JP7051967B2 - Disinfectant - Google Patents

Description

The present invention relates to a disinfectant.

Conventionally, various agents have been known as disinfectants, and their usage modes are also various.
For example, Patent Document 1 describes mold, yeast, virus, which are present in the air of a closed space such as a room.
A composition for air sterilization containing glycol ether is disclosed as a sterilizing agent for microorganisms such as bacteria, and it is described that the above microorganisms and the like are sterilized by volatilizing the composition in a space. Has been done.
Further, Patent Document 2 discloses a disinfectant such as benzalkonium chloride as a disinfectant against microorganisms such as molds that float in the air or adhere to furniture and propagate. A method of storing the agent in a pressure-accumulation type spray container and spraying the agent is described.
Further, Patent Document 3 discloses a space sterilization tool that sterilizes bacteria and viruses existing in the space by releasing chlorine dioxide into the space.

On the other hand, azodicarbonamide is known as one kind of organic foaming agent, and Patent Document 4 describes a foaming agent composition containing azodicarbonamide as an organic foaming agent.

Japanese Unexamined Patent Publication No. 2007-097738 Japanese Unexamined Patent Publication No. 2010-08306 JP-A-2015-093811 Japanese Unexamined Patent Publication No. 7-305050

As described in the above-mentioned Patent Documents 1 to 3, various agents have been known so far as disinfectants. Therefore, an object of the present invention is to provide a new disinfectant different from the above disinfectant.

The present inventors have found that a decomposition product of azodicarbonamide acts effectively as a disinfectant. Conventionally, azodicarbonamide is known as one of the organic foaming agents used in the rubber and plastic industries because it causes a foaming action when it is thermally decomposed by heating. Azodicarbonamide is also used as an organic foaming agent in the foaming agent composition described in Patent Document 4.

As described above, it has been well known that azodicarbonamide can be used as an organic foaming agent. However, as a result of diligent research on azodicarbonamide, the present inventors have surprisingly found that the decomposition product of azodicarbonamide is effective as a disinfectant having a good disinfecting effect on molds and germs. We have newly found that it acts on the subject, and have completed the present invention.

That is, the present invention is as follows.
(1) A disinfectant containing a decomposition product of azodicarbonamide as an active ingredient.
(2) The disinfectant according to (1) above, which further contains a fragrance.

According to the present invention, the decomposition product of azodicarbonamide can exert a good sterilizing effect against molds, germs and the like.

It is sectional drawing of the self-heating apparatus 1 for demonstrating the water heating system which is one heating means for generating the decomposition product of azodicarbonamide which is an active ingredient of the disinfectant of this invention. It is a schematic diagram of the bathroom in which the disinfectant of this invention was volatilized in Test Example 2 and Test Example 4-2.

The disinfectant of the present invention is a disinfectant containing a decomposition product of azodicarbonamide as an active ingredient. Hereinafter, the disinfectant of the present invention will be described in more detail.

The decomposition product of azodicarbonamide, which is the active ingredient of the disinfectant of the present invention, can be obtained, for example, by heating the azodicarbonamide. As described above, azodicarbonamide is one of the organic foaming agents used in the rubber and plastic industries, and commercially available products or those synthesized by a known method can be used. Examples of commercially available products include "uniform AZ (trade name)" manufactured by Otsuka Chemical Co., Ltd. and "cell microphone (trade name)" manufactured by Sankyo Kasei Co., Ltd.
The decomposition start temperature of azodicarbonamide is about 200 ° C., the amount of gas generated during decomposition is large, and the azodicarbonamide is excellent in diffusivity. When azodicarbonamide is thermally decomposed by heating, foaming action occurs and a decomposition product of azodicarbonamide is produced. There are three decomposition products of azodicarbonamide: gaseous, liquid (including mist), and solid. Produced as a decomposition product of the state. Among them, the decomposition products of azodicarbonamide are the decomposition products suspended in the air (hereinafter referred to as floating substances) whose main components are gaseous and mist-like decomposition products, and their own weight whose main components are solid decomposition products. It is divided into decomposition products that fall (hereinafter referred to as falling materials).

As described above, the decomposition product of azodicarbonamide having an effective sterilizing effect of the present invention is generated from the suspended matter suspended in the air and the falling substance falling due to its own weight, which is generated during the decomposition of the azodicarbonamide. However, as shown in the following Examples (Test Examples 4-1 and 4-2),
As a result of various tests, it is presumed that among the decomposition products of these azodicarbonamides, it is the suspended matter that exerts a particularly good sterilizing effect on molds and germs.
Further, from the viewpoint of the sterilizing effect, the suspended matter is preferably generated within 30 minutes immediately after the start of heating of the azodicarbonamide. More preferably, the suspended matter generated within 30 minutes immediately after the start of heating of the azodicarbonamide and remaining within 15 minutes to 30 minutes after the start of heating is more preferable. Here, the "suspended substance that survives within 15 to 30 minutes after the start of heating" specifically means, for example, after starting heating of the azodicarbonamide in the Tedlar bag, as shown in the following test example. It refers to the suspended matter existing in the Tedlar bag between 15 and 30 minutes, and even if the suspended matter is generated within 15 minutes after the start of heating, it continues within 15 to 30 minutes after the start of heating. It means that it also includes floating substances.

