JPH07206609A - Antimicrobial agent - Google Patents

Abstract

PURPOSE:To provide a new type antimicrobial and antiseptic agent capable of reducing and killing various microorganisms in a wide range. CONSTITUTION:An antimicrobial agent contains a nitrogen-containing halogen compound of formula I (R1,R2 are H, methyl, carboxylmethyl, hydroxyethyl, Cl, Br or I, but at least one of the R1 and R2 is Cl, Br, I; n is 0-2; X is H, carboxyl, N,N-dicarboxymethylamino, sulfonic acid, amino, polyaminoethyl), e.g. taurine chloramine. The compound of formula I is obtained by reacting a nitrogen containing organic compound of formula II (R1,R2 are H, methyl, carboxymethyl, hydroxyethyl; n, X are the same as the n, X of formula I) or its salt with (A) a halogen or (B) a hypohalogenous acid and/or its salt, or by mixing the nitrogen-containing organic compound of formula II or its salt with (C) a halide and subsequently electrolyzing the mixture solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicide, and more particularly to a novel fungicide containing a nitrogen-containing halogen compound as an active ingredient.

[0002]

2. Description of the Prior Art Chlorine, hypochlorous acid, hypochlorite, dichloroisocyanurate, bleaching powder, and other halogen-based preparations represented by chlorine have strong oxidizing power, but on the other hand, they are uncomfortable. Since it has the disadvantage of releasing various bleaching tools, its use as a germicide is therefore limited. Especially, it is not used for household disinfectants, disinfectants for toilets, living rooms, refrigerators, etc. due to the smell of chlorine.

On the other hand, regarding taurine chloramine, the following chemical compound 3 is produced by the action of the enzyme myeloperoxidase in vivo.
It is known to produce taurine chloramine according to the reaction formula shown in (Eur. J. Biochem.
Vol. 45, 305-312, 1974), taurine chloramine is not known to be used as a sterilizing or disinfecting agent in vitro.

[0004]

[Chemical 3]

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to develop a new system for sterilizing and disinfecting various microorganisms in a wide range and very efficiently.

[0006]

The present invention has been made in order to achieve the above-mentioned object, and taurine chloramine produced in vivo does not decompose even in a severe environment in vitro. Moreover, we have obtained extremely effective new knowledge that it kills various microorganisms such as bacteria and fungi extensively and extremely strongly. Furthermore, they have found that this novel and useful bactericidal and disinfecting action is also found in other nitrogen-containing halogen compounds, and completed the present invention.

That is, the present invention has as its basic technical idea a bactericide containing a nitrogen-containing halogen compound having the general formula (I) represented by the following chemical formula 4.

[0008]

[Chemical 4]

The fungicide according to the present invention is produced by subjecting a nitrogen-containing organic compound (and / or a salt thereof) having the general formula (II) shown below to halogen treatment. Examples of the halogen treatment include reaction with halogen, reaction with hypohalous acid / a salt thereof, electrolysis of a mixed solution with a halogenated salt, and the like.

[0010]

[Chemical 5]

As the compound represented by the general formula (I),
For example, taurine chloramine is exemplified. To artificially produce this taurine chloramine (referring to taurine monochloramine and / or taurine dichloramine): 1) Taurine / a salt thereof and hypochlorous acid / a salt thereof React. 2) React with taurine / salt and chlorine. 3) Electrolyze the mixed solution of taurine / a salt thereof and a halogenated salt. Various halogen derivatives other than chlorine can be easily obtained by treating according to the above.

In the case of producing the fungicide according to the present invention, the above-mentioned compound is used as one of the raw material compounds, and the preferable examples thereof include the following: sulfamic acid , Glycine, sarcosine, 2-aminoethanol, 2-aminoethanol acid sulfate, taurine, methyltaurine, N, N-dihydroxyethyltaurine, ethylenediamine, ethylenediamine-4acetic acid (EDTA), polyethyleneimine and urea,
Ammonia / (bi) carbonate, these mineral salts.

Examples of the halogen compound which reacts with the above-mentioned nitrogen-containing compound include the following. 1) Direct reaction: Halogen gas, halogen water, hypohalous acid / alkali (earth) metal salt 2) Electrolysis: Alkali (earth) metal salt of halogenated compound (chlorine, bromine, iodine)

In the above reaction, when the reaction is carried out directly, the nitrogen-containing compound, the halogen gas, the halogen water and the hypohalous acid / alkali (earth) metal salt may be reacted in an aqueous solution. In the case of electrolysis, it can be easily produced by putting an aqueous solution of a nitrogen-containing compound and a halogen salt in an electrolytic cell and energizing.

