KR20170109575A - Residential space treatment agent for piezo sprayer - Google Patents

Abstract

(A): an inorganic chemical containing a transition metal; (B) a component: an organic solvent having a boiling point of 70 ° C or higher and lower than 150 ° C; (C) a component of a boiling point (B) / (C) is 0.1 to 1.0, wherein the mass ratio of the component (B) to the component (C) is from 0.1 to 1.0.

Description

Residential space treatment agent for piezo sprayer

The present invention relates to a living space treatment agent for a piezo atomizer.

The present application claims priority based on Japanese Patent Application No. 2015-019350 filed on February 3, 2015, the contents of which are incorporated herein by reference.

It is difficult to clean by a spray type chlorine-based fungicide, and it is a place where microorganisms such as bacteria and fungi can easily breed.

Further, in a residence space, microorganisms are likely to multiply in various places other than the vicinity of water such as a bathroom (for example, an entrance hall, a window sash, a hook, a closet, etc.). However, in such a place, the detergent can not be easily rinsed with water, so it is difficult to clean with a chlorine-based fungicide.

In addition, since microorganisms propagate in various places, it is insufficient as a fungicidal effect in locally responding only to wiping a sterilization spray and the like, and is also poor in use.

Therefore, there is a demand for a method of easily maintaining a clean space by removing microorganisms in various places in these residence spaces and preventing reproduction.

To this demand, a fuming type antifungal agent has been proposed as a method for easily spraying an inorganic agent (antibacterial agent) such as silver, which has a high antifungal effect, on the entire space.

However, recently, there is also a demand for a method of preventing fungi in order to suppress the amount of smoke or to prevent smoke from taking into consideration the use in various places in the residential space.

Thus, a method of spraying a chemical solution into a space by a piezo-type atomizer has been proposed. A piezo-type atomizer is a device that atomizes a chemical liquid by ultrasonic vibration using a piezo (piezoelectric) element, and is easier to use than a manual spray type, and can further make a chemical liquid more atomized. In addition, the piezo type atomizer has a smaller amount of smoke than the heating and vaporization type atomizer.

As a spatial treatment agent using a piezo sprayer, for example, Patent Document 1 discloses a piezo sprayer chemical solution containing an organic medicine such as transfluthrin as a pest control agent and an organic solvent having a boiling point of 150 to 250 占 폚.

Patent Document 2 discloses a pest repellent method in which a pesticide component and a pesticide solution containing an organic solvent such as an ethylene glycol solvent or a propylene glycol solvent are evaporated in a space using a piezo sprayer.

Patent Document 3 discloses a method of spraying a deodorant / aromatic agent, which is obtained by immersing or dispersing a carrier having an orientation component and a metal ion supported on an ethylene vinyl acetate copolymer in an aqueous solvent having a boiling point of less than 200 占 폚, using an ultrasonic atomizer have.

Japanese Patent Application Laid-Open No. 2007-70349 Japanese Patent Application Laid-Open No. 2009-143868 Japanese Patent Application Laid-Open No. 2009-165686

However, when an inorganic agent such as silver is sprayed as an active ingredient with a piezo-type atomizer, the technique described in Patent Documents 1 and 2 has a poor vaporization property of an inorganic agent and can not sufficiently exhibit a mold prevention effect. In addition, there was a problem in the persistence of the antifungal effect.

In addition, the technique described in Patent Document 3 poses an effect on the direction of space and deodorization, but there is a problem in the vaporization property of the inorganic chemical agent and the persistence of the mold prevention effect.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a residential space treating agent for a piezo sprayer which is excellent in the volatility of an inorganic chemical agent and has a high persistence of a mold prevention effect.

As a result of intensive investigations, the inventors of the present invention have found that the use of two kinds of organic solvents having different boiling points at a specific ratio improves the volatility and diffusibility of the inorganic agent, and furthermore, the inorganic agent sufficiently adheres to the object surface, The present invention has been completed.

That is, the present invention has the following aspects.

(1) A living space treatment agent for a piezo-electric atomizer having a mass ratio of the component (A), the component (B), and the component (C) .

(A) Component: an inorganic agent containing a transition metal

(B): Organic solvent having a boiling point of 70 ° C or more and less than 150 ° C

(C): an organic solvent having a boiling point of 150 ° C or more and less than 250 ° C

[2] The method according to [1]

A living space treatment agent for a piezo sprayer further comprising the following component (D).

(D) Component: Nonionic surfactant

[3] The method according to [2]

Wherein the component (D) comprises at least one nonionic surfactant having an HLB of 2 or more and less than 16.

[4] The method according to [2] or [3]

(C) / (D), wherein the weight ratio of the component (C) to the component (D) is 10 to 700.

[5] The method according to any one of [1] to [4]

Wherein the component (A) is at least one member selected from the group consisting of silver, zinc, copper, and a compound thereof.

[6] The method according to any one of [1] to [5]

Wherein the component (B) is at least one member selected from the group consisting of ethanol, 2-propanol, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and propylene glycol monoisopropyl ether At least one kind selected from the group consisting of the following.

[7] The method according to any one of [1] to [6]

Wherein the component (C) is at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol, At least one kind of piezo-electric atomizer.

[8] The method according to [3]

Wherein the nonionic surfactant having an HLB of 2 or more and less than 16 is selected from the group consisting of sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acids, sucrose fatty acid esters, ethylene glycol fatty acid esters, propylene glycol fatty acid esters, glycerin alkyl ethers, Oxyethylene-sorbitan fatty acid esters, polyoxyethylene-glycerin fatty acid esters, polyoxyethylene-propylene glycol fatty acid esters, polyoxyethylene-alkyl ethers, polyoxyethylene-polyoxypropylene-alkyl ethers, alkanolamides Wherein the at least one species is selected from the group consisting of:

[9] The method according to any one of [2] to [4] and [8]

 Wherein the content of the component (D) is 0.1 to 3.0 mass% with respect to the total mass of the residence space treating agent.

[10] The method according to [3] or [8]

 Wherein the content of the nonionic surfactant having an HLB of 2 or more and less than 16 is 60 to 100 mass% with respect to the total mass of the component (D).

[11] The method according to any one of [1] to [10]

Wherein the content of the component (A) is 0.001 to 1.0% by mass relative to the total mass of the residence space treating agent as a single amount of the transition metal.