In the present invention, the mechanism by which the decomposition product of azodicarbonamide exerts a good sterilizing effect against molds and germs is not clear, but the decomposition product of azodicarbonamide is the bacterial cells such as molds and germs. It is presumed that it acts on the cell wall and kills the cells.

The heating temperature for decomposing the azodicarbonamide is preferably 200 ° C. or higher, more preferably 200 to 700 ° C., and more preferably 300 to 500 ° C. from the viewpoint of improving the sterilizing effect. Is even more preferable.

The heating means for decomposing the azodicarbonamide is not particularly limited as long as a decomposition product of the active ingredient azodicarbonamide can be obtained. For example, a method of directly igniting and heating, a method of heating by contacting with a heat source such as a heater, a method of heating using a heat source such as a heating agent, and the like can be mentioned. Above all, from the viewpoint of ease of handling and efficient volatilization of the decomposition product of azodicarboxylic amide, heating is performed using a hydrothermal system that generates exothermic heat using a hydrothermal substance and a hydrothermal reaction solution as a heating agent. It is preferable to do so. By using a hydrothermal system, a decomposition product of azodicarbonamide (active ingredient of the disinfectant of the present invention) can be efficiently generated and volatilized, and many decomposition products of azodicarbonamide can be applied to the place of application (the application site (). For example, it can be diffused indoors).

As a heating condition for satisfactorily exerting this effect, azodicarbonamide is used at a temperature of 1.
It is preferable to heat so that the time to reach 00 ° C. or higher is 700 seconds or longer, more preferably to heat to 800 seconds or longer, and further preferably to heat to 900 seconds or longer.
Further, the time for the temperature to reach 200 ° C. or higher is preferably 250 seconds or longer, more preferably 300 seconds or longer, and even more preferably 350 seconds or longer.
Further, the time for the temperature to reach 300 ° C. or higher is preferably 150 seconds or longer, and more preferably 200 seconds or longer.
Further, the time for the temperature to reach 350 ° C. or higher is preferably 130 seconds or longer, and more preferably 150 seconds or longer.

As a heating condition for satisfactorily exerting this effect, the total temperature of 100 ° C. or higher when the heating temperature is measured at 1-second intervals from the start of heating to the end of heating is 140,000. The temperature is preferably ℃ · s or higher, more preferably 170,000 ° C. · s or higher, and even more preferably 200,000 ° C. · s or higher.
Further, the total temperature of 200 ° C. or higher is preferably 70,000 ° C. · s or higher, more preferably 90,000 ° C. · s or higher, and 120,000 ° C. · s or higher. More preferred.
Further, the total temperature of 300 ° C. or higher is preferably 40,000 ° C. · s or higher, more preferably 60,000 ° C. · s or higher, and 80,000 ° C. · s or higher. More preferred.
Further, the total temperature of 350 ° C. or higher is preferably 30,000 ° C. · s or higher, more preferably 45,000 ° C. · s or higher, and 60,000 ° C. · s or higher. More preferred.

As an example of the means for heating the azodicarbonamide, a means for heating the azodicarbonamide using a water heating system will be described below. The water heating system is a system in which a water heating substance and a water heating reaction liquid are subjected to a water heating reaction, and the heat source in this system is the self-heating device 1 shown in FIG. Azodicarbonamide is heated using the heat of reaction generated by the heat of water reaction, and a decomposition product of azodicarbonamide, which is the active ingredient of the sterilizing agent of the present invention, is generated and volatilized. The hydrothermal substance is a substance that self-heats due to the reaction with the hydrothermal reaction solution, and examples thereof include calcium oxide (quick lime), magnesium chloride, and aluminum chloride. Examples of the hydrothermal reaction solution include water or a solution obtained by adding various additives to water. Examples of such additives include those that do not hinder the volatilization of decomposition products of azodicarbonamide and those that do not reduce the reactivity of water with pyrogens, and specific examples thereof include organic solvents and liquid stabilizers. Can be done.
In the present invention, for example, when the self-heating device 1 is used as a heat source, the heating temperature of the azodicarbonamide can be obtained by measuring the temperature of the bottom X of the partition member 4 shown in FIG.

