JP6945337B2 - Heated fumigant composition - Google Patents

Description

The present invention relates to a heated fumigant composition.

The heated fumigant composition is also called a fumigant or a fumigant (hereinafter, also simply referred to as a fumigant composition), and by volatilizing the chemical with heat, it treats articles and spaces in the house, vehicle, etc. It is for killing, eradicating, and antibacterial harmful organisms and microorganisms.

By the way, examples of places where microorganisms can easily propagate include places with high humidity such as bathrooms and closets. Conventionally, smoke-type fungicides have been proposed for places where such microorganisms are likely to grow.
Patent Document 1 proposes a smoke agent composition containing an active ingredient and an organic foaming agent.

Japanese Unexamined Patent Publication No. 2016-113369

However, although the smoke agent composition of Patent Document 1 can kill microorganisms, there is a problem that microbial stains (colored stains caused by propagated microorganisms) remain. Since microbial stains can be visually recognized even after the microorganisms have died, it is difficult to visually determine whether or not the microorganisms have died, which causes repeated sterilization treatments. In addition, if there is microbial stains in the bathroom or closet, it causes discomfort to the user even after the sterilization treatment.
The present invention has been made in view of the above circumstances, and an object of the present invention is a heated fumigant composition capable of decolorizing microbial stains.

As a result of diligent studies, the present inventors have found that the following fumigant composition can solve the above-mentioned problems.
That is, the present invention has the following aspects.
[1] Ingredient (A): Volatilizer and
(B) Component: A heated fumigant composition containing an aldehyde compound.
The content of the component (B) is 0.05% by mass or more with respect to the total mass of the heated fumigation composition.
The component (B) contains an acyclic aldehyde compound (B1).
A heated fumigant composition in which the content of the component (B1) is 20% by mass or more with respect to the total mass of the component (B).
[2] The component (A) is at least one selected from the group consisting of azodicarbonamide, propylene glycol, ethylene glycol, dipropylene glycol, tripropylene glycol, and 1,3-butylene glycol [1]. The heated fumigant composition according to.
[3] The heated fumigation composition according to [1] or [2], wherein the component (B1) is an acyclic aldehyde compound having a linear or branched hydrocarbon group having 6 to 16 carbon atoms. ..
[4] The heated fumigation composition according to any one of [1] to [3], further comprising a component (C): a drug.
[5] Microbial stains, which are characterized in that the heated fumigant composition according to any one of [1] to [4] is heated ^{and volatilized so as to be 0.1 to 30 g / m 3.} Decolorization method.
[6] A method for decolorizing microbial stains, which comprises heating the heated fumigation composition according to any one of [1] to [4] at 200 ° C. or higher for 60 seconds or longer to volatilize it.
[7] A housing having a cylindrical main body, a bottom portion, and a lid portion,
A heating unit in which the exothermic agent is housed in the housing,
A metal smoke agent container provided in the housing and located above the heating unit is provided.
An indirect heating type fumigation device, wherein the smoke agent container is filled with the heating type fumigant composition according to any one of [1] to [4].

According to the present invention, it is possible to provide a heated fumigant composition capable of decolorizing microbial stains.

It is sectional drawing which shows an example of the indirect heating type smoking apparatus. It is a perspective view of the evaluation box used in an Example.

The heated fumigant composition of the present invention contains the following components (A) to (B). As used herein, the term "heated fumigant composition" means a composition that volatilizes by heat. Here, "volatilization" means that the fumigant composition is made into fine particles and dispersed in the air. The average particle size of the fumigant composition when volatilized is preferably 10 μm or less. The average particle size can be measured with a laser diffraction type particle size distribution measuring device.

<Component (A): Volatilizer>
The component (A) is a volatilizer. By blending the component (A), the component (B) is easily volatilized.
Examples of the component (A) include an organic foaming agent (hereinafter, also referred to as (A1) component) and a polyol (hereinafter, also referred to as (A2) component).

As the component (A1), a component that is thermally decomposed by heating to generate a large amount of heat and also generates carbon dioxide gas, nitrogen gas, etc. (hereinafter, generally referred to as foaming gas) is used. For example, azodicarbonamide, p. , P'-oxybis (benzenesulfonylhydrazide), N, N'-dinitrosopentamethylenetetramine, azobisisobutyronitrile and the like. Of these, azodicarbonamide is preferable from the viewpoint of decomposition temperature, amount of foaming gas generated, and the like. These (A1) components may be used alone or in combination of two or more.

When the fumigant composition of the present invention contains the component (A1), the content of the component (A1) is preferably 40 to 90% by mass, preferably 50 to 85% by mass, based on the total mass of the fumigation composition. More preferably, 60 to 75% by mass is further preferable.
When the content of the component (A1) is not more than the above upper limit value, contamination by decomposition products can be reduced.
When the content of the component (A1) is at least the above lower limit value, the component (B) is easily volatilized.

The "polyol" of the component (A2) is a compound having two or more hydroxyl groups in the molecule, a compound having two hydroxyl groups is called a dihydric alcohol (glycol), and a compound having three hydroxyl groups is called a trihydric alcohol. Those having more than one are also collectively referred to as polyhydric alcohols. The polyol has a characteristic that when heated at 150 to 450 ° C., a white smoke-like substance is generated like the current smoke agent, and is used as a smoke base in the present invention. The component (A2) is not particularly limited, and among those used in pharmaceuticals, quasi-drugs, cosmetics, miscellaneous goods, industrial products, etc., the component (B) is volatile, soluble / dispersible, and at the time of use. It is appropriately selected in consideration of the heating temperature and the like. The boiling point of the component (A2) is preferably 150 to 300 ° C., more preferably 170 to 300 ° C. from the viewpoint of volatilization of the component (A2). Examples of the component (A2) include divalent alcohols (glycols), trihydric or higher polyhydric alcohols, sugars, sugar alcohols and the like.