[12] The method according to any one of [1] to [11]

Wherein the content of the component (B) is 10 to 50 mass% with respect to the total mass of the residence space treating agent.

[13] The method according to any one of [1] to [12]

 Wherein the content of the component (C) is 45 to 80 mass% with respect to the total mass of the residence space treating agent.

[14] A method of treating a residential space in which a residence space treating agent for a piezo sprayer described in any one of [1] to [13] is filled in a piezo sprayer and sprayed into a residential space.

[15] A container for a living body according to any one of the above [1] to [13], wherein the container comprises a container accommodating space treating agent for a piezo-electric atomizer, a rod-shaped absorption axis provided in the container, an ultrasonic vibrator, and an ultrasonic oscillator Wherein the upper end of the absorption liquid core protrudes from the upper opening of the container and is directly or indirectly connected to the ultrasonic vibrator and the lower end of the absorption liquid is immersed in the living space treatment agent in the container.

[16] A method of treating a living space using a piezo-electric atomizing device as set forth in [15], comprising the steps of: absorbing a living space treating agent to an upper end of the absorbing core; and ultrasonic vibrating the ultrasonic vibrator, Wherein the living space treatment agent is sprayed into the air from the absorption liquid.

(Effects of the Invention)

According to the present invention, it is possible to provide a residential space treating agent for a piezo sprayer which is excellent in the volatility of an inorganic chemical agent and has a high persistence of mold prevention effect.

1 is a cross-sectional view showing one embodiment of a piezo sprayer used in the present invention.
2 is a schematic view for explaining a method of evaluating the fungicidal effect in [Example].
Fig. 3 is a schematic view for explaining a method for evaluating the persistence of the antifungal effect in [Example]. Fig.

The present invention relates to a residential space treating agent for piezo-electric atomizers, which is excellent in the volatility of an inorganic chemical agent and has a high persistence of anti-bearish effect.

Another aspect of the present invention is an antifungal agent that is transferred to the inner wall of the space used in the residence space.

Another aspect of the present invention is a fungi propagation inhibitor electrodeposited on the inner wall of the space used in a residence space.

Another aspect of the present invention is a fungicide which is electrodeposited on the inner wall of the space used in a residence space.

Another aspect of the present invention is a bacterial growth inhibitor which is electrodeposited on the inner wall of the space used in a residence space.

Another aspect of the present invention is a disinfectant electrodeposited on the inner wall of the space used in a residence space.

(B) component: an organic solvent having a boiling point of 70 占 폚 or more and less than 150 占 폚; (C) a component having a boiling point of 150 占 폚 or more and 250 占 폚 or less; Deg.] C and the mass ratio of the component (B) / component (C) is 0.1 to 1.0, is injected into the residence space by filling the piezo sprayer with the organic solvent.

(B) component: an organic solvent having a boiling point of 70 占 폚 or more and less than 150 占 폚; (C) a component having a boiling point of 150 占 폚 or more and 250 占 폚 or less; (B) component / (C) component having a mass ratio of 0.1 to 1.0, and an ultrasonic oscillator and an ultrasonic oscillator provided in the container, Wherein the upper end of the absorption column is protruded from the upper opening of the container and is directly or indirectly connected to the ultrasonic vibrator and the lower end of the absorption column is immersed in the living space treatment agent in the container.

Another aspect of the present invention is a method for processing a residence space using the piezo spray apparatus.

In addition, in the present invention, " prevention of fungi " means prevention of propagation of fungi and prevention of propagation of microorganisms other than fungi (for example, bacteria). In addition, " prevention of fungi " includes reduction of microorganisms other than fungi and fungi (e.g., bacteria). Hereinafter, the reduction of microorganisms other than fungi or fungi is also referred to as " fungus sterilization ".

The boiling point is a value measured under a condition of 1 atm.

Hereinafter, one embodiment of the present invention will be described in detail.

(Hereinafter simply referred to as " space treatment agent ") of the present invention is a liquid composition containing components (A), (B) and (C) shown below. Also. The spatial treatment agent is preferably a liquid composition further containing the component (D) shown below.

It is also assumed that the total content of all components contained in the spatial treatment agent is 100% by mass.

≪ Component (A) >

(A) is an inorganic chemical containing a transition metal. By using the component (A), the antifungal effect is exhibited. By exhibiting the antifungal effect, it is possible to inhibit odors caused by the growth of microorganisms and also to exhibit a deodorizing effect.

Here, the " inorganic agent containing a transition metal " is a pharmaceutical agent containing at least one member selected from the group consisting of a transition metal and its compound (transition metal compound) as an active ingredient.

Examples of the group of transition metals include silver, zinc, copper, and nickel.

Examples of the transition metal compound include oxides of a transition metal, salts of a counter ion with a transition metal ion, and the like. Examples of salts include chloride salts, nitrate salts, sulfate salts, gluconate salts, sulfonate salts, carbonate salts, formate salts and acetate salts.

As the component (A), silver, zinc, copper or a compound thereof is preferable from the viewpoints of a mold prevention effect and a deodorizing effect, and silver or silver compounds are more preferable.

As the component (A), a single substance or a transition metal compound of a transition metal supported on a carrier (hereinafter also referred to as " carrier ") may be used.

Examples of the carrier include zeolite, silica-alumina, silica gel, low-molecular-weight glass, calcium phosphate, silicate and titanium oxide.

Examples of the carrier include zeolite-based inorganic antibacterial agents carrying a transition metal such as silver, silver oxide, silver nitrate, copper sulfate and zinc chloride, silica-alumina inorganic antibacterial agents, silica gel inorganic antibacterial agents, titanium oxide- , Silicate-based inorganic antibacterial agents, and the like. By using such a carrier as the component (A), it is possible to smoothen the treatment surface uniformly, and a stable mold prevention effect can be exhibited.

The form of the component (A) is not particularly limited, but can be determined in consideration of the width of the object space and the like. As the particle (A) becomes finer, the effect of the component (A) can be sufficiently exerted and it spreads to the wide area. On the other hand, if the particles of the component (A) are too small, it becomes difficult to fall after being diffused, and it takes time to develop the effect of the component (A) under the object space.

