JP2002187803A - Fungicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fungicide capable of exhibiting excellent fungicidal action, excellent in an effect for controlling a musty smell, and especially suitably used as the fungicide for metallic parts. SOLUTION: This fungicide contains a nitrogen-containing heterocyclic antimicrobial and a quaternary ammonium salt of which the counter ion comprises elements other than halogen as active ingredients. A quaternary ammonium salt of which the counter ion comprises a 1-3C alkyl sulfate is preferably used as the active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicide which exhibits excellent fungicidal properties and has an excellent effect of suppressing mold odor, and is particularly suitable as a fungicide for metal parts.

[0002]

2. Description of the Related Art In recent years, in Japan, the ratio of condominiums such as condominiums made of reinforced concrete and steel-framed concrete has increased, and even in wooden houses, the airtightness of rooms has increased due to the spread of aluminum sashes.

[0003] Under these circumstances, although the heating and cooling efficiency has been improved, the humidity of the entire house has risen in hot and humid climatic conditions in Japan, and not only the relatively humidified bathrooms and kitchens, but also the living spaces. Mold has begun to appear in places. This not only impairs aesthetic appearance but also causes a serious problem such as allergy caused by scattering of mold spores. In addition, since there are many types of mold generated in a house, it is impossible to avoid mold damage unless all these are eliminated.

For example, Japanese Patent Publication No. Sho 62-3804 discloses a fungicide which is effective against a wide range of molds by combining 2- (4-thiazolyl) -benzimidazole with a long-chain alkyldimethylbenzylammonium salt. Has been obtained. Also, JP-A-63-19650
No. 2 discloses an industrial bactericidal composition comprising a combination of 2-pyridinethiol-1-oxide or a metal salt thereof and 2- (4-thiazolyl) -benzimidazole. Japanese Patent Application Publication No. JP-A-2003-115139 discloses an industrial fungicidal composition in which one or more benzimidazole-based compounds are combined with a methylenebisthiocyanate compound.

On the other hand, the air-conditioning penetration rate in Japan is in line with the above-mentioned changes in the residential environment, and according to a survey by the Economic Planning Agency's Research Bureau, the national average in 1999 exceeded 84%. The air conditioner functions to reduce indoor humidity by condensing indoor moisture into cooling fins during dry or cooling operation. For this reason, although it has the effect of suppressing the generation of mold in the room, the humidity inside the air conditioner rises, so that the contamination of the mold spreads inside. For this reason, the generation of a so-called mold odor and the spores of mold scattered from an air outlet have recently been regarded as problems.

Under these circumstances, a cleaning agent for cooling fins and a fungicide for the inside of an air conditioner have recently been marketed, but a sufficient fungicidal effect and an inhibitory effect on mold odor have not yet been obtained. Is the current situation. Therefore, the above-mentioned Japanese Patent Publication Sho 62
The use of a fungicide in combination with 2- (4-thiazolyl) -benzimidazole or the like described in JP-A-3804, JP-A-63-196502 and JP-A-3-251507 makes it possible to control the inside of an air conditioner. Has a suppressing effect on a wide range of molds,
There is still a problem that the effect of suppressing the mold odor is not sufficient. In addition, these antifungal agents have a metal corrosive action due to chloride ions of ammonium salts, and are not suitable for spraying on electric appliances having metal parts.

On the other hand, Japanese Patent Application Laid-Open No. 11-286405 discloses that a mold having a carbon chain length of 1
Although it is disclosed that a dialkyldimethylammonium salt of 0 to 14 is blended, the dialkyldimethylammonium salt is a chloride, because the tile joint such as a bathroom is designed as a main place of use. Similarly, the problem of metal corrosion has not been solved.

