JP2017061571A - Bactericidal agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new bactericidal agent.SOLUTION: The present invention provides a bactericidal agent comprising a decomposition product of azodicarbonamide as an active ingredient.SELECTED DRAWING: None

Description

  The present invention relates to a disinfectant.

Conventionally, various medicines are known as disinfectants, and their use modes are also various.
For example, Patent Document 1 discloses a composition for sterilizing air containing glycol ether as a sterilizing agent for microorganisms such as mold, yeast, virus, and bacteria present in air in a closed space such as a room. In addition, it is described that the microorganisms and the like are sterilized by volatilizing the composition into the space.
Patent Document 2 discloses a disinfectant such as benzalkonium chloride as a disinfectant for microorganisms such as mold that floats in the air or adheres to furniture or the like and propagates. A method of storing the agent in a pressure-accumulating spray container and spraying is described.
Moreover, patent document 3 is disclosing the space disinfection tool which disinfects the bacteria and virus which exist in space by releasing chlorine dioxide in space.

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

JP 2007-09738 A JP 2010-083806 A Japanese Patent Laying-Open No. 2015-093911 Japanese Patent Laid-Open No. 7-305050

  As described in Patent Documents 1 to 3, various drugs have been known as disinfectants so far. Then, this invention aims at providing the new disinfectant different from the said disinfectant.

  The present inventors have found that the degradation product of azodicarbonamide acts effectively as a disinfectant. Conventionally, azodicarbonamide has been known as one of organic foaming agents used in the rubber and plastics industry because a foaming action occurs when it is thermally decomposed by heating. Also in the foaming agent composition described in Patent Document 4, azodicarbonamide is used as an organic foaming agent.

  Thus, it has been well known that azodicarbonamide can be used as an organic foaming agent. However, as a result of intensive research on azodicarbonamide, the present inventors have surprisingly found that the degradation product of azodicarbonamide is effective as a disinfectant having a good disinfecting effect against molds and bacteria. As a result, the present invention has been completed.

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

  According to the present invention, the degradation product of azodicarbonamide can exhibit a good sterilizing effect against mold, germs and the like.

It is sectional drawing of the self-heating apparatus 1 for demonstrating the hydrolysis heat | fever system which is one heating means for generating the decomposition product of the azodicarbonamide which is an active ingredient of the disinfection agent of this invention. It is a schematic diagram of the bathroom which volatilized the bactericidal agent of this invention in Test Example 2 and Test Example 4-2.

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

The degradation product of azodicarbonamide, which is an active ingredient of the disinfectant of the present invention, can be obtained, for example, by heating azodicarbonamide. As described above, azodicarbonamide is one of organic foaming agents used in the rubber and plastics industries, and commercially available products or those synthesized by known methods 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.
Azodicarbonamide has a decomposition initiation temperature of about 200 ° C., generates a large amount of gas during decomposition, and is excellent in diffusibility. When azodicarbonamide is thermally decomposed by heating, a foaming action is generated, and a decomposition product of azodicarbonamide is generated. This decomposition product of azodicarbonamide is composed of three components: gaseous, liquid (including mist), and solid. It is produced as a decomposition product of the state. Among them, azodicarbonamide decomposition products are decomposition products floating in air (hereinafter referred to as floating materials) mainly composed of gaseous and mist decomposition products, and self-weights composed mainly of solid decomposition products. Are separated into falling products (hereinafter referred to as falling objects).

As described above, the degradation product of azodicarbonamide having an effective sterilizing effect of the present invention is generated from the degradation of azodicarbonamide, which is suspended from the suspended matter floating in the air and the falling matter falling by its own weight. As shown in the following examples (Test Examples 4-1 and 4-2), as a result of various tests, the degradation products of these azodicarbonamides are particularly good against molds and bacteria. It is presumed that it is a floating substance that has a good sterilizing effect.
Moreover, it is preferable that the said suspended | floating matter generate | occur | produces within 30 minutes immediately after the heating start of azodicarbonamide from a viewpoint of a microbe elimination effect. More preferably, it is a floating substance generated within 30 minutes immediately after the start of heating of azodicarbonamide, and a floating substance remaining within 15 minutes to 30 minutes after the start of heating. Here, the “floating matter remaining within 15 to 30 minutes after the start of heating” specifically refers to, for example, after starting heating of azodicarbonamide in a Tedlar bag as shown in the following test example. It refers to the floating material that exists in the Tedlar bag between 15 and 30 minutes, and even if it is generated within 15 minutes after the start of heating, it remains within 15 to 30 minutes after the start of heating. It means to include the suspended matter.