The most suitable glycol is one for every two carbon atoms of an aliphatic hydrocarbon having two or more carbon atoms and having an ether oxygen atom (-O-) inserted between the carbon atoms. Examples thereof include compounds having a structure in which hydroxyl groups are bonded to each other.

The most suitable glycol is one for every two carbon atoms of an aliphatic hydrocarbon having two or more carbon atoms and having an ether oxygen atom (-O-) inserted between the carbon atoms. Examples thereof include compounds having a structure in which hydroxyl groups are bonded to each other.
In the compound, the aliphatic hydrocarbon may be saturated or unsaturated. Further, the aliphatic hydrocarbon may be chain-like, cyclic, or a combination thereof, and is preferably chain-like. When it is in the form of a chain, the aliphatic hydrocarbon may be in the form of a linear chain or a branched chain. When cyclic, the aliphatic hydrocarbon may be monocyclic or polycyclic. More specific examples of such a compound include a compound represented by the following general formula (A2-1) or (A2-2).
HO-R ^1- OH ... (A2-1)
HO- (R ² O) _n- H ... (A2-2)
[In the formula, R ¹ and R ² are independently divalent aliphatic hydrocarbon groups having 2 to 18 carbon atoms, and n is an integer of 2 to 14. ]

Wherein (A2-1), the number of carbon atoms of the divalent aliphatic hydrocarbon group for ^{R 1} is preferably 2 to 18 is more preferable 2 to 4, more preferably 3 or 4. As R ¹ is a propylene group is particularly preferred.
The compound represented by the formula (A2-2) is a so-called polyether.
In the formula (A2-2), ^{examples of R 2} are the ^{same as those of R 1,} and an ethylene group or a propylene group is preferable, and an ethylene group is particularly preferable.
n is preferably an integer of 2 to 14, more preferably an integer of 2 to 4.

Examples of the compound represented by the above general formula (A2-1) are ethylene glycol, propylene glycol, 1,3-butylene glycol, trans-2-butene-1,4-diol, 2-butin-1,4-. Glycol, 2,5-hexanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2,4-heptandiol , 2,2-Diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-butyl-1,3-propanediol, isoprene glycol, trimethylene glycol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11- Undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecandiol, 1,17-heptadecanediol, 1,18 -Octadecanediol, 1,19-nonadecandiol, 1,20-icosandiol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1, Examples thereof include 2-hexadecanediol and 1,2-octadecanediol. Of these, propylene glycol is preferable.
Examples of the compound represented by the general formula (A2-2) include diethylene glycol, triethylene glycol, polyethylene glycol having an average molecular weight of 200 to 20000, dipropylene glycol, tripropylene glycol, polypropylene glycol having an average molecular weight of 300 to 2000, and the like. Can be mentioned. Of these, dipropylene glycol is preferable. Polyethylene glycol having an average molecular weight of 200 to 20000 is also called macrogol, and is polyethylene glycol 200 (average molecular weight 190 to 210), polyethylene glycol 300 (average molecular weight 280 to 320), polyethylene glycol 400 (average molecular weight 380 to 420), polyethylene. Glycol 600 (average molecular weight 570-630), polyethylene glycol 1000 (average molecular weight 950-1050), polyethylene glycol 1500 (equal mixture of polyethylene glycol 300 and polyethylene glycol 1540), polyethylene glycol 1540 (average molecular weight 1290 to 1650), polyethylene Glycol 2000 (average molecular weight 1850-2150), polyethylene glycol 4000 (average molecular weight 2600-3800), polyethylene glycol 6000 (average molecular weight 7300-9300), polyethylene glycol 10000 (average molecular weight 9300-12500), polyethylene glycol 20000 (average molecular weight 15500) ~ 20000) and the like. Of these, polyethylene glycol having a molecular weight of 200 to 600 is preferable.
As these polyethylene glycols, commercially available products available from Sanyo Chemical Industries, Ltd. and NOF Corporation can be used, for example. Commercially available products of polyethylene glycol are usually given an average molecular weight as a numerical value, and depending on the product, # may be added between the polyethylene glycol and the numerical value, for example, polyethylene glycol # 1000.
The average molecular weight of the above polyethylene glycol indicates the average molecular weight described in the quasi-drug raw material standard 2006, and is a value according to the measurement method described in the quasi-drug raw material standard 2006.
Examples of polypropylene glycols having an average molecular weight of 300 to 2000 have a degree of polymerization of 4 to 34, and such polypropylene glycols include Nieuport PP-400, PP-1000, and PP-2000 (Sanyo Chemical Industries, Ltd.). A commercially available product such as (manufactured) can be used.
The average molecular weight of polypropylene glycol is a number average molecular weight, which is a value obtained from the hydroxyl value.

Among the sugars, suitable ones include monosaccharides such as glucose and fructose; disaccharides such as sucrose, lactose, maltose and trehalose; and polysaccharides having trisaccharide or more.
Suitable sugar alcohols include glycerin, diglycerin, polyglycerin, erythritol, xylitol, D-sorbitol, mannitol, maltitol and the like. As the glycerin, diglycerin, and polyglycerin, commercially available products such as Sakamoto Yakuhin Kogyo Co., Ltd. can be used.