In Japanese Patent Application Laid-Open Nos. 9-77610 and 9-132504, antibacterial agents having low skin irritation and low metal corrosivity have a counter ion of phosphoric acid or organic carboxylic acid. Although they disclose quaternary ammonium salts, at present, they have not yet obtained a sufficient antifungal effect and an inhibitory effect on mold odor.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems and the problems of the prior art, and has a broad antifungal spectrum, has an excellent effect of suppressing so-called mold odor, An object of the present invention is to provide a fungicide having no corrosive property.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned problems in the prior art and the like. When combined with a heterocyclic antibacterial agent, and when the counter ion of the quaternary ammonium salt is a lower alkyl sulfate having 1 to 3 carbon atoms, the quaternary ammonium salt alone can achieve the above object. Thus, the present invention was completed based on this finding. That is, the antifungal agent of the present invention has the following
(1) to (4). (1) An antifungal agent comprising as active ingredients a nitrogen-containing heterocyclic antibacterial agent and a quaternary ammonium salt whose counter ion is a substance other than halogen. (2) The counter ion of the quaternary ammonium salt is a sulfate ion,
The antifungal agent according to the above (1), which is at least one selected from the group consisting of sulfonic acid ions, alkyl sulfate ions, alkylsulfonic acid ions, phosphate ions, carboxylate ions, nitrate ions, and alkylamine ions. (3) The antifungal agent according to the above (1) or (2), wherein the counter ion of the quaternary ammonium salt is a lower alkyl sulfate having 1 to 3 carbon atoms. (4) A fungicide comprising a quaternary ammonium salt whose lower ion is a lower alkyl sulfate having 1 to 3 carbon atoms as an active ingredient.

[0011]

Embodiments of the present invention will be described below in detail. The antifungal agent of the first invention is characterized by comprising a nitrogen-containing heterocyclic antibacterial agent and a quaternary ammonium salt whose counter ion is a substance other than halogen as active ingredients, The antifungal agent of the second invention is characterized by using a quaternary ammonium salt whose counter ion is a lower alkyl sulfate having 1 to 3 carbon atoms as an active ingredient. In the following, the “present invention” refers to the case including the above first and second inventions.

The nitrogen-containing heterocyclic antibacterial agent used in the first invention includes, for example, pyrrole, pyridine, pyrimidine, pyrazole, imidazole, benzimidazole, 1,3,5-triazine, hexahydro, -1,3,5-triazine, triazole, isoxazole, thiazole, benzothiazole, thiazolin-2-one, isothiazolin-3-one,
Examples thereof include a combination of one or more antibacterial agents selected from benzoisothiazolin-3-ones, benzothiazolin-2-ones, and tetrahydrothiazine-2-thiones. As a preferable nitrogen-containing heterocyclic antibacterial agent, a benzimidazole antibacterial agent is desirable from the viewpoint of further safety, cost, antifungal property and stability. As the benzimidazole-based antibacterial agent, 2- (4-thiazolyl) -benzimidazole is particularly preferred from the viewpoint of safety and antifungal property.

The quaternary ammonium salt having a counter ion other than halogen used in the present invention includes, for example, dialkylethylmethylammonium salt, dialkyldiethylammonium salt, alkyldimethylbenzylammonium, alkylphenoxyethoxyalkyldimethylbenzylammonium salt and the like. One or a combination of two or more selected from the above. As a counter ion of these quaternary ammonium salts, any substance other than halogen can exert the effects of the present invention. However, sulfate ions and sulfonic acids are particularly preferred in terms of low metal corrosivity and productivity. ion,
Desirable is at least one (single or a mixture of two or more) selected from alkyl sulfate ions, alkyl sulfonate ions, phosphate ions, carboxylate ions, nitrate ions, alkylamine ions, and lower alkyl sulfates having 1 to 3 carbon atoms. . As these quaternary ammonium salts, dialkylethylmethylammonium salts are more preferable from the viewpoint of productivity, and dialkylethylmethylammonium ethosulfate is particularly desirable.