  In the present invention, the mechanism by which the degradation product of azodicarbonamide exerts a good sterilization effect against mold, germs, etc. is not clear, but the degradation product of azodicarbonamide is a fungus such as mold or bacteria. It is presumed to act on the cell wall and kill the cells.

  The heating temperature for decomposing 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 sterilization effect. More preferably.

  The heating means for decomposing azodicarbonamide is not particularly limited as long as a decomposition product of azodicarbonamide as an active ingredient can be obtained. For example, means such as a method of directly igniting and heating, a method of heating in contact 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. In particular, from the viewpoint of ease of handling and efficient volatilization of the decomposition product of azodicarbonamide, heating is performed using a hydrothermal system that generates heat using a hydrothermal exothermic substance and a hydrothermal reaction liquid as a heating agent. It is preferable to do. When the hydrothermal exothermic system is used, a decomposition product of azodicarbonamide (an effective component of the disinfectant of the present invention) can be efficiently generated and volatilized, and a large amount of decomposition products of azodicarbonamide can be applied to the place where For example, it can be diffused indoors.

As heating conditions for satisfactorily exhibiting this effect, it is preferable to heat azodicarbonamide so that the time at which the temperature is 100 ° C. or higher is 700 seconds or longer, and is heated to be 800 seconds or longer. More preferably, it is more preferable to heat so that it may become 900 second or more.
Further, the time at which the temperature is 200 ° C. or higher is preferably 250 seconds or longer, more preferably 300 seconds or longer, and further preferably 350 seconds or longer.
Moreover, it is preferable that time for temperature to become 300 degreeC or more is 150 seconds or more, and it is more preferable that it is 200 seconds or more.
Further, the time when the temperature is 350 ° C. or higher is preferably 130 seconds or longer, and more preferably 150 seconds or longer.

As heating conditions for satisfactorily exhibiting this effect, the total temperature of 100 ° C. or higher when the heating temperature is measured at intervals of 1 second between the start of heating and the end of heating is 140,000. It is preferable that it will be at least ° C.s, more preferably at least 170,000 ° C.s, and even more preferably at least 200,000 ° C.s.
Moreover, it is preferable that the sum total of the temperature which becomes 200 degreeC or more becomes 70,000 degreeC * s or more, It is more preferable that it is 90,000 degreeC * s or more, It may become 120,000 degreeC * s or more. Further preferred.
Moreover, it is preferable that the sum total of the temperature which becomes 300 degreeC or more becomes 40,000 degreeC.s or more, It is more preferable that it is 60,000 degreeC.s or more, It is 80,000 degreeC.s or more. Further 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. Further preferred.

As an example of the means for heating azodicarbonamide, a means for heating azodicarbonamide using a hydrothermal system will be described below. The hydrothermal exothermic system is a system that causes hydrothermal exothermic substances and hydrothermal exothermic reaction liquid to undergo hydrothermal exothermic reaction. In this system, the heat source is the self-heating device 1 shown in FIG. The azodicarbonamide is heated using the reaction heat generated by the hydrothermal exothermic reaction, and a decomposition product of azodicarbonamide, which is an active ingredient of the disinfectant of the present invention, is generated and volatilized. The hydrothermal exothermic substance is a substance that self-heats by reaction with the hydrothermal exothermic reaction solution, and examples thereof include calcium oxide (quick lime), magnesium chloride, and aluminum chloride. Examples of the hydrothermal reaction liquid include water or a liquid obtained by adding various additives to water. Examples of such additives include those that do not hinder volatilization of the decomposition product of azodicarbonamide, and those that do not reduce the reactivity of water with respect to the exothermic substance, and specifically include organic solvents and liquid stabilizers. Can do.
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 a hydrothermal system, for example, an electric heating system using a heating wire such as a nichrome wire, a flat plate shape or a ring shape, and a heater using a semiconductor; an oxidizing agent such as iron powder and ammonium chlorate A mixture of a metal and a metal oxide or oxidizer having a lower ionization tendency than the metal, and a mixture of iron and potassium sulfate, iron sulfate, metal chloride, iron sulfide, etc. is brought into contact 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 metal and bisulfate is brought into contact with water, and a mixture of aluminum and an alkali metal nitrate. A system that generates heat due to an oxidation reaction such as the addition of water; an exothermic reaction that uses a metal sulfide oxidation reaction in which a mixture of sodium sulfate and iron carbide is in contact with oxygen Using the system and the like, it can also be heated.