These (A2) components may be used alone or in combination of two or more. Depending on the type of the (A2) component or the combined use of different (A2) components, the color depth of the smoke-like substance, the amount of the smoke-like substance generated, and the time during which the smoke-like substance continues to be generated (smoke duration) Further, the amount of the component (B) volatilized into the space can also be controlled.

When the fumigant composition of the present invention contains the component (A2), the content of the component (A2) is preferably 30% by mass or more, preferably 50 to 99.9% by mass, based on the total mass of the fumigation composition. Is more preferable.
When the content of the component (A2) is within the above range, the component (B) is easily volatilized.

<Component (B): Aldehyde compound>
The component (B) is an aldehyde compound. By containing the component (B), microbial stains can be decolorized. As used herein, the term "aldehyde compound" means a compound having an aldehyde group in the molecule.
The component (B) includes an acyclic aldehyde compound (B1) (hereinafter, also referred to as a component (B1)). As used herein, the term "acyclic aldehyde compound" means a compound having no ring structure in the molecule and having an aldehyde group.
Examples of the ring structure include alicyclic hydrocarbons (cycloalkane, cycloalkene, etc.), aromatic hydrocarbons (benzene, naphthalene, etc.), heterocycles (pyridine, etc.), and major ring compounds (porphyrin, etc.).
The component (B1) is preferably an aldehyde compound having a linear or branched hydrocarbon group having 6 to 16 carbon atoms. Examples of the hydrocarbon group include an alkyl group and an alkenyl group.
The components (B1) include citral, citronellal, hydroxycitronellal, octylaldehyde, nonylaldehyde, decylaldehyde, undecylaldehyde, trimethylhexylaldehyde, trans-2-hexanal, 2,6-nonadienal, and cis-4-decanal. And so on.
Examples of the aldehyde compound other than the component (B1) include benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, synamic aldehyde, hydratropic aldehyde, anisaldehyde, p-methylphenylacetaldehyde, cuminaldehyde, cyclamen aldehyde, ligstral and lylar.
These components (B) may be used alone or in combination of two or more.

The content of the component (B1) is 20% by mass or more, preferably 40% by mass or more, and more preferably 60% by mass with respect to the total mass of the component (B). The content of the component (B1) may be 100% by mass with respect to the total mass of the component (B).
When the content of the component (B1) is at least the above lower limit value, the microbial stains are easily decolorized.

The content of the component (B) is 0.05% by mass or more, preferably 0.08 to 5% by mass, and more preferably 0.1 to 2% by mass, based on the total mass of the fumigant composition.
When the content of the component (B1) is not more than the above upper limit value, the decrease in the volatilization rate can be suppressed.
When the content of the component (B1) is at least the above lower limit value, the microbial stains are easily decolorized.

The mass ratio represented by the component (A) / component (B) (hereinafter, also referred to as A / B ratio) is preferably 25 to 1000, more preferably 60 to 600.
When the A / B ratio is not more than the above upper limit value, the diffusibility of the component (B) is likely to be improved.
When the A / B ratio is equal to or higher than the above lower limit value, the component (B) tends to show a medicinal effect.

<Arbitrary ingredient>
Further, the fumigant composition of the present invention may contain any component other than the components (A) to (B) in addition to the components (A) to (B).
Examples of the optional component include a drug, a binder, a surfactant, an excipient, a heat-generating aid, a stabilizer, an efficacy enhancer, an antioxidant, a fragrance, water and the like.
The optional component may be used alone or in combination of two or more.

By using a drug (hereinafter, also referred to as the component (C)), it is possible to exert a microbial suppression effect such as sterilization, antibacterial, antifungal and antifungal, a deodorant effect, an insecticidal effect and the like. Further, by using the component (C) in combination, it becomes easier to decolorize microbial stains.

The component (C) is appropriately selected according to the purpose. Examples of the component (C) include those that act as microbial control agents such as bactericides, antibacterial agents, antifungal agents, and antifungal agents, deodorants, and insecticides, and among them, bactericides and antibacterial agents. , Antifungal agents, antifungal agents, and other microbial control agents and deodorants can be preferably used. Here, the microbial control agent is a general term for agents that suppress the action of microorganisms by preventing the growth of microorganisms, preventing the adhesion of microorganisms, sterilizing, and the like. As these components (C), microorganism control agents such as insecticides, organic agents, and inorganic agents, which have been conventionally used for smoke agents, can be used.