For example, when the component (A) is supported, the volume average particle diameter of the component (A) is preferably 0.01 to 10 탆, more preferably 0.01 to 1 탆, and even more preferably 0.01 to 0.1 탆.

The volume average particle diameter refers to a value obtained by a laser diffraction / scattering type particle size distribution measuring apparatus and can be measured as follows. (A) is dispersed in distilled water so as to have a solid content of 1% by mass and used as a sample. This sample is put into a laser diffraction / scattering type particle size distribution measuring apparatus, dispersed by an ultrasonic wave in the apparatus, and then a laser is irradiated 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 component (A) may be used alone or in combination of two or more. The content of the component (A) in the spatial treatment agent is determined depending on the kind of the active ingredient in the component (A), the concentration of the active ingredient, and the function required for the spatial treatment agent.

The content of the component (A) is preferably 0.001 to 1.0% by mass, more preferably 0.05 to 0.1% by mass, based on the total mass of the spatial treating agent, When the content of the component (A) is 0.001% by mass or more, a mold prevention effect is sufficiently obtained. On the other hand, if the content of the component (A) exceeds 1.0% by mass, improvement in the effect can not be expected.

When the component (A) is supported, the content of the component (A) is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass based on the total mass of the spatial treatment agent as the carrier. When the content of the component (A) is 0.01 mass% or more, a mold prevention effect is sufficiently obtained. On the other hand, when the content of the component (A) is 5% by mass or less, it is possible to suppress the lowering of the atomizing force due to the clogging of the piezo atomizer.

≪ Component (B) >

(B) is an organic solvent having a boiling point of 70 ° C or more and less than 150 ° C. By using the component (B), the vaporization and diffusibility of the component (A) when the piezo-electric atomizer is used can be improved, and a uniform antifungal effect can be exhibited throughout the processing space. If the boiling point of the component (B) is less than 70 캜, the component (B) spontaneously evaporates, the concentration of the spatial treatment agent becomes excessively high, clogging of the piezo sprayer tends to occur, and the continuous atomizing force may deteriorate.

The boiling point of the organic solvent in the component (B) is preferably 75 占 폚 or higher, and more preferably 120 占 폚 or lower.

Examples of the component (B) include ethanol, 2-propanol, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoisopropyl ether And the like. Of these, ethanol is preferred.

The component (B) may be used alone or in combination of two or more. When two or more solvents are used in combination, the boiling points of the respective organic solvents used as the component (B) are respectively set to 70 占 폚 or more and less than 150 占 폚.

The content of the component (B) in the spatial treatment agent is preferably 10 to 50 mass%, more preferably 10 to 30 mass%, based on the total mass of the spatial treatment agent. When the content of the component (B) is within the above range, the component (A) has better vaporization and diffusibility, and the mold prevention effect is further enhanced. Particularly, when the content of the component (B) is 10 mass% or more, the component (A) has better vaporization and diffusibility. On the other hand, if the content of the component (B) is 50 mass% or less, the adhesion of the component (A) to the object surface such as a ceiling or a wall can be maintained satisfactorily and the persistence of the antifungal effect is further enhanced.

≪ Component (C) >

(C) is an organic solvent having a boiling point of 150 ° C or more and less than 250 ° C. By using the component (C), the dispersibility of the component (A) in the spatial treatment agent is improved. Further, the adhesion and spreadability of the component (A) after spraying to the object surface is improved, and the mold prevention effect can be maintained uniformly throughout the processing space. If the boiling point of the component (C) exceeds 250 占 폚, the vaporization property and diffusibility of the component (A) deteriorate, and the mold prevention effect can not be sufficiently exhibited. In addition, there is a concern (for example, discoloration or the like) on the object surface when the component (C) is adhered to the object surface.

The boiling point of the organic solvent in the component (C) is preferably 160 ° C or higher, and more preferably 220 ° C or lower.

Examples of the component (C) include ethylene glycol, propylene glycol, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol, Hydrocarbons (specifically, "neothiazole" manufactured by Chuo Kasei Co., Ltd., "IP solvent" manufactured by Idemitsu Kosan Co., Ltd.), and the like. Of these, propylene glycol is preferred.

The component (C) may be used alone or in combination of two or more. When two or more solvents are used in combination, the boiling points of the respective organic solvents used as the component (C) are respectively set to be 150 ° C or more and less than 250 ° C.

The content of the component (C) in the spatial treatment agent is preferably 45 to 80 mass%, more preferably 50 to 75 mass%, based on the total mass of the spatial treatment agent. When the content of the component (C) is within the above range, the adhesion of the component (A) to the object surface becomes better, and the persistence of the antifungal effect is further enhanced. In particular, when the content of the component (C) is 45 mass% or more, the adhesion of the component (A) to the ceiling and the wall is further improved, and the persistence of the mold prevention effect is further enhanced. On the other hand, when the content of the component (C) is 80 mass% or less, the diffusibility of the component (A) can be well maintained.

The content of the component (C) in the spatial treatment agent is such that the mass ratio represented by the component (B) / (C) is 0.1 to 1.0, preferably 0.2 to 0.5. When the mass ratio is within the above range, the component (A) has improved hydratability and diffusibility. In addition, the adhesion and spreadability of the component (A) after spraying to the object surface is improved, and the persistence of the antifungal effect is enhanced. In particular, when the mass ratio is 0.1 or more, the component (A) is improved in the vaporization property and diffusibility by the component (B). Further, the component (A) is uniformly adhered to the object surface, and the mold prevention effect can be sufficiently exhibited. On the other hand, when the mass ratio is 1.0 or less, the adhesion of the component (A) to the object surface by the component (C) is improved, and the persistence of the antifungal effect is enhanced.

≪ Component (D) >

Component (D) is a nonionic surfactant. By using the component (D), the uniform spreadability of the component (A) on the object surface is further improved, the mold prevention effect (in particular, the mold sterilization effect) is further improved, and the persistence of the mold prevention effect is further enhanced.

(Hereinafter also referred to as "component (D1)") having a HLB of 2 or more and less than 16, a nonionic surfactant having an HLB of less than 2 (hereinafter, also referred to as "component (D2)") And a nonionic surfactant having an HLB of 16 or more (hereinafter, also referred to as " component (D3) "). Among these, the component (D1) is preferable in that the dispersibility of the component (A) in the spatial treatment agent is further improved.