In the first invention, the compounding amount of the nitrogen-containing heterocyclic antibacterial agent is 0.002 to the total amount of the fungicide.
To 20% by mass (hereinafter simply referred to as "%"), preferably 0.02% to 10%, more preferably 0.1% to
5% is desirable. In the first invention, the amount of the quaternary ammonium salt whose counter ion is other than halogen is 0.002 to 20%, preferably 0.02% to 10%, based on the total amount of the fungicide. More preferably, 0.1% or more
5% is desirable. The effect of the present invention is exhibited when one or both of the amount of the nitrogen-containing heterocyclic antibacterial agent and the amount of the counter ion of the quaternary ammonium salt other than halogen are less than 0.002%. Not be able to
If either one or both of these amounts exceeds 20%, the effect of the present invention is not changed, but it is not preferable because there is a problem of solubility in a solvent depending on storage conditions. Furthermore, in order to further improve the effects of the present invention, specifically, at a low concentration, and over a long period of time, the first fungicide is required to exhibit an excellent antifungal effect and an inhibitory effect on mold odor. In the present invention, the compounding ratio (mass ratio) of the nitrogen-containing heterocyclic antibacterial agent and the quaternary ammonium salt having a counter ion other than halogen is preferably 1: 9 to 9: 1, and more preferably 1: 9. Desirably, the ratio is 4 to 4: 1.

The antifungal agent of the second invention is characterized in that a quaternary ammonium salt whose counter ion is a lower alkyl sulfate having 1 to 3 carbon atoms is used as an active ingredient. In the second invention, the counter ion is a quaternary ammonium salt which is a lower alkyl sulfate having 1 to 3 carbon atoms. Specifically, the counter ion has 1 to 3 carbon atoms.
Or a combination of two or more selected from dialkylethylmethylammonium salt, dialkyldiethylammonium salt, alkyldimethylbenzylammonium, alkylphenoxyethoxyalkyldimethylbenzylammonium salt, etc., which becomes lower alkyl sulfate. As these quaternary ammonium salts,
Preferably, a dialkylethylmethylammonium salt, particularly dialkylethylmethylammonium ethosulfate, is desirable from the viewpoint of productivity.

In the second invention, when the lower alkyl sulfate having 1 to 3 carbon atoms is a counter ion, the invention of the present invention can be used alone without being combined with a nitrogen-containing heterocyclic antibacterial agent, as compared with the first invention. The effect, that is, an excellent antifungal effect and an effect of suppressing mold odor over a long period of time without causing a problem of metal corrosion. Also,
In the second invention, the amount of the quaternary ammonium salt whose counter ion is a lower alkyl sulfate having 1 to 3 carbon atoms is 0.002 to 20%, preferably 0.1 to 2%, based on the total amount of the fungicide. 02% to 10%, more preferably 0.
1% to 5% is desirable. If the compounding amount of the quaternary ammonium salt is less than 0.002%, the effect of the present invention cannot be exhibited, and if it exceeds 20%, the effect of the present invention does not change. Under some conditions, there is a problem of solubility in a solvent, which is not preferable.

The antifungal agent of the present invention thus constituted may further include, for example, lavender oil, cis-3-hexenol, α-pinene, Various flavor components such as pine oil, eucalyptus oil, rosemary oil, peppermint oil, orange oil, lemon oil, limonene, menthol, terpineol, linalool, linalyl acetate, terpinyl acetate, and lilial can be blended.
In addition, the antifungal agent of the present invention includes, for the purpose of preventing rust of a metal can used as a container and rust of an antifungal object, an amino acid-based cationic surfactant, a carboxylate of an organic amine, a benzotriazole derivative, or the like. Various rust preventives can be blended. In addition, the antifungal agent of the present invention includes not only mold odor but also household odor at home (tobacco odor, cooking odor, oil and fat oxidation odor, stuffy smell of shoes, refrigerator odor, garbage odor, odor emitted from drains, etc.). For the purpose of deodorization, various plant extracts (tea, apple, persimmon, corn, bamboo, sugarcane, genoshoko, butterbur, sasa, mugwort, conifer, etc.), catechin,
Various deodorants such as charcoal, activated carbon, cyclodextrin, zinc ricinoleate and the like can also be blended. These fragrances, rust inhibitors and deodorants can be used alone (one type) or in combination of two or more types.

In the present invention, in addition to the quaternary ammonium salt, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant are compounded as surfactants. A cleaning effect can also be imparted.

The antifungal agent of the present invention may be water (purified water, ion-exchanged water, pure water, etc.) or an alcohol having a carbon number (C1 to C3),
The liquid may be dissolved, suspended or emulsified in a solvent such as propylene glycol, glycerin, sorbitol or a mixed solvent thereof. Thereby, it is used by being filled in a commonly used ejection container and ejected in the form of a mist or a foam. Examples of the ejection mode include a trigger type, an aerosol type, and a dispenser type.

