular, if the content of the zeolitic inorganic antibacterial agent is more than 1% by mass, the scattering property may be lowered.
On the other hand, when the component (B) is an organic drug, the content thereof is preferably 1 to 30% by mass, more preferably 5 to 20% by mass with respect to the total mass of the smoke agent. If the content of the organic drug is less than 1% by mass, the effect of the organic drug may be reduced. On the other hand, when the content of the organic chemical exceeds 30% by mass, an unpleasant odor, for example, a burnt odor, is generated during the smoke treatment, and the unpleasant odor may remain after the smoke treatment.

<Optional component>
The smoke agent may further contain various additives. Examples include fragrances, binders, surfactants, excipients, exothermic aids, stabilizers, efficacy enhancers, antioxidants and the like.
These additives may be used alone or in combination of two or more.

A fragrance | flavor plays the role which improves a palatability, an effective feeling, etc. by the provision of the fragrance by soot, the masking effect of the smoke agent odor at the time of soot, etc.
The fragrance is not particularly limited, and examples thereof include fragrances described in the following documents.
“Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994),
"Synthetic fragrance chemistry and product knowledge", Motoichi Into, Chemical Industry Daily (1996),
"Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994),
"Encyclopedia of Scent", Japan Fragrance Association, Asakura Shoten (1989),
“Performer Material Performance V.3.3”, Boelens Aroma Chemical Information Service (1996),
“Flower oils and Floral Compounds in Performance”, Dante Lajaujis Anonis, Allured Pub. Co. (1993) et al.

  The content of the fragrance is preferably 0.1 to 2% by mass, more preferably 0.3 to 1% by mass, and still more preferably 0.4 to 0.8% by mass with respect to the total mass of the smoke smoke agent. If content of a fragrance | flavor is 0.1 mass% or more, in addition to the fragrance of a smoke agent after a preservation | save, the fragrance after smoke will also become favorable. On the other hand, if the content of the fragrance is 2% by mass or less, it is easy to impart an appropriate scent by smoke. Moreover, while the scent of the smoke agent after a preservation | save becomes more stable, the scattering rate of (B) component tends to become high.

If the smoke agent contains a binder, the moldability is improved.
Examples of the binder include celluloses (carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose, etc.), starch polymer compounds (starch, starch, etc.), natural polymer compounds (arabic gum, etc.), synthetic polymer compounds ( Polyvinyl alcohol, polyvinyl pyrrolidone, etc.).

  The content of the binder is preferably 3 to 8% by mass, and more preferably 3 to 4% by mass with respect to the total mass of the smoke smoke agent. If the content of the binder is 3% by mass or more, the time from installation to the start of smoke can be made longer, and it is easy to prevent the user from smoking at the start of smoke. On the other hand, if the content of the binder is 8% by mass or less, good smoke performance (jet power) is easily obtained.

If the smoke agent contains a surfactant, the smoke performance becomes more stable.
Examples of the surfactant include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonate, polyoxyethylene (POE) -alkyl ether sulfate, α-olefin sulfonate, and higher alcohol sulfate.
Examples of the cationic surfactant include alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl amine salt and the like.
Nonionic surfactants include, for example, sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acids, sucrose fatty acid esters, propylene glycol fatty acid esters, glycerin alkyl ethers, POE-sorbitan fatty acid esters, POE- Examples include glycerin fatty acid esters, POE-propylene glycol fatty acid esters, POE-alkyl ethers, POE / polyoxypropylene (POP) -alkyl ethers, alkanolamides, and the like.

As the surfactant, a fatty acid ester of a polyhydric alcohol or an ethylene oxide adduct thereof is preferable, and sorbitan fatty acid esters, POE-sorbitan fatty acid esters, and glycerin fatty acid esters that are liquid at room temperature are more preferable.
Examples of sorbitan fatty acid esters include monooleate (polyoxyethylene sorbitan monooleate), monolaurate, and the like.
Examples of glycerin fatty acid esters include glyceryl monocaprylate.

