WO2015159816A1

WO2015159816A1 - Self-jetting spatial processing agent

Info

Publication number: WO2015159816A1
Application number: PCT/JP2015/061223
Authority: WO
Inventors: 美香渡部; 弘山岸
Original assignee: ライオン株式会社
Priority date: 2014-04-16
Filing date: 2015-04-10
Publication date: 2015-10-22
Also published as: JPWO2015159816A1; JP6615088B2

Abstract

A self-jetting spatial processing agent which contains (A) silver, a silver compound or a material loaded with silver or a silver compound, and (B) a compound represented by general formula (I). R¹-O-(AO)_x-R² (I) (In formula (I), each of R¹ and R² independently represents a hydrogen atom or a hydrocarbon group having 1-6 carbon atoms; AO represents oxyalkylene groups including an oxyethylene group and an oxypropylene group and/or an oxybutylene group; and x represents a number of 20-500.)

Description

Self-propelled space treatment agent

The present invention relates to a self-injecting space treatment agent.
This application claims priority based on Japanese Patent Application No. 2014-084755 filed in Japan on April 16, 2014, the contents of which are incorporated herein by reference.

In humid spaces (such as bathrooms) where microorganisms such as bacteria and mold are likely to grow, especially for places that are difficult to reach such as ceilings and high wall surfaces, use a spray-type chlorine mold remover. It is a difficult place and fungi are easy to breed. In order to prevent the occurrence and growth of mold and the like in such places, it is a common practice to treat the sealed space with a space treatment agent containing an active ingredient such as a fungicide. As the space treatment agent used for such a purpose, a fumigant (fumigant), a total injection aerosol agent, and the like are common.
By using the space treatment agent, it is possible to reduce the time and effort of cleaning and maintain a clean space easily.

For example, Patent Document 1 discloses a smoke agent composition containing a silver-containing agent and an organic foaming agent as a spatial treatment agent having an excellent microorganism suppressing effect.
In Patent Document 2, a mixture of an organic drug such as zinc pyrithione as an antifungal component and a water-soluble polymer such as hydroxypropylcellulose, carboxymethylcellulose, or polyvinyl alcohol as a spreading component is sprayed or smoked by self-injection. A method of fumigation is disclosed.

JP 2011-12051 A Japanese Patent No. 2003-286104

However, when the smoke composition described in Patent Document 1 or the mixed liquid described in Patent Document 2 is used, the active ingredient is washed away in water in places where water flows frequently, such as bathroom walls. Cheap. Therefore, the adhesion amount of the active ingredient tends to decrease, and as a result, the antifungal effect may decrease. Therefore, further improvement in sustainability of the mold prevention effect is desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a self-injection type space treating agent having a high antifungal effect.

As a result of intensive studies, the present inventors use silver or a silver compound (also referred to as an active ingredient) having a high antifungal effect and a specific polyalkylene glycol in combination, so that water frequently flows on a bathroom wall or the like. The present inventors have found that the active ingredient is likely to remain on the wall or the like at any place and can maintain the antifungal effect, and have completed the present invention.

That is, this invention has the following aspects.
[1] Component (A): Silver, a silver compound, or a support of silver or a silver compound, and (B) component: a self-injecting space treating agent containing a compound represented by the following general formula (I) .
R ¹ —O— (AO) _x —R ² (I)
(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, AO represents an oxyalkylene group. (AO) _x represents an oxyethylene group. And at least one of an oxypropylene group and an oxybutylene group, and x is a number of 20 to 500.)
[2] The self-injecting space treating agent according to [1], wherein (AO) _x includes an oxyethylene group and an oxypropylene group.
[3] The self-injecting space treating agent according to [1] or [2], wherein (AO) _x is a triblock type in which an oxyethylene group is sandwiched between oxypropylene groups.
[4] The compound represented by the general formula (I) is R ¹ —O— (PO) _f — (EO) _g — (PO) _h —R ² (iii)
The self-injecting space treating agent according to [3].
(In the formula (iii), f is 5 to 150, g is 5 to 250, h is 5 to 150, and the sum of f, g, and h is the same as the value of x.)
[5] The self-injection section treating agent according to any one of [1] to [4], wherein R ¹ and R ² of the compound represented by the general formula (I) are hydrogen atoms.
[6] Component (C1): The self-injecting space treating agent according to any one of [1] to [5], further comprising an organic foaming agent.
[7] The self-injecting space treating agent according to [6], wherein the mass ratio represented by (B) component / (C1) component is 0.01 to 0.5.
[8] Component (C2): The self-injecting space treating agent according to any one of [1] to [5], further containing a propellant.
[9] The self-injecting space treating agent according to [8], wherein the mass ratio represented by (B) component / (C2) component is 0.01 to 0.25.

According to the present invention, it is possible to provide a self-injecting space treatment agent having a high antifungal effect.

It is sectional drawing which shows an example of the smoke device of one Embodiment of this invention. It is a perspective view which shows the state before use of the total injection type aerosol apparatus of one Embodiment of this invention. It is a III-III sectional view of a full-quantity injection type aerosol device. It is the schematic explaining the evaluation method of the sustainability of the antifungal effect in [Example]. It is the schematic explaining the evaluation method of the fungicidal effect especially among the fungicidal effects in [Example].