In addition to heating by the water heating system, for example, an electric heating system using a heating wire such as a nichrome wire, a flat plate or a ring, and a heating heater using a semiconductor; an oxidizing agent such as iron powder and ammonium chlorate. Mixing with, mixing a metal with a metal oxide or oxidizing agent having a smaller ionization tendency than the metal, contacting iron with a mixture of potassium sulfate, iron sulfate, metal chloride, iron sulfide, etc. with water or oxygen. A mixture of a metal having a higher ionization tendency than iron and a halide of a metal having a lower ionization tendency than iron is brought into contact with water, a mixture of a metal and a heavy sulfate is brought into contact with water, and a mixture of aluminum and an alkali metal nitrate. It can also be heated by using a system that generates heat by an oxidation reaction such as adding water; a system that generates heat by utilizing an oxidation reaction of a metal sulfide that brings a mixture of sodium sulfate and iron carbide into contact with oxygen.

In addition to the decomposition product of azodicarbonamide, the disinfectant of the present invention may contain any component as long as the effect of the present invention is exhibited. As the optional component, for example, a fragrance, a solvent, a deodorant, a volatilization aid, a stabilizer, an insecticide, a pest repellent and the like can be used.

Examples of the fragrance include natural fragrances extracted from various plants and animals, chemically synthesized synthetic fragrances, and compounded fragrances made by mixing a large number of these fragrance components.
Fragrances are described in various literatures, such as "Perfume and Flavor Materi".
als of Natural Origin ”, Stephen Arctander
, Allured Pub. Co. (1960), "Encyclopedia of Fragrances", edited by Japan Fragrance Association, Asakura Shoten (1989), "Flower oils and Floral Compou"
nds In Performance ”, Danute Pajaudis Anonis
, Allured Pub. Co. (1993), "Perfume and Flav"
or Chemicals (aroma chemicals) ”, Vols. I an
d II, Stephen Arctander, Allured Pub. Co. (1
994), "Basic knowledge of fragrances and fragrances", edited by Motoki Nakajima, Sangyo Tosho (1995), "Synthetic fragrance chemistry and product knowledge", Motokazu Indo, The Chemical Daily (1996), "Encyclopedia of fragrances""
, Mitsuyoshi Yatagai ed., Maruzen (2005) can be used. Each is incorporated herein by reference. Specific examples of fragrances are given below, but the fragrances are not limited thereto.

Natural fragrances include, for example, orange oil, lemon oil, lavender oil, lavandin oil, bergamot oil, patchouli oil, cedarwood oil, peppermint oil, thyme oil, clove oil, etc.
Examples thereof include natural essential oils such as cinnamon oil, eucalyptus oil, and tea tree oil.
Examples of the synthetic fragrance include hydrocarbon terpenes such as α-pinene, β-pinen, limonene, p-cymen, turpinolene, α-turpinen, γ-turpinen, α-ferrandren, kanphen, etc .; heptanal, octanal, decanal, etc. Aldehydes such as benzaldehyde, salicylic aldehyde, phenylacetaldehyde, citronellal, hydroxycitronellal, citral, α-hexylcinnamic aldehyde, lilial, cyclamenaldehyde, lylar, heliotropin, helional, vanillin, ethylvanillin; ethylformate, Methylacetate, Methylpropionate, Meethylisobutyrate, Propylbutyrate, Isobutylacetate, Isobutylbutyrate,
Isobutylisovalerate, ethyl-2-methylvalerate, isoamyl acetate, amylpropionate, allylhexanoate, ethylacetacetate, ethylheptylate, methylbenzoate, ethylbenzoate, ethyloctylate, benzylacetate, nonylacetate , Ortho-ter-butylcyclohexyl acetate, linaryl benzoate, ethyl cinnamate, methyl salicylate, hexyl salicylate, hexyl butyrate, mentyl acetate, turpinyl acetate, phenylethyl isobutyrate, methyl jasmonate, methyl dihydro jasmonate, Ester lactones such as ethylene brushlate, γ-undecalactone, γ-nonyllactone, cyclopentadecanolide, coumarin; anisole, p-cresylmethyl ether, dimethylhydroquinone,
Methyl eugenol, β-naphthol methyl ether, β-naphthol ethyl ether,
Ethers such as anethole, diphenyl oxide, rose oxide, galaxolide, ambrox; isopropyl alcohol, cis-3-hexenol, heptanol,
Alcohols such as 2-octanol, dimethol, dihydromilsenol, linalol, benzyl alcohol, citronellol, geraniol, nerol, tarpineol, l-menthol, cedrol, timole, anis alcohol, phenylethyl alcohol, hexanol; diacetyl, menton, isomenton , Acetphenone, α- or β-damascon, α- or β-damasenone, α-, β- or γ-yonone, α-, β- or γ-methylyonone, methyl-β-naphthylketone, benzophenone, tentalome, acetylce Drain, α- or β-isomethylyonone, α-, β- or γ-iron, maltor, cis
-Ketones such as jasmon, dihydrojasmon, l-carboxylic, dihydrocarboxylic, methylamylketone, camphor, 1,8-cineole, allylamylglycolate, isopulegol, ligstral, allylcaproate and the like can be mentioned. These fragrances may be used alone or in combination of two or more as a blended fragrance. Further, the fragrance can also be used as a mixture (fragrance composition) containing a fragrance component, a solvent, a fragrance stabilizer and the like.