Examples of the insecticide include methoxadiazone as an oxadiazole-based compound. Examples of the carbamate compound include propoxul, carbyl and the like.
The pyrethroid compound may be any of pyrethrin, which is a natural insecticidal component contained in pyrethrum, pyrethrin extract obtained by extracting dried flowers of pyrethrum with a solvent, or synthesized pyrethrin-like compound (synthetic pyrethroid), and the pyrethroid moiety. As long as it is an ester compound composed of a pyrethrin and an alcohol portion, it is not particularly limited whether it is a natural product or a synthetic product. Specifically, Jochugiku extract, Piretrin (for example, product name: Piretrin manufactured by Sumitomo Chemical Co., Ltd.), Aresulin (for example, product name: Pinamine manufactured by Sumitomo Chemical Co., Ltd.), dl, d-T80-Aresulin (for example, Sumitomo Chemical Co., Ltd.) Product name made by Chemical Co., Ltd .: Pinamine Forte), Phthalthrin (for example, product name made by Sumitomo Chemical Co., Ltd .: Neopinamine), d-T80-phthalthrin (Product name made by Sumitomo Chemical Co., Ltd .: Neopinamine) Forte), Resmetrin (for example, product name: Chrislon manufactured by Sumitomo Chemical Co., Ltd.), d-T80-Resmetrin (for example, product name: Chrislon Forte manufactured by Sumitomo Chemical Co., Ltd.), d-T80-Flametrin (for example, Sumitomo Chemical Co., Ltd.) Product name made by Sumitomo Chemical Co., Ltd .: Pinamine-D Forte), Phenotrin (for example, product name made by Sumitomo Chemical Co., Ltd .: Smithlin), Permethrin (for example, product name made by Sumitomo Chemical Co., Ltd .: Exmin), d-T80- Ciphenotrin (for example, trade name: Gokirato manufactured by Sumitomo Chemical Co., Ltd.), d, d-T-cyphenotrin (for example, trade name: Gokirato S manufactured by Sumitomo Chemical Co., Ltd.), d, d-T80-Plaretrin (for example, Sumitomo Chemical Co., Ltd. product name: Etoc), EZ-Empentrin (for example, Sumitomo Chemical Co., Ltd. product name: Vaporthrin), Imiprothrin (for example, Sumitomo Chemical Co., Ltd. product name: Pral), Transflu Examples thereof include trin (for example, trade name: Biothrin manufactured by Sumitomo Chemical Co., Ltd.) and metoflutrin (for example, trade name: Eminence manufactured by Sumitomo Chemical Co., Ltd.). By containing these insecticides, it is possible to control harmful organisms at the same time as decolorizing molds.
Examples of the organic agent for the microbial control agent include 3-methyl-4-isopropylphenol (IPMP), 3-iodo-2-propynylbutylcarbamate (IPBC), o-phenylphenol (OPP), methoxadiazone and the like. , IPMP and IPBC are preferable.
Examples of inorganic agents for microbial control include silver alone having antibacterial, bactericidal, antifungal, antifungal, and deodorant effects as an active ingredient; silver oxide; silver chloride, silver nitrate, silver sulfate, silver carbonate, and sulfonic acid. Inorganic silver salts such as silver salts; those containing silver compounds such as organic silver salts such as silver nitrate and silver acetate can be mentioned.

Further, as the inorganic drug, silver alone or the silver compound is supported on a substance such as zeolite, silica gel, low molecular weight glass, calcium phosphate, silicate, titanium oxide (hereinafter, may be referred to as a carrier) (hereinafter, may be referred to as a carrier). Hereinafter, it may be referred to as a carrier). Examples of the carrier include a zeolite-based antibacterial agent, a silica gel-based antibacterial agent, a titanium oxide-based antibacterial agent, and a silicate supporting a simple substance of silver, silver oxide, or a silver compound (for example, inorganic silver salt, organic silver salt, etc.). Examples include system antibacterial agents.
Among them, as the component (C), an inorganic silver salt such as silver simple substance, silver oxide or silver nitrate, or a silver-containing inorganic drug in which these are supported on a carrier is preferable from the viewpoint of further reducing the odor derived from the component (C). In particular, a zeolite-based antibacterial agent carrying a silver compound is preferable. By using an inorganic chemical, the odor derived from the component (C) during the smoke treatment and after the smoke treatment can be further reduced.
These (C) components may be used alone or in combination of two or more.

The form of the component (C) is not particularly limited, but can be determined in consideration of the size of the target space and the like. When a silver compound is used as the component (C), the finer the particles, the easier it is to smoke, the effect of the component (C) can be fully exerted, and the particles are diffused over a wide area. On the other hand, if the particles of the component (C) are too small, they are difficult to fall after being diffused, and it takes time for the effect of the component (C) to appear in the lower part of the target space.
The volume average particle size refers to a value obtained by a laser diffraction / scattering type particle size distribution measuring device (LA910, manufactured by HORIBA, Ltd.), and can be measured as follows. The component (A) is dispersed in distilled water so as to have a solid content of 1% by mass to prepare a sample. This sample is put into a laser diffraction / scattering type particle size distribution measuring device, dispersed by ultrasonic waves in the device, and then irradiated with a laser to measure the particle size distribution. The diameter at which the cumulative volume frequency is 50% (volume) is defined as the volume average particle diameter.

The content of the component (C) is determined according to the type of the component (C), the concentration of the active ingredient, and the function required for the fumigation composition. For example, when a silver compound is used as a microorganism control agent, the content of the component (C) is preferably an amount such that the silver concentration in the fumigant composition is 0.001 to 1% by mass, and is 0.05 to 0.5. The amount to be mass% is more preferable.
When the content of the component (C) is not more than the above upper limit value, it is possible to suppress a decrease in the volatilization rate of the component (C).
When the content of the component (C) is at least the above lower limit value, the effect on microorganisms can be easily improved.
On the other hand, when an organic drug (IPMP or the like) is used as the microbial control agent, the content of the component (C) is preferably 1 to 30% by mass, preferably 5 to 20% by mass, based on the total mass of the fumigation composition. More preferred.
When the content of the component (C) is not more than the above upper limit value, it is possible to suppress the generation of an unpleasant odor when it is heated and volatilized.
When the content of the component (C) is at least the above lower limit value, the effect on microorganisms can be easily improved.
When an insecticide is used, the content of the component (C) is preferably 5 to 30% by mass, more preferably 10 to 30% by mass, based on the total mass of the fumigation composition.
When the content of the component (C) is not more than the above upper limit value, the effect of controlling pests is excellent when it is heated and volatilized.