Here, the HLB in the present application is represented by IOB x 10 in the organic conceptual diagram.

The IOB in the organic conceptual diagram refers to the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, the "inorganic value (IV) / organic value (OV)".

The above-mentioned organic conceptual concept is proposed by Atsushi Fujita and the details are described in "Pharmaceutical Bulletin", 1954, vol.2, 2, pp. 163-173, "Area of Chemistry", 1957, vol. 11, 10, pp. 719-725, " Fragrance Journal ", 1981, vol. 50, pp. 79-82. That is, all the organic compounds are assumed to be methane (CH ₄ ), all other compounds are regarded as derivatives of methane, and a certain numerical value is set for each of the carbon number, the substituent, the transformation part and the ring, And an inorganic value. Then, these values are plotted on the drawing where the organic value is the X-axis and the inorganic value is the Y-axis. This organic concept diagram is also shown in "Organic Conceptual Diagram - Fundamentals and Applications" (SANKYO SHUPPAN Co., Ltd., 1984).

The HLB of the component (D1) is 2 or more and less than 16, preferably 2 to 12, and more preferably 6 to 12. When the HLB is 2 or more, the uniform dispersibility of the component (A) in the spatial treatment agent is further improved, and the effect of preventing fungi on the entire treatment space such as a bathroom is further enhanced. On the other hand, even when the HLB is less than 16, the homogeneous dispersibility of the component (A) is further improved. Further, the persistence of the mold prevention effect in a high-humidity environment such as a bathroom is further enhanced.

Examples of the component (D1) include sorbitan fatty acid esters having an HLB of 2 to 16, glycerin fatty acid esters, polyglycerin fatty acids, sucrose fatty acid esters, ethylene glycol fatty acid esters, propylene glycol fatty acid esters, glycerin alkyl ethers , Polyoxyethylene (POE) -sorbitan fatty acid esters, POE-glycerin fatty acid esters, POE-propylene glycol fatty acid esters, POE-alkyl ethers, POE polyoxypropylene (POP) And the like.

Among them, fatty acid esters of polyhydric alcohols or ethylene oxide adducts thereof are preferable, and sorbitan fatty acid esters or polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters and ethylene glycol fatty acid esters which are liquid at room temperature are more preferable.

Examples of the sorbitan fatty acid ester include monooleic acid sorbitan and monolauric acid sorbitan. Examples of the glycerin fatty acid ester include monocaprylic acid glyceryl and monoisostearic acid glyceryl. Examples of the ethylene glycol fatty acid esters include ethylene glycol dilaurate and the like. These (D1) components may be used singly or in combination of two or more.

Examples of the component (D2) include cetyl caprylate, cetyl palmitoate, and stearyl stearate.

Examples of the component (D3) include polyoxyethylene (30EO) lauryl ether, polyoxyethylene (50EO) lauryl ether, and the like.

These (D2) and (D3) components may be used singly or in combination of two or more.

The component (D) may be used singly or in combination of two or more kinds.

The content of the component (D) in the spatial treatment agent is preferably 0.1 to 3.0 mass%, more preferably 0.5 to 2.0 mass%, based on the total mass of the spatial treatment agent. When the content of the component (D) is 0.1 mass% or more, the uniform dispersibility of the component (A) in the spatial treatment agent and the persistence of the antifungal effect are further improved. On the other hand, when the content of the component (D) is 3.0% by mass or less, clogging of the piezo-electric atomizer can be suppressed and more sufficient vaporization property can be obtained.

The content of the component (D1) in the component (D) is preferably 60 to 100 mass%, more preferably 80 to 100 mass%, based on the total mass of the component (D). When the content of the component (D1) is 60 mass% or more, the uniform dispersibility of the component (A) in the spatial treatment agent is further improved.

The content of the component (D) in the spatial treatment agent is preferably such that the mass ratio represented by the component (C) / (D) is from 10 to 800, more preferably from 10 to 700, To 200 is more preferable. When the mass ratio is within the above range, the component (A) has improved vaporization and diffusibility. In addition, the adhesion and spreadability of the component (A) after spraying on the object surface is improved, and the persistence of the antifungal effect is further enhanced. In particular, when the mass ratio is 10 or more, the component (A) has improved hydratability and diffusibility. Further, the component (A) is easily attached uniformly to the object surface, and the mold prevention effect can be sufficiently exhibited. On the other hand, if the mass ratio is less than 800, the adhesion of the component (A) to the object surface is improved, and the persistence of the antifungal effect is enhanced.

<Optional ingredients>

The spatial treatment agent may contain optional components such as water and perfume ingredients as long as the effect of the present invention is not impaired.

When the spatial treatment agent contains water, the content of water is preferably 0.1 to 10 mass% with respect to the total mass of the spatial treatment agent.

If the spatial treatment agent contains a perfume ingredient, it is possible to impart a perfume in use and masking the odor of the space treating agent.

The fragrance ingredient is not particularly limited, but a list of fragrance ingredients that can be used is described in various publications, for example, Perfume and Flavor Chemicals, Vol. I and II, Steffen Arctander, Allured Pub. (1994), &quot; Perfume and Flavor Materials of Natural Origin &quot;, Steffen Arctander, Allured Pub. &Lt; RTI ID = 0.0 & "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996), "Flower oils and products" Floral Compounds In Perfumery ", Danute Lajaujis Anonis, Allured Pub. Co. (1993).

<Manufacturing Method>

The spatial treatment agent can be produced, for example, by mixing the component (A), the component (B), the component (C), and optionally the component (D) and optional components.

<How to use>

The spatial treatment agent may be prepared by mixing the component (A), the component (B) and the component (C), and optionally the component (D) and optional components, and then filling the mixture into a piezo-electric atomizer.

The filling amount of the spatial treatment agent in the piezo sprayer is determined in consideration of the area of the object to be treated and the area of the treated surface (object surface), and for example, the amount of the component (A) The amount of the metal is preferably from 0.02 to 20 mg, more preferably from 0.2 to 5 mg.

The piezo type sprayer is not particularly limited, and conventionally known piezo type sprayers can be used.

Hereinafter, one embodiment of the piezo sprayer will be described with reference to Fig. However, the piezo-electric atomizer in the present invention is not limited to this embodiment, and the shape and the like of the container can be appropriately changed.