Further, by mixing the antifungal agent of the present invention with a high-viscosity base material, high-viscosity preparations such as pastes and gels can be prepared. Further, the antifungal agent of the present invention is charged into a device for periodically or irregularly spraying or spraying by electric or mechanical method, and is used for electric appliances such as air conditioners, vacuum cleaners, refrigerators, clog boxes, bathtubs, wash basins and the like. By installing it, the antifungal effect can be exhibited continuously.

The antifungal agent of the present invention can prevent exfoliation of the antifungal agent by adding a material having an adhesive effect such as polyvinyl alcohol or polyvinyl butyral, and can maintain the effect. Specifically, the fungicide of the present invention can be formed into a paste using a base material such as polyvinyl alcohol or polyvinyl butyral, and can be applied directly with a brush or the like at the time of use. In addition, a solvent such as polypropylene glycol can be added to the antifungal agent of the present invention in order to prevent a whitening phenomenon due to drying of the liquid agent-adhering surface.

Further, by extending the nozzle of the injection container filled with the fungicide of the present invention into a straw shape, it is possible to spray the inside of a complicated structure. Furthermore, by attaching a structure for atomizing the fungicide to the tip of the straw-shaped nozzle, the fungicide becomes fine particles, which can be effectively sprayed into the inside of a complicated structure. Can be widely spread.

The antifungal agent of the present invention thus constituted has a broad antifungal spectrum, exhibits excellent antifungal properties, and has an excellent effect of suppressing mold odor. A fungicide can be provided. The fungicide of the present invention having such an effect is
For example, not only non-metals such as plastics and tiles, tile joints, enamels, wood, paper, wallpaper, carpets, tatami mats, painted parts, leather products, etc., but also metal parts such as sinks and faucets, or air conditioners with mixed metal parts And electric products such as vacuum cleaners, refrigerators, microwave ovens and ovens, furniture such as shoe boxes and wash basins, buildings such as aluminum sashes and drains, and metal parts for automobiles and bicycles.

The antifungal agent of the present invention is effective not only against eukaryotic fungi and yeasts but also against prokaryotic bacteria and actinomycetes. As well as an antibacterial agent (this point will be described in detail in Test Examples and the like which will be described later).

[0025]

EXAMPLES Next, the present invention will be further described with reference to examples and comparative examples based on test examples, but the present invention is not limited to these examples.

[Test Example 1] Formula 1 shown in Table 1 below
-5, that is, 2- (4-thiazolyl) -benzimidazole (hereinafter abbreviated as “TBZ”), benzalkonium chloride (hereinafter abbreviated as “AMB”), and didecyldimethylammonium phosphate (hereinafter, abbreviated as “TBM”). "DDA
P "), didecylethylmethylammonium ethosulfate (hereinafter abbreviated as" DEMAS "), a mixture of TBZ and AMB, and a mixture of TBZ and DEMAS according to JIS Z2911-
1992 "Mold resistance test method, 7, paint test", anti-mold test was performed. That is, filter paper (Toyo Filter Paper, No. 2, diameter 3) was added to the ethanol solution of each sample.
0mm), soak it and leave it indoors for 2 hours.
Placed in the center of the culture surface of a predetermined culture medium placed in a petri dish,
1 mL of the test mold spore suspension is evenly sprayed thereon,
Subsequently, the petri dish was covered and cultured at a temperature of 28 ° C. for 7 days. As a culture medium at this time, distilled water 1000 mL,
A composition having a composition of 40 g of glucose, 10 g of peptone and 25 g of agar was used. The following molds were used for the test. I. Aspergillus niger IAM3001 II. Penicillium citrinum IAM7316 III. Cladosporium cladosporioides IFO6348 IV. Aspergillus sp. (Separated from mold damage) Trichoderma sp. (Isolated from mold-damaged parts) These results are shown in Table 2 below as the minimum effective concentration of the active ingredient for each strain.