Examples of the solvent include water, alcohols such as ethanol, propanol and benzyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, glycerin and 1,3-butanediol, ethylene glycol monomethyl ether and ethylene glycol mono. Ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Diethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monobutyl ether , Dipropylene glycol dimethyl ether, phenylcarbitol, phenylcellosolve, glycol ethers such as benzylcarbitol, liquid paraffin, paraffins such as n-paraffin, esters such as diethylphthalate, benzylbenzoate, triethylcitrate, isopropyl myristate, etc. , Other 3-Methyl-4-methoxybutanol, N
-Methylpyrrolidone, propylene carbonate and the like can be mentioned. These solvents may be used alone or in any combination of two or more. It can also be mixed with the above fragrance components and used as a fragrance composition.

The fragrance can be appropriately contained in the disinfectant of the present invention so as to have a predetermined balance. The fragrance is usually contained in the disinfectant in an amount of 0.01 to 20% by mass, preferably 0.1 to 10% by mass. When a fragrance is contained, if the content is less than 0.01% by mass, a sufficient scent may not be obtained, and if it exceeds 20% by mass, the scent may be too strong.
When the fragrance is volatilized in the space together with the decomposition product of azodicarbonamide, it is preferably contained in the disinfectant of the present invention so that the volatilization concentration of the fragrance is 1 to 300 mg / m ³ . It is more preferable to contain it so as to be 5 to 150 mg / m ³ . Within the above range, the sterilizing effect can be enhanced synergistically with the decomposition product of azodicarbonamide. In addition, the unpleasant odor generated when the azodicarbonamide is volatilized can be suppressed, and the actual feeling of use can be further enhanced.

Examples of the deodorant include lauryl methacrylate, geranyl crotonate, and catechin.
Examples include polyphenols and charcoal.

Examples of the volatilization aid include zinc stearate, aluminum stearate, barium stearate, calcium stearate, zinc carbonate, calcium carbonate, titanium dioxide, and the like.
Examples thereof include carbon black, antimony trioxide, decabromodiphenylene oxide, trimellitic anhydride, maleic anhydride, benzotriazole, 4,4'-oxybis (benzenesulfonyl hydrazide), urea and the like.

Examples of the stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, tocopherol and the like.

Examples of pesticides include natural pyrethrins, pyrethrins, allethrins, phthalthrins, etc.
Pirethroid insecticides such as resmethrin, flamethrin, permethrin, phenothrin, ciphenothrin, praretrin, transfluthrin, metoflutrin, profluthrin, imiprothrin, empentrin, etofenprox, sirafluofen; Organic phosphorus-based insecticides such as; oxadiazole-based insecticides such as methoxadiazone; phenylpyrazole-based insecticides such as fipronil; neonicotinoid-based insecticides such as imidacloprid and dinotefuran; Pyrrole compounds; insecticidal hormone-like compounds such as metoprene and hydroprene; anti-insecticide-like compounds such as plecosene; dehulling hormone-like compounds such as ecdison; Essential oils; one or more of IBTA, IBTE, quaternary ammonium salts, benzyl salicylate and the like.
Among them, pyrethroid insecticides, carbamate insecticides, oxadiazole insecticides and sulfonamide insecticides are preferable because they improve volatilization well, and in particular, cyphenothrin, permethrin, metoxadiazone, propoxul, amideflumeth and etofenprox. Is preferable.

Examples of the pest repellent include one or more of DEET, di-n-butylsuccinate, hydroxyanisole, rotenone, ethyl-butylacetylaminopropionate and the like.

In the present invention, "sterilization" means that the number of microorganisms such as molds and bacteria that can grow from an object (for example, an indoor ceiling or wall) decreases (the number of viable bacteria).
In the present invention, the target to be sterilized includes bacteria and fungi. As a bacterium,
Specifically, Pseudomonas genus bacteria such as Pseudomonas aeruginosa, Escherichia genus such as Escherichia coli, Bacillus subtilis,
Bacillus genus bacteria such as Bacillus cereus, Methy
Methamphetamine such as lobacterium methamphetamine
Staphylococcus au, genus ylobacterium
Examples include Staphylococcus genus such as reus) and gram-positive bacteria such as lactic acid bacteria. Specifically, the fungus is Cladospor.
Cladosporium such as ium cladosporioides)
ium) genus, Penicillium citrinum, etc.
The genus llium, the genus Aspergillus such as Aspergillus brasiliensis, the genus Alternaria such as Alternaria alternata, and the genus Fusarium such as Fusarium solani.
Eurotiomycetes (Eurot) such as the genus rium and Eurotiomycetes
Genus ium, genus Rhodotorula such as red yeast (Rhodotorula mucilaginosa), aureobasidium (Aureobasidium)
), Black yeasts such as Exophiala, Phoma
), Candida, Saccharomyces
) Genus etc.