The present invention relates to a self-injecting space treatment agent having a high antifungal effect.
One aspect of the present invention is a self-foaming fungicide for a bathroom.
Another aspect of the present invention is a self-foaming fungicide that is spread on the inner wall of a bathroom.
The size of the space targeted by the present invention is, for example, the size of a shower room to the size of a public bath. The size of the space targeted by the present invention is, for example, 0.5 m ³ to 150 m ³ .
Another aspect of the present invention is a self-injecting fungicide used in a space where water is frequently used and spread on the inner wall of the space.
Another aspect of the present invention is a mold growth inhibitor that is self-expelling for a bathroom.
Another aspect of the present invention is a bacterial growth inhibitor that is self-spraying for a bathroom.
Another aspect of the present invention is a self-expelling fungicide for a bathroom.
Another aspect of the present invention is a self-expelling fungicide for a bathroom.
Another aspect of the present invention is: (A) component: silver, a silver compound, or a carrier of silver or silver compound, (B) component: a compound represented by the following general formula (I), and (C1) component A smoke device having a smoke agent containing portion filled with a smoke agent containing an organic foaming agent, and a heating unit for heating the smoke agent.
R ¹ —O— (AO) _x —R ² (I)
(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, AO represents an oxyalkylene group. (AO) _x represents an oxyethylene group. And at least one of an oxypropylene group and an oxybutylene group, and x is a number of 20 to 500.)
Another aspect of the present invention is a smoke device having a heat transfer unit that transfers heat generated in the heating unit to the smoke agent.
Another aspect of the present invention is a smoke agent contained in the smoke device.
Another aspect of the present invention is the use of the smoke agent to produce the smoke device.
Another aspect of the present invention is: (A) component: silver, a silver compound, or a carrier of silver or silver compound, (B) component: a compound represented by the following general formula (I), and (C2) component : A full-injection aerosol device in which a spray can is filled with a full-injection aerosol containing a propellant, and the full-injection aerosol device has a nozzle cap on the top of the spray can, and the nozzle cap is pushed and injected A full injection aerosol device comprising a push button fixed in position and a nozzle through which the contents of the spray can are injected in full when the push button is fixed in the injection position.
R ¹ —O— (AO) _x —R ² (I)
(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, AO represents an oxyalkylene group. (AO) _x represents an oxyethylene group. And at least one of an oxypropylene group and an oxybutylene group, and x is a number of 20 to 500.)
Another aspect of the present invention is a total injection aerosol device in which the total injection aerosol is contained in a total injection aerosol container, wherein the total injection aerosol container includes a cap body covering the container, and the total injection aerosol. A full-injection aerosol device comprising a push button for full-injection.
Another aspect of the present invention is a total injection aerosol agent housed in the total injection aerosol device.
Another aspect of the present invention is the use of the full-injection aerosol to produce the full-injection aerosol device.
Hereinafter, the present invention will be described in detail.
In the present invention, “mold prevention” includes preventing the growth of microorganisms such as bacteria and mold, and killing these microorganisms (sterilization, mold killing). Hereinafter, killing microorganisms such as bacteria and molds is also called “mold killing”.
Further, in the present invention, the “self-injection type” is a method in which spraying of an active ingredient of a space treatment agent such as a solid or liquid antifungal agent can be continued even if an operator is not present.
Examples of the self-injection type include a full-injection type smoke agent (fumigant) and a full-injection type aerosol formulation (full-injection aerosol agent).
A total amount injection type fumigant (fumigant) is an indirect heating method that heats a spatial treatment agent containing active ingredients and organic foaming agents using the heat of reaction between calcium oxide and water. A method is used in which the active ingredient is sprayed by causing self-decomposition to cause injection of the space treatment agent. In addition, those using a method in which an organic foaming agent is ignited using a match head or the like and a spatial treatment agent is sprayed by thermal decomposition of the organic foaming agent are also included in the total amount injection type fumigant (fumigant).
On the other hand, the aerosol injection type of the full-volume injection type is filled with a space treatment agent containing an active ingredient and a propellant in a pressure-resistant container, and almost all of the contents of the container is put into a container by one operation (opening of a valve, etc.) by any injection means. A method of spraying outside is used.

The self-injecting spatial treatment agent of the present invention (hereinafter simply referred to as “spatial treatment agent”) contains the following components (A) and (B). Moreover, it is preferable that a space processing agent further contains the (C1) component or (C2) component shown below.

<(A) component>
The component (A) is silver, a silver compound, or a support of silver or a silver compound. The space treating agent has an antifungal effect by containing the component (A). That is, the active ingredient in the present invention is the component (A). By exhibiting the antifungal effect, the odor due to the growth of microorganisms can be suppressed, and the deodorizing effect is also achieved.
Silver is silver alone.
Examples of the silver compound include silver oxide; inorganic silver salts such as silver chloride, silver nitrate, silver sulfate, silver carbonate and silver sulfonate; and organic silver salts such as silver formate and silver acetate.

The carrier of silver or silver compound is to carry silver or silver compound on a substance such as zeolite, silica / alumina, silica gel, low molecular glass, calcium phosphate, silicate, titanium oxide (hereinafter sometimes referred to as carrier). It is a thing. Here, “supporting silver or a silver compound on a carrier” is a state in which silver or a silver compound is chemically, physically or electrically bound or adsorbed on the carrier. Examples of the carrier include a zeolite inorganic antibacterial agent supporting silica alone or a silver compound (silver oxide, inorganic silver salt, organic silver salt, etc.), silica / alumina inorganic antibacterial agent, silica gel inorganic antibacterial agent, titanium oxide. -Based inorganic antibacterial agents and silicate-based inorganic antibacterial agents.

As the component (A), among those described above, from the viewpoint of further reducing the odor derived from the component (A) during and after the use of the space treating agent, silver alone, silver oxide, inorganic silver salt (silver nitrate, etc.), or A support in which these are supported on a carrier is preferable, and a support is more preferable. Among the supports, zeolite-based inorganic antibacterial agents, silica / alumina-based inorganic antibacterial agents, and silicate-based inorganic antibacterial agents are preferable, and zeolite-based inorganic antibacterial agents are particularly preferable.
In the case of using a support of silver or a silver compound, the ratio of silver in the support is, for example, 0.01 to 10% by mass of silver in the support relative to the total mass of the support. 05-1.5% by weight is used.
(A) A component may be used individually by 1 type and may use 2 or more types together.

The form of the component (A) is not particularly limited, but can be determined in consideration of the size of the target space. As the particle (A) becomes finer, the smoke rate increases, and the effect of the component (A) can be sufficiently exerted and diffused over a wide area. On the other hand, if the particle of the component (A) is too small, it is difficult to fall after diffusing, and it takes time until the effect of the component (A) in the lower part of the target space is manifested.
For example, the volume average particle diameter of the component (A) is preferably 0.01 to 1000 μm, more preferably 0.5 to 100 μm, and even more preferably 1 to 5 μm. In the space treating agent of the present invention, even such a component (A) having a relatively large particle size can be smoked and diffused. Here, “smoke” the spatial treatment agent means that the component (A) is diffused into the target space.
The volume average particle diameter is a value obtained by a laser diffraction / scattering particle size distribution measuring apparatus, and the volume average particle diameter of the component (A) can be measured as follows. (A) A component is disperse | distributed to distilled water so that it may become 1 mass% of solid content, and it is set as a sample. This sample is put into a laser diffraction / scattering type particle size distribution measuring apparatus, dispersed in ultrasonic waves in the apparatus, 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 average particle diameter.

The content of the component (A) in the space treatment agent is determined according to the type of component (A), the effective component concentration, and the function required for the space treatment agent. For example, the content of the component (A) in the space treatment agent is preferably such that the ratio of the mass of silver in the space treatment agent to the total mass of the space treatment agent is 0.001 to 1% by mass. An amount of 0.05 to 0.5% by mass is more preferable. If the ratio of the mass of silver in the space treatment agent to the total mass of the space treatment agent is less than 0.001% by mass, the effect of the component (A) may be reduced, and even if it exceeds 1% by mass, the component (A) There is a possibility that the effect of is saturated and further improvement of the effect cannot be achieved.

<(B) component>
Component (B) is a compound represented by the following general formula (I).
R ¹ —O— (AO) _x —R ² (I)
(In the formula (I), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, AO represents an oxyalkylene group. (AO) _x represents an oxyethylene group. And at least one of an oxypropylene group and an oxybutylene group, and x is a number of 20 to 500.)
The component (B) has the effect of adhering the component (A), which is an active component, to the treatment surface, that is, the surface to be treated with the spatial treatment agent, and keeping it in place (ie, the spreading effect). Therefore, since the space treatment agent contains the component (B), the component (A) adhering to the treated surface is not easily washed away with water even in places where water flows frequently, such as bathroom walls. The mold effect can be sustained. Moreover, the antifungal effect (particularly the fungicidal effect) is further improved by the combined use of the component (B) and the component (A).

R ¹ and R ² in the formula (I) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group include an alkyl group and an alkenyl group.
Examples of the hydrocarbon group for R ¹ or R ² include linear or branched hydrocarbon groups. R ¹ and R ² are preferably a hydrocarbon group having 1 to 3 carbon atoms and hydrogen, more preferably hydrogen.