When the fumigant composition of the present invention contains a binder, the granule moldability is improved.
Examples of the binder include celluloses (carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, etc.), starch-based polymer compounds (starch, starch, etc.), natural polymer compounds (Arabic rubber, etc.), and synthetic high. Molecular compounds (polyvinyl alcohol, polyvinylpyrrolidone, etc.) and the like can be mentioned.

When the fumigant composition of the present invention contains a binder, the content of the binder in the fumigant composition (100% by mass) of the present invention is preferably 3 to 8% by mass. When the content of the binder is at least the lower limit value, the time from installation to the start of smoking can be made longer, and it is easy to prevent the user from being smoked at the start of smoking. When the content of the binder is not more than the upper limit value, good smoke performance (spout output) can be easily obtained.

As the surfactant, a nonionic surfactant is preferable, and a fatty acid ester of a polyhydric alcohol or an ethylene oxide adduct thereof, and a copolymerization type nonionic surfactant of oxypropylene and oxyethylene are more preferable.
As the fatty acid ester of the polyhydric alcohol or the ethylene oxide adduct thereof, sorbitan fatty acid esters, POE-sorbitan fatty acid esters, and glycerin fatty acid esters are more preferable. For example, monooleic acid ester, monolauric acid ester, glyceryl monocaprylate and the like can be mentioned.
As the copolymerization type nonionic surfactants of oxypropylene and oxyethylene, a triblock type nonionic surfactant represented by the formula (I) in which EO is sandwiched between POs is preferable.
R ^10- O- (PO) _f- (EO) _g- (PO) _h- R ²⁰ ... (I)
^{R 10} and R ²⁰ of the formula (I) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and both are preferably hydrogen atoms. f represents the average number of repetitions (average number of moles added) of PO (oxypropylene group), preferably 5 to 150, and more preferably 10 to 30. g represents the average number of repetitions (average number of moles added) of EO (oxyethylene group), preferably 5 to 250, and more preferably 5 to 30. h represents the average number of repetitions of PO (average number of moles added), preferably a number of 5 to 150, and more preferably a number of 10 to 30. Further, it is preferable that f + g + h = 20 to 500. Examples of commercially available products include "Pluronic RPE1740" and "PluronicRPE2525" manufactured by BASF Japan Ltd.

Examples of the excipient include inorganic mineral substances (clay, quartz, crystal, etc.) and the like.
When the fumigant composition of the present invention contains an excipient, the content of the excipient in the fumigant composition of the present invention (100% by mass) is preferably 2 to 45% by mass, preferably 10 to 30%. More preferably by mass. When the content of the excipient is equal to or higher than the lower limit, the granule moldability is improved and the smoke performance becomes more stable. When the content of the excipient is not more than the upper limit value, sufficient smoke performance (spout output) can be easily obtained.

Examples of the fever aid include zinc oxide, calcium phosphate, melamine and the like.
Examples of the stabilizer include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and epoxy compounds (epoxidized soybean oil, epoxidized flax oil, etc.).
Examples of the efficacy enhancer include piperonyl butoxide, S-421 and the like.
Examples of the antioxidant include dibutylhydroxytoluene (BHT), tocopherol and the like.
The total content of the components (A) to (B) and the optional components does not exceed 100% by mass.

<Manufacturing method of fumigant composition>
When used for an indirect heating type fumigation device, the fumigant composition of the present invention is prepared as a solid preparation such as powdery, granular or tablet, or a liquid preparation.
As a method for producing a solid fumigation composition, a known production method is used depending on the desired dosage form. For example, in the case of a granular preparation, a known method for producing a granulated product such as an extrusion granulation method, a compression granulation method, a stirring granulation method, a rolling granulation method, or a fluidized bed granulation method is used.
The fumigant composition is obtained by mixing the components (A) to (B).

As a specific example of the production method by the extrusion granulation method, each component of the fumigant composition is mixed by a kneader or the like, and if necessary, an appropriate amount of water is added and mixed, and the obtained mixture is mixed with an arbitrary opening diameter. Examples thereof include a method of granulating with a pre-extrusion or lateral extrusion granulator using a die having a die. The granulated product may be further cut into an arbitrary size with a cutter or the like and dried for removing water.
Examples of the drying method include a heat drying method using a conventionally known dryer.
The drying temperature is not particularly limited, but is preferably 50 to 80 ° C. from the viewpoint of suppressing volatilization of fragrances and the like.
The drying time is appropriately determined according to the drying temperature.
The water content of the fumigation composition after drying is not particularly limited, but is preferably 5% by mass or less, more preferably 2% by mass or less, and may be 0% by mass. When the water content is 5% by mass or less, the volatilization rate of the component (A) is good.
Examples of the method for producing a liquid fumigation composition include a method of preparing by mixing the components (A) to (B) and, if necessary, an arbitrary component.