  The content of the surfactant is preferably 2 to 10% by mass and more preferably 3 to 8% by mass with respect to the total mass of the smoke smoke agent. If the content of the surfactant is 2% by mass or more, it is easy to lengthen the time from installation to the start of smoke, and it is easy to prevent the user from smoking at the start of smoke. On the other hand, if the content of the surfactant is 10% by mass or less, good smoke performance (jet power) is obtained, and the time until the start of smoke does not become too long.

Examples of the excipient include inorganic mineral substances (clay, kaolin, talc, diatomaceous earth, etc.).
The content of the excipient is preferably 2 to 45% by mass and more preferably 10 to 30% by mass with respect to the total mass of the smoke agent. If the content of the excipient is 2% by mass or more, the smoke performance becomes more stable. On the other hand, when the content of the excipient is 45% by mass or less, sufficient smoke performance (jet power) is easily obtained.

Examples of exothermic aids include zinc oxide and melamine.
Examples of the stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, epoxy compounds (epoxidized soybean oil, epoxidized linseed oil, and the like).
As an efficacy enhancer, piperonyl butoxide, S-421, etc. are mentioned, for example.
Examples of the antioxidant include dibutylhydroxytoluene (BHT) and tocopherol.

<Manufacturing method>
The smoke agent is prepared as a solid preparation such as powder, granule, tablet, etc. by mixing the component (A), the component (B) and, if necessary, optional components to a predetermined amount. The solid preparation can be prepared using a known production method according to the intended dosage form. For example, in the case of a granular preparation, it can be produced by a known granulated production method such as extrusion granulation method, compression granulation method, stirring granulation method, rolling granulation method, fluidized bed granulation method, etc. .
As a specific example of the production method by the extrusion granulation method, each component of the smoke agent is mixed by a kneader and the like, and further, an appropriate amount of solvent is added and mixed, and the obtained mixture is formed into a die having pores of a certain area. And granulate using a pre-extrusion granulator or a horizontal extrusion granulator. The obtained granulated product may be further cut into a certain size using a cutter or the like and dried. Although what is illustrated below is mentioned as a solvent, For example, when using water as a solvent, it is preferable to dry at the temperature of about 60-90 degreeC.

Examples of the solvent used in producing the smoke agent include water; alcohols such as ethanol, propanol and benzyl alcohol; paraffins such as liquid paraffin and n-paraffin; ethers such as butyl diglycol; isopropyl myristate; Such as esters; polyhydric alcohols such as glycerin; N-methylpyrrolidone; and propylene carbonate.
These solvents may be used alone or in combination of two or more.
In addition to mixing and kneading at the time of granulation, the solvent can be held by spraying and dipping after granulation.

<How to use>
As a method for using the smoke agent, a method similar to a method for using a general smoke agent can be used. Specifically, the smoke agent is accommodated in an arbitrary container such as a metal container or a ceramic container, and the smoke agent is heated indirectly or directly.
Examples of the method of indirectly heating include a method in which a smoke agent is accommodated in a metal container and the smoke agent is heated through the metal container.
As a heating method, a conventionally known method can be used, for example, a method of contacting a substance that generates heat upon contact with water and using the reaction heat; iron powder and an oxidizing agent (such as ammonium chlorate). Or a metal oxide or an oxidant having a smaller ionization tendency than the metal and utilizing the heat of oxidation reaction. Among these, from the viewpoint of practicality, a method (water type) in which a substance that generates heat upon contact with water is brought into contact with water and the reaction heat is used.
Examples of substances that generate heat upon contact with water include calcium oxide, magnesium chloride, aluminum chloride, calcium chloride, and iron chloride. Of these, calcium oxide is preferred.

  On the other hand, as a method of directly heating, there is a method (slip plate type) using a match head or the like, igniting a smoke agent with a heating element (ignition tool), and utilizing thermal decomposition of the combustion agent. .

The amount of fumigant may be appropriately set according to the volume of the object space, preferably 0.1~5g per 1m ^3, 0.5~3.5g is more preferable.