AO represents an oxyalkylene group. (AO) _x includes an oxyethylene group (EO) and at least one of an oxypropylene group (PO) and an oxybutylene group (BO). That is, (AO) _x can be expressed as [EO / A′O] _x . Here, A′O represents PO or BO. [EO / A′O] _x necessarily includes EO and includes at least one of PO and BO. Moreover, EO / A'O may add EO and A'O in the block form, and may add it in the random form.
x means the average of the total number of AO repeats in the compound represented by the general formula (I) (average total number of added moles), and is a number of 20 to 500, preferably a number of 30 to 180. If x is in the above range, it is possible to exhibit excellent mold-killing effect and sustainability of the mold-proofing effect. The value of x can be controlled by a synthesis technique common in the field.

(AO) _x preferably contains EO and PO in terms of excellent durability of the antifungal effect, and is composed of EO and PO, that is, a block adduct or a random adduct of EO and PO is more preferable. And a PO adduct of PO.

Specific examples of the component (B) in which (AO) _x is a block adduct of EO and PO include compounds represented by the following general formulas (i) to (iii).
R ¹ —O— (EO) _a — (PO) _b —R ² (i)
R ¹ —O— (EO) _c — (PO) _d — (EO) _e —R ² (ii)
R ¹ —O— (PO) _f — (EO) _g — (PO) _h —R ² (iii)

In the case of the general formula (i), (AO) _x in the general formula (I) is a diblock type composed of EO and PO.
In formula (i), a represents the average number of EO repeats (average number of added moles), preferably a number of 10 to 300, and more preferably 10 to 200. b represents the average number of repeating POs (average number of added moles), preferably a number of 5 to 250, and more preferably 10 to 60. However, the sum of a and b is the same as the value of x.

In the case of general formula (ii), (AO) _x in general formula (I) is a triblock type in which PO is sandwiched between EO.
In the formula (ii), c represents an average number of EO repeats (average number of added moles), preferably a number of 5 to 150, more preferably 10 to 100. d represents the average number of repetitions of PO (average number of added moles), preferably a number of 5 to 250, more preferably a number of 10 to 60. e represents the average number of repetitions of EO (average number of added moles), preferably 5 to 150, and more preferably 10 to 100. However, the sum of c, d, and e is the same as the value of x.

In the case of the general formula (iii), (AO) _x in the general formula (I) is a triblock type in which EO is sandwiched by PO.
In formula (iii), f represents the average number of repetitions of PO (average number of added moles), preferably a number of 5 to 150, more preferably 10 to 30. g represents the average number of EO repeats (average number of moles added), preferably a number from 5 to 250, and more preferably a number from 5 to 30. h represents an average number of repetitions of PO (average number of added moles), preferably a number of 5 to 150, and more preferably a number of 10 to 30. However, the sum of f, g, and h is the same as the value of x.

Among the above-mentioned, as the component (B), a compound represented by the general formula (iii) is preferable in that it has excellent spreadability on the treated surface and the sustainability of the fungicidal effect is more easily obtained.

The weight average molecular weight of the component (B) is preferably 1500 to 4000. If the mass average molecular weight of (B) component exists in the said range, it will be excellent in spreading property and it will become easier to obtain the sustainability of an antifungal effect.
The mass average molecular weight of the component (B) is a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent using PEG (polyethylene glycol) as a calibration curve.

The component (B) is easily obtained on the market. Examples of commercially available compounds represented by the general formula (ii) include “Pluronic PE6400” manufactured by BASF Japan Ltd .; “Unilube 70DP-600B” manufactured by NOF Corporation, and the like. Examples of commercially available compounds represented by the general formula (iii) include “Pluronic RPE 1740” and “Pluronic RPE 2525” manufactured by BASF Japan Ltd.
Moreover, as (B) component, you may use what was synthesize | combined by the method described in various publications.
(B) A component may be used individually by 1 type and may use 2 or more types together.

The content of the component (B) in the spatial treatment agent, that is, the ratio of the mass of the component (B) in the spatial treatment agent to the total mass of the spatial treatment agent is preferably 1 to 15% by mass, more preferably 5 to 10% by mass. preferable. If content of (B) component is 1 mass% or more, the sustainability of a mold prevention effect will become easier to be obtained. On the other hand, if the content of the component (B) is 15% by mass or less, the spraying performance of the space treating agent can be maintained well, and the component (A) as an active component is easily distributed and adhered to the treated surface. Become. As a result, the fungicidal effect of the component (A) is more easily exhibited.

<Dosage form>
Examples of the dosage form of the spatial treatment agent of the present invention include a fumigant (fumigant) and a full-injection aerosol. In the present invention, the smoke agent and the fumigant are synonymous. In the present invention, the “smoke agent (fumigant)” refers to a smoke agent or a fumigant.
Smoke agents are agents mainly composed of an exothermic base mixed with various combustion agents, foaming agents, and the like, and an active ingredient as an antifungal agent. When the smoke agent is heated at the time of use, the exothermic base burns or decomposes to generate smoke (gas and fine particles), and the active ingredient is volatilized in the air by the action of the smoke.
Hereinafter, the present invention will be further described by dividing it into a case where the spatial treatment agent of the present invention is used as a smoke agent (fumigant) and a case where it is used as a full-injection aerosol agent.

<< Fumigant (Fumigant) >>
When the space treating agent of the present invention is used as a smoke agent, the space treating agent preferably further contains an organic foaming agent (hereinafter referred to as “component (C1)”). As one aspect of the present invention, when a space treatment agent is used as a smoke agent, the space treatment agent, that is, the smoke agent, is a composition contained in a smoke agent container of a smoke container described below. Say.
The component (C1) is a component that foams and melts with the component (A) and the component (B) by heating, and smokes the component (A) and the component (B) by thermal decomposition of the organic foaming agent or the action of the combustion gas. is there.

As the component (C1), azodicarbonamide, nitrocellulose, p, p′-oxybis (benzenesulfonylhydrazide), N, N′-dinitrosopentamethylenetetramine, azobisisobutyronitrile, etc. are heated or burned. A material that generates a large amount of heat by pyrolysis and generates carbon dioxide gas or nitrogen gas is used. These organic foaming agents may be used individually by 1 type, and may use 2 or more types together.
Among these, azodicarbonamide and nitrocellulose are preferable in that the decomposition temperature is low and the amount of foaming gas generated is large.

The content of the component (C1) in the space treatment agent, that is, the amount of the component (C1) in the space treatment agent with respect to the total mass of the space treatment agent (the total mass of the contents filled in the smoke container containing portion of the smoke container). The mass ratio is preferably 50 to 90 mass%, more preferably 60 to 80 mass%. When the content of the component (C1) is within the above range, the reachability of the component (A) and the component (B) to the treated surface and the sustainability of the antifungal effect become better.

The content of the component (C1) in the space treating agent is the mass ratio represented by (B) component / (C1) component, that is, the mass ratio of the component (B) to the component (C1) in the space treating agent. An amount of 0.01 to 0.5 is preferable, and an amount of 0.05 to 0.15 is more preferable. If mass ratio is in the said range, the sustainability of a mold prevention effect will improve more.