<How to use the fumigant composition>
The fumigant composition of the present invention is used for decolorizing microbial stains by heating and volatilizing.
The fumigant composition of the present invention is preferably used by being volatilized by a fumigator. As the fumigation device, for example, an indirect heating type fumigation device is preferable.
When the fumigant composition of the present invention is used for an indirect heating type fumigation device, a known method can be adopted as the fumigation method. For example, a method in which the fumigant composition of the present invention is contained in a container such as a metal container or a ceramic container, and the fumigant composition is directly or indirectly heated in a closed target space to smoke. Can be mentioned.
By indirectly heating the fumigant composition, the odor derived from the components (A) and (B) during fumigation can be reduced, and the burning residue of the fumigant composition, etc. It is easy to reduce indoor pollution caused by.
The target space is not particularly limited, and examples thereof include a vehicle, a bathroom, a living room, a closet, and a toilet.

As a method of indirectly heating the smoker composition, any method may be used as long as it can supply heat energy to the smoker composition to a temperature at which the component (A) can be thermally decomposed without burning the smoker composition. , A known heating method usually used for the indirect heating method of smoking can be adopted.
Specifically, for example, a method (i) in which a substance that generates heat in contact with water is brought into contact with water and the heat of reaction is used to heat the fumigant composition, iron powder and an oxidizing agent (ammonium chlorate). Etc.), or a method of heating the fumigant composition using the heat generated by the oxidation reaction by mixing the metal with a metal oxide or an oxidizing agent having a smaller ionizing tendency than the metal (ii). ) Etc. can be mentioned. Of these, method (i) is preferable from the viewpoint of practicality.

Examples of substances that generate heat in contact with water include calcium oxide, magnesium chloride, aluminum chloride, calcium chloride, iron chloride and the like. Among them, calcium oxide is preferable as a substance that generates heat when it comes into contact with water from the viewpoint of practicality.

The amount of fumigant compositions of the present invention may be appropriately set according to the volume of the space for performing the smoking treatment, preferably ^{0.1~30g / m 3, 0.3~20g / m} 3 Gayori preferable.
The temperature at which the fumigation composition is heated is preferably 200 ° C. or higher, more preferably 200 to 300 ° C.
The time for heating the fumigation composition is preferably 60 seconds or more, more preferably 120 to 1000 seconds.
The smoke treatment time (the time from the start of smoking to the release of the sealing of the target space) is not particularly limited, but is preferably about 60 minutes, and if it is less than 30 minutes, the sterilization effect may be insufficient, and 120 If it is more than a minute, the usability will decrease.

Hereinafter, as an example of the fumigation method using the fumigant composition of the present invention, the fumigation method using the fumigation device 10 illustrated in FIG. 1 will be described.
As shown in FIG. 1, the smoke device 10 is roughly composed of a housing 12, a heating unit 20 provided inside the housing 12, and a smoke agent unit 32 provided inside the housing 12. Has been done. The housing 12 is composed of 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 fumigant container 30 is provided in the housing 12, and the fumigant composition is filled in the fumigant container 30 to form a fumigant portion 32.

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

The smoke agent container 30 functions as a container for filling the smoke agent unit 32 and also functions as a heat transfer unit for transmitting the heat energy generated in the heating unit 20 to the smoke agent unit 32. Examples of the smoke agent container 30 include a metal container and the like.

The heating unit 20 is not particularly limited, and can be appropriately determined in consideration of the amount of heat required for smoking the smoke agent unit 32. The heating unit 20 is preferably formed by filling with a substance that generates heat in contact with water, and is particularly preferably formed by filling with calcium oxide. Further, the heating unit 20 may be formed by partitioning the iron powder and the oxidizing agent with a partitioning material and filling the heating portion 20, and partitioning the metal and the metal oxide or the oxidizing agent having a lower ionization tendency than the metal with the partitioning material. It may be filled and formed.

The bottom portion 16 may be appropriately determined according to the mechanism of the heating portion 20. For example, when the heating portion 20 is made of a substance (calcium oxide or the like) that generates heat when it comes into contact with water, a non-woven fabric, a metal mesh, or the like can be used for the bottom portion 16. By forming the bottom portion 16 into a non-woven fabric or a metal mesh, water can be infiltrated into the heating portion 20 from the bottom portion 16 to generate heat of reaction, and the fumigant composition 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 is heated according to the mechanism of the heating unit 20. For example, when the heating portion 20 filled with calcium oxide is provided, the bottom portion 16 is immersed in water. When the heating unit 20 generates heat, the smoke agent unit 32 is heated via the smoke agent container 30. In the fumigant composition of the heated fumigant section 32, gas is generated by the decomposition of the component (A), and the component (B) is smoked together with the gas and ejected through the through hole of the lid portion 18. As a result, the component (B) is diffused in the target space, and the effect of the component (B) can be obtained.

When the fumigation composition is a liquid, in addition to the indirect heating type fumigation device, a fumigation device of a type in which a fibrous mat is impregnated with the fumigation composition and heated by a heating element to volatilize it is used. Alternatively, a fumigation device of a type in which the lower part of the liquid absorbing core is immersed in the fumigant composition and the upper part of the liquid absorbing core is heated by a heating element to volatilize may be used.

The fumigant composition of the present invention can decolorize microbial stains. In particular, it is effective in decolorizing microbial stains that have been blackened by black fungi such as black mold.
The fumigant composition of the present invention is particularly suitable as a fumigant for controlling microorganisms (antifungal, antifungal, etc.) for living rooms and bathrooms. Of these, it is preferable that the composition is an antifungal fumigant composition for bathrooms.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The composition (content (% by mass)) of the fumigant composition of each example is shown in Tables 1 to 5.
If there is a blank compounding ingredient in the table, that compounding ingredient is not blended.
In the table, "balance" means the balance added so that the total amount of all the ingredients contained in the fumigation composition is 100% by mass.
The raw materials used in this example are as follows.