<Effect>
Since the smoke agent of the present invention described above has both the (A1) component and the (A2) component described above as a combustion agent at a specific mass ratio, the smoke is suppressed from being ejected vigorously and continuously. Can generate mild smoke. As a result, smoke is sufficiently diffused not only upward (vertical direction) but also around (lateral direction). Therefore, unevenness is less likely to occur in the control effect when used in a space with a low ceiling. And if it is a smoke agent of this invention, the contamination in the space by smoke can also be suppressed.

The smoke agent of the present invention is used for processing a space that can be sealed, which is required to suppress the growth of microorganisms such as bacteria, viruses, and molds, and is used particularly in a narrow space with a relatively low ceiling. It is suitable for.
The processing target of the smoke agent of the present invention is not particularly limited as long as it can be sealed, and examples thereof include a closet, a shoe box, a closet, and a loft.

[Smoke device]
The soot device of the present invention contains the above-described soot agent of the present invention, and includes heating means for heating the stored soot agent. Below, with reference to FIG. 1, the smoke apparatus which concerns on one Embodiment of this invention is demonstrated.
A smoke device 10 in FIG. 1 is an indirect heating type smoke device, and is provided in a housing 12, a heating unit (heating means) 20 provided in the housing 12, and the housing 12. It is roughly composed of a smoke agent part 32. The housing 12 includes a substantially cylindrical main body 14, a bottom portion 16, and a lid portion 18 provided on the upper portion of the main body 14. A smoke agent container 30 is provided in the housing 12, and the smoke agent container 30 is filled with the smoke agent to form a smoke agent part 32.

The lid portion 18 has a through hole, and examples thereof include a mesh, punching metal, and a lattice frame. Examples of the material of the lid portion 18 include metals and ceramics.
The material of the main body 14 is the same as that of the lid 18.

The smoke agent container 30 functions as a container that fills the smoke agent part 32 and also functions as a heat transfer part that transmits the thermal energy generated in the heating part 20 to the smoke agent part 32.
Examples of the smoke agent container 30 include a metal container.

  The heating unit 20 is not particularly limited, and is appropriately determined in consideration of the amount of heat necessary for the smoke agent unit 32 to smoke. The heating unit 20 is preferably formed by filling a substance that generates heat upon contact with the water, and particularly preferably formed by filling calcium oxide. Further, the heating unit 20 may be formed by partitioning and filling iron powder and an oxidant with a partition material, and a metal and a metal oxide or an oxidizer having a smaller ionization tendency than the metal are partitioned by the partition material. It may be formed by filling.

  What is necessary is just to determine the bottom part 16 according to the mechanism of the heating part 20 suitably. For example, when the heating unit 20 is made of a substance (calcium oxide or the like) that generates heat upon contact with water, a nonwoven fabric or a metal mesh can be used for the bottom 16. By making the bottom part 16 into a nonwoven fabric or a metal mesh, water can penetrate | invade into the heating part 20 from the bottom part 16, reaction heat | fever can be generated, and a smoke agent can be heated.

  In the smoke method using the smoke device 10, the smoke device 10 is first installed in the target space. Next, the heating unit 20 generates heat according to the mechanism of the heating unit 20. For example, when the heating part 20 filled with calcium oxide is provided, the bottom part 16 is immersed in water. When the heating unit 20 generates heat, the smoke agent part 32 is heated via the smoke agent container 30. As for the smoke smoke agent of the heated smoke agent part 32, gas arises by decomposition | disassembly of (A) component, (B) component smokes with this gas, passes through the through-hole of the cover part 18, and ejects. Thereby, (B) component diffuses in object space, and the prevention effect is acquired.