[0027]

[Table 1]

[0028]

[Table 2]

As is clear from the results of Tables 1 and 2, TBZ, AMB,
Each of the DDAPs alone cannot completely suppress the growth of five strains that are frequently isolated at these sites affected by the living environment even at 0.4%, but the DEMA within the scope of the present invention.
TB alone is 0.4% or less, and TBZ + A which is a comparative reference example (described in Japanese Patent Publication No. 62-3804).
Similarly to MB, TBZ + D falls within the scope (example) of the present invention.
By using EMAS together, it was found that their growth could be completely suppressed at a concentration as low as 0.16%.

Test Example 2 Formulation Examples 1 to 5 shown in Table 3 below
For the antifungal agent, a metal corrosion test was conducted by the following method. The following metal specimens (2.5cm x 6cm)
0.2 mL of an ethanol solution of the fungicide mixture of Formulation Examples 1 to 5 shown in Table 3 below was applied. The coated metal test piece was left in a high-temperature, high-humidity bath at a temperature of 40 ° C. and a humidity of 75% for 3 months, and the appearance of the coated surface was observed with the naked eye and a stereoscopic microscope (magnification: 20 ×, manufactured by Olympus Corporation). The evaluation was based on criteria. Evaluation criteria: ++: markedly corroded +: corroded ±: slightly corroded-: not corroded Further, the following metal pieces were used for the test. I. Iron II. Copper III. Aluminum IV. Stainless steel (SUS304) Brass These results are shown in Table 4 below as the degree of rust generation for each metal piece.

[0031]

[Table 3]

[0032]

[Table 4]

Test Example 3 Formulation Examples 1, 3, and 5 in Table 3 above
Aerosol can (volume: 220 m)
A test was carried out on 81 air conditioner holders filled with l) and having a moldy odor, for each of the antifungal agents, 27 persons in three groups. The evaluation of this test was performed by the following method. To evaluate the degree of mold contamination, the number of molds before and after the use of the above mildewproofing agent was measured by pressing the food stamp "Nissui" CP-added potato dextrose agar (manufactured by Nissui Pharmaceutical Co., Ltd.) on the cooling fins of the air conditioner. 25 ℃
For 5 days, and the number of grown colonies was counted. The mold odor suppressing effect was confirmed by the sensory evaluation of the mold odor intensity before and one month after the air conditioner owner used the above-mentioned mildewproofing agent. The rust condition inside the air conditioner was evaluated by sensory evaluation of the rust condition of the metal part of the air conditioner before and one month after the use of the fungicide. All air conditioners were used after the first year of use. The results are shown in Table 5 below.

[0034]

[Table 5]

As is clear from the results shown in Table 5 above, Formulation Examples 1, 3, and 5, which are the fungicides of the present invention, are excellent in the effect of suppressing the mold odor by the effect of suppressing the mold in the air conditioner. It was also found to be low in corrosiveness to metals.

Test Example 4 Formulation Examples 1, 3 and 5 in Table 3 above
Into a trigger container (capacity: 220 ml)
Approximately 10 ml of the product was sprayed on a place where mold is likely to occur in the home, and the condition of mold development 3 months later was evaluated according to the following evaluation criteria. The results are shown in Table 6 below. Evaluation criteria:-: No mold generated ±: Very slight mold generated +: Mold generated

[0037]

[Table 6]

As is evident from the results in Table 6, Formulation Examples 1, 3, and 5, which are the fungicides of the present invention, are excellent in the effect of suppressing the generation of mold over a long period of time in actual households. I understood.

[Test Example 5] DEMAS alone, TBZ and D
The minimum inhibitory concentration (MIC) against bacteria and mold was determined for a 1: 1 mixture of EMAS and a 1: 1 mixture of TBZ and AMB. That is, the above fungicide and the mixture thereof were diluted with ethanol in consideration of the concentration at which the fungicide and the test bacteria were allowed to act in the medium. In this case, the concentration of ethanol in the medium was set to 1% or less, and the same test was performed for a control containing only ethanol. In the case of inoculated bacteria, bacteria were cultured in a Soybean casein digest (abbreviated as SCD) medium at 30 ° C. for 18 to 24 hours, and the bacterial solution was inoculated on a control SCD agar plate medium with and without a fixed amount of a drug. In the case of mold, Glucose peptone ag
After culturing in ar (abbreviated as GPA) medium at 25 ° C. for 7 days, a loopful of spores was prepared using 5 mL of a loop suspension (physiological saline), and a fixed amount thereof was used as a control with and without drug. The powder was inoculated on a GPA plate medium. The MIC of the fungicide was determined using the lowest concentration at which growth was completely inhibited after culturing at 30 ° C. for 72 hours for bacteria and 25 ° C. for 7 days for molds.

