JP6041747B2 - Water-based fungicide - Google Patents

Description

The present invention relates to a highly safe aqueous fungicide capable of maintaining an effect for a long period of time under a high humidity condition where mold is likely to occur.

Originally, in Japan, which is hot and humid, there is much damage to mold. In recent years, the number of houses with high airtightness has increased, and the damage has increased. However, it is difficult to prevent the generation of mold under hot and humid conditions, and in the most damaged bathroom, mold occurs on tile joints and darkens, and then is oxidized and bleached with hypochlorous acid preparation. Is the current situation. Hypochlorous acid preparations generate dangerous chlorine gas when mixed with acidic type bleaching agents, etc., so they are essentially products that should be restricted, but there are no other products to replace. It is used. It can be said that the use of dangerous hypochlorous acid products indicates the difficulty of mold prevention treatment. Under such circumstances, there is a demand for a fungicide that exhibits a sustained effect.

As an antifungal method, Patent Document 1 (Japanese Patent Application Laid-Open No. 2009-107933) discloses that at least one compound selected from a specific quaternary ammonium salt and an amine oxide and a metal sequestering agent having a calcium chelation constant of 4 to 12. Although the antifungal agent to contain is proposed, the durability of the antifungal effect is not shown. Patent Document 2 (Japanese Patent Application Laid-Open No. 2013-28555) proposes a mold control method and a liquid mold control composition characterized by applying lauryldimethylamine oxide to an object. There is no indication of the persistence of the mold effect.

In general, in order to maintain the effect of the fungicide, a water repellent compound is used in combination with the fungicide, but in the bathroom, the clothes are taken off and become naked, and contact with the compound is more direct. Therefore, a safer preparation is desired. Fluorine-based and silicone-based water repellents that have been frequently used as water repellents have a problem of causing poisoning symptoms, and currently, attention is given to avoid using them in sealed spaces. In addition, the water-insoluble polyvinyl resin has poor compatibility with the tile joint which is hydrophilic, and has a drawback that the durability is lowered when a surfactant is added to improve the compatibility. Moreover, since a water-repellent substrate is used, a process such as emulsification is required, and the manufacturing method becomes complicated.

The inventors of the present invention previously described in Patent Document 3 (Japanese Patent Application Laid-Open No. 11-286405) as an antifungal agent that is easy to manufacture and takes safety into consideration, as an antifungal component and a water repellent film-forming component. An alcohol preparation containing a dialkyldimethylammonium salt having a carbon chain length of 10 to 14 is proposed, and a patent for it is obtained. However, the antifungal agent according to this proposal is an alcohol preparation, and therefore has a disadvantage that an odor of alcohol is unavoidable when used in a bathroom with high sealing properties. Patent Document 4 (Japanese Patent Application Laid-Open No. 2006-188468) ) Proposed an aqueous fungicide comprising a fungicide component and a monoalkyltrimethylammonium salt having a carbon chain length of 16 to 18 as a water repellent film forming component. However, there was a need to further improve the irritation during spraying.

JP 2009-107933 A JP 2013-28555 A Japanese Patent Laid-Open No. 11-286405 JP 2006-188468 A

An object of the present invention is to provide an aqueous antifungal agent having a high antifungal effect, a long antifungal effect and excellent safety with little irritation during spraying.

The present invention has been found that the following constitution has an excellent effect for achieving the above object.
(1) (A) myristyl dimethylamine oxide and,
(B) As a foaming component , one selected from decyldimethylamine oxide, lauryldimethylamine oxide, lauryldimethylacetate betaine, and
(C) An aqueous fungicide containing 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide as a cationic antibacterial substance .
(2) water-based fungicides described in the (A) comprising myristyl dimethyl amine oxide and 0.05 to 1.0 mass% (1).

The water-based antifungal agent of the present invention has a very high practicality because it is easy to manufacture, has an antifungal effect, and has low eye irritation and high safety.

The aqueous antifungal agent of the present invention requires the use of (A) myristyldimethylamine oxide and (B) a foaming component.
Myristyl dimethylamine oxide has higher antifungal effect than other alkyl dimethylamine oxides with different carbon numbers, but has poor foaming when sprayed with aerosol or aerosol, and has problems of scattering. There was a difficult aspect.
Therefore, the present inventors have intensively studied, and by coexisting with (A) myristyldimethylamine oxide and (B) a foaming component, foaming can be performed when the aqueous solution is sprayed, and fine droplets generated during jetting are scattered. It has been found that it can prevent irritation caused by and can provide a durable antifungal effect.