The space treatment agent may further contain various additives. Additives include combustion aids, stabilizers, binders, excipients, and the like.
Examples of the combustion aid include zinc oxide, magnesium oxide, urea, melamine, melamine derivatives (industrial melamine, melamine nitrate, melamine formalin resin, etc.). The ratio of the mass of the combustion aid in the space treatment agent to the total mass of the space treatment agent (that is, the total mass of the contents filled in the smoke container housing portion of the smoke container) is 0.5 to 5% by mass. It is preferably 1 to 3% by mass.
Examples of the stabilizer include sorbitan fatty acid ester, dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, epoxy compounds (epoxidized soybean oil, epoxidized linseed oil, etc.) and the like. The ratio of the mass of the stabilizer in the space treatment agent to the total mass of the space treatment agent (the total mass of the contents filled in the smoke container container of the smoke container) is preferably 0.01 to 15% by mass. 1 to 10% by mass is more preferable.
As binders, cellulose compounds (methyl cellulose, ethyl cellulose, carboxymethyl cellulose and its Ca salts and Na salts, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, etc.), starch compounds (starch, pregelatinized starch, dextrin, hydroxypropyl starch, carboxy) Methyl starch Na salt, etc.), natural product compounds (gum arabic, sodium alginate, tragacanth, gelatin, etc.), synthetic polymer compounds (polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, etc.) and the like. The ratio of the mass of the binder in the space treatment agent to the total mass of the space treatment agent (the total mass of the contents filled in the smoke container container of the smoke container) is preferably 0.1 to 10% by mass, 2 to 6% by mass is more preferable.
Examples of the excipient include clay, talc, diatomaceous earth, kaolin, bentonite, white carbon, calcium carbonate and the like. In the present application, clay refers to a white powdery product industrially purified from clay minerals such as wax (including pyrophyllite) including aluminum silicate and quartz, and includes fine particles. The volume average particle diameter of the clay is preferably from 0.1 to 100 μm, more preferably from 1 to 30 μm. The volume average particle diameter is a value obtained by a laser diffraction / scattering particle size distribution measuring apparatus. Examples of the clay include those containing silicon oxide and aluminum silicate.
The ratio of the mass of the excipient in the spatial treatment agent to the total mass of the spatial treatment agent is preferably 2 to 50% by mass, and more preferably 10 to 30% by mass. These additives may be used alone or in combination of two or more.

In addition, the space treatment agent may be blended with other additives such as a fragrance and a pigment as necessary, as long as the effects of the present invention are not impaired.

When using the space treatment agent of the present invention as a smoke agent, the smoke agent is filled in a smoke container. A device in which a smoke agent is accommodated in a smoke agent storage portion of a smoke container and a heating material is stored in a heating portion is called a smoke device.

Hereinafter, one aspect of a smoke device to which the present invention is applied will be described with reference to the drawings. The smoke device of the present invention is not limited to the smoke device described below.
FIG. 1 is a cross-sectional view of a smoke device 10 of the present invention. The smoke device 10 is roughly configured by a housing 11, a heating unit 12 provided in the housing 11, and a smoke agent 13 provided in the housing 11. The housing 11 includes a substantially cylindrical main body 14, a bottom portion 15, and a lid portion 16. A smoke agent container 17 is provided in the housing 11, and the smoke agent container 17 is filled with the smoke agent.

The lid portion 16 has a hole, and examples thereof include a mesh, a punching metal, and a lattice frame.

The smoke storage container 17 functions as a container that fills the smoke 13 and also functions as a heat transfer unit that transmits heat energy generated in the heating unit 12 to the smoke 13. As for the smoke agent accommodating part 17, a metal container etc. are mentioned, for example.

The exothermic substance accommodated in the heating unit 12 is not particularly limited, and can be determined in consideration of the amount of heat necessary for the smoke agent 13 to be smoked. For example, the heating unit 12 may be filled with a substance that generates heat upon contact with water (for example, calcium oxide or the like), or is filled with iron powder and an oxidizing agent separated by a partitioning material. Alternatively, a metal and a metal oxide or oxidizer having a smaller ionization tendency than the metal may be partitioned and filled with a partition material. Among them, it is preferable to fill with a substance that generates heat upon contact with water, and it is preferable to fill with calcium oxide.

The bottom 15 can be determined according to the mechanism of the heating unit 12. For example, when the heating unit 12 contains a substance that generates heat upon contact with water such as calcium oxide, the bottom 15 has a nonwoven fabric or metal. Made of mesh or the like can be used. By making the bottom part 15 into a nonwoven fabric or a mesh, water can penetrate into the heating part 12 from the bottom part 15 and can be heated.

<Manufacture of space treatment agent (smoke agent) for application to smoke device>
A method for producing a spatial treatment agent when the spatial treatment agent of the present invention is used as a smoke agent will be described. The smoke agent of the present invention can employ a known production method according to the target shape, for example, extrusion granulation method, compression granulation method, stirring granulation method, rolling granulation method, fluidized bed granulation Law. Extrusion granulation is preferred.
As specific examples of the extrusion granulation method, (A) component, (B) component, (C-1) component, and various additives are stirred and mixed with a kneader, and then the total amount of the composition is set to 100 parts by mass. -15 parts by weight, more preferably 8-12 parts by weight of water are added and mixed to obtain a mixture. The obtained mixture is granulated by a pre-extrusion or lateral extrusion granulator using a die having a certain area of openings (also called a die) to obtain a granulated product. The obtained granulated product is cut by a cutter, a flash mill or the like and dried, and the granules are dried with a diameter of 1 to 5 mm, preferably 1.5 to 3 mm, and a length of 2 to 20 mm, preferably 5 to 10 mm. Get smoke agent.

<Manufacture of smoke devices>
As an aspect in the case of using the space treatment agent as the smoke agent, 1 to 50 g of the smoke agent is accommodated in the smoke agent container of the smoke container, and 10 to 80 g of calcium oxide is further added to the heating part in the smoke container. And smoke device.

<< All-injection aerosols >>
The all-injection aerosol agent refers to a liquid agent (chemical solution) and a propellant (hereinafter also referred to as “(C2) component”), and is used by filling a pressure-resistant container (hereinafter also referred to as “total-injection aerosol container”). A full-injection aerosol device filled with a full-injection aerosol container is called a full-injection aerosol device. The all-injection type aerosol apparatus is capable of injecting almost the entire amount of the contents of the all-injection aerosol container to the outside of the container by a single operation (opening a valve or the like) by an arbitrary injection means.
When the spatial treatment agent of the present invention is used as a total spray aerosol agent, the spatial treatment agent preferably further contains a solvent that dissolves or disperses the active ingredient.
The component (C2) is a component for injecting almost the entire amount of the liquid agent in which the component (A) and the component (B) are dissolved or dispersed in the solvent to the outside of the injection aerosol container in a single operation (such as opening a valve). .

(C2) The component is preferably dimethyl ether. When the spatial treatment agent contains dimethyl ether, the dispersibility and jetting power of the component (A) and the component (B) are improved, and the component (A) and (A) when the spatial treatment agent of the present invention is used in a bathroom or the like. B) Reachability of the component to the treated surface (such as a bathroom ceiling or wall surface) is improved.