Alternatively, the aqueous fungicide according to the present invention can be directly produced by mixing the nitrogen-containing compound / the salt thereof (general formula II) and the chlorine-based preparation in an aqueous system. For example, by dissolving the compound of the general formula (II) in water and then mixing this with a chlorine-based formulation (which may be watered), the desired aqueous solution of the bactericide can be directly produced. This method is particularly suitable, for example, for fresh preparation.

In the above, as the chlorine-based preparation, chlorine, hypochlorous acid (salt), dichloroisocyanuric acid salt, bleaching powder, as well as mold killer (trade name) and other commercially available products can be appropriately used.

In the present invention, salts include not only alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, but also mineral salts, (bi) carbonates and various inorganic or organic salts. Widely include.

Regarding the active ingredient compounds of the present invention such as taurine chloramine, N-methyl taurine chloramine and N-chlorosarcosine, their production or their existence can be confirmed by the ultraviolet absorption spectrum. Products such as taurine chloramine are relatively stable, but it is better to make them just before use. The molar ratio at the time of the reaction is 0.25 mol or more, preferably 0.5, of a nitrogen compound with respect to 1 halogen atom.
-2 mol is good.

The bactericide according to the present invention is a conventional external sterilizer,
It can be used just like a disinfectant. Moreover, since there is no strong irritation, no particular side effect is observed even if it adheres to the skin, and there is an advantage that the safety is high.

Furthermore, in the present invention, a nitrogen-containing compound (general formula II) and a commercially available chlorine-based preparation are prepared separately, and when both are mixed in an aqueous system at the time of use, the desired concentration can be freely obtained. It is possible to obtain the bactericide of the present invention, and the present invention is also excellent in this respect.

The present invention will be further described below with reference to Examples. The effective chloride ion concentration was determined by titration with sodium thiosulfate after adding potassium iodide to the aqueous solution.

[0022]

[Example 1: Preparation of taurine chloramine aqueous solution] Water 50
11.3 g of taurine was dissolved in a flask containing g, and mold killer (trade name: effective chloride ion concentration 3.24) was added to the solution.
% (W / w)) 99.05 g was mixed so that the inside of the flask would not foam. The prepared aqueous solution had an effective chlorine ion concentration of 2,000 ppm.

[0023]

[Example 2: Bactericidal test against bacteria] The aqueous taurine chloramine solution prepared in Example 1 was used at a predetermined concentration (p
pm) and added to the broth medium. Then, the bacteria (Escherichia c
oli K-12, Staphylococcus a
ureus 209P, Pseudomonas ae
ruginosa) was inoculated with 1 platinum loop each. 37
After culturing at 72 ° C. for 72 hours, the viability of the cells was determined by the turbidity of the medium. As a control, the physiological saline used for dilution of taurine chloramine was used. In addition, mold killer without taurine was used as a comparison. The results are shown in Table 1 below.

[0024]

[Table 1]

[0025]

[Example 3: Fungicidal test against fungi] The aqueous solution of taurine chloramine prepared in Example 1 was added to PD agar medium to a predetermined concentration to prepare a plate medium. Fungus (Penicillium citrinum, Asp
ergillus niger, cultivated at 25 ° C. for 7 days, 1 platinum loop volume of 5 ml of suspension (polysorbate 80)
0.05% physiological saline) to make a spore suspension,
The 1 platinum loop was streak-inoculated on a drug-added or non-added control plate. As a comparison, physiological saline was used for no drug addition, and mold killer without taurine was used for comparison. 25 ° C
After culturing for 7 days, the presence or absence of cells on the plate was judged. The results are shown in Table 2 below.

[0026]

[Table 2]

[0027]

Example 4 Preparation of Taurine Bromamine Aqueous Solution 150 ml of an aqueous solution of taurine 0.1M and potassium bromide 0.2M was dissolved in a platinum electrode plate at a voltage of 15V to 3 ml.
Electrolysis was carried out for an hour. This aqueous solution has an effective bromine concentration of 17
It was 70 ppm. The effective bromine concentration complies with the method for measuring the effective chlorine concentration. [0028]

Example 5: Preparation of taurine-iodamine aqueous solution 100 ml of an aqueous solution of taurine 0.05M and potassium iodide 0.1M was electrolyzed at a voltage of 15V for 3 hours using a platinum electrode plate. This aqueous solution had an effective iodine concentration of 1140 ppm. The effective iodine concentration conforms to the method for measuring the effective chlorine concentration. [0029]

Example 6: Fungicidal test against fungi The taurine bromamine aqueous solution prepared in Example 4 is added to PD agar medium to a predetermined concentration to prepare a plate medium. To this, fungus (Aspergillus niger, Pe
A spore suspension was prepared by using 5 ml of a suspension (polysorbate 80 0.05% physiological saline) of 5 ml of one platinum loop of Nichillium citrinum (cultivated at 25 ° C. for 7 days). Inoculate a streak onto a control plate. After culturing at 25 ° C. for 7 days, the presence or absence of cells on the plate is evaluated. The results are shown in Table 3 below.