<Ingredient (A)>
-A-1: Azodicarbonamide, trade name: Dieblo AC. 2040 (C), manufactured by Dainichiseika Kogyo Co., Ltd.
-A-2: Propylene glycol, reagent special grade, manufactured by Genuine Kagaku Co., Ltd.
<Ingredient (B)>
-B-1: Citral, trade name: Citral, manufactured by Wako Pure Chemical Industries, Ltd.
-B-2: Citronellal, trade name: (-)-Citronellal, manufactured by Tokyo Chemical Industry Co., Ltd.
-B-3: Octylaldehyde, trade name: n-octanal, manufactured by Tokyo Chemical Industry Co., Ltd.
-B-4: Nonanal aldehyde, trade name: n-nonal aldehyde, manufactured by Yoneyama Yakuhin Kogyo Co., Ltd.
-B-5: Decanaldehyde, trade name: Decanal, manufactured by Tokyo Chemical Industry Co., Ltd.
-B-6: Trans-2-hexanal, trade name: trans-2-hexanal, manufactured by Tokyo Chemical Industry Co., Ltd.
-B'-1: Hexyl cinnamic aldehyde, trade name: α-hexyl cinnamaldehyde, manufactured by Tokyo Chemical Industry Co., Ltd., comparative product of component (B).
-B'-2: Anisaldehyde, trade name: p-anisaldehyde, manufactured by Tokyo Chemical Industry Co., Ltd., (B) component comparison product.
-B'-3: Lilial (4-tert-3- (4-tert-butylphenyl) -propanal), trade name: Lilial, manufactured by Givaudan, a comparative product of the component (B).
-B'-4: Linalool, product name: Linalool, manufactured by Tokyo Chemical Industry Co., Ltd., (B) component comparison product.
-B'-5: thymol, trade name: thymol, manufactured by Wako Pure Chemical Industries, Ltd., (B) component comparison product.
-B'-6: α-pinene, trade name: (-)-α-pinene, manufactured by Yoneyama Yakuhin Kogyo Co., Ltd., (B) component comparison product.
-B'-7: Limonene, trade name: limonene, manufactured by Wako Pure Chemical Industries, Ltd., (B) component comparison product.
-B'-8: Menthone, product name: (-)-Mentone, manufactured by Tokyo Chemical Industry Co., Ltd., (B) component comparison product.
-B'-9: Geraniol, trade name: geraniol, manufactured by Tokyo Chemical Industry Co., Ltd., (B) component comparison product.
-B'-10: Hydroquinone, trade name: Hydroquinone, manufactured by Yoneyama Yakuhin Kogyo Co., Ltd., (B) component comparison product.
<Arbitrary ingredient>
C-1: Silver zeolite, trade name: Zeomic AJ10N, manufactured by Sinanen Zeomic Co., Ltd., silver concentration 2.5% by mass.
-C-2: IPMP, trade name: Biosol, manufactured by Osaka Kasei Co., Ltd.
-C-3: Metoxasiazone, manufactured by Sumitomo Chemical Co., Ltd.
-D-1: HPMC (hydroxypropyl methylcellulose), trade name: Metrose Shin-Etsu Chemical Co., Ltd.
-E-1: Polyoxyethylene polyoxypropylene block polymer, trade name: Pluronic RPE1740, manufactured by BASF.
-F-1: Clay, product name: MK-300, manufactured by Showa KDE Co., Ltd.

<Manufacturing method of fumigant composition>
[Examples 1 to 20, 22 to 26, Comparative Examples 1 to 16]
Under room temperature (20 ° C.) conditions, each component is stirred and mixed with a kneader (S5-2G type, manufactured by Moriyama Co., Ltd.) according to the composition shown in the table, and then 10 parts of water is added and mixed with the total composition as 100 parts. The mixture was obtained. The obtained mixture was granulated using a die front-extruded granulator (EXK-1, manufactured by Fuji Paudal Co., Ltd.) having an opening having a diameter of 2 mm to obtain a granulated product. The obtained granules were cut to a length of 2 to 5 mm with a flash mill (FL300, manufactured by Fuji Powder Co., Ltd.) and dried for 2 hours with a dryer (RT-120HL, manufactured by Alp Co., Ltd.) set at 70 ° C. The mixture was allowed to obtain a granular smoker composition. Various evaluation tests were carried out on the obtained composition using the amounts listed in the table.
[Example 21, Comparative Examples 17-18]
Each component was mixed according to the composition shown in the table to obtain a liquid fumigant composition. Various evaluation tests were carried out on the obtained composition using the amounts listed in the table.