As the component (C2), a propellant other than dimethyl ether may be used in combination. Examples of other propellants include liquefied gases other than dimethyl ether (liquefied petroleum gas, chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroolefin, etc.), compressed gas (carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc.), etc. Is mentioned. Of these, liquefied gas is preferable from the viewpoint of injection force (injection momentum).
A propellant may be used individually by 1 type and may use 2 or more types together.

The ratio of dimethyl ether to the total of (C2) component in component (C2) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 100% by mass. When the proportion of dimethyl ether is 50% by mass or more, the effect of dimethyl ether can be sufficiently obtained.
In addition, there is no problem even if other propellants are mixed as the component (C2) for the purpose of adjusting the jetting performance, but there is a possibility that problems may arise when the amount of other propellants increases. For example, when the component (C2) is only liquefied petroleum gas (LPG), there is a possibility of causing a problem in compatibility with other components.
Moreover, in the case of only compressed gas, there is a possibility that the momentum of injection is insufficient and the components (A) and (B) do not reach the ceiling of the bathroom sufficiently.
The component (C2) is particularly preferably composed only of dimethyl ether.

The content of the component (C2) in the spatial treatment agent, that is, the ratio of the mass of the component (C2) in the spatial treatment agent to the total mass of the contents filled in the total amount sprayed aerosol container is preferably 50 to 90% by mass, More preferably, it is 60 to 80% by mass. When the content of the component (C2) is within the above range, the reachability of the component (A) and the component (B) to the treated surface and the sustainability of the antifungal effect become better.

The content of the component (C2) in the space treating agent is preferably such that the mass ratio represented by the component (B) / component (C2) is 0.01 to 0.25, preferably 0.05 to 0.00. An amount of 2 is more preferred. If the mass ratio is within the above range, the dispersibility of the component (A) and the component (B) and the adhesion / spreading property to the treated surface will be good, and the sustainability of the antifungal effect will be improved.

Solvents include ethanol, methanol, acetone, glycol ethers (ethylene glycol and derivatives thereof, diethylene glycol and derivatives thereof, other alkylene glycols and derivatives thereof), propylene carbonate, dimethyl carbonate, N-methylpyrrolidone, N-ethylpyrrolidone Γ-butyrolactone, methyl lactate, ethyl lactate, dibutyl lactate, kerosene, water and the like.
The content of the solvent in the space treatment agent, that is, the ratio of the mass of the solvent with respect to the total mass of the contents filled in the total amount sprayed aerosol container is preferably 1 to 30% by mass, and more preferably 10 to 20% by mass.
A solvent may be used individually by 1 type and may use 2 or more types together.

The space treatment agent may further contain various additives. Examples of the additive include the combustion aids, stabilizers, binders and excipients exemplified above.
Moreover, other additives, such as a fragrance | flavor and a pigment | dye, may be mix | blended with a space treating agent as needed in the range which does not impair the effect of this invention.

As shown in FIGS. 2 and 3, for example, as shown in FIGS. 2 and 3, the container used for the full-amount aerosol device includes a cap body that covers the container, one end side supported by the cap body, and the other end side to the fixed position. A push button that pushes a stem provided in the container by pressing and ejects the contents ejected from the stem from an ejection port, and the cap body locks the push button at a fixed position. A locking portion is provided.
Hereinafter, an aspect of a full-volume aerosol container used for a full-volume spray aerosol apparatus to which the present invention is applied will be described in detail with reference to FIGS. The full-amount aerosol container of the present invention is not limited as long as it can eject almost the entire amount of the contents of the container to the outside of the full-injection aerosol container by one operation (opening a valve, etc.). The container is not limited to the container described below.

The all-injection aerosol container 20 includes a spray can 21 that contains the contents, and a nozzle cap 22 that is attached to the spray can 21 and injects the contents contained in the spray can 21 in a full amount. The spray can 21 protrudes from the upper center of the spray can 21 and is supported by a stem 23 supported so as to be movable in the vertical direction while being urged upward, and by pressing the stem 23 downward. And a valve mechanism (not shown).

The nozzle cap 22 has a cap body 24 attached to the top of the spray can 21, a push button 25 for pressing the stem 23 of the spray can 21, and the stem 23 of the spray can 21 by pressing the stem 23. And an injection nozzle 26 for injecting the contents ejected from the nozzle.

The cap body 24 is a plastic cover member that covers the top of the spray can 21.

The push button 25 can press the stem 23 of the spray can 21 by pressing the operation unit 27. Further, the push button 25 is arranged at the center of the lower surface of the push button 25 and is fitted to the stem 23 of the spray can. A flow path 29 is provided for guiding the contents to the injection nozzle 26.

An injection nozzle 26 that is a nozzle member is provided on one end side of the push button 25. The injection nozzle 26 communicates with the flow path 29 of the push button 25 and injects the contents ejected from the stem 23 through the ejection port 26a provided at the tip thereof.

By the way, the nozzle cap 22 is provided with a lock mechanism 30 for fixing the push button 25 at a fixed position when the push button 25 is pressed. Specifically, the lock mechanism 30 is disposed on the cap body 24 side, and is disposed on the push button 25 side with a locking portion 31 that locks the push button 25 in a fixed position. And a locked portion 32 that is locked to the locking portion 31.

In this lock mechanism 30, when the push button 25 is pushed down against the biasing force of the stem 23 biased upward, the latched portion (projection portion) 32 becomes the latching portion (projection portion) of the shoulder cover 33. The slidable member 31 is slid into contact with the locking part 31. At this time, when the pressing on the push button 25 is released, the stem 23 biased upward presses the push button 25 upward, but the locked portion 32 of the push button 25 is the locking portion of the shoulder cover 33. It will be in the state latched by this latching | locking part 31 without getting over 31. FIG. As a result, the push button 25 is fixed, that is, when the push button 25 is pressed, the stem 23 is pressed, and the contents ejected from the stem 23 are ejected from the ejection port 26a of the ejection nozzle 26. It can be fixed at the injection position. Thus, since the push button 25 is fixed at the fixed position by the lock mechanism 30, the pressed state of the stem 23 is maintained. Thus, the injection is continued until the content stored in the spray can 21 is exhausted while the valve mechanism of the spray can 21 is opened, and the injection is terminated when the gas pressure by the propellant disappears.

<Manufacture of all-injection aerosol device>
A method for manufacturing a full-amount-injection aerosol apparatus when the spatial treatment agent of the present invention is used as a full-injection aerosol will be described. (A) A component, (B) component, a solvent, and various additives are mixed and a chemical | medical solution is prepared. The obtained chemical solution is put into a total amount sprayed aerosol container and further filled with the component (C2) to obtain a space treating agent. For example, when dimethyl ether is used as the propellant, it is preferable that the total amount of the spray aerosol is filled so that the internal pressure of the container is 0.3 to 0.6 MPa at 25 ° C., and is 0.4 to 0.5 MPa. More preferably, the filling is performed.