  In addition to the degradation product of azodicarbonamide, the disinfectant of the present invention may contain any component as long as the effects of the present invention are exhibited. As optional components, for example, fragrances, solvents, deodorants, volatilization aids, stabilizers, insecticides, pest repellents and the like can be used.

Examples of the fragrances include natural fragrances extracted from various plants and animals, synthetic fragrances synthesized chemically, and blended fragrances made by mixing a large number of these fragrance components.
Fragrances can be found in various literatures, for example, “Perfume and Flavor Materials of Natural Origin”, Steffen Arctander, Allured Pub. Co. (1960), “Encyclopedia of Scents”, edited by Japan Fragrance Association, Asakura Shoten (1989), “Flowers oils and Floral Compounds In Perfumery”, Danute Pajaudis Anonis, Allred Pub. Co. (1993), “Perfume and Flavor Chemicals (aroma chemicals)”, Vols. I and II, Stephen Arctander, Allured Pub. Co. (1994), “Fundamentals of perfumes and fragrances”, edited by Motoki Nakajima, Sangyo Tosho (1995), “Synthetic perfumes Chemistry and product knowledge”, Motokazu Into, Kagaku Kogyo Nipposha (1996) The fragrances described in “Encyclopedia”, Mitsatsu Yatakai, Maruzen (2005) can be used. Each of which is incorporated herein by reference. Specific examples of the fragrance are specifically shown below, but are not limited thereto.

Examples of natural perfumes include natural essential oils such as orange oil, lemon oil, lavender oil, lavandin oil, bergamot oil, patchouli oil, cedarwood oil, peppermint oil, thyme oil, clove oil, cinnamon oil, eucalyptus oil, tea tree oil, etc. Is mentioned.
Examples of the synthetic fragrances include hydrocarbon terpenes such as α-pinene, β-pinene, limonene, p-cymene, terpinolene, α-terpinene, γ-terpinene, α-ferrandolene, camphene, etc .; heptanal, octanal, decanal, Aldehydes such as benzaldehyde, salicylic aldehyde, phenylacetaldehyde, citronellal, hydroxycitronellal, citral, α-hexylcinnamic aldehyde, lyial, cyclamenaldehyde, rilal, heliotropin, helional, vanillin, ethyl vanillin; Methyl acetate, methyl propionate, meethyl isobutyrate, propyl butyrate, isobutyl acetate, isobutyl butyrate, isobutyl isovarate, ethyl 2-methyl valerate, isoamyl acetate, amyl propionate, allyl hexanoate, ethyl acetoacetate, ethyl heptylate, methyl benzoate, ethyl benzoate, ethyl octylate, benzyl acetate, nonyl acetate, ortho-ter-butylcyclohexyl Acetate, linalyl benzoate, ethyl cinnamate, methyl salicylate, hexyl salicylate, hexyl butyrate, menthyl acetate, terpinyl acetate, phenylethyl isobutyrate, methyl jasmonate, methyl dihydrojasmonate, ethylene brushate, γ-un Esters and lactones such as decalactone, γ-nonyllactone, cyclopentadecanolide, coumarin; anisole, p-cresyl methyl ether, dimethyl Ethers such as hydrohydroquinone, methyl eugenol, β-naphthol methyl ether, β-naphthol ethyl ether, anethole, diphenyl oxide, rose oxide, galaxolide, ambrox; isopropyl alcohol, cis-3-hexenol, heptanol, 2-octanol, Dimetol, dihydromyrsenol, linalool, benzyl alcohol, citronellol, geraniol, nerol, terpineol, l-menthol, cedrol, thymol, anis alcohol, phenylethyl alcohol, hexanol, and other alcohols; diacetyl, menthone, isimenton, acetophenone, α -Or β-Damascon, α- or β-Damasenone, α-, β- or γ-ionone, α-, β- or γ-methylyonone, methyl -Β-naphthyl ketone, benzophenone, tentalome, acetyl cedrene, α- or β-isomethyl ionone, α-, β- or γ-iron, maltol, cis-jasmon, dihydrojasmon, l-carvone, dihydrocarvone, methyl amyl ketone And ketones such as camphor, 1,8-cineol, allyl amyl glycolate, isopulegol, ligustral, allyl caproate and the like. These fragrances can be used alone or in combination of two or more kinds as a blended fragrance. Furthermore, a fragrance | flavor can also be used as a mixture (fragrance | flavor composition) containing a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc.