1 is a cross-sectional view showing an embodiment of a piezo sprayer.

The piezo-electric atomizer 10 of this embodiment includes a container 11 for containing the spatial treatment agent A, a rod-like absorption axis 12, an ultrasonic vibrator 13, and an ultrasonic oscillator 14. [

The absorbing core 12 has an upper end protruding from the upper opening of the container 11 and a lower end immersed in the spatial treatment agent A in the container 11, (Not shown). Further, the upper end of the absorption axis 12 is connected to the ultrasonic vibrator 13 through the joint piece 16.

As the material of the absorption core 12, a material having a large surface tension is preferable, and examples thereof include a sponge, a felt, a surface, and a porous material. Particularly, a porous material is preferable in that it exerts a liquid-absorbing function only when an ultrasonic wave is applied, and functions exclusively when ultrasonic waves are not applied. Among them, a molded article composed of a mixture of a carbonaceous fine powder and a binder is more preferable.

As the material of the joining piece 16, metal, ceramics and the like can be mentioned.

The material of the core support 15 is not particularly limited.

The ultrasonic oscillator 14 is connected to an ultrasonic oscillator 13 and a power source (not shown). Examples of the power source include a battery and the like.

A method of using the spatial treatment agent using the piezo sprayer 10 shown in Fig. 1 is as follows.

First, a predetermined amount of the spatial treatment agent A is contained in the vessel 11, and the spatial treatment agent A is sufficiently absorbed to the upper end of the absorption axis 12. In this state, the ultrasonic oscillator 14 is operated, a signal is sent from the ultrasonic oscillator 14 to the ultrasonic oscillator 13, and the ultrasonic oscillator 13 and the joint piece 16 are ultrasonically vibrated. Ultrasonic vibration energy higher than the surface tension of the spatial treatment agent A and higher than the viscosity of the surface treatment agent A is applied to the upper end of the absorption axis 12 to spray the space treatment agent A from the absorption axis 12 into the air.

The frequency of the ultrasonic oscillator 14 is preferably 30 to 500 kHz.

The spraying of the spatial treatment agent (A) may be continuous or intermittent spraying in which driving and stopping are alternately performed.

The liquid amount of the spatial treatment agent (A) sprayed by one driving operation is preferably 0.01 to 1 μL.

The upper end of the absorption axis 12 and the ultrasonic vibrator 13 may be in direct contact with each other without forming the joining piece 16 in the piezo sprayer 10 shown in Fig.

In addition, although the diffuser of the spatial treatment agent may be increased by using a blower, it is preferable to spray the spatial treatment agent without using an air blower from the viewpoint of suppressing power consumption.

As the piezo-electric atomizer, a commercially available product may be used, for example, OMRON HEALTHCARE Co., Ltd. &Quot; Mesh type nebulizer NE-U22 &quot;

As the piezo-electric atomizer, for example, a spray device described in JP-A-6-320083, JP-A-7-24374, and JP-A-7-256170 may be used.

&Lt; Action >

The above-described spatial treatment agent of the present invention sprayes the chemical solution (component (A)) into the space by means of the piezo-type sprayer, thereby suppressing the amount of smoke or eliminating microorganisms at various places in the living space, Can be prevented.

In addition, since the spatial treatment agent of the present invention contains the above-mentioned components (A), (B) and (C), the component (A) has better hydratability and diffusibility and uniform mold prevention Effect can be exhibited. Further, the adhesion and spreadability of the component (A) after spraying to the object surface is improved, and the mold prevention effect can be maintained uniformly throughout the processing space.

The spatial treatment agent of the present invention is used for treatment of a living space where it is required to inhibit microorganisms such as bacteria and fungi.

Examples of the object to be treated with the spatial treatment agent of the present invention include a bathroom, a washroom, a kitchen, a toilet, a porch, a living room, a window sash, a hook, a closet and the like.

From the viewpoint of the utility of the present invention, the spatial treatment agent of the present invention is particularly preferable for preventing mold.

(A), (B) and (C), wherein the mass ratio of the component (B) / component (C) is 0.1 to 1.0, (B) is 10 to 30% by mass with respect to the total mass of the residing space treating agent, and the content of the component is 0.05 to 0.1% by mass based on the total mass of the residing space treating agent, (C) is 50 to 75% by mass with respect to the total mass of the residence space treating agent.

Another aspect of the present invention is a curable composition comprising a component (A), a component (B), a component (C) and a component (D), wherein the mass ratio represented by the component (B) / , And the mass ratio of the component (C) / (D) is 30 to 200.

Another aspect of the present invention is a curable composition comprising a component (A), a component (B), a component (C) and a component (D), wherein the mass ratio represented by the component (B) / , And the mass ratio of the component (C) / (D) is 45 to 140.

Another aspect of the present invention is a curable composition comprising a component (A), a component (B), a component (C) and a component (D), wherein the mass ratio of the component (B) / , And the mass ratio of the component (C) / (D) is 10 to 700.

Another aspect of the present invention is a curable composition comprising a component (A), a component (B), a component (C) and a component (D), wherein the mass ratio of the component (B) / , And the mass ratio of the component (C) / (D) is 30 to 200.

Another aspect of the present invention is a curable composition comprising a component (A), a component (B), a component (C) and a component (D), wherein the mass ratio of the component (B) / , And the mass ratio of the component (C) / (D) is 45 to 140.

(A) Component: an inorganic agent containing a transition metal

(B): Organic solvent having a boiling point of 70 ° C or more and less than 150 ° C

(C): an organic solvent having a boiling point of 150 ° C or more and less than 250 ° C

(D) Component: Nonionic surfactant

One aspect of the present invention is a curable composition comprising a component (A '), a component (B') and a component (C '), wherein the mass ratio of the component (B' Is a residential space treatment agent.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B') and a component (C '), wherein the mass ratio of the component (B' Is a residential space treatment agent.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' It is a living space treating agent having a mass ratio of 0.1 to 1.0.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' Is a living space treating agent having a mass ratio of from 0.1 to 1.0 and a mass ratio of from (C ') to (D') of from 10 to 700.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' Is a living space treating agent having a mass ratio of from 0.1 to 1.0 and a mass ratio of from (C ') to (D') of from 30 to 200.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' Is a living space treating agent having a mass ratio of from 0.1 to 1.0 and a mass ratio of from (C ') to (D') of from 45 to 140.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' Is a living space treating agent having a mass ratio of from 0.2 to 0.5 and a mass ratio of from (C ') to (D') of from 10 to 700.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' Is a living space treating agent having a mass ratio of 0.2 to 0.5 and a mass ratio of 30 to 200 expressed by the component (C ') / (D').