<How to use>
The space treatment method is not particularly limited, and conventionally known methods such as smoke treatment using a smoke device and spray treatment using a full-amount spray aerosol device can be used depending on the dosage form of the space treatment agent.
For example, as a method of using the space treatment agent as a smoke agent, a method similar to a general method of using a smoke agent can be used. Specifically, the space treatment agent is accommodated in an arbitrary container such as a metal container or a ceramic container, and the space treatment agent is used indirectly or directly heated.
Examples of the method of indirectly heating include a method in which a space treatment agent is accommodated in a metal container and the smoke agent is heated through the metal container.
As a heating method, a conventionally known method can be used, for example, a method of contacting a substance that generates heat upon contact with water and using the reaction heat; iron powder and an oxidizing agent (such as ammonium chlorate). Or a metal oxide or an oxidant having a smaller ionization tendency than the metal and utilizing the heat of oxidation reaction. Among these, from the viewpoint of practicality, a method of contacting a substance that generates heat upon contact with water with water and utilizing the reaction heat is preferable. Examples of substances that generate heat upon contact with water include calcium oxide, magnesium chloride, aluminum chloride, calcium chloride, and iron chloride. Of these, calcium oxide is preferred.
As a method of directly heating, using a match head or the like, a heating element (ignition tool) is ignited to directly heat a part of the space treatment agent, and then the organic foaming agent in the space treatment agent is heated. For example, a method using heat generated by pyrolysis can be used.

On the other hand, as a method of using the space treating agent as the total amount spray aerosol, a method similar to a general method of using the total amount spray aerosol can be used. Specifically, a component other than the component (C2) is mixed to prepare a chemical solution, the chemical solution and the component (C2) are filled into an arbitrary pressure resistant container, and an almost total amount of the contents of the container is removed by an optional injection means. Use by spraying outside the container with a single operation (opening the valve, etc.).

What is necessary is just to determine suitably the usage-amount of the space treating agent of this invention in the case of space processing according to a dosage form, the breadth of space, etc.
In the present invention, the space treating agent of the present invention is particularly preferably used in an amount of 0.03 mg or more in terms of silver concentration per 1 m ^{3 of} space, and more preferably in an amount of 0.25 to 3 mg. .

<Effect>
Since the spatial treatment agent of the present invention described above is a self-injection type, the component (A) reaches a treatment surface that is difficult to reach, such as a bathroom ceiling or a high part of the wall surface, and is excellent. Anti-mold effect is demonstrated.
In addition, since the spatial treatment agent of the present invention contains the component (A) and the component (B) described above, the component (A) tends to adhere to the treated surface. Therefore, even in places where water flows frequently, such as bathroom walls, the component (A) adhering to the treated surface is difficult to flow with water, and the fungicidal effect can be maintained.
The following can be considered as the reason why the above-mentioned effect is obtained. That is, the liquid droplets containing the component (A) and the component (B) are moderately thickened, adhere well to the treated surface, do not easily flow down from the treated surface even after adhering, and are not easily washed away even when splashed with water. Since it is easy to stay in place, it is thought that the mold prevention effect can be sustained.

The space treatment agent of the present invention is used for the treatment of a sealable space that is required to suppress microorganisms such as bacteria and fungi.
The treatment target of the space treating agent of the present invention is not particularly limited as long as it can be sealed, and examples thereof include a bathroom, a washroom, a kitchen, a toilet, a living room, and a closet.
From the viewpoint of the usefulness of the present invention, the space treating agent of the present invention is particularly suitable for bathroom mold prevention.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples.

[Raw materials]
As the component (A), the following compounds were used.
A-1: Silver-supported zeolite-based inorganic antibacterial agent (“Zeomic AJ10N” manufactured by Sinanen Zeomic Co., Ltd., volume average particle diameter 2.5 μm, true specific gravity 2 g / cm ³ (20 ° C.), bulk specific gravity 0.4 g / cm ³ (20 ° C., silver content 2.5 mass%)
A-2: Silver-supported silica-alumina inorganic antibacterial agent (manufactured by JGC Catalysts & Chemicals, "ATOMY BALL- (UA)", volume average particle size 15 nm, silver content 0.07% by mass)
A-3: Silver-supported silicate inorganic antibacterial agent (manufactured by JGC Catalysts & Chemicals, “AIS-NAZ320”, volume average particle diameter 2 μm, silver content 1.2% by mass)
A-4: Water-soluble silver antibacterial agent (manufactured by J-Chemical Co., Ltd., “CF-01”, silver oxide as water-soluble silver, silver content 2.5 mass%)

As the component (B), the following compounds were used.
B-1: HO— (PO) ₁₄ — (EO) ₂₄ — (PO) ₁₄ —H
B-2: HO— (PO) ₂₀ — (EO) ₁₈ — (PO) ₂₀ —H
B-3: HO— (EO) ₁₅ — (PO) ₃₀ — (EO) ₁₅ —H
B-4: HO— (EO) ₈₀ — (PO) ₅₀ — (EO) ₈₀ —H

Synthesis method of B-1:
Propylene glycol (1 mol) and a catalytic amount of potassium hydroxide were charged into an autoclave, the inside of the autoclave was replaced with nitrogen, and dehydration was performed under reduced pressure.
Next, while maintaining the temperature in the autoclave at 120 ° C. and the pressure at 0.3 MPa or less, propylene oxide (14 mol) was introduced and reacted while stirring to obtain a PO adduct (first stage).
Subsequently, while maintaining the temperature in the autoclave at 150 ° C. and the pressure at 0.3 MPa or less, ethylene oxide (24 mol) was introduced and reacted while stirring to obtain a PO-EO adduct (second stage).
Subsequently, while maintaining the temperature in the autoclave at 120 ° C. and the pressure at 0.3 MPa or less, propylene oxide (14 mol) was introduced and reacted with stirring (third stage), then cooled, and acetic acid was used. The pH was adjusted to 6 to 8 to obtain B-1.
The mass average molecular weight of B-1 obtained was measured by GPC and found to be 2800.

Synthesis method of B-2:
B-1 except that the molar amount of propylene oxide used in the first step was changed to 20 mol, the molar amount of ethylene oxide used in the second step was changed to 18 mol, and the molar amount of propylene oxide used in the third step was changed to 20 mol. Similarly, B-2 was obtained.
The mass average molecular weight of B-2 obtained was measured by GPC and found to be 3350.

Synthesis method of B-3:
Instead of propylene oxide (14 mol) in the first step, ethylene oxide (15 mol) is used in the second step, propylene oxide (30 mol) is used instead of ethylene oxide (24 mol), and propylene oxide in the third step. B-3 was obtained in the same manner as B-1, except that ethylene oxide (15 mol) was used instead of oxide (14 mol).
The mass average molecular weight of the obtained B-3 was measured by GPC and found to be 2900.

Synthesis method of B-4:
Instead of propylene oxide (14 mol) in the first stage, ethylene oxide (80 mol) is used, in the second stage, propylene oxide (50 mol) is used instead of ethylene oxide (24 mol), and in the third stage B-4 was obtained in the same manner as B-1, except that ethylene oxide (80 mol) was used instead of oxide (14 mol).
The mass average molecular weight of the obtained B-4 was measured by GPC and found to be 10,000.