  Examples of the solvent include water, ethanol, propanol, benzyl alcohol and other alcohols, ethylene glycol, diethylene glycol, dipropylene glycol, glycerin, 1,3-butanediol and other polyhydric alcohols, ethylene glycol monomethyl ether, 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 Dimethyl 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 mono Glycol ethers such as butyl ether, dipropylene glycol dimethyl ether, phenyl carbitol, phenyl cellosolve and benzyl carbitol, paraffins such as liquid paraffin and n-paraffin, esters such as diethyl phthalate, benzyl benzoate, triethyl citrate and isopropyl myristate , Other 3-methyl- - methoxybutanol, N- methylpyrrolidone, propylene carbonate, and the like. These solvents may be used alone or in any combination of two or more. Moreover, it can mix with the said fragrance | flavor component and can also be used as a fragrance | flavor composition.

A fragrance | flavor can be suitably contained in the disinfectant of this invention so that it may become a predetermined | prescribed 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 the fragrance is contained, if the content is less than 0.01% by mass, sufficient fragrance may not be obtained, and if it exceeds 20% by mass, the scent may be too strong.
Further, when the perfume 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 perfume is 1 to 300 mg / m ³ . It is more preferable to contain so that it may become 5-150 mg / m < ³ >. By setting it in the above range, the sterilization effect can be enhanced synergistically with the degradation product of azodicarbonamide. Moreover, the unpleasant odor which arises when volatilizing azodicarbonamide is suppressed, and use feeling can be improved more.

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

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

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

Examples of insecticides include natural pyrethrin, pyrethrin, allethrin, phthalthrin, resmethrin, framethrin, permethrin, phenothrin, ciphenothrin, praretrin, transfluthrin, methfluthrin, profluthrin, imiprothrin, empentrin, ethofenprox, and sylfluofen. Insecticides; Carbamate insecticides such as propoxur and carbaryl; Organophosphorus insecticides such as fenitrothion and DDVP; Oxadiazole insecticides such as methoxadiazone; Phenylpyrazole insecticides such as fipronil; Neonicochi such as imidacloprid and dinotefuran Noid insecticides; sulfonamide insecticides such as amidoflumet; pyrrole compounds such as chlorfenapyr; metoprene, hydroprene Insect juvenile hormone-like compounds; anti-juvenile hormone-like compounds such as plecosene; molting hormone-like compounds such as ecdysone; essential oils such as phytoncide, light-loading oil, orange oil, cinnamon oil, clove oil; IBTA, IBTE, quaternary 1 type (s) or 2 or more types, such as ammonium salt and a benzyl salicylate, are mentioned.
Of these, pyrethroid insecticides, carbamate insecticides, oxadiazole insecticides, and sulfonamide insecticides are preferable because of their improved volatility, and in particular, ciphenothrin, permethrin, methoxadiazone, propoxle, amidoflumet, etofenprox. Is preferred.

  As a pest repellent, 1 type (s) or 2 or more types, such as a diet, di-n-butyl succinate, hydroxyanisole, rotenone, ethyl-butylacetylamino propionate, are mentioned, for example.