<Evaluation of decolorization effect>
[Examples 1 to 26, Comparative Examples 1 to 16]
Cladosporium cladosporioides HMC1064 (bathroom isolate) cultured on a slope medium of potato dextrose agar at 25 ° C. for 1 week was inoculated into a plate medium of potato dextrose agar at 3 points using a loop loop. After culturing at 25 ° C. for 1 day, the mold plate 1 was used for the test.
As shown in FIG. 2, a mold plate 1 inoculated with bacteria by the following method was placed on the floor surface of an evaluation box 100 (22 cm × 26 cm × 44 cm) having a volume of 25 L.
As a smoke device for evaluation, a heating container of "Look bath anti-mold smoke agent" was prepared, and the smoke agent portion in the container was filled with 0.5 g of the smoke agent composition of each example, and the container was filled. The smoke device 10 was prepared by filling the heated portion inside with 37 g of calcium oxide. A plastic container for water supply containing 23 mL of water was installed in the center of the floor of the evaluation box. The produced smoke device was placed in a plastic container for water supply to start smoking, and the evaluation box 100 was sealed. Fifteen hours after the start of smoke generation, the evaluation box 100 was opened and the mold plate 1 was collected. The area ratio of the whitened portion to the entire colony after standing at 25 ° C. for 3 days was measured to determine the degree of whitening.
Specifically, the collected mold plate 1 was photographed with a digital camera so that the entire surface could be captured, and printed so as to fill the A4 copy paper. The colony of the printed matter is divided into a portion α having a saturation of 0 or 1 and a brightness of 8 or more (refer to the actual colony) α and the other portion β in the Munsell color system, and the mass of each is measured with a precision balance. The occupancy rate was calculated by the following formula (4 digits after the decimal point).
Degree of whitening = [mass of α (whitening part) / mass of α + β (whole colony)] × 100 (%)
Judgment was made according to the evaluation criteria described below.
[criterion]
◎ ◎: Whitening degree is 70% or more ◎: Whitening degree is 50% or more and less than 70%.
◯: The degree of whitening is 30% or more and less than 50%.
Δ: The degree of whitening is 10% or more and less than 30%.
X: The degree of whitening is less than 10%.

[Comparative Example 17]
A filter paper in which 0.5 g of the composition was dropped was placed in the center of the floor surface of the evaluation box (22 cm × 26 cm × 44 cm) having a volume of 25 L.
The mold plate prepared in the same manner as in Example 1 was placed on the floor surface at a distance of 3 cm from the filter paper, and allowed to stand at 25 ° C. for 15 hours. Then collect the mold plate. The size of the colony after standing at 25 ° C. for 3 days was measured, and the degree of whitening was evaluated in the same manner as in Example 1.

[Comparative Example 18]
As a trigger spray container for evaluation, "Lion look kitchen garbage deodorant spray spray container" was used. The composition was placed in a trigger spray container, and one push spray (about 0.3 g) was applied to a mold plate prepared in the same manner as in Example 1. After allowing this to stand and drying, the size of the colony after standing culture at 25 ° C. for 3 days was measured, and the degree of whitening was evaluated in the same manner as in Example 1.

From the results shown in Tables 1 to 5, Examples 1 to 26 to which the present invention was applied decolorized microbial stains.
In Comparative Examples 1 to 10 containing no component (B1), the microbial stain could not be decolorized.
In Comparative Examples 11 to 13 in which the content of the component (B1) was less than 20% by mass with respect to the total mass of the component (B), the microbial stain could not be decolorized.
In Comparative Examples 14 to 15 in which the content of the component (B) was less than 0.05% by mass with respect to the total mass of the fumigant composition, the microbial stain could not be decolorized.
In Comparative Example 16 containing no component (B), the microbial stain could not be decolorized.
In Comparative Example 17 in which the fumigant composition was naturally volatilized without heating, the microbial stain could not be decolorized.
In Comparative Example 18 in which the fumigant composition was sprayed without heating, the microbial stain could not be decolorized.

10: Smoke device 20: Heating unit 30: Smoke agent container 32: Smoke agent unit 1: Mold plate 100: Evaluation box

Claims (10)

(A) Ingredients: Organic foaming agent and
(B) Component: A heated fumigant composition containing an aldehyde compound.
The content of the component (B) is 0.05% by mass or more with respect to the total mass of the heated fumigation composition.
The component (B) contains an acyclic aldehyde compound (B1).
A heated fumigant composition in which the content of the component (B1) is 20% by mass or more with respect to the total mass of the component (B). At least one selected from the group in which the component (A) consists of azodicarbonamide, p, p'-oxybis (benzenesulfonyl hydrazide), N, N'-dinitrosopentamethylenetetramine, and azobisisobutyronitrile. The heated smoldering agent composition according to claim 1. The heated smoker composition according to claim 1 or 2, wherein the component (B1) is an acyclic aldehyde compound having a linear or branched hydrocarbon group having 6 to 16 carbon atoms. The heated fumigant composition according to any one of claims 1 to 3, wherein the content of the component (A) is 60 to 75% by mass with respect to the total mass of the heated fumigant composition. The heated fumigant composition according to any one of claims 1 to 4, wherein the mass ratio represented by the component (A) / the component (B) is 60 to 600. The heated fumigant composition according to any one of claims 1 to 5, further comprising the component (C): at least one selected from the group consisting of a microbial control agent, a deodorant, and an insecticide. The heated fumigant composition according to claim 6, wherein the content of the component (C) is 0.05 to 0.5% by mass with respect to the total mass of the heated fumigant composition. A method for decolorizing microbial stains, which comprises heating the heated fumigation composition according to any one of claims 1 to ^{7 and volatilizing it to a concentration of 0.1 to 30 g / m 3.} A method for decolorizing microbial stains, which comprises heating the heated fumigation composition according to any one of claims 1 to 7 at 200 ° C. or higher for 60 seconds or longer to volatilize it. A housing with a tubular body, bottom, and lid,
A heating unit in which the exothermic agent is housed in the housing,
A metal smoke agent container provided in the housing and located above the heating unit is provided.
An indirect heating type fumigation device, wherein the smoke agent container is filled with the heating type fumigant composition according to any one of claims 1 to 7.

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