The composition of the medium used in Test Example 5 is shown below. Soybean casein digest (SCD) medium Casein peptone 17g soy peptone 3g Sodium chloride 5 g K ₂ HPO ₄ 2.5g glucose 2.5g distilled water 1000mL Glucose peptone agar (GPA) medium Glucose 20g Yeast extract 2g MgSO ₄ · 7H ₂ O 0.5g Polypeptone 5g K ₂ HPO ₄ 1g Agar 20g Distilled water 1000mL

The following bacteria and fungi were used in Test Example 5. I. Staphylococcus aureus II. Escherichia coli III. Pseudomonas aeruginosa IV. Aspergillus sp. (Separated from mold damage) Trichoderma sp. (Isolated from the part where mold damage occurred) These results were used as MICs for each strain as shown in Table 7 below.
Shown in

[0042]

[Table 7]

As is clear from the results shown in Table 7, the DEMAS alone or the mixture of TBZ and DEMAS within the scope of the present invention can inhibit the growth of bacteria at a low concentration, similarly to mold. Was.

Test Example 6 Next, an actual air conditioner was sprayed with the antifungal agent of the present invention using the following Embodiments I to IV, and a deep air conditioner was sprayed by the following evaluation method. The adhesion state, the antifungal effect, and the antifungal effect were confirmed. The results are shown in Tables 9 and 10 below. I. The composition was TBZ (Hoxstar HP: Hokuko Sangyo Co., Ltd.) 0.5%, DEMAS (Lion Akzo Co., Ltd.) 0.
2%, deodorant (sugar cane extract MSX-245: manufactured by Mitsui Sugar Co., Ltd.) 1.0%, fragrance 0.05%, ethanol (9
9.5% Vitrex denaturation: manufactured by Japan Alcohol Sales Co., Ltd.)
65% of the remaining undiluted solution, liquefied petroleum gas (LP
G) A fungicide composition containing 35% of (0.25 MPa) was added to a vapor-tapped valve (stem diameter φ0.4 m).
m, under tap diameter φ 0.8 mm, vapor tap diameter φ 0.35 mm: Mitani Valve Co., Ltd.) and an aerosol can equipped with a straw-shaped nozzle type button (Mitani Valve Co., Ltd.) provided with a structure that sprays in a mist at the tip. (AE220 neck-in can without coat: manufactured by Toyo Seikan Co., Ltd.) and sprayed on a wall-mounted air conditioner for home use (manufactured by Toshiba Corporation). II. As a composition, TBZ (manufactured by Merck) 0.4%, DE
MAS (manufactured by Lion Akzo) 0.3%, deodorant (zinc lysinate TEGO Sorb80: manufactured by Goldschmidt) 0.3 %%, fragrance 0.1%, ethanol (9
9.5% undenatured: manufactured by Japan Alcohol Sales Co., Ltd.) 84% of the remaining stock solution, LPG (0.45 MPa) as a propellant
A structure in which a fungicide composition containing 8% and 11.2% of dimethyl ether (DME) is sprayed in the form of a mist with a valve (stem diameter φ0.4 mm, under tap diameter φ0.8 mm: Mitani Valve Co., Ltd.) and the tip. Aerosol can (AE22) with a straw-shaped nozzle button (Mitani Valve Co., Ltd.)
0 Neck-in can No coating: filled into a Toyo Seikan Co., Ltd.) and sprayed on a wall-mounted air conditioner for home use (Matsushita Electric Co., Ltd.). III. As a composition, TBZ (manufactured by Sanai Sekiyu KK) 0.2%,
DEMAS (manufactured by Lion Akzo) 0.5%, deodorant (softwood extract Super Puriere A-10, manufactured by Matsushita Electric Works, Ltd.) 0.5%, fragrance 0.1%, water 40%, ethanol ( 95% Vitrex modified: manufactured by Japan Alcohol Sales Co., Ltd.) Trigger type container provided with a straw-shaped nozzle provided with a structure for spraying the remaining fungicide composition in the form of a mist at the tip (manufactured by Yoshino Kogyo Co., partially modified) ) And sprayed on a wall-mounted air conditioner for home use (Hitachi, Ltd.). IV. The composition was TBZ (Hoxstar HP: Hokuko Sangyo Co., Ltd.) 0.5%, DEMAS (Lion Akzo Co., Ltd.) 0.
Stock solution of 2%, deodorant (sugar cane extract MSX-245: manufactured by Mitsui Sugar Co., Ltd.) 1.0 %%, fragrance 0.05%, ethanol (99.5% vitrex modified: manufactured by Nippon Alcohol Sales Co., Ltd.) And a valve with a vapor tap (stem diameter φ0.4) containing a fungicide composition containing 65% and 35% liquefied petroleum gas (LPG) (0.25 MPa) as a propellant.
mm, under tap diameter φ0.8 mm, vapor tap diameter φ0.35 mm: Mitani Valve Co., Ltd.) and an aerosol can (AE220 neck-in can) with a normal mist spray button (Mitani Valve Co., Ltd.) No coating: Toyo Seikan And sprayed on a wall-mounted air conditioner for home use (Fujitsu General). Note that Embodiment I
The fragrances used in ~ IV were mixed with fragrance components shown in Table 8 below. In addition, all the air conditioners were not cleaned at all from the start of use, and were used for the second to third years.