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' And the mass ratio of the component (C ') / (D') is 45 to 140,

One aspect of the present invention is a curable composition comprising a component (A '), a component (B') and a component (C '), wherein the mass ratio of the component (B' , The content of the component (A ') is 0.001 to 1.0% by mass relative to the total mass of the residing space treating agent as the amount of the transition metal as a single component, and the content of the component (B' Is 10 to 50% by mass, and the content of the component (C ') is 45 to 80% by mass with respect to the total mass of the residence space treating agent.

One aspect of the present invention is a curable composition comprising a component (A '), a component (B'), a component (C ') and a component (D' (C ') / (D') is in the range of 10 to 700, and the content of the component (A ') is the amount of the transition metal in terms of a single unit, (B ') is 10 to 50 mass% with respect to the total mass of the residence space treating agent, and the content of the component (C') is in the range of 0.001 to 1.0 mass% (D ') is from 45 to 80 mass%, and the content of the component (D') is 0.1 to 3.0 mass% with respect to the total mass of the living space treating agent.

(A ') Component: silver or silver compound

Component (B '): at least one member selected from the group consisting of ethanol, propylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate

(C ') Component: at least one member selected from the group consisting of propylene glycol, diethylene glycol dimethyl ether, and triethylene glycol monomethyl ether

(D ') Component: sorbitan monooleate, sorbitan monolaurate, ethylene glycol dilaurate, polyoxyethylene sorbitan monooleate (ethylene oxide adduct of monooleic acid sorbitan), cetyl cetyl, poly At least one member selected from the group consisting of oxyethylene lauryl ether

<How to handle the living space>

The method for treating the dwelling space in the present invention is a method for spraying the above-described space treating agent of the present invention in a piezo-electric atomizer and spraying it in a residence space.

As the piezo-type atomizer, for example, the piezo-type atomizer 10 shown in Fig. 1 can be mentioned, but the present invention is not limited to this and a commercially available product may be used.

<Piezo atomizing device>

The piezo spraying apparatus of the present invention is, for example, one in which the space treatment agent (A) of the present invention is housed in the vessel 11 of the piezo sprayer 10 shown in Fig. That is, the piezo type atomizing apparatus comprises a container 11 containing the spatial treatment agent A of the present invention, a rod-shaped absorption axis 12 provided in the vessel 11, an ultrasonic vibrator 13, an ultrasonic oscillator 14).

The upper end of the absorbing core 12 protrudes from the upper opening of the container 11 and is directly or indirectly connected to the ultrasonic vibrator 13. The lower end of the absorbing core 12 is connected to the inside of the container 11 And is immersed in the spatial treatment agent (A).

In the method of treating a living space using the piezo-electric spraying apparatus, a spatial treatment agent is absorbed to the upper end of the absorption axis, and the ultrasonic vibrator is subjected to ultrasonic vibration to impart ultrasonic vibration energy to the upper end of the absorption axis, The living space is treated by spraying in air from the liquid core.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

[Materials used]

As the component (A), the following compounds were used.

A-1: Water-soluble silver (antioxidant) antibacterial agent (J-CHEMICAL, INC., "CF-01", silver content 2.5 mass%)

A-2: silver supported silica-alumina inorganic antibacterial agent (ATOMY BALL- (UA), volume average particle diameter 15 nm, silver content 0.075 mass%, carrier concentration 1.5 mass%, manufactured by JGC Corporation)

A-3: zinc gluconate 3H ₂ O (produced by FUSO CHEMICAL CO., LTD., "Hercules" Zn, zinc content 12.8% by mass)

(B) or a comparative product thereof as shown below.

B-1: Ethanol (reagent grade, manufactured by Junsei Chemical Co., Ltd., boiling point: 78.37 ° C)

B-2: Propylene glycol monomethyl ether ("HiSolve MP" manufactured by TOHO Chemical Industry Co., Ltd., boiling point 120 ° C.)

B-3: Ethylene glycol monomethyl ether acetate ("MC acetate" manufactured by TOHO Chemical Industry Co., Ltd., boiling point: 145 ° C)

B-4: n-heptane (boiling point: 36 DEG C)

As the component (C) or a comparative product thereof, the following compounds were used.

C-1: propylene glycol (reagent grade, manufactured by Junsei Chemical Co., Ltd., boiling point 188.2 占 폚)

C-2: diethylene glycol dimethyl ether ("HiSolve MDM" manufactured by TOHO Chemical Industry Co., Ltd., boiling point: 162 ° C)

C-3: triethylene glycol monomethyl ether ("HiMolTM" manufactured by TOHO Chemical Industry Co., Ltd., boiling point 249 ° C)

C-4: tetraethylene glycol dimethyl ether ("HiSolve MTEM", product of TOHO Chemical Industry Co., Ltd., boiling point 275 ° C.)

As the component (D), the following compounds were used.

· D1-1: sorbitan monooleate (manufactured by Kao Corporation, "EMERZOL O-10V", HLB9)

D1-2: Sorbitan monolaurate ("EMERZOL L-10V", manufactured by Kao Corporation, HLB12)

D1-3: Ethyleneglycol dilaurate ("EMALEX EG-di-L", HLB2, produced by NIHON EMULSION Co., Ltd.)

D1-4: sorbitan monooleate (ethylene oxide average 20 moles adduct) ("EMERZOL O-120V", manufactured by Kao Corporation, HLB14)

D2-1: capric acid cetyl (EMALEX CC-10, HLB1 from NIHON EMULSION Co., Ltd.)

D3-1: polyoxyethylene lauryl ether (ethylene oxide average 30 moles adduct) (manufactured by NIHON EMULSION Co., Ltd., "EMALEX730", HLB16)

Water and the perfume composition shown in Table 1 were used as optional ingredients.