Examples of the dosage form of the disinfectant of the present invention include granules, powders, fine granules, and liquids.
Above all, it is preferable to make granules, powders, fine granules and the like solid.

In order to granulate and dry the disinfectant of the present invention, the disinfectant of the present invention may contain the following binders, excipients and the like. Thereby, the dosage form of the disinfectant of the present invention can be made into granules, powders, fine granules and the like. When granulating the disinfectant of the present invention, for example, in the case of granules, the particle size is preferably about 1 to 5 mm.

Examples of the binder used when granulating the disinfectant of the present invention include celluloses such as carboxymethyl cellulose, hydroxymethyl cellulose and hydroxypropyl methyl cellulose; starch-based compounds such as starch and starch, and natural polymer compounds such as Arabic rubber. One or more of synthetic polymer compounds such as polyvinyl alcohol can be mentioned.
These binders may be contained in an amount of 0.5 to 5% by mass with respect to the disinfectant of the present invention.

Examples of excipients include pearlite, talc, diatomaceous earth, bentonite, clay minerals and the like.

When the dosage form of the disinfectant of the present invention is a liquid, for example, the powder can be dissolved in a liquid carrier to prepare a liquid. The carriers used in preparing the liquid preparation include, for example, water, alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, hexane, kerosene, paraffin and petroleum. Aliper hydrocarbons such as benzine, benzene,
Examples thereof include aromatic hydrocarbons such as toluene, esters such as ethyl acetate, and halogenated hydrocarbons such as dichloroethane.

If necessary, the disinfectant of the present invention may further contain a disintegrant or the like, and for example, organic acid esters such as paraoxybenzoic acid ester, stearic acid ester, ethyl lactate and chlorophenyl salicylate; malic acid, When a disintegrant such as an organic acid such as fumaric acid, tartaric acid, malic acid, and succinic acid is used, the disintegration of the preparation by heating is promoted, and the disinfectant of the present invention can be smoothly volatilized.
Further, if necessary, various surfactants, efficacy enhancers, dyes and the like can be contained.

The sterilizing effect of the sterilizing agent of the present invention can be evaluated by the sterilizing rate. The sterilization rate is expressed by the following formula. Details are obtained by the method described in Examples described later.
Sterilization rate (%) = {1-Number of bacteria after sample processing (number of colonies) / Number of bacteria without sample treatment (number of colonies)} x 100
The sterilization rate is preferably 90% or more, and more preferably 99% or more.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples.

<Test Example 1>
The efficacy of eradication of the active ingredient azodicarbonamide degradation product against fungi was evaluated.

[Preparation of PDA medium inoculated with fungus]
A PDA medium inoculated with Kurokawa mold was prepared by the following procedure.
1. 1. A PDA slope medium was prepared in a test tube using 10 mL of PDA (potato dextrose agar).
2. 2. Above 1. Cladosporium on the PDA slope medium prepared in
Cladosporioides) spores were inoculated and the black squirrel was cultured at 25 ° C. for 4 days.
3. 3. Above 2. 9 mL of physiological saline and 1 mL of PDB (potato dextrose medium) were added to the slope medium of black spores prepared in 1.
4. Above 3. The spore solution was filtered, and the filtrate was diluted 10,000-fold with physiological saline.
5. Above 4. Inoculate 100 μL of the solution prepared in 1 into a PDA medium prepared using 12 mL of PDA in a sterilized petri dish of φ85 mm (trade name: Full Steri Deep Petri Dish sterilized φ90 × 20), and “PDA medium inoculated with fungus”. Was produced.

[Sample processing]
In a 1.30 cm × 30 cm × 30 cm container, a φ9 cm metal petri dish containing the fungus-inoculated PDA medium and 5 g of powdered azodicarbonamide prepared above was placed.
2. 2. The azodicarbonamide was ignited by bringing it directly to the fire, and after sufficient foaming was confirmed to generate smoke, the container was sealed for 90 minutes (hereinafter referred to as heat treatment (Example 1)).
3. 3. Further, the azodicarbonamide was dispersed in water so as to be 5 g / 900 cm ² .
A medium that was uniformly applied to the above-mentioned medium was prepared (hereinafter referred to as non-heat treatment (Comparative Example 1)).
4. Further, the prepared medium to which the azodicarbonamide was not applied was prepared (hereinafter referred to as untreated (reference example)).
5. Three media, heat-treated (Example 1), non-heat-treated (Comparative Example 1), and untreated (reference example), were allowed to stand at 25 ° C. for 4 days to incubate black sardines.

[evaluation]
The sterilization effect was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
⊚: No colonization is seen ○: Colonization is hardly seen △: Colonization is seen in a part ×: Colonization is seen as a whole

From the above results, it was found that the decomposition product of azodicarbonamide generated by heating the azodicarbonamide has a good sterilizing effect.