  Since the soot device of the present invention described above is filled with the above-described soot agent of the present invention, the control effect is less likely to be uneven when used in a low ceiling space. And if it is a smoke device of this invention, the contamination in the space by smoke can also be suppressed.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Raw materials]
As the component (A), the following compounds were used.
A1-1: 5-amino-1H-tetrazole (Toyobo Co., Ltd., trade name: “HAT”)
A1-2: 5,5′-bi-1H-tetrazole diammonium salt (manufactured by Toyobo Co., Ltd., trade name: “BHT-2NH3”)
A1-3: 5-methyl-1H-tetrazole (Toyobo Co., Ltd., trade name: “M5T”)
A2-1: Azodicarbonamide (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: “Dieblow AC. 2040 (C)”)
A2-2: N, N′-dinitrosopentamethylenetetramine (manufactured by Eiwa Kasei Kogyo Co., Ltd.)

As the component (B), the following compound B-1: water-soluble silver antibacterial agent (manufactured by J-Chemical Co., Ltd., trade name: “CF-01”, silver concentration 2.5% by mass)
B-2: Silver-supported zeolite-based inorganic antibacterial agent (manufactured by Sinanen Zeomic Co., Ltd., trade name: “Zeomic AJ10N”, silver concentration 2.5 mass%)
B-3: Silver-supported silica / alumina-based inorganic antibacterial agent (manufactured by JGC Catalysts & Chemicals, trade name: “ATOMY BALL- (UA)”, silver concentration 0.07% by mass (support 1.5% by mass) )
B-4: 3-methyl-4-isopropylphenol (manufactured by Osaka Kasei Co., Ltd., trade name: “Biosol”)
B-5: 3-iodo-2-propynylbutyl carbamate (Lonza Japan Co., Ltd., trade name: “GLYCACIL”)

The following compounds were used as optional components.
Perfume: Perfume having the composition shown in Table 1. Sorbitan fatty acid ester: polyoxyethylene (20) sorbitan monooleate (trade name: “Emazole O-120V” manufactured by Kao Corporation)
HPMC: Hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “Metroze 60SH-50”)
・ Clay: Showa KDE Co., Ltd., trade name: “MK-300”

[Evaluation]
<Evaluation of microbial control effect>
(1) Mold killing evaluation 1
First, as shown in FIG. 2, the following method ^{* 1} is applied to the center of the ceiling and wall of the evaluation chamber (1.8 m × 0.9 m × height 1.0 mm) 40 having a volume of 1.62 m ³ that can be sealed. The prepared test slide glass (slide glass inoculated with bacteria) 41 was attached with the surface inoculated with the bacteria facing inward.
Next, a plastic container for water supply containing 20 mL of water is installed in the center of the floor of the evaluation room 40, and the smoke device 42 prepared by the following method ^{* 2} is placed in the plastic container to start smoke. did. During the soot, the evaluation chamber 40 was sealed.
After 90 minutes from the start of soot, the air in the evaluation chamber 40 was exhausted, and the test slide glass 41 was recovered.
A bacterial solution recovered from the test glass slide 41 by the following method ^{* 3} , which is appropriately diluted with physiological saline so as to have a measurable concentration, is smeared on a potato dextrose agar medium at 25 ° C. After culturing for 5 days, the number of colonies formed was counted visually. The number of viable bacteria was determined from the measured number of colonies and the dilution rate of the bacterial solution, and the value was defined as the “number of bacteria after treatment”.
Separately, the bacterial solution collected from an untreated test glass slide that has not been smoked is appropriately diluted with physiological saline so as to have a measurable concentration, and then smeared on a potato dextrose agar medium, After culturing at 25 ° C. for 5 days, the number of colonies formed was counted visually. The number of viable bacteria was determined from the measured number of colonies and the dilution rate of the bacterial solution, and the value was defined as “the number of untreated bacteria”.
From the above results, the fungus control effect was evaluated according to the following evaluation criteria.

(* 1: Test glass production method)
Cladospodium cladosporoids HMC1064 (hereinafter referred to as “Cladosporium”) cultured at 25 ° C. for 1 week in a slant medium of potato dextrose agar (Difco), 0.05% Tween 80 (manufactured by Kanto Chemical Co., Inc.) About 10 ⁶ CFU / mL suspension was prepared in aqueous solution. Next, 0.1 mL of the obtained suspension was inoculated on a slide glass, allowed to stand overnight at room temperature, and then dried and fixed.