In the present invention, “sterilization” refers to a decrease in the number of microorganisms such as molds and bacteria that can be grown from an object (for example, indoor ceiling or wall).
In the present invention, the bacteria to be sterilized include bacteria and fungi. Specific examples of the bacteria include bacteria belonging to the genus Pseudomonas such as Pseudomonas aeruginosa, Escherichia such as Escherichia coli, bacteria belonging to the genus Bacillus subtilis, Bacillus subtilis, and Bacillus subtilis. And gram-positive bacteria such as Staphylococcus genus such as Staphylococcus aureus, lactic acid bacteria, and the like. Specific examples of fungi include the genus Cladosporium (Cladosporum), such as Cladosporium cladosporioides, and the genus Penicillium (Acergillus sp.), Such as Penicillium citrus, etc. Rhodotorula (Rhodotorula, Rhodotorula, Rhodotorula, Rhodotorula, Rhodotorula, Auridium, Rhodotorula mucilaginosa, etc. Examples thereof include black yeasts such as genus reobasidum and genus Exophiala, genus Forma, genus Candida, genus Saccharomyces, and the like.

Examples of the dosage form of the disinfectant of the present invention include granules, powders, fine granules, and liquids.
Especially, it is preferable to set it as solid forms, such as a granule, a powder agent, and a fine granule.

  In order to granulate and dry the disinfectant of the present invention, the disinfectant of the present invention can 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, if it is a granule, the particle size should be about 1 to 5 mm.

Examples of binders used when granulating the disinfectant of the present invention include celluloses such as carboxymethylcellulose, hydroxymethylcellulose, and hydroxypropylmethylcellulose; starch-based starches such as starch and starch, and natural polymer compounds such as gum arabic. One type or two or more types of synthetic polymer compounds such as polyvinyl alcohol.
What is necessary is just to contain these binders so that it may become 0.5-5 mass% with respect to the disinfectant of this invention.

  Examples of the excipient include pearlite, talc, diatomaceous earth, bentonite, clay mineral and the like.

  When the dosage form of the disinfectant of the present invention is used as a liquid, it can be made into a liquid by, for example, dissolving the powder in a liquid carrier. Carriers used in preparing the liquid form 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, petroleum Examples thereof include aliphatic hydrocarbons such as benzine, aromatic hydrocarbons such as benzene and toluene, esters such as ethyl acetate, and halogenated hydrocarbons such as dichloroethane.

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

The disinfection effect of the disinfectant of the present invention can be evaluated by the disinfection rate. The sterilization rate is expressed by the following formula. Details are obtained by the method described in Examples described later.
Bacteria elimination rate (%) = {1−the number of bacteria after specimen treatment (number of colonies) / the number of bacteria untreated with specimen (number of colonies)} × 100
The sterilization rate is preferably 90% or more, and more preferably 99% or more.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not restrict | limited to the following example at all.

<Test Example 1>
The effectiveness of the azodicarbonamide degradation product as an active ingredient against fungi was evaluated.

[Preparation of PDA medium inoculated with fungi]
A PDA medium inoculated with black mold was prepared according to the following procedure.
1. Using 10 mL of PDA (potato dextrose agar), a PDA slant medium was prepared in a test tube.
2. Above 1. Inoculated with spores of Cladosporium cladosporoides on the PDA slant culture medium prepared in the above, and the black mold was cultured at 25 ° C. for 4 days.
3. 2. 9 mL of physiological saline and 1 mL of PDB (potato dextrose medium) were added to the slant culture medium of black mold prepared in step 1, and the black mold was scraped from the medium surface using a platinum loop to prepare a spore solution.
4). 3. above. The spore solution was filtered, and the filtrate was diluted 10,000 times with physiological saline.
5. 4. above. 100 μL of the solution prepared in the above is inoculated 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 manufactured by Actect Co., Ltd.), and “PDA medium inoculated with fungus” Was made.

[Sample processing]
In a container of 1.30 cm × 30 cm × 30 cm, a φ9 cm metal petri dish containing the PDA medium inoculated with the fungus and 5 g of powdered azodicarbonamide prepared above was placed.
2. A fire was brought close to the azodicarbonamide and ignited. After sufficient foaming and smoke generation were confirmed, the container was sealed for 90 minutes (hereinafter referred to as heat treatment (Example 1)).
3. Further, azodicarbonamide was dispersed in water so as to be 5 g / 900 cm ² and uniformly applied to the above-prepared medium (hereinafter, referred to as non-heat treatment (Comparative Example 1)).
4). Furthermore, the above-prepared medium without applying azodicarbonamide was prepared (hereinafter referred to as untreated (reference example)).
5. Black mold was cultured by leaving the three culture media of heat treatment (Example 1), non-heat treatment (Comparative Example 1), and untreated (Reference Example) at 25 ° C. for 4 days.

