JP3151016B2 - Vaporizable fungicide and fungicide and method for fungus and fungus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing bacteria,
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vaporizable fungicidal / fungicidal agent for preventing the occurrence of fungi and a method for achieving fungicidal / fungicidal use using the same.

[0002]

2. Description of the Related Art As methods for suppressing the generation of bacteria and molds, there are two methods: (i) indirect means such as removal of nutrients, drying, and maintenance of anoxic condition (in the case of aerobic bacteria); ) There are methods using direct killing means such as heating, ultraviolet irradiation, and disinfectant treatment.

[0003] What measures to take to control the occurrence of bacteria and molds are actually limited by the structure and characteristics of the object, conditions of the storage place, safety issues, and the like.

[0004] For example, when the object is clothing, leather goods, books, paintings, etc., spraying or impregnating the agent with a fungicidal and / or fungicidal agent does not affect the subject even if the fungicidal / antifungal effect is great. It is unsuitable because of possible contamination. In such a case, a method using a dehumidifier using a hygroscopic agent such as silica gel, calcium chloride, or a method of suppressing the growth of bacteria and mold using a deoxidizer using iron powder is appropriate. As a more effective method, a method using a vaporizable fungicide / fungicide is suitable.

[0005] As the vaporizable fungicide and fungicide for this purpose, conventionally, camphor, naphthalene, paradichlorobenzene, orthophenylphenol, parachlorometacresol, parachlorometaxylenol, pentachlorophenol, α
-Bromcinnamaldehyde, 3-methyl-6-isopropylphenol, stabilized chlorine dioxide and the like have been used or proposed. Among them, α-bromocinnamaldehyde is disclosed in JP-B-46-11044,
Japanese Patent Publication No. 50-19605 discloses a method, and 3-methyl-6-isopropylphenol is disclosed in
This is disclosed in -87602.

[0006]

However, since the above-mentioned vaporizable fungicide has an unpleasant odor, it may give an unpleasant feeling to a handler or smell the object.
It may cause stains such as stains, discoloration, and coloring on the target object, that the toxicity may not be negligible, and that the antibacterial and antifungal effects are often insufficient as in the comparative examples described below. There were problems, and they did not always achieve the intended purpose.

[0007] Under such a background, the present invention not only has an excellent antibacterial and fungicidal effect, but also has no unpleasant odor, does not contaminate the object, and has a low toxicity. An object of the present invention is to provide a fungicide and a method for preventing germs and fungi using the same.

[0008]

DISCLOSURE OF THE INVENTION The vaporizable fungicide of the present invention is 3-iodo-2-Nn-butylcarbamic acid.
It utilizes a vaporized gas of propynyl ester.

Further, in the method of the present invention, a space in which a vaporized gas can be retained is filled with a vaporized gas of N-n-butylcarbamic acid 3-iodo-2-propynyl ester, and the object to be brought into contact with the vaporized gas. It is characterized in that it is intended to prevent bacteria and fungi of the product.

Hereinafter, the present invention will be described in detail.

Nn-butylcarbamic acid 3-iodo-
The 2-propynyl ester is a white to pale yellow crystalline powder or granular solid, has a negligible odor, and is stable over a wide pH range from weakly acidic to slightly alkaline. Low toxicity, acute toxicity LD50 Oral 1470mg / kg (rat) 2000mg / kg / quail (quail) Dermal 2000mg / kg / rat (rat) 2000mg / kg / rat (rabbit) No reported skin irritation Have been. further,
Even if the compound itself or its vaporized gas touches an object such as clothing, no coloring or contamination occurs. Therefore, at least in the range of the practical use amount described later, the above-mentioned problems of off-flavor, coloring / contamination, and toxicity do not occur at all.

The Nn-butylcarbamic acid 3-iodo-2-propynyl ester is gradually vaporized even at room temperature, and the vaporized gas effectively prevents the generation of bacteria and mold. The effect is greater than the antibacterial and antifungal effect of the conventional vaporizable antifungal agent described above.

[0013] Nn-butylcarbamic acid 3-iodo-2-propynyl ester itself is a compound already known as a bactericide, and is used in the form of oils, emulsions, powders, and wettable powders. I have. However, the antibacterial and antifungal effects of this compound on "vaporized gas" are unknown, and such compounds have not been used in the past.

[0014] In the present invention, the vaporizable germicidal fungicide comprises:
The above-mentioned Nn-butylcarbamic acid 3-iodo-2-propynyl ester is used in various forms as it is, or by holding it on a suitable carrier or substrate, or adding a suitable compounding agent.