(* 2: Production of smoke device)
Prepare a container of “Barusan starting with water (for 6-8 tatami mats)” (manufactured by Lion Co., Ltd.), fill the smoke agent filling part in the container with 5 g of smoke agent, and further add the exothermic agent filling part in the container Into this, 30 g of calcium oxide was filled to produce a smoke device.

(* 3: Method for collecting bacteria from slide glass)
Put slide glass inoculated with fungus and 10 mL of SCDLP medium (manufactured by Nippon Pharmaceutical Co., Ltd.) into a sterilized plastic petri dish (manufactured by Aswan Co., Ltd.) Extracted.

(Evaluation criteria)
For the slide glass installed at the center of the ceiling and wall, the calculated number of viable bacteria is converted into the common logarithm (log), and the value obtained by subtracting the number of treated bacteria from the number of untreated bacteria (log (number of untreated bacteria)) -Log (the number of bacteria after treatment)) was determined, and the value was taken as the control effect. From this value, the control effect against mold was evaluated according to the following criteria.
<Criteria>
A: Control effect is 4 or more.
A: The control effect is 3 or more and less than 4.
○: Control effect is 2 or more and less than 3.
Δ: The control effect is 1 or more and less than 2.
X: Control efficacy is less than 1.

(2) Mold killing evaluation 2
Except for using the test slide glass prepared by the following method ^{* 4} , the control effect was determined in the same manner as the fungicidal evaluation 1, and the control effect on the mold was evaluated. The criteria for determination are the same as for mold kill evaluation 1. The test slide glass was attached only to the wall.

(* 4: Method for producing test slide glass)
Penicillium citrinum (hereinafter referred to as “Penicillium”) cultured in a potato dextrose agar (Difco) slant medium at 25 ° C. for 1 week in a sterilized 0.05% Tween 80 (Kanto Chemical Co., Ltd.) aqueous solution. A suspension of about 10 ⁶ CFU / mL was prepared. Next, 0.1 mL of the obtained suspension was inoculated on a slide glass, allowed to stand overnight at room temperature, and then dried and fixed.

<Evaluation of contamination>
A slide glass and a plastic container for water supply containing 20 mL of water are installed in the center of the floor of a sealable evaluation chamber (1.8 m × 0.9 m × height 1.0 mm) with a volume of 1.62 m ^3. Then, the smoke device produced by the following method ^{* 5} was put in the plastic container, and smoke was started (smoke treatment 1). The evaluation room was sealed during the soot.
Two hours after the start of smoking, the slide glass set on the floor surface of the evaluation room was taken out, and the surface state was visually observed.
Separately, smoke was smoked in the same manner as the smoke treatment 1 except that only azodicarbonamide was used instead of the smoke smoke agent (the smoke treatment 2), and 2 hours after the start of the smoke, on the floor of the evaluation room The slide glass that had been installed was taken out, and its surface condition was visually observed. The amount of azodicarbonamide charged into the smoke device was set to be the same as the amount of azodicarbonamide in the smoke agent used in the smoke treatment 1. That is, for example, when the smoke treatment 1 is performed using 2.5 g of a smoke agent containing 65% by mass of azodicarbonamide, in the smoke treatment 2, 1.625 g of azodicarbonamide is charged into the smoke device. Went smoke.
From the above results, the floor contamination after smoking was evaluated according to the following evaluation criteria.

(* 5: Production of smoke device)
A smoke device having the same configuration as that shown in FIG. 1 was produced. Specifically, a heating container including a cylindrical casing 12 having a bottom 16 made of a nonwoven fabric and a smoke agent container 30 provided in the casing 12 is prepared, and the heating container The smoke agent container 30 of the container is filled with 2.5 g of smoke agent to form a smoke agent part 32, and 30 g of calcium oxide is added between the casing 12 of the container for heating and the smoke agent container 30. The heating unit 20 was formed by filling, and the smoke device 10 was produced.