[Evaluation]
The sterilization effect was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
◎: No colony formation is observed ○: Colony formation is hardly seen △: Colony formation is seen in part ×: Colony formation is seen overall

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

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

[Example 2]
[Preparation of formulation]
In the formulation described in Table 2, each component was mixed, granulated, and dried to prepare a granular preparation 7. The particle diameter of one preparation 7 is about 3 mm and the length is about 5 mm.

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

[Production of self-heating device]
A self-heating device 1 as shown in FIG. 1 was prepared as follows in order to heat the preparation 7 with a hydrothermal exothermic system.
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, 65 g of hydrothermal exothermic substance 8 (calcium oxide) was accommodated. The outer container 2 has a plurality of water holes at the bottom, and the water holes were closed with a non-woven sheet 3 having water permeability. Further, the inside of the outer container 2 was partitioned into two spaces by the partition member 4. The partition member 4 has a cylindrical shape and the bottom portion has a substantially hollow hemispherical shape, and its side wall is arranged concentrically with the peripheral wall of the outer container 2. The hydrothermal exothermic substance 8 is filled in the space formed by the peripheral wall of the outer container 2, the partition member 4 and the nonwoven fabric sheet 3, and 5 g of the prepared preparation 7 (4.9 g of azodicarbonamide) is contained inside the partition member 4. ) Accommodated. Further, the upper open surface of the outer container 2 is covered with a lid member 5 in which seven openings of 0.8 cm ² are formed in a region corresponding to the upper open surface of the partition member 4, and the opening of the lid member 5 is The self-heating device 1 of Example 2 was produced by closing the film with a hot-melt resin film 6 having air holes.

[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 fungi]
A PDA medium inoculated with black mold was prepared according to the following procedure.
1. Using 10 mL of PDA (potato dextrose agar), a PDA slant medium was prepared in a test tube.
2. Above 1. Inoculated with spores of Cladosporium cladosporoides on the PDA slant culture medium prepared in the above, and the black mold was cultured at 25 ° C. for 4 days.
3. 2. 9 mL of physiological saline and 1 mL of PDB (potato dextrose medium) were added to the slant culture medium of black mold prepared in step 1, and the black mold was scraped from the medium surface using a platinum loop to prepare a spore solution.
4). 3. above. The spore solution was filtered, and the filtrate was diluted 10,000 times with physiological saline.
5. 4. above. 100 μL of the solution prepared in the above is inoculated 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 manufactured by Actect Co., Ltd.), and “PDA medium inoculated with fungus” Was made.

[Test method]
4.4m ³ (1.6m (vertical) × 1.25m (horizontal) × 2.2m (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 (location indicated by black circles (●) in FIG. 2). As a control (untreated), the medium was left outside the bathroom. The temperature and humidity of the bathroom 11 are as shown in Table 3.
The self-heating device 1 was installed at the center of the bathroom 11 and immersed in a container 9 containing 22 mL of water (hydrolysis exothermic reaction solution) W to start the hydrothermal reaction and heat the preparation 7.
After starting the heating, the bathroom 11 was brought into an unventilated state and sealed for 90 minutes. Thereafter, ventilation was performed for 30 minutes.
Thereafter, the medium was collected, and left to stand at 25 ° C. for 4 days to culture black mold.

[Evaluation]
The number of bacteria (colony number) of black mold on the PDA slant medium was counted, and the average value of the number of bacteria (colony number) for each ceiling, wall, and floor of the bathroom was calculated. Moreover, the sterilization rate represented by the following formula was calculated.
Bacteria elimination rate (%) = {1−the number of bacteria in the culture medium after treatment of the specimen (number of colonies) / the number of bacteria in the culture medium not subjected to the specimen (number of colonies)} × 100
The above test was performed twice in total, and the calculated number of bacteria (colony number) and the sterilization rate are shown in Table 3 (the number of bacteria and the sterilization rate in Table 3 are the values calculated in the test performed twice in total. Average value).

  As shown in Table 3, when the disinfectant of the present invention was volatilized by the hydrothermal system, a good disinfecting effect was observed in any of the ceiling 13, wall 14 and floor 15 of the bathroom 11. .