As such a form, for example, (a)
Powder or tablet form, (b) alcohols, ketones, ethers, petroleum, solutions dissolved in solvents such as halogenated hydrocarbons, or emulsifiers emulsified in water by adding emulsifier, paper, Textile woven fabric, non-woven fabric, wood and bamboo products, pottery, charcoal,
Activated carbon, silica gel, activated alumina, silicic acid anhydride, talc, gypsum, diatomaceous earth, zeolite, cyclodextrin, etc. The form of the material kneaded into it, (d) paradichlorobenzene,
Examples include the form of a composition formed by mixing with a sublimable substance such as naphthalene, adamantane, and the like, and each form may be used in combination.

The place where the vaporizable fungicide / fungicide of the present invention is used must be a space in which vaporized gas can stay to some extent. Such places include Komuro, closet,
Examples include a closet, a clothing box, a clog box, a storage box, a cabinet, a storage bag, a storage box, inside individual shoes, in a cover of a clothes hook, under a tatami mat, and the like. If the vaporizable antibacterial and fungicide of the present invention is put in such a place, the vaporized gas of Nn-butylcarbamic acid 3-iodo-2-propynyl ester is filled and stored therein. It is possible to prevent the generation of bacteria and molds for a long time on the object. The germicidal and fungicidal effect can also be improved by wrapping or contacting the object with a processed material containing the vaporizable germicidal and fungicide of the present invention.

The amount of the vaporizable germicidal fungicide of the present invention used is
Since the gas generation rate of Nn-butylcarbamic acid 3-iodo-2-propynyl ester and the amount of N-butylcarbamic acid 3-iodo-2-propynyl ester reaching the object are related, the operating temperature, Nn-butylcarbamic acid 3-iodo-2-propynyl ester, surface area of the ester, the presence of the vaporized auxiliary substances, can not be indiscriminately defined by the degree or the like of the sealing site of use, the closed space 1 m ³ per at 25 ° C.
0.01 g to 100 g, preferably 0.1 g to 20 g
It is. Nn-butylcarbamic acid 3-iodo-2-
If the amount of propynyl ester used is less than the lower limit, the effect is insufficient, and if the amount exceeds the upper limit, no particular adverse effect is observed, but no increase in fungicidal and fungicidal effects is expected, and economically Disadvantageous.

The volatile fungicide of the present invention comprises a volatile insecticide such as camphor, paradichlorobenzene, naphthalene or empentrin, 3-methyl-6-isopropylphenol, alkyl benzoate or the like as an active ingredient. Vaporizable antibacterial agent, dicyclohexylammonium nitrite, in combination with a vaporizable rust inhibitor such as benzotriazole,
Applications can be expanded and effects can be enhanced.

[0019]

[Action] 3-iodo-2-Nn-butylcarbamic acid
The propynyl ester is gradually vaporized even at room temperature, and the vaporized gas effectively prevents the generation of bacteria and molds.

[0020]

The present invention will be described in more detail with reference to examples and comparative examples.

Examples 1 to 4, Comparative Examples 1 to 5, and Comparative Example 1 The following chemicals were used as isopropanol solutions, and the solutions were applied to a circular filter paper (No. 3 manufactured by Advantech Toyo Co., Ltd.) having a diameter of 90 mm. Evaporate the solvent at room temperature and dry. 0.1mg, 1mg, 3mg,
A sample was prepared so as to adhere to 10 mg or 30 mg. BCIP: N-n-butylcarbamic acid 3-iodo-2-propynyl ester PDCB: p-dichlorobenzene TBZ: 2- (4-thiazolyl) benzimidazole MIP: 3-methyl-6-isopropylphenol PCMX: p-chloromethaxylenol

On the other hand, 5 ml of JIS Z was placed on the bottom of a waist high petri dish (diameter: 90 mm, height: 158 mm) (internal volume: 1,000 ml).
After injecting and solidifying 2911 inorganic medium, the mixture was allowed to stand at room temperature for 24 hours in combination with the canopy of the above-mentioned petri dish, and Nn-
A test medium was prepared by bringing a vaporized gas of butylcarbamic acid 3-iodo-2-propynyl ester (BCIP) into contact with the medium. Next, on the medium, Aspergillus niger, Penicillium citrinum, Cladospo
Each of the cells of rium cladosporioides and Myrothecium verrucaria was punched out with a 5 mm diameter cork borer and placed on the floor.