As a comparative product of the component (B) (component (B ′)), the following compounds were used.
-B'-1: Polyethylene glycol (manufactured by Lion Corporation, "PEG # 6000", mass average molecular weight: 6000)
B′-2: polyvinyl alcohol (manufactured by Kanto Chemical Co., Ltd., mass average molecular weight: 22000)
B′-3: polyacrylic acid sodium salt (manufactured by Nippon Shokubai Co., Ltd., “Aquaclick YS100”, mass average molecular weight: 2800)
B′-4: C ₁₈ H ₃₇ —O— (PO) ₆ — (EO) ₂₈ — (PO) ₂ —H (manufactured by Lion Corporation, “FP-7800E”, mass average molecular weight: 2200)

As the component (C1) and the component (C2), the following compounds were used.
C1-1: Azodicarbonamide (manufactured by Dainichi Seika Kogyo Co., Ltd., “Dieblow AC.2040 (C)”)
C1-2: Nitrocellulose (manufactured by TN C. INDUSTRIAL CO., LTD., “TV cotton”)
・ C2-1: Dimethyl ether (Mitsubishi Gas Chemical Co., Ltd.)

The following compounds were used as solvents and optional components.
EtOH: Ethanol (special reagent grade, manufactured by Junsei Chemical Co., Ltd.)
ZnO: Zinc oxide (Japanese Pharmacopoeia Zinc Oxide, Sakai Chemical Industry Co., Ltd., average particle size 0.6 μm, true specific gravity 5.6 g / cm ³ (20 ° C.))
HPMC: Hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., “Metroze 60SH-50”)
Clay: “NK-300” SiO ₂ 75% by mass, Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O 25%, average particle size 10 μm, manufactured by Showa KDE Co., Ltd.

[Evaluation]
<Evaluation of sustainability of mold prevention effect>
First, as shown in FIG. 4, in the center of the ceiling surface of the evaluation room (height from the floor surface to the ceiling surface: about 2 m) 40 having the same volume as the 1818 type (for the meter module) bathroom, Two slide glasses (Matsunami Glass Industrial Co., Ltd., white edge polishing No. 2, 76 × 26 mm) 41 and 42 were mounted side by side.
Next, the device (smoke device or full-amount aerosol injection type device) 43 produced in each example was placed on the central floor surface of the evaluation chamber 40, and the contents were injected (injection process).
90 minutes after the start of jetting of the contents, the air in the evaluation chamber 40 was exhausted, and the two

slide glasses

41 and 42 were collected.
Place one of the collected

slide glasses

41 and 42 into a 1L beaker containing about 1L of tap water (amount that the entire slide glass is immersed) and a stirrer, and remove it after water treatment for 1 minute while stirring the stirrer at 500 rpm. And dried at room temperature. This is based on the assumption that water is applied to the floor and wall treatment surfaces after spraying in a bathroom in a real home.
Of the collected slide glasses, the water-treated slide glass is referred to as “slide glass (SG1)”, and the slide glass not subjected to water treatment is referred to as “slide glass (SG2)”. Further, an untreated slide glass that has not been sprayed is referred to as “slide glass (SG3)”.

Next, Cladosporium cladosporoides HMC1064 (bathroom isolate) cultured at 25 ° C. for 1 week on a potato dextrose agar medium (manufactured by Difco) and a potato dextrose liquid medium diluted to 50% and sterilized. A spore solution of 10 ² CFU / mL was prepared.
0.1 mL of the spore solution was inoculated on the slide glass (SG1), the slide glass (SG2), and the slide glass (SG3).
Films cut into 20 mm x 20 mm on slide glass (SG1), slide glass (SG2), and slide glass (SG3) inoculated with spore solution (JIS Z 2801 (antibacterial test method / antibacterial effect of antibacterial processed products)) The film described above was covered so as to cover the spore solution, and cultured for 7 days at 25 ° C. and a relative humidity of 98% or more.
After culturing, all the bacteria on the slide glass are recovered from the slide glass (SG1), slide glass (SG2), and slide glass (SG3), and appropriately diluted with physiological saline so as to obtain a measurable concentration. After smearing the potato dextrose agar medium and culturing at 25 ° C. for 5 days, the number of colonies formed was counted visually. Under this condition, the number of viable bacteria recovered from the cultured slide glass (SG3) is 1 × 10 ⁴ to 9 × 10 ⁴ CFU.
The viable cell count (CFU / slide glass (SG)) of the slide glass (SG1), slide glass (SG2), and slide glass (SG3) was determined from the counted number of colonies and the dilution ratio of the bacterial solution. From the change in the viable cell count of the slide glass (SG1) and the slide glass (SG2), the sustainability of the fungicidal effect when water was applied was evaluated.

(Evaluation criteria)
Viable count of slide glass (SG1) (SG1 viable count), viable count of slide glass (SG2) (SG2 viable count), viable count of untreated slide glass (SG3) (SG3 viable count) From these values, the sustainability of the antifungal effect was calculated using the following formulas (1) to (3), and the sustainability of the antifungal effect was determined from the value according to the following criteria. The higher the antifungal effect, the better the antifungal effect does not decrease even when treated with tap water.
Mold prevention rate after water treatment (%) = {1- (SG1 viable count / SG3 viable count)} × 100 (1)
Mold prevention rate without water treatment (%) = {1- (SG2 viable count / SG3 viable count)} × 100 (2)
Percentage of mold prevention effect (%) = {(mold prevention ratio after water treatment / mold prevention ratio without water treatment)} × 100 (3)

<Criteria>
◎◎: The antifungal effect lasts 80% or more.
A: The antifungal effect has a duration of 65% or more and less than 80%.
○: Sustainability of the antifungal effect is 50% or more and less than 65%.
(Triangle | delta): The sustainability rate of a mold prevention effect is 35% or more and less than 50%.
X: The antifungal effect persistence is less than 35%.

<Evaluation of fungicidal effect>
First, as shown in FIG. 5, in the center of the ceiling surface of the evaluation room (height from the floor surface to the ceiling surface: about 2 m) 50 having approximately the same volume as the 1818 type (for the meter module) bathroom, A test slide glass (slide glass inoculated with bacteria) 51 prepared by the following method ^{* 1} was attached with the surface inoculated with the bacteria facing the floor side.
Next, the device (smoke device or full-amount aerosol injection type device) 53 produced in each example was placed on the central floor surface of the evaluation chamber 50, and the contents were injected (injection process).
Ninety minutes after the start of injection of the contents, the air in the evaluation chamber 20 was exhausted, and the test slide glass 51 was collected.
All the bacteria on the test slide glass 51 are collected, and the collected bacteria are appropriately diluted with physiological saline so as to have a measurable concentration, and then smeared on a potato dextrose agar medium at 25 ° C. After culturing for 5 days, the number of colonies formed was counted visually. The number of viable bacteria was determined from the measured number of colonies and the dilution rate of the bacterial solution, and the value was defined as the “number of bacteria after treatment”.
Separately, collect all the bacteria on the untreated specimen slide glass that has not been sprayed, and appropriately dilute the collected bacteria with physiological saline to a measurable concentration in potato dextrose agar medium. After smearing and inoculating at 25 ° C. for 5 days, the number of colonies formed was counted visually. The number of viable bacteria was determined from the measured number of colonies and the dilution rate of the bacterial solution, and the value was defined as “the number of untreated bacteria”.
From the above results, the fungicidal effect was evaluated according to the following evaluation criteria.

(* 1: Method for producing test slide glass)
Poma sp. Cultivated on a potato dextrose agar medium (manufactured by Difco) at 25 ° C. for 1 week. About 10 ⁶ CFU / mL spore solution was prepared using (bathroom isolate) and a sterilized 0.05% Tween 80 (manufactured by Kanto Chemical Co., Ltd.) aqueous solution. Next, 0.1 mL of the spore solution was inoculated into a slide glass (manufactured by Matsunami Glass Industrial Co., Ltd., white edge polishing No. 2, 76 × 26 mm), left to stand overnight at room temperature, and then dried and fixed.