(Evaluation criteria)
The slide glass after the smoke treatment 1 was checked for contamination.
If the slide glass after the smoke treatment 1 is contaminated, check how much the contamination is improved compared to the surface condition (contamination state) of the slide glass after the smoke treatment 2 Then, according to the following evaluation criteria, the pollution status of the floor after smoking was evaluated.
A: The surface of the slide glass after the smoke treatment 1 is not contaminated.
○: Contamination is improved.
Δ: The contamination is slightly improved.
X: It is equal to or less than the surface state (contamination state) of the slide glass after the smoke treatment 2.

[Examples 1 to 19 and Comparative Examples 1 to 5]
Smoke agents having the compositions shown in Tables 2 to 4 were produced by the following procedure.
The unit of the compounding amount of each component in Tables 2 to 4 is mass%. Among the components (B), the amount of B-1 to B-3 is the silver concentration (mass%) in 100% by mass of the smoke agent. The “balance” of the clay is such an amount that the total amount of smoke agent becomes 100% by mass.
Under room temperature (20 ° C.) conditions, each component was stirred and mixed with a kneader (manufactured by Moriyama Co., Ltd., “S5-2G type”) according to the composition shown in Tables 2 to 4, and the total amount of the composition was 10 parts by mass. Part of water was added and mixed to obtain a mixture. The obtained mixture was granulated using a die pre-extruder granulator ("EXK-1" manufactured by Fuji Powder Co., Ltd.) having an opening having a diameter of 2 mm to obtain a granulated product. The obtained granulated product was cut into a length of 2 to 5 mm by a flash mill (Fuji Paudal Co., Ltd., “FL300”) and set at 70 ° C. (Alp Co., Ltd., “RT-120HL”). Was dried for 2 hours to obtain a granular smoke agent.
About the obtained smoke agent, the microorganisms control effect and pollution property were evaluated. The results are shown in Tables 2-4.

As can be seen from Tables 2 and 3, the smoke smoke agents of each Example were less likely to cause unevenness in the fungicidal effect when used in a space with a low ceiling, and could suppress contamination.
On the other hand, as is clear from Table 4, the smoke agents of Comparative Examples 1 to 5 in which the mass ratio represented by (A1) component / (A) component is less than 0.05 or greater than 0.8 are Unevenness occurred in the mold effect. In particular, the smoke agent of Comparative Example 2 containing no component (A1) could not suppress contamination.

DESCRIPTION OF SYMBOLS 10 Smoke apparatus 20 Heating part 30 Smoke agent container 32 Smoke agent part 40: Evaluation room 41: Test glass slide 42: Smoke apparatus

Claims (4)

Component (A): A tetrazole-type gas generating agent that is at least one selected from 5-amino-1H-tetrazole, 5,5′-bi-1H-tetrazole diammonium salt and 5-methyl-1H-tetrazole ( An organic foaming agent comprising A1) and an organic foaming agent (A2) other than a tetrazole-type gas generating agent that is at least one of azodicarbonamide and N, N′-dinitrosopentamethylenetetramine ;
(B) component: containing a drug,
Content of the said (A) component is 24-99 mass% with respect to the total mass of a smoke agent ,
The smoke agent whose mass ratio represented by a tetrazole type gas generating agent (A1) / (A) component is 0.05-0.8.   The smoke agent according to claim 1, wherein the tetrazole-type gas generating agent is at least one selected from 5-amino-1H-tetrazole and 5,5'-bi-1H-tetrazole diammonium salt.   The component (B) is an inorganic drug containing silver or at least one organic drug selected from 3-methyl-4-isopropylphenol and 3-iodo-2-propynylbutylcarbamate. The smoke agent according to 1 or 2.   A smoke device in which the smoke agent according to any one of claims 1 to 3 is accommodated and provided with heating means for heating the smoke agent.

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