[evaluation]

&Lt; Evaluation of fungicidal effect &

Priority one disclosed hereafter (the corner of the corner and the center, four) ^{* 1} Method for the cloth to two locations in the scene in as shown in Fig. 2 by volume acrylic first chamber (40 × 40 × 60㎝) ( 20) of 96L (Slide glass inoculated with microorganisms) 21 and 22 were attached with the surface inoculated with the bacteria directed toward the bottom side.

Next, the spraying apparatus 23 produced in each example was placed on the center bottom surface of the chamber 20, and the space treating agent was sprayed for 8 hours (spray treatment).

After the spraying treatment, the air in the chamber 20 was exhausted, and the slide glasses for release 21, 22 were recovered.

The bacterial solution recovered in the following method ^{* 2} from the slide glasses for disclosure 21 and 22 was appropriately diluted with physiological saline to a measurable concentration and inoculated onto a potato dextrose agar medium and cultured at 25 ° C for 5 days , And the number of colonies formed in the naked eye was measured. The viable cell count was obtained from the measured number of colonies and the dilution ratio of the bacterial solution, and the value was defined as &quot; number of bacteria after treatment &quot;.

Separately, the mycelial liquid recovered from the untreated, untreated slide glass was appropriately diluted with physiological saline to a measurable concentration, inoculated onto a potato dextrose agar medium, and cultured at 25 DEG C for 5 days. And the number of colonies formed was measured. The viable cell count was obtained from the measured number of colonies and the dilution ratio of the bacterial solution, and the value was set as &quot; untreated bacteria &quot;.

From the results, the fungicidal effect and the uniformity of the fungicidal effect were evaluated according to the following evaluation criteria.

(* 1: Production method of slide glass for disclosure)

A solution of 0.05% Tween 80 (manufactured by KANTO KAGAKU) in sterilized Cladosporium cladosporioides HMC1064 (bath separating bacteria) cultured on slanting medium of potato dextrose agar medium (manufactured by Difco) at 25 ° C for 1 week was about 10 ⁶ CFU / mL spore solution was prepared. Subsequently, the spore solution was inoculated with 0.1 mL of the spore solution in a slide glass (manufactured by Matsunami Glass Ind., Ltd., white grinding No. 2, 76 x 26 mm), allowed to stand at room temperature overnight, dried and fixed .

(* 2: Method of collecting bacteria from slide glass)

10 mL of slide glass (manufactured by Matsunami Glass Ind., Ltd., bag polishing No. 2, 76 × 26 mm) and SCDLP medium (manufactured by NIHON PHARMACEUTICAL CO., LTD.) Were inoculated into a sterile plastic chalet (AS ONE Corporation. Manufactured by NISSUI PHARMACEUTICAL CO., LTD.), And the bacteria were extracted from the slide glass.

(Evaluation standard)

{Fungicidal effect: ceiling center}

The number of bacteria obtained for the slide glass 21 provided at the center of the ceiling was converted to a logarithm (logarithm), and the value obtained by subtracting the number of bacteria after the treatment from the number of untreated bacteria (log (number of untreated bacteria) ) Was obtained, and the value was called a mold sterilization effect. The fungicidal effect was evaluated based on the following criteria.

<Criteria>

◎: Fungicidal effect of 4 or more.

○: The fungicidal effect is 2 or more and less than 4.

△: Fungicidal effect is 1 or more and less than 2.

X: Fungicidal activity is less than 1.

{Uniformity of fungicidal effect: difference between the center of the ceiling and the corner}

Similarly to the above, log (number of untreated bacteria) -log (number of bacteria after treatment) was determined for the slide glass 22 for public use placed at the corner of the ceiling scene, and the value was referred to as a mold sterilization effect.

The difference between the sterilization effect of the fungus in the center of the ceiling and the fungicidal effect of the ceiling corner (the difference between the center and the corner) was calculated, and the uniformity of the fungicidal effect was judged from the value based on the following criteria.

<Criteria>

◎: Difference between center and corner is less than 1.

A: The difference between the center and the corners is 1 or more and less than 2.

B: Difference between center and corner is 2 or more and less than 3.

X: The difference between the center and the corners is 3 or more.

&Lt; Evaluation of Persistence of Fungicidal Effect >

3, two slide glasses (manufactured by Matsunami Glass Ind., Ltd .; back abrasive No. 2, manufactured by Matsunami Glass Ind., Ltd.) were placed in the center of a ceiling scene in an acrylic chamber (40 x 40 x 60 cm) , 76 x 26 mm) 31, 32 were attached side by side.

Next, the spraying apparatus 33 produced in each example was placed on the center bottom surface of the chamber 30, and the space treating agent was sprayed for 8 hours (spraying treatment).

After the spraying treatment, the air in the chamber 30 was evacuated and the two slide glasses 31 and 32 were recovered.

The recovered slide glasses 31 and 32 were left in the laboratory under the condition that the sprayed surfaces of the slide glasses 31 and 32 were exposed. The slide glass 31 was left in the laboratory for one day and the slide glass 32 was left in the laboratory for one week in order to confirm the continuity of the mold prevention effect when left in the room.

Next, Cladosporium cladosporioides HMC1064 (bath-isolate) cultured at 25 占 폚 for 1 week in a potato dextrose agar medium (manufactured by Difco) was diluted to 50%, and then cultured in a potato dextrose liquid medium A spore suspension of about 10 &lt; ² &gt; CFU / mL was prepared.

0.1 mL of spore solution was inoculated on the slide glass (31, 32) after being left standing.

(Film described in JIS Z 2801 (antimicrobial activity test method · antibacterial effect of antibacterial activity product) cut into 1 cm x 1 cm on slide glass 31 and 32 inoculated with spores liquid) Lt; 0 &gt; C and a relative humidity of 98% or more for 1 week.

After the incubation, the bacteria were recovered from the slide glasses 31 and 32 by the above-described method ^{* 2} , and they were inoculated into a potato dextrose agar medium in an appropriate dilution with physiological saline to obtain a measurable concentration. After culturing, the number of colonies formed by naked eyes was measured.

From the above results, the sustainability of the fungicidal effect was evaluated according to the following evaluation criteria.