<Test Example 2>
Azodicarbonamide was heated using a hydrothermal system to generate a degradation product of azodicarbonamide, and the efficacy of eradication against fungi was evaluated.

[Example 2]
[Preparation of pharmaceutical product]
In the formulation shown in Table 2, each component was mixed, granulated and dried to prepare a granular formulation 7. The particle size per grain of the pharmaceutical product 7 is about 3 mm, and the length is about 5 mm.

The following active ingredients were used.
Active ingredient: Azodicarbonamide (trade name: uniform AZ Ultra # 1067-
1 (manufactured by Otsuka Chemical Co., Ltd.))

[Manufacturing of self-heating device]
In order to heat the pharmaceutical product 7 by the water heating system, a self-heating device 1 as shown in FIG. 1 was manufactured as follows.
65 g of hydrothermal substance 8 (calcium oxide) was contained from the bottom to the side of the bottomed cylindrical outer container 2 having a diameter of 53 mm, a height of 63 mm, and a depth of 40 mm. The outer container 2 has a plurality of water passage holes at the bottom, and the water passage holes are closed by a water-permeable nonwoven fabric sheet 3. In addition, the outer container 2
The inside of was divided into two spaces by a partition member 4. The partition member 4 is cylindrical and has a substantially hollow hemisphere at the bottom, and its side wall is arranged concentrically with the peripheral wall of the outer container 2. Pyrogeneous substance 8
Filled the space formed by the peripheral wall of the outer container 2, the partition member 4, and the non-woven fabric sheet 3, and 5 g (azodicarbonamide 4.9 g) of the above-prepared pharmaceutical product 7 was housed inside the partition member 4. Further, on the upper open surface of the outer container 2, 0.8c is formed in a region corresponding to the upper open surface of the partition member 4.
A lid member 5 having seven openings of m ² was covered, and the openings of the lid member 5 were closed with a heat-melted resin film 6 having ventilation holes to prepare the self-heating device 1 of Example 2.

[Example 3]
A self-heating device 1 was produced in the same manner as in Example 2 except that the amount of calcium oxide was 37 g.

[Preparation of PDA medium inoculated with fungus]
A PDA medium inoculated with Kurokawa mold was prepared by the following procedure.
1. 1. A PDA slope medium was prepared in a test tube using 10 mL of PDA (potato dextrose agar).
2. 2. Above 1. Cladosporium on the PDA slope medium prepared in
Cladosporioides) spores were inoculated and the black squirrel was cultured at 25 ° C. for 4 days.
3. 3. Above 2. 9 mL of physiological saline and 1 mL of PDB (potato dextrose medium) were added to the slope medium of black spores prepared in 1.
4. Above 3. The spore solution was filtered, and the filtrate was diluted 10,000-fold with physiological saline.
5. Above 4. Inoculate 100 μL of the solution prepared in 1 into a PDA medium prepared using 12 mL of PDA in a sterilized petri dish of φ85 mm (trade name: Full Steri Deep Petri Dish sterilized φ90 × 20), and “PDA medium inoculated with fungus”. Was produced.

[Test method]
Either Example 2 or Example 3 is placed in the bathroom 11 in a closed space of 4.4 m ³ (1.6 m (vertical) × 1.25 m (horizontal) × 2.2 m (height)) shown in FIG. One self-heating device 1 was installed, and the medium prepared above was installed for each of the ceiling portion 13, the wall portion 14, and the floor surface portion 15 of the bathroom 11 (points indicated by black circles (●) in FIG. 2). As a control (untreated), the above medium was allowed to stand outside the bathroom. The temperature and humidity of the bathroom 11 are as shown in Table 3.
The self-heating device 1 was installed in the central part of the bathroom 11 and was immersed in a container 9 containing 22 mL of water (hydraulic exothermic reaction liquid) W to start the hydrothermal reaction and heat the pharmaceutical product 7.
After the heating was started, the bathroom 11 was placed in a non-ventilated state and sealed for 90 minutes. Then, ventilation was performed for 30 minutes.
Then, the medium was collected and allowed to stand at 25 ° C. for 4 days to incubate the black squirrel.

[evaluation]
The number of bacteria (number of colonies) of Kurokawa mold on the PDA slope medium was counted, and the average value of the number of bacteria (number of colonies) for each of the ceiling, wall and floor of the bathroom was calculated. In addition, the sterilization rate represented by the following formula was calculated.
Sterilization rate (%) = {1-Number of bacteria in the medium after sample treatment (number of colonies) / Number of bacteria in the medium without sample treatment (number of colonies)} x 100
The above tests were performed twice in total, and the calculated number of bacteria (number of colonies) and sterilization rate are shown in Table 3 (Table 3).
The number of bacteria and the sterilization rate in the medium are the average values calculated in the tests conducted twice in total).

As shown in Table 3, when the sterilizing agent of the present invention was volatilized by a water heating system, a good sterilizing effect was observed in all of the ceiling portion 13, the wall portion 14 and the floor surface portion 15 of the bathroom 11. ..