Although the compounding quantity of (A) myristyl dimethylamine oxide in this invention is not specifically limited, It is preferable to use 0.05-10 mass% with respect to the whole aqueous | water-based antifungal agent. If the blending amount is less than 0.05% by weight, the antifungal effect may not be sustained, and even if it is used in excess of 10% by weight, the effect cannot be maintained, and a feeling of being slimy may remain on the treated surface. Yes, it may become slippery. More preferably, it can set to the range of 0.05-5 mass%.

The (B) foaming component in the present invention refers to an organic substance having a property of generating bubbles by performing various treatments such as spraying as an aqueous solution. In particular, it is not limited as long as it foams when the water-based antifungal agent of the present invention is sprayed with a trigger spray or the like.
As the foaming component, a foaming surfactant is preferred. Examples of the surfactants include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, and a small amount of amphoteric surfactant or alkylamine oxide-based interface having high foaming properties. An activator (however, the alkyl group has 12 or less carbon atoms) is more preferred. As the amphoteric surfactants, betaine-based amphoteric surfactants are preferred, such as lauryl dimethyl acetate betaine, coconut alkyl dimethyl acetate betaine, lauryl amide propyl dimethyl acetate betaine, coconut alkyl amide propyl dimethyl acetate betaine, coconut alkyl dimethyl sulfobetaine, lauryl dimethyl. -Propylsulfobetaine, lauryldimethyl-2-hydroxypropylsulfobetaine, myristyldimethyl-2-hydroxypropylsulfobetaine, palmityldimethyl-2-hydroxypropylsulfobetaine, alkylamidopropyldimethylpropylsulfobetaine, palm alkylamidopropyldimethylhydroxy And propylsulfobetaine. Alkylamine oxide surfactants (however, the alkyl group has 12 or less carbon atoms) include octyl dimethylamine oxide, decyl dimethylamine oxide, lauryl dimethylamine oxide, coconut alkyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide. Etc. When using these, the blending amount may be adjusted as appropriate so as to foam during spraying and suppress irritation.

In the present invention, in addition to (A) myristyldimethylamine oxide and (B) foaming component, (C) a cationic antibacterial substance can be further added to enhance a durable antifungal effect. Moreover, the effect of (A) myristyl dimethylamine oxide and (C) cationic antibacterial substance has a synergistic effect, and by blending (A) myristyl dimethylamine oxide and (C) cationic antibacterial substance, The blending amount can be set smaller. The cationic antibacterial substance (C) that can be blended in the present invention is not limited as long as it is used as a normal cationic antibacterial component. For example, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyltrimethylammonium chloride, methylbenzethonium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, gemini-type quaternary ammonium salts, polyhexamethylene biguanide salts, polyhexamethylene Examples thereof include guanidine salt, polylysine, chitosan and the like. These may be used alone or in combination. As a compounding quantity of a cationic antibacterial substance, 0.01-5 mass% is used with respect to the whole water-system antifungal agent. If it is less than 0.01% by mass, a synergistic effect with (A) myristyl dimethylamine oxide may not be observed. On the other hand, even if it exceeds 5% by mass, no further effect is observed, so the cost High and uneconomical product. The blending amount of the cationic antibacterial substance is more preferably set to 0.05 to 1.0% by mass.

The aqueous fungicide of the present invention is an aqueous type, and the place where it is used is a place where mold is likely to occur, such as a tile joint in a bathroom. Therefore, water is mainly used as a solvent. Examples of water include purified water, ion exchange water, reverse osmosis membrane water, normal tap water, industrial water, deep sea water, and the like. However, lower alcohols such as ethanol and isopropyl alcohol may be added as appropriate to the extent that the purpose of the present invention is low irritation. Similarly, glycols having 3 to 6 carbon atoms such as butylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, and glycol ethers. Ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, tri Ethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether Diethylene glycol n-butyl ether, triethylene glycol n-butyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n- Butyl ether or the like can be added as appropriate.

In addition, the water-based antifungal agent of the present invention may further include an inorganic antibacterial agent, an organic antibacterial agent, and an antialgae so as to impart an antibacterial effect, an antialgal effect, a rustproofing effect, a cleaning effect, etc. Add fragrances, rust inhibitors, surfactants, solvents, chelating agents, acid agents, alkaline agents, etc., or add fragrances and deodorizing ingredients to add fragrance and deodorant properties. May be.

If the aqueous fungicide of the present invention thus obtained is applied or sprayed to a place where mold is likely to occur, such as a bathroom tile joint, the occurrence of mold can be suppressed over several weeks to several months. The aqueous antifungal agent of the present invention is extremely practical because it can be applied safely and easily unlike a hypochlorous acid preparation which is dangerous and difficult to handle.

Next, the aqueous fungicide of the present invention will be described in more detail based on specific test examples and examples, but the present invention is not limited to these.