(Evaluation standard)

The ratio of the number of colonies G2 formed from the bacteria recovered from the slide glass 32 left in the laboratory for one week relative to the number of colonies G1 formed from the bacteria recovered from the slide glass 31 left in the laboratory for one day is represented by It was calculated by the formula, and the value was called the persistence rate of the antifungal effect. From this value, the persistency of the antifungal effect was judged on the basis of the following criteria.

(%) = (Number of colonies (G1) / number of colonies (G2)) 占 100

<Criteria>

◎: The persistence rate of mold prevention effect is 80% or more

○: The persistence rate of the mold prevention effect is 60% or more and less than 80%

△: The persistence rate of the mold prevention effect is 40% or more and less than 60%

X: The persistence rate of the antifungal effect is less than 40%

[Examples 1 to 26, Comparative Examples 1 to 7]

&Lt; Preparation of a spatial treatment agent &

Spatial treatment agents having the compositions shown in Tables 2 to 5 were prepared in the following order. The unit of the blending amount of each component in Tables 2 to 5 is mass%. The amount of the component (A) is the single concentration (% by mass) of the transition metal in 100 mass% of the spatial treating agent. The carrier concentration in 100 mass% of the spatial treatment agent in Example 10 was 0.1 mass%.

The &quot; balance &quot; of water is such that the total amount of the spatial treatment agent becomes 100 mass%.

The components other than water were mixed in accordance with the compositions shown in Tables 2 to 5, and water was further added thereto so that the total amount became 100% by mass and further mixed to prepare a spatial treatment agent.

<Production of atomizing device>

Using the obtained spatial treatment agent, a spraying apparatus was produced as follows.

5 g of a space treating agent was filled in a container of "Glade deodorant puff puff" (manufactured by SC JOHNSON COMPANY LIMITED), and a spraying device was produced.

The obtained spray device was used to evaluate the mold sterilization effect and the persistence of mold prevention effect. The results are shown in Tables 2 to 5.

As is apparent from Tables 2 to 4, the spatial treatment agents of the respective Examples all had a good fungicidal effect and a high uniformity of the fungicidal effect. From these results, it was shown that the spatial treatment agent of each example was excellent in the vaporization property of the component (A) (inorganic agent). In addition, the spatial treatment agents of the respective Examples had a good persistence of mold prevention effect.

In particular, the fungicidal effect and the persistence of the antifungal effect were excellent when a nonionic surfactant having an HLB of 2 or more and less than 16 was blended.

On the other hand, as apparent from Table 5, the spatial treatment agent of Comparative Example 1 which does not contain the component (A) had a low sterilizing effect on the mold and a low persistence of the mold preventing effect.

The spatial treatment agent of Comparative Example 2 containing no component (B) had a low uniformity of the fungicidal effect and deteriorated the volatility of the component (A).

(B-4) having a boiling point of 36 占 폚 in place of the component (B) was low in uniformity of the fungicidal effect and deteriorated in the volatility of the component (A). Also, the persistence of the mold inhibition effect was low.

The spatial treatment agent of Comparative Example 4 containing no component (C) had a low uniformity of the fungicidal effect and deteriorated the volatilization of the component (A). Also, the persistence of the mold inhibition effect was low.

The spatial treatment agent of Comparative Example 5 using tetraethylene glycol dimethyl ether (C-4) having a boiling point of 275 占 폚 instead of the component (C) was low in uniformity of the mold germicidal effect and deteriorated in the volatility of the component (A) .

The spatial treatment agent of Comparative Example 6 in which the mass ratio of the component (B) / component (C) was 0.06 was low in uniformity of the fungicidal effect and deteriorated in the volatility of the component (A).

The spatial treatment agent of Comparative Example 7 having a mass ratio of 1.38 represented by the component (B) / (C) was low in homogeneity of the fungicidal effect and deteriorated in the volatility of the component (A). Also, the persistence of the mold inhibition effect was low.

(Industrial applicability)

The residence space treating agent for the piezo sprayer of the present invention is excellent in the volatility of the inorganic agent and has a high persistence of the antifungal effect.

10 Piezo atomizer 11 containers
12 Absorption axis 13 Ultrasonic vibrator
14 ultrasonic oscillator 15 core support
16 junction piece 20 chamber
21 Sliding Glass for Disclosure 22 Sliding Glass for Disclosure
23 Spraying device 30 chamber
31 Slide glass 32 Slide glass
33 Spraying device A Spatial processing agent

Claims (8)

A living space treatment agent for a piezo sprayer containing the following components (A), (B), and (C) and having a mass ratio of 0.1 to 1.0 represented by component (B) / component (C).
(A) Component: an inorganic agent containing a transition metal
(B): Organic solvent having a boiling point of 70 ° C or more and less than 150 ° C
(C): an organic solvent having a boiling point of 150 ° C or more and less than 250 ° C The method according to claim 1,
A living space treatment agent for a piezo sprayer further comprising the following component (D).
(D) Component: Nonionic surfactant 3. The method of claim 2,
Wherein the component (D) comprises at least one nonionic surfactant having an HLB of 2 or more and less than 16. The method according to claim 2 or 3,
(C) / (D), wherein the weight ratio of the component (C) to the component (D) is 10 to 700. 5. The method according to any one of claims 1 to 4,
Wherein the component (A) is at least one member selected from the group consisting of silver, zinc, copper, and a compound thereof. 6. The method according to any one of claims 1 to 5,
Wherein the component (B) is at least one member selected from the group consisting of ethanol, 2-propanol, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and propylene glycol monoisopropyl ether At least one kind selected from the group consisting of the following. 7. The method according to any one of claims 1 to 6,
Wherein the component (C) is at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol, Wherein the agent is at least one member selected from the group consisting of a surfactant and a surfactant. The method of claim 3,
Wherein the nonionic surfactant having an HLB of 2 or more and less than 16 is selected from the group consisting of sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acids, sucrose fatty acid esters, ethylene glycol fatty acid esters, propylene glycol fatty acid esters, glycerin alkyl ethers, Oxyethylene-sorbitan fatty acid esters, polyoxyethylene-glycerin fatty acid esters, polyoxyethylene-propylene glycol fatty acid esters, polyoxyethylene-alkyl ethers, polyoxyethylene-polyoxypropylene-alkyl ethers, alkanolamides Wherein the at least one species is selected from the group consisting of:

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