Table 4 shows examples of effective prescriptions for carrying out the present invention.

<Test Example 3>
In this test, the temperature of the heat source (self-heating device 1) used in Example 2 in Test Example 2 is set to 1.
The heating temperature of azodicarbonamide is measured by measuring every second, and the temperature is 100 ° C or higher.
The time for reaching 200 ° C. or higher, 300 ° C. or higher, and 350 ° C. or higher was measured, respectively. also,
The total temperature of 100 ° C. or higher, the total temperature of 200 ° C. or higher, the total temperature of 300 ° C. or higher, and the total temperature of 350 ° C. or higher were obtained.

First, heat generation was started for the self-heating device 1 (heat source) excluding the pharmaceutical product 7 from the self-heating device 1 of Example 2, and the transition of the heat generation temperature was measured for each. Specifically, in the self-heating device 1 of FIG. 1, after removing the pharmaceutical product 7, a temperature probe (K-type thermocouple (manufactured by Shinko Kogyo Co., Ltd .: sheath thermocouple φ0) is located at the center of the bottom X of the partition member 4. .3 mm (MAX 600 ° C.))) was brought into contact. Since the temperature probe is linear, it was passed through the glass tube, the tip was bent, and the probe was pressed by the end of the glass tube to vertically adhere to and fix it to the bottom of the can. Heat generation was started in this state, and the heat generation temperature was measured and recorded over time every second using MT100 manufactured by Graphtec Corporation. This test was performed a total of 3 times (samples 1 to 3).
Next, based on the obtained temperature data, the temperature is 100 ° C or higher, 200 ° C or higher, 300.
The time for the temperature to reach ° C or higher and 350 ° C or higher was measured. The results are shown in Table 5. Further, the total temperature of 100 ° C. or higher, the total temperature of 200 ° C. or higher, the total temperature of 300 ° C. or higher, and the total temperature of 350 ° C. or higher were obtained. The results are shown in Table 6.

As can be seen from the results in Table 5, the time when the temperature is 100 ° C. or higher is 900 seconds or more on average, the time when the temperature is 200 ° C. or higher is 350 seconds or more on average, and the temperature is 300 ° C.
The time for the above was 200 seconds or more on average, and the time for the temperature to be 350 ° C. or higher was 150 seconds or more on average.
Further, as can be seen from the results in Table 6, the total temperature of 100 ° C. or higher is 200 on average.
The total temperature of 000 ℃ ・ s or more and 200 ℃ or more is 120,000 ℃ on average.
・ It was found that the total temperature of s or higher and 300 ° C or higher averaged 80,000 ° C.s or higher, and the total temperature of 350 ° C or higher averaged 60,000 ° C.s or higher. rice field.

<Test Example 4>
In the decomposition products of azodicarbonamide, which is the active ingredient, the sterilizing effects of suspended matter and falling matter were evaluated.

(Test Example 4-1)
In this test, among the decomposition products of azodicarbonamide, which is the active ingredient, the sterilizing effect of suspended matter was evaluated.
[Collection of gas components of decomposition products of azodicarbonamide]
A decomposition product of azodicarbonamide was collected by the following procedure.
1. 1. The self-heating device 1 of Example 2 produced in Test Example 2 is placed in a 200 L Tedlar bag and immersed in a container 9 containing 22 mL of water (hydraulic exothermic reaction liquid) W to cause a hydrothermal reaction in the Tedlar bag. Was started, and the pharmaceutical product 7 was heated and smoked.
2. 2. After the start of heating, at regular intervals (immediately after the start of heating, 5 minutes, 15 minutes, 30 minutes, 60 minutes, 90 minutes) from the above Tedlar bag, a 0.22 μm filter made of PTFE (Millilex-). While removing the solid component using FG (registered trademark), MILLIPORE), the gas was extracted with a glass syringe, and the suspended matter of the decomposition product of azodicarbonamide was collected.

[Preparation of test board inoculated with fungus]
A PDA medium inoculated with Kurokawa mold was prepared by the following procedure.
1. 1. A PDA slope medium was prepared in a test tube using 10 mL of PDA (potato dextrose agar).
2. 2. Above 1. Cladosporium on the PDA slope medium prepared in
Cladosporioides) spores were inoculated and the black squirrel was cultured at 25 ° C. for 4 days.
3. 3. Above 2. 9 mL of physiological saline and 1 mL of PDB (potato dextrose medium) were added to the slope medium of black spores prepared in 1.
4. Above 3. Filter the spore solution of the above, and add 100 μL of the filtrate to two test plates (FRP, 5 cm × 5).
4 μL per 1 cm ² of the surface of cm) was evenly divided into 25 places, and dried and fixed at room temperature for 30 minutes.