(Evaluation criteria)
For the slide glass installed in the center of the ceiling surface, the calculated number of bacteria is converted into the common logarithm (log), and the value obtained by subtracting the number of treated bacteria from the number of untreated bacteria (log (untreated bacteria number) -log (The number of bacteria after treatment)) was determined, and the value was defined as the fungicidal effect. From that value, the fungicidal effect was determined according to the following criteria.
<Criteria>
A: The fungicidal effect is 4 or more.
○: The fungicidal efficacy is 2 or more and less than 4.
Δ: The fungicidal efficacy is 1 or more and less than 2.
X: The fungicidal efficacy is less than 1.

[Examples 1 to 18, Comparative Examples 1 to 6]
<Manufacture of space treatment agent>
Spatial treatment agents having the compositions shown in Tables 1 to 3 were produced by the following procedure. The unit of the blending amount of each component in Tables 1 to 3 is mass%. (A) The quantity of a component is a ratio (mass%) of the mass of silver in the space treating agent with respect to the total mass of a space treating agent. The “balance” of clay is an amount such that the total mass of the space treating agent is 100% by mass.
Under room temperature (20 ° C.) conditions, each component was stirred and mixed with a kneader (manufactured by Moriyama Co., Ltd., “S5-2G type”) according to the composition shown in Tables 1 to 3, and then 10 parts by mass with a total composition of 100 parts by mass. Part of water was added and mixed to obtain a mixture. The obtained mixture was granulated using a die pre-extruding granulator having a diameter of 2 mm ("EXK-1" manufactured by Fuji Powder Co., Ltd.) to obtain a granulated product. The resulting granulated product was cut to a length of 2 to 5 mm with a flash mill (Fuji Paudal Co., Ltd., “FL300”) and set at 70 ° C. (Alp Co., Ltd., “RT-120HL”) Was dried for 2 hours to obtain a granular space treating agent.

<Production of smoke device>
Using the obtained space treatment agent as a smoke agent, a smoke device was produced as follows.
Prepare a “Look Bath Mold Smoke Agent” (manufactured by Lion Co., Ltd.), store 5 g of the space treatment agent in the smoke container inside the container, and then store it in the heating agent storage part in the container. 37 g of calcium oxide was accommodated to produce a smoke device.
Using the obtained smoke device, the sustainability of the antifungal effect and the fungicidal effect were evaluated. The results are shown in Tables 1 to 3. In addition, when evaluating, the plastic container for water supply which put 23 mL of water was installed, the smoke apparatus was put in the plastic container, and the smoke was started.

[Example 19]
<Fabrication of all aerosol spray type device>
A full-amount aerosol injection type apparatus filled with a space treating agent having the composition shown in Table 2 was prepared by the following procedure. The unit of the blending amount of each component in Table 2 is mass%. (A) The quantity of a component is a ratio (mass%) of the mass of silver in the space treating agent with respect to the total mass of a space treating agent. The “balance” of ethanol is such an amount that the total mass of the space treating agent becomes 100% by mass.
(A) component, (B) component, and ethanol were mixed so that it might become a composition shown in Table 2, and the chemical | medical solution was prepared. Put the resulting chemical into a spray can equipped with a valve mechanism ("Valsan Pro EX Non-Smoke Fog Type (for 6-10 tatami mats)" (Lion Co., Ltd.) container). After sealing, a nozzle cap was attached to produce a full-amount aerosol spray type device. The total amount of contents used for filling the spray can was adjusted to 15 g.
Using the obtained aerosol injection type device, the sustainability of the antifungal effect and the fungicidal effect were evaluated. The results are shown in Table 2.

As is clear from Tables 1 and 2, each of the spatial treatment agents of each Example had a high antifungal effect and a good fungicidal effect. From these results, it is shown that the spatial treatment agent of each example has a sustaining rate of the mold prevention effect of 60% or more, and can maintain the mold prevention effect even in a place where water frequently flows in the bathroom. It was done.

On the other hand, as apparent from Table 3, the spatial treatment agent of Comparative Example 1 containing no component (A) had a low fungicidal effect and did not exhibit the fungicidal effect. Moreover, the space treatment agent of Comparative Example 2 that does not contain the component (B) had an antifungal effect sustained rate of 25%, and the antifungal effect sustained rate was insufficient. Also, the fungicidal effect was low.
The spatial treatment agents of Comparative Examples 3 to 6 containing any of B′-1 to B′-4 instead of the component (B) have a mold prevention effect of 30%, and the mold prevention effect is sustained. The rate was insufficient. Moreover, the fungicidal effect was low as compared with each Example.

According to the present invention, it is possible to provide a self-injecting space treatment agent having a high antifungal effect. Therefore, the present invention can be suitably used as a self-injecting space treatment agent and is extremely important in industry.

DESCRIPTION OF SYMBOLS 10: Smoke apparatus 11: Housing | casing 12: Heating part 13: Smoke agent 14: Main body 15: Bottom part 16: Lid part 17: Smoke agent accommodating part 20: Total amount injection aerosol container 21: Spray can 22: Nozzle cap 23 : Stem 24: Cap body 25: Push button 26: Injection nozzle 26a: Injection steel 27: Operation part 28: Fitting part 29: Flow path 30: Lock mechanism 31: Locking part 32: Locked part 33: Shoulder cover 40: Evaluation room 41: Slide glass 42: Slide glass 43: Apparatus 50: Evaluation room 51: Test glass slide 53: Apparatus

Claims

(A) component: silver, a silver compound, or a support of silver or a silver compound;
(B) component: The self-injection-type space treating agent containing the compound represented by the following general formula (I).
R 1 —O— (AO) x —R 2 (I)
(In the formula (I), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, AO represents an oxyalkylene group, and the AO represents an oxyethylene group; And at least one of an oxypropylene group and an oxybutylene group, and x is a number of 20 to 500.)
The self-injecting space treating agent according to claim 1, wherein the AO contains an oxyethylene group and an oxypropylene group.
The self-injecting space treating agent according to claim 1 or 2, wherein the AO is a triblock type in which an oxyethylene group is sandwiched between oxypropylene groups.
The compound represented by the general formula (I) is R 1 —O— (PO) f — (EO) g — (PO) h —R 2 (iii)
The self-injecting space treating agent according to claim 3.
(In the formula (iii), f is 5 to 150, g is 5 to 250, h is 5 to 150, and f + g + h = x.)
The self-injection section treating agent according to any one of claims 1 to 4, wherein R 1 and R 2 of the compound represented by the general formula (I) are hydrogen atoms.
(C1) component: The self-injecting space treating agent according to any one of claims 1 to 5, further comprising an organic foaming agent.
The self-injecting space treating agent according to claim 6, wherein the mass ratio represented by (B) component / (C1) component is 0.01 to 0.5.
(C2) component: The self-injecting space treating agent according to any one of claims 1 to 5, further comprising a propellant.
The self-injecting space treating agent according to claim 8, wherein a mass ratio represented by (B) component / (C2) component is 0.01 to 0.25.