(A) Myristyldimethylamine oxide 1.0% by mass, (B) Decyldimethylamine oxide 0.5% by mass as a foaming component, (C) 1,4-bis (3,3 ′-(1) as a cationic antibacterial substance -Decylpyridinium) methyloxy) butanedibromide 0.1% by mass and water were blended to prepare the aqueous fungicide of the present invention. This aqueous fungicide was filled in a bottle, and a T-95 trigger (1 cc, with a former) manufactured by Canyon was attached.

When the water-based antifungal agent of the present invention was sprayed on the tile joints in the bathroom, it was sprayed in the form of foam and did not feel irritation. One month later, darkening due to growth of mold was observed on the untreated joint, but darkening due to growth of mold was not observed on the treated surface, and its antifungal effect was high and practical. .

[Test Example 1]
According to Example 1, water-based antifungal agents having the compositions shown in Tables 1 and 2 were prepared, and the following antifungal test, antifungal sustainability test and spray irritation test were performed.
(1) Antifungal test 1) Divide a 10 x 10 cm semi-porcelain tile into 4 equal parts (5 x 5 cm), and place a water-based antifungal agent on the unglazed surface at a distance of 30 cm with a T-95 trigger (1 cc, with a former) made by Canyon Spray once and dry overnight.
2) Cladosporium
A mixture of cladosporioides mold dispersion and 1/2 diluted glucose peptone medium at a ratio of 1: 1 was dropped on the unglazed surface of the tile treated in 1) and cultured at 25 ° C for 7 days to grow mold. The mold prevention effect is evaluated by the following criteria.
++++: Control and mold growth do not change ++: Mold growth is 1/3 to 2/3 of control
+: Mold growth is less than 1/3 δ +: Mold hardly grows (1 and 2 mold growth can be confirmed with a microscope)
-: No mold growth (2) Antifungal sustainability test (quasi-field test)
1) Spray an antifungal agent on the back side of a 10 × 10 cm semi-porcelain tile from a distance of 30 cm with a T-95 trigger (1 cc, with a former) manufactured by Canyon, and dry overnight.
2) Stand the unglazed surface treated with a water-based fungicide on the surface of an actual bathroom where mold and slime are likely to grow, and let the shower water splash on it. An untreated tile was also installed as a control.
3) After standing for 4 weeks, mold and pink slime growing on the unglazed surface were observed and evaluated according to the following criteria.
++++: Control and mold growth do not change ++: Mold growth is 1/3 to 2/3 of control
+: Mold growth is less than 1/3 δ +: Mold hardly grows (1 and 2 mold growth can be confirmed with a microscope)
-: No mold growth (3) Spray stimulation test A 10-liter plastic bucket was sprayed 5 times with a canyon T-95 trigger (1 cc, with a former) and a water-based fungicide was tested. It was evaluated with.
○: No irritation when spraying.
Δ: Slight irritation is felt during spraying.
X: Shown when spraying.

[Table 1]

As in Examples 2 and 3, (A) myristyldimethylamine oxide blended with (B) foaming component foams well, so there is no irritation at the time of spraying, and good mold prevention test and mold prevention A lasting effect was observed. In addition, Examples 5 to 11 in which (A) myristyl dimethylamine oxide, (B) foaming component, and (C) cationic antibacterial substance were combined had synergistic effects of (A) myristyldimethylamine oxide and (C) cationic antibacterial substance. The antifungal effect and the antifungal sustaining effect were recognized even with a small blending amount, and there was no irritation during spraying due to the effect of the foaming component.
On the other hand, in Comparative Examples 1 to 3, lauryl dimethylamine oxide, decyl dimethylamine oxide and lauryl dimethyl acetate betaine are effective as (B) foaming components, but (A) a cationic system such as (C) myristyl dimethylamine oxide. There was no synergistic effect with any antibacterial substance, and no antifungal sustaining effect was observed. Moreover, although the comparative example 4 which did not mix | blend a foaming component had the antifungal effect, the fall of the antifungal sustaining effect was recognized, and irritation | stimulation was recognized at the time of spray, and there existed a problem. In Comparative Example 5, only myristyldimethylamine oxide was used, so that the antifungal effect was recognized at the beginning, but the sustained effect was not sufficient, and irritation was observed.

The aqueous antifungal agent of the present invention may be used not only in the antifungal field, but also in fields such as sterilization and antibacterial.

Claims (2)

(A) myristyl dimethylamine oxide and,
(B) As a foaming component , one selected from decyldimethylamine oxide, lauryldimethylamine oxide, lauryldimethylacetate betaine, and
(C) A water-based fungicide containing 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) butanedibromide as a cationic antibacterial substance . (A) the aqueous antifungal agent according to claim 1 Symbol mounting, characterized in that the myristyl dimethyl amine oxide comprising from 0.05 to 1.0 mass%.