[Test method]
The two test plates prepared above were placed in a 1.2 L tedler bag, and suspended matter of a decomposition product of azodicarbonamide collected at regular intervals was injected into each.
2. 2. 90 minutes after injecting the gas component of the decomposition product of azodicarbonamide, two test plates were collected from the Tedlar bag, and each test plate was washed out with 10 mL of GPLP medium.
3. 3. 100 μL of the GPLP medium was seeded on the PDA medium and stored at 25 ° C. for 5 days.
4. Further, 100 μL of the GPLP medium was diluted with 900 μL of GPLP medium, 100 μL of the diluted medium was seeded on the PDA medium, and the mixture was stored at 25 ° C. for 5 days.
From the media of 5.3 and 4, select a medium that can count the number of bacteria (colony number) in which growth was observed, count the number of bacteria, and count the number of bacteria 100 times in the case of 3 medium and in the case of 4 medium. The number of bacteria per test plate was calculated by multiplying by 1000.
[evaluation]
The number of bacteria on the test plate before injecting the suspended matter of the azodicarbonamide decomposition product (the number of untreated specimens) and the test plate stored after injecting the suspended matter of the azodicarbonamide decomposition product (after the sample treatment). The average value of the number of bacteria) was calculated, and the sterilization rate represented by the following formula was calculated.
Sterilization rate (%) = {1-Number of bacteria after sample processing / Number of bacteria without sample processing} x 100
Based on the above-calculated sterilization rate, the sterilization effect was evaluated according to the following evaluation criteria. The results are shown in Table 7.
Shown in.
(Evaluation criteria)
⊚: Sterilization rate 99% or more ○: Sterilization rate 90% or more and less than 99% △: Sterilization rate 80% or more and less than 90% ×: Sterilization rate less than 80%

As shown in Table 7, the suspended matter of the decomposition product of azodicarbonamide collected up to 30 minutes after the start of heating had a high sterilizing effect, but the decomposition product of azodicarbonamide collected after 60 minutes. The sterilizing effect of the suspended matter was low. From the above results, at least immediately after the start of heating 3
It was suggested that the suspended matter of the decomposition product of azodicarbonamide collected in 0 minutes contained a component having sterilizing activity.

(Test Example 4-2)
In this test, among the decomposition products of azodicarbonamide, which is the active ingredient, the sterilizing effect of falling substances was evaluated.
[Test method]
4.4 m ³ (1.6 m (vertical) x 1.25 m (horizontal) x 2. shown in FIG. 2 used in Test Example 2.
Three empty petri dishes with the lid open were installed on the floor surface 15 of the bathroom 11 in a closed space of 2 m (height) (points indicated by black circles (●) on the floor surface 15 in FIG. 2). Then, by immersing the self-heating device 1 of Example 2 in a container 9 containing 22 mL of water (hydraulic exothermic reaction liquid) W in the bathroom, the hydrothermal reaction is started, and the pharmaceutical product 7 is heated and smoked. rice field.
After the heating was started, the bathroom 11 was placed in a non-ventilated state and sealed for 90 minutes. After that, when the installed petri dish was recovered, it was confirmed that the fallen substance of the decomposition product of azodicarbonamide was present on all the petri dishes. A PDA medium and a spore solution of black spore were injected into a petri dish in which the fallen substance was present, and the mixture was mixed and allowed to stand at 25 ° C. for 4 days to incubate the black spore. Hereinafter, it is referred to as a medium after sample processing.
In addition, as a control, PDA medium and spore solution of black spores were injected into three empty petri dishes, and the spores were mixed and allowed to stand at 25 ° C. for 4 days to incubate the black spores. Hereinafter, it is referred to as a sample untreated medium.
[evaluation]
The number of bacteria (the number of colonies) of Kurokawa mold in the medium after the sample treatment and the medium in which the sample was not treated were counted, the average value was calculated, and the sterilization rate represented by the following formula was calculated.
Sterilization rate (%) = {1-Number of bacteria in the medium after sample treatment (number of colonies) / Number of bacteria in the medium without sample treatment (number of colonies)} x 100
Based on the calculated sterilization rate, the sterilization effect was evaluated using the same evaluation criteria as in Test Example 4-1. The results are shown in Table 8.

As shown in Table 8, it was found that among the decomposition products of azodicarbonamide, the falling products also had a certain sterilizing effect. On the other hand, the falling material of the decomposition product of azodicarbonamide is Test Example 4-
Compared with the suspended matter of the decomposition product of azodicarbonamide in No. 1, the sterilization effect was inferior.

1 Self-heating device 2 Outer container 3 Non-woven fabric sheet 4 Partition member 5 Lid member 6 Heat-melted resin film 7 Formulation 8 Hydrothermal substance 9 Container W water

Claims (2)

A sterilization method comprising heating an azodicarbonamide to generate a decomposition product of azodicarbonamide that is solid and falls due to its own weight, and applying the decomposition product to a sterilization target. A sterilizing agent containing a decomposition product of azodicarbonamide, which is solid and drops due to its own weight, produced by the sterilizing method according to claim 1 as an active ingredient.

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