[0045]

[Table 8]

[Evaluation Method of Adhesion State to Deep Layer of Air Conditioner] Evaluation of the adhesion state to the air conditioner is made by observing the discolored state visually with the following evaluation criteria using heat-sensitive paper discolored by the adhesion of ethanol. evaluated. Evaluation criteria: 〇: good adhesion, △: non-adhered part x: drug dripping

[Method of Evaluating the Fungicidal Effect on the Deep Section of the Air Conditioner] The antifungal effect was evaluated by pressing a food stamp “Nissui” CP-added potato dextrose agar (manufactured by Nissui Pharmaceutical Co., Ltd.) on the part where mold of the air conditioner was likely to occur 25 hits
After culturing at 5 ° C. for 5 days, the number of grown colonies was counted, and the degree of mold contamination was determined by the number of colonies.

[Evaluation Method of Mold Smell Suppressing Effect] The evaluation of the mold odor suppressing effect was carried out by seven evaluators by the following six-step absolute evaluation of the odor intensity before and after using the above-mentioned fungicide. did. Evaluation score of odor intensity: 0: odorless 1: odor that can be detected at last 2: weak odor 3: odor that can be easily detected 4: strong odor 5: strong odor

[0049]

[Table 9]

[0050]

[Table 10]

As is clear from the results of Tables 9 and 10, the fungicide of the present invention can be spread in an air conditioner by using a straw type nozzle or the like. It turned out that. As a result, it is possible to reduce the degree of mold contamination in the deep part of the air conditioner, and it has been found that the mold odor of the air conditioner can be effectively suppressed.

[0052]

According to the present invention, there is provided a fungicide which exhibits excellent fungicidal properties and has an excellent effect of suppressing mold odor, and is particularly suitable as a fungicide for metal parts.

Claims (4)

[Claims] 1. A fungicide comprising as active ingredients a nitrogen-containing heterocyclic antibacterial agent and a quaternary ammonium salt whose counter ion is a substance other than halogen. 2. The counter ion of the quaternary ammonium salt is selected from the group consisting of sulfate ion, sulfonate ion, alkyl sulfate ion, alkyl sulfonate ion, phosphate ion, carboxylate ion, nitrate ion and alkylamine ion. The fungicide according to claim 1, which is at least one kind. 3. The fungicide according to claim 1, wherein the counter ion of the quaternary ammonium salt is a lower alkyl sulfate having 1 to 3 carbon atoms. 4. A fungicide comprising a quaternary ammonium salt whose lower ion is a lower alkyl sulfate having 1 to 3 carbon atoms as an active ingredient.