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

<Test Example 3>
In this test, the temperature of the azodicarbonamide was measured by measuring the temperature of the heat source (self-heating device 1) used in Example 2 in Test Example 2 every second, and the temperature was 100 ° C. or higher and 200 ° C. Above, the time which becomes 300 degreeC or more and 350 degreeC or more was measured, respectively. Moreover, the sum total of the temperature used as 100 degreeC or more, the sum total of the temperature used as 200 degreeC or more, the sum total of the temperature used as 300 degreeC or more, and the sum total of the temperature used as 350 degreeC or more were calculated | required, respectively.

First, heat generation was started for the self-heating device 1 (heat source) obtained by removing the preparation 7 from the self-heating device 1 of Example 2, and the transition of the heat generation temperature was measured for each. Specifically, after removing the preparation 7 in the self-heating device 1 of FIG. .3 mm (MAX 600 ° C.))). Since the temperature probe is linear, the temperature probe was passed through the glass tube, the tip was bent, and the probe was pressed down at the end of the glass tube, so that the temperature probe was closely attached and fixed to the can bottom. 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 three times in total (Samples 1 to 3).
Next, based on the obtained temperature data, the time during which the temperature was 100 ° C. or higher, 200 ° C. or higher, 300 ° C. or higher, and 350 ° C. or higher was measured. The results are shown in Table 5. Moreover, the sum total of the temperature used as 100 degreeC or more, the sum total of the temperature used as 200 degreeC or more, the sum total of the temperature used as 300 degreeC or more, and the sum total of the temperature used as 350 degreeC or more were calculated | required, respectively. 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. or higher. The average time was 200 seconds or more, and the average time for the temperature to be 350 ° C. or higher was 150 seconds or more.
Further, as can be seen from the results in Table 6, the sum total of the temperatures exceeding 100 ° C. averages 200,000 ° C. · s or more, and the sum total of temperatures exceeding 200 ° C. averages 120,000 ° C. · s. Thus, it was found that the sum of the temperatures at 300 ° C. or higher averaged 80,000 ° C. · s or more, and the sum of the temperatures at 350 ° C. or higher averaged 60,000 ° C. · s or more.

<Test Example 4>
In the degradation product of azodicarbonamide, which is an active ingredient, the sterilization effect of suspended matter and falling matter was evaluated.

(Test Example 4-1)
In this test, among the degradation products of azodicarbonamide, which is an active ingredient, the sterilization effect of floating substances was evaluated.
[Collecting gas components of decomposition products of azodicarbonamide]
The degradation product of azodicarbonamide was collected by the following procedure.
1. The self-heating device 1 of Example 2 prepared in Test Example 2 is installed in a 200 L Tedlar bag and immersed in a container 9 containing 22 mL of water (hydrolysis exothermic reaction solution) W, so that the hydrothermal reaction occurs in the Tedlar bag. The formulation 7 was heated and smoked.
2. A PTFE 0.22 μm filter (Millex-) was removed from the Tedlar bag at regular intervals (5 minutes, 15 minutes, 30 minutes, 60 minutes, 90 minutes) immediately after the start of heating. While removing solid components using FG (registered trademark), MILLIPORE), gas was extracted with a glass syringe, and the suspended matter of the decomposition product of azodicarbonamide was collected.

[Preparation of test plate inoculated with fungi]
A PDA medium inoculated with black mold was prepared according to the following procedure.
1. Using 10 mL of PDA (potato dextrose agar), a PDA slant medium was prepared in a test tube.
2. Above 1. Inoculated with spores of Cladosporium cladosporoides on the PDA slant culture medium prepared in the above, and the black mold was cultured at 25 ° C. for 4 days.
3. 2. 9 mL of physiological saline and 1 mL of PDB (potato dextrose medium) were added to the slant culture medium of black mold prepared in step 1, and the black mold was scraped from the medium surface using a platinum loop to prepare a spore solution.
4). 3. above. The spore solution was filtered, and 100 μL of the filtrate was added dropwise at 25 locations evenly at 4 μL per 1 cm ² of the surface of ^two test plates (FRP, 5 cm × 5 cm), and dried and fixed at room temperature for 30 minutes.

[Test method]
Two test plates prepared as described above were placed in a 1.2 L Tedlar bag, and suspended substances of azodicarbonamide degradation products collected at regular intervals were respectively injected.
2. Ninety minutes after injecting the gas component of the azodicarbonamide decomposition product, two test plates were collected from the Tedlar bag, and each test plate was washed out with 10 mL of GPLP medium.
3. 100 μL of the GPLP medium was seeded on 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 inoculated on PDA medium, and stored at 25 ° C. for 5 days.
Select a medium that can count the number of bacteria (colony number) in which growth was observed among the mediums of 5.3 and 4, and count the number of bacteria. 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 product of the degradation product of azodicarbonamide (the number of untreated samples) and the test plate that was stored after injecting the suspended product of the degradation product of azodicarbonamide (after sample treatment) The average value of the number of bacteria) was calculated, and the sterilization rate represented by the following formula was calculated.
Bacteria elimination rate (%) = {1−the number of bacteria after sample treatment / the number of untreated samples} × 100
Based on the calculated sterilization rate, the sterilization effect was evaluated according to the following evaluation criteria. The results are shown in Table 7.
(Evaluation criteria)
◎: Bactericidal rate 99% or more ○: Bactericidal rate 90% or more and less than 99% △: Bactericidal rate 80% or more and less than 90% ×: Bactericidal rate less than 80%

  As shown in Table 7, the azodicarbonamide degradation products collected up to 30 minutes after the start of heating had a high sterilization effect, but the azodicarbonamide degradation products collected after 60 minutes. The sterilization effect of the floating substance was low. From the above results, it was suggested that the suspended matter of the degradation product of azodicarbonamide collected at least 30 minutes immediately after the start of heating contains a component having sterilizing activity.

(Test Example 4-2)
In this test, the sterilization effect of falling objects was evaluated among the degradation products of azodicarbonamide, which is an active ingredient.
[Test method]
A lid is applied to the floor 15 of the bathroom 11 in the enclosed space of 4.4 m ³ (1.6 m (vertical) × 1.25 m (horizontal) × 2.2 m (height)) shown in FIG. Three empty petri dishes in the open state were installed (locations indicated by black circles (●) in the floor portion 15 in FIG. 2). Thereafter, the self-heating device 1 of Example 2 was immersed in a container 9 containing 22 mL of water (hydrolysis exothermic reaction solution) W in the bathroom to start a hydrothermal exothermic reaction, and the formulation 7 was heated and smoked. It was.
After starting the heating, the bathroom 11 was brought into an unventilated state and sealed for 90 minutes. Thereafter, the installed petri dishes were collected. As a result, the presence of falling azodicarbonamide degradation products was confirmed on all the petri dishes. PDA medium and spore solution of black mold were poured into the petri dish where the fallen objects were present, and the mixture was allowed to stand at 25 ° C. for 4 days to culture black mold. Hereinafter, it is referred to as a culture medium after sample treatment.
As a control, PDA medium and spore solution of black mold were poured into three empty petri dishes, mixed, and allowed to stand at 25 ° C. for 4 days to culture black mold. Hereinafter, the specimen-untreated medium is referred to.
[Evaluation]
The number of black mold (colony number) in the medium after the sample treatment and the medium not subjected to the sample were counted, the average value was obtained, and the sterilization rate represented by the following formula was calculated.
Bacteria elimination rate (%) = {1−the number of bacteria in the culture medium after treatment of the specimen (number of colonies) / the number of bacteria in the culture medium not subjected to the specimen (number of colonies)} × 100
Based on the calculated sterilization rate, the sterilization effect was evaluated by 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 the fallen product among the decomposed products of azodicarbonamide also has a certain degree of sterilization effect. On the other hand, the fall product of the degradation product of azodicarbonamide resulted in inferior sterilization effect compared with the suspended matter of the degradation product of azodicarbonamide in Test Example 4-1.

DESCRIPTION OF SYMBOLS 1 Self-heating device 2 Outer container 3 Nonwoven fabric sheet 4 Partition member 5 Lid member 6 Hot melt resin film 7 Formulation 8 Hydrolysis heat substance 9 Container W Water

Claims (2)

  A disinfectant containing a decomposition product of azodicarbonamide as an active ingredient.   The disinfectant according to claim 1, further comprising a fragrance.

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