[0030]

[Table 3]

[0031]

[Example 7: Test of bactericidal activity against fungi] The taurine-iodamine aqueous solution prepared in Example 5 is added to PD agar medium to a predetermined concentration to prepare a plate medium. To this, fungus (Aspergillus niger, Pe
spore suspension was prepared by using 5 ml of a suspension (polysorbate 80 0.05% physiological saline) of 5 ml of 1 platinum loop of Nitricillium citrinum (cultivated at 25 ° C. for 7 days). Inoculate the streak onto the added control plate. After culturing at 25 ° C. for 7 days, the presence or absence of cells on the plate is evaluated. The results are shown in Table 4 below.

[0032]

[Table 4]

[0033]

Example 8 250 m containing 12.5 gr (0.1 mol) of taurine and 3.55 gr (0.1 atom) of available chlorine
1 of sodium hypochlorite was mixed and dissolved to obtain a colorless and odorless taurine chloramine solution.

[0034]

[Embodiment 9] Inner diameter 100 mm and height 45 mm in a refrigerator
Place a platinum electrode in a cylindrical electrolytic cell made of glass of 100mM including taurine 5mMOL and potassium chloride 10mMOL.
The 1-solution was electrified at 18 V and 0.3 A for electrolysis for 3 hours. As a result, a taurine chloramine solution containing 0.14% of available chlorine was obtained.

[0035]

[Embodiment 10] The same procedure as in Embodiment 8 is carried out to obtain chlorine water and N
An N-methyl taurine chloramine aqueous solution containing 0.3% of available chlorine was obtained from -methyl taurine.

[0036]

[Example 11] Taurine of Example 9 was replaced with 2-aminoethanol, and potassium chloride was replaced with potassium bromide to obtain 15V, 0.1.
5A was flown and electrolysis was performed for 3 hours to obtain a bromine-containing germicide.

[0037]

Example 12 1.5 V, 0.28 with taurine in Example 9 replaced with ethylenediamine and potassium chloride replaced with potassium bromide
A was flown and electrolysis was performed for 3 hours to obtain a bromine-containing germicide.

[0038]

Example 13 250 containing 8.9 gr (0.1 mol) of sarcosine and 3.55 gr (0.1 atom) of available chlorine.
By mixing and dissolving ml of hypochlorite, a colorless and odorless N-chlorosarcosine solution was obtained.

[0039]

INDUSTRIAL APPLICABILITY According to the present invention, a new type of sterilization capable of widely inhibiting and killing various microorganisms,
A disinfectant is provided.

Claims (6)

[Claims] 1. A bactericide comprising a nitrogen-containing halogen compound having the general formula (I) represented by the following chemical formula 1. [Chemical 1] 2. A nitrogen-containing halogen compound having the general formula (I) is a nitrogen-containing organic compound having a general formula (II) represented by the following chemical formula (II) (salt thereof), which is any of (A) to (C). The bactericide according to claim 1, wherein the bactericide is treated by the method of (1): (A) is reacted with halogen; (B) is reacted with hypohalous acid and / or a salt thereof; (C) The mixed solution with the halogenated salt is electrolyzed. [Chemical 2] 3. A nitrogen-containing halogen compound having the general formula (I), characterized in that the nitrogen-containing compound having the general formula (II) (salt thereof) and a chlorine-based preparation are mixed in an aqueous system. Aqueous fungicide. 4. The bactericide according to claim 3, wherein the chlorine-based preparation is chlorine, hypochlorous acid, hypochlorite, dichloroisocyanurate, or a bleaching powder. 5. A nitrogen-containing compound having the general formula (II) is
Sulfamic acid, glycine, sarcosine, 2-aminoethanol, 2-aminoethanol acidic sulfate, taurine, methyltaurine, N, N-dihydroxyethyltaurine, ethylenediamine, ethylenediamine-4acetic acid (EDTA), polyethyleneimine, urea, ammonia, The fungicide according to any one of claims 2 to 4, which is selected from the group consisting of the mineral acid salt, ammonia carbonate, and ammonia bicarbonate. 6. A fungicide, which comprises an aqueous solution of taurine chloramine as an active ingredient.