After the filter paper sample prepared by the above-described method is fixed to the top of the petri dish with a vinyl tape and fixed,
Culture was carried out at 28 ° C. for 14 days together with the bottom of the petri dish, and the growth status of the mold on the medium was observed, and judged by the following criteria. As a control example 1, a blank test was performed simultaneously. Table 1 shows the results. 0: No growth of cells was observed. 1: Growth diameter of bacterial cells less than 10 mm 2: Growth diameter of bacterial cells from 10 mm to less than 20 mm 3: Growth diameter of bacterial cells from 20 mm to less than 30 mm 4: Growth diameter of bacterial cells: 30 mm or more

[0024]Table 1 Example Comparative example Control example 1 2 3 4 1 2 3 4 5 1 Drugs used BCIP BCIP BCIP BCIP PDCB TBZ MIP PCMX PCMX- Use amount (mg / 1000ml) 10 3 1 0.1 30 30 10 1 0.1 0 A. niger 0 0 0 1 4 4 4 2 4 4 P. citrinum 0 0 1 2 4 4 4 2 4 4 C. cladosporioides 0 0 0 0 2 2 1 2 1 2 M. verrucaria 0 0 1 2 4 4 1 2 3 4

From Table 1, it can be seen that Nn-butylcarbamic acid 3
-Iodo-2-propynyl ester (BCIP) is composed of parachlorometaxylenol (PCMX) and 3-methyl-6-isopropylphenol (MIP), which are relatively effective among conventional vaporizing fungicides. It can be seen from comparison that the efficacy is several to several tens of times greater. Nn-butylcarbamic acid 3-iodo-2-propynyl ester (BCIP) is also excellent in that it has almost no odor.

Examples 5 to 8 and Control Example 2 3-methyl-3 using Nn-butylcarbamic acid 3-iodo-2-propynyl ester (BCIP) as a solvent
Dissolved in methoxybutanol and the solution
After adhering a predetermined amount to a polypropylene fiber non-woven fabric with a basis weight of 30 g / m ² cut into a circular shape of mm, the solvent was sufficiently evaporated and dried at room temperature, and N-n-butylcarbamic acid 3-iodo-2 per one non-woven fabric was used. -Propynyl ester (BCI
P) was prepared so as to adhere to 0.1 mg, 1 mg, 3 mg or 10 mg to prepare a sample.

Next, the nonwoven fabric sample was attached to a canopy of a waist high petri dish (inner volume: 1000 ml) having a diameter of 90 mm and a height of 158 mm with a vinyl tape and fixed.

On the other hand, 5 ml of an ordinary agar medium was injected and solidified at the bottom of the petri dish, and then allowed to stand at room temperature for 24 hours together with the canopy of the petri dish to give 3-iodo-2-Nn-butylcarbamic acid. -Propynyl ester (BCI
The vaporized gas of P) was brought into contact with the medium to obtain a test medium.

Next, Staphylococcus aureus was used as a cell.
And Bacillus cereus with physiological saline for about 10
^{A 6} / ml bacterial solution was prepared, streaked on this medium with a platinum loop, and then cultured at 37 ° C. for 24 hours with the canopies together to observe the growth of the bacteria. As a control example 2, a blank test was performed simultaneously. Table 2 shows the results.

The growth of the cells was evaluated according to the following criteria. -: No growth of bacterial cells was observed. +: Growth of bacterial cells is observed (the larger the number of +, the larger the number of growth).

Table 2 Example Control Example 5 6 7 8 2 Drugs used BCIP BCIP BCIP BCIP- Usage (mg / 1000 ml) 10 3 1 0.10 Cell growth status S. aureus---+ +++++ B. cereus--+++ +++++

From Table 2, it can be seen that Nn-butylcarbamic acid 3
It can be seen that a sufficient antibacterial and antifungal effect can be obtained when the amount of iodo-2-propynyl ester (BCIP) used is about 1 to 3 mg / 1000 ml.

[0033]

According to the present invention, the vaporizable fungicide / fungicide of the present invention has an excellent effect of effectively preventing the generation of bacteria and molds simply by placing it in a space where vaporized gas can stay.
In addition to being easily handled, there is an advantage that the object is not stained or deteriorated during use, has almost no odor, and has high safety.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Fusao Matsuoka 2-6-11 Nakajima, Nishiyodogawa-ku, Osaka-shi, Osaka Inside the head office plant of Osaka Chemical Co., Ltd. (56) References JP-A-2-191204 (JP, A JP-A-50-31036 (JP, A) JP-A-3-184904 (JP, A) JP-A-2-152911 (JP, A) Japanese Society of Antimicrobial and Fungicide Dictionary Editing Committee, "Antibacterial and antifungal agent" Dictionary, (Showa 61-8-22), Japan Society of Antimicrobial and Fungicide p. 221 “Bactericidal and fungicide” 18 [8] (1990) pp. 365-370 (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 47/12 A01N 25/18 102

Claims (2)

(57) [Claims] (1) Niobutylcarbamic acid 3-iodo-
A vaporizable fungicide / fungicide utilizing a vaporized gas of 2-propynyl ester. 2. A space in which a vaporized gas can stay is filled with a vaporized gas of N-n-butylcarbamic acid 3-iodo-2-propynyl ester, and fungicide and fungicide of an object contacting the vaporized gas is achieved. A method for preventing germs and fungi, characterized by: