JP3208074B2 - Fungicide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used in a wide range of fields such as medical treatment, industry, and agriculture, has no foaming property, is easy to clean, has a low unpleasant odor of iodine molecules in a practical concentration range, and has a bactericidal effect. It relates to an excellent fungicide.

[0002]

_2. Description of the Related Art Iodine molecules (I ₂ ) are the oldest and used iodine fungicides as main components of tincture of iodine and the like. It is irritating, and has drawbacks such as dyeability to the skin and instability to light. Further, the transpiration from the solution is intense, which not only promotes instability, but also gives an unpleasant odor and corrodes metals around the solution.

[0003] To overcome some of these disadvantages of iodine molecules, iodoholes such as povidone iodine have been developed. These suppress irritation while maintaining high bactericidal activity by binding iodine molecules to the carrier,
Prevents iodine sublimation and transpiration. However, dilution to a low concentration releases iodine molecules, which limits the concentration that has advantages for iodine molecules. In addition, since the carrier has foaming properties, it takes a lot of time and labor to clean, and in addition, the production requires a complicated process, which is expensive.

[0004] Therefore, there is no foaming property and cleaning is easy.
There is a need for a disinfectant that exhibits a sufficient disinfecting effect in a practical concentration range that exhibits a sufficient disinfecting effect, has a low unpleasant odor of iodine molecules, and has an excellent disinfecting effect.

[0005] An object of the present invention is easy to wash without foaming, practical less unpleasant odor molecular iodine at a concentration range to provide an excellent sterilizing agent bactericidal effect.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a liquid obtained by adding an alkali to an acidic aqueous solution containing iodine ions (I ⁻ ) and manganese ions (Mn ²⁺ ). Have a strong bactericidal activity, and have completed the present invention.

Incidentally, iodine is an iodine molecule (I
₂₎ hypoiodite, hypoiodite ion, iodate ion, iodide ion (I ^-), it is present in the form such as a three iodine ions, having the inner bactericidal activity, molecular iodine, hypochlorous It is iodic acid and hypoiodite ion, and it is said that iodine ion alone, which is a component of the present invention, has no bactericidal activity. Also, the bactericidal activity of manganese ions alone is not known.

That is, the present invention is characterized by being obtained by adding an alkali to an acidic aqueous solution containing iodine ion (I ⁻ ) and manganese ion (Mn ²⁺ ) and adjusting the pH to 2.5 to 7.0. Disinfectant.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

The iodine ion in the present invention is provided by iodide which dissociates into iodine ion in an aqueous solution.
As the iodide, iodine ion (I ⁻ )
The compound is not particularly limited as long as it is a compound that dissociates into an alkali metal iodide (specifically, sodium iodide, potassium iodide, etc.) and an alkaline earth metal iodide (specifically, magnesium iodide, And the like. Specific examples of the non-metallic iodide include ammonium iodide.

The manganese ion (Mn ²⁺ ) in the present invention
Is provided by a compound that dissociates into manganese ions in aqueous solution. The compound is not particularly limited as long as it is a compound that dissociates into manganese ions in an aqueous solution. For example, a salt with an acid and manganese (specifically, manganese sulfate,
Manganese chloride) and a double salt containing an acid and manganese (specifically, manganese ammonium sulfate and the like).

[0012] acidic aqueous solution containing iodine ions and manganese ions in the present invention, the acidic solution obtained by adding an acid in water, dissociate into manganese ions in an iodide and an aqueous solution dissociates into iodide ion in aqueous solution Obtained by dissolving the compound. Alternatively, it can be easily prepared according to a normal method for preparing an acidic aqueous solution such as mixing an acid with an aqueous solution containing iodine ions and manganese ions.
Further, it can be prepared by adding an acid to alkaline or neutral natural water containing iodine ions and manganese ions, but is not particularly limited to the above method.
The acid used here is preferably an inorganic strong acid such as sulfuric acid, hydrochloric acid and nitric acid. It is also possible to directly use acidic natural water containing iodine ions and manganese ions as an acidic aqueous solution containing iodine ions and manganese ions.

The alkali used in the present invention is not particularly limited as long as it is a compound which shows alkalinity when converted into an aqueous solution or a compound which can be added to an acidic aqueous solution to bring the pH closer to neutrality. For example, alkali metal and alkaline earth metal hydroxides (sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc.), alkaline earth metal oxides (magnesium oxide,
Salts such as calcium oxide), salts which exhibit alkalinity in the form of an aqueous solution (such as sodium metasilicate), and salts (such as sodium carbonate and sodium acetate) which bring the pH closer to neutrality by being added to an acidic aqueous solution.

The bactericide of the present invention can be used directly as a bactericidal solution by adjusting the concentration of manganese ion and iodine ion in an acidic aqueous solution so as to have a bactericidal activity suitable for the purpose, and adding an alkali thereto. . Alternatively, a bactericide may be prepared by adding an alkali to manganese ions and iodine ions having a higher concentration than the required bactericidal activity, and the bactericide may be diluted and used as a bactericidal solution.

In the present invention, the weight ratio of manganese ion to iodine ion in the acidic aqueous solution is usually from 10: 1 to 10: 1.
The ratio is preferably 1:30, particularly preferably 1: 1 to 1:10. In addition, since the bactericidal activity greatly depends on the ionic species having a small content of manganese ions or iodine ions contained in the acidic aqueous solution, the ratio of manganese ions to iodine ions closer to 1 is higher for the ion concentration. This is preferable in that the bactericidal activity is efficient.

A high ratio of iodine ions to manganese ions is preferable in that precipitation does not easily occur.

In the present invention, the concentration of iodine ions in the acidic aqueous solution is usually preferably 1 ppm or more, which shows strong bactericidal activity. However, from the viewpoint of good bactericidal activity efficiency per ion concentration, the concentration of iodine ions is 10,000 ppm or less. Is preferred.

The amount of the alkali added to the acidic aqueous solution in the present invention is excellent in preventing precipitation.
Any amount may be used as long as the pH after the addition becomes 2.5 to 7.

[0019]

The present invention will be described below in detail with reference to Test Examples and Examples. In the following, "%" means% by weight. Unless otherwise specified, iodine ions were prepared from potassium iodide and manganese ions were prepared from manganese sulfate, and the bactericidal activity was measured by a bactericidal test shown below.

Bactericidal test [0020] Staphylococcus aureus FDA 209P strain cultured at 37 ° C overnight in SCD medium “Digo” (manufactured by Nippon Pharmaceutical Co.) was inoculated into 5% volume SCD medium. The cells were cultured with shaking at 37 ° C. for 2 hours. The cells were washed twice with a saline solution (8 g / l) at room temperature, suspended in an equal volume of the same saline solution, diluted with the same saline solution so that OD ₃₉₀ = 1.0, and kept at 25 ° C. . Test sample 4
0.04 ml of the cell suspension was added to each ml, and the change in the number of viable cells was maintained when the suspension was kept at 42 ° C. for 10 minutes. The initial number of bacteria in this test was 1-2 × 10 ⁶ cells / ml.

Test Example 1 (Bactericidal activity of manganese ion and iodine ion) An acidic aqueous solution containing 1 g / l of manganese ion, 1 g / l of iodine ion, and 1 g / l of sulfuric acid was prepared. Similarly, an acidic aqueous solution containing 1 g / l of iodine ion and 1 g / l of sulfuric acid but not containing manganese ion, and 1 g / l of manganese ion
An acidic aqueous solution containing 1 g / l of sulfuric acid but not containing iodine ions was prepared. Note that an aqueous solution of manganese sulfate or manganese chloride was used as the manganese ion, and an aqueous solution of potassium iodide or sodium iodide was used as the iodine ion. These acidic aqueous solutions (pH 1.8-1.9)
Was added with sodium hydroxide to prepare a test solution. Test solution
0.1%, 0.3% in 50 mM phosphate buffer (pH 3.0)
%, And then subjected to a bactericidal test. Table 1 shows the results.

[0022]

[Table 1]

Test Example 2 (Bactericidal activity of manganese ion and iodine ion) An acidic aqueous solution (pH 1.8 to 1.9) containing a maximum concentration of 1 g / l of manganese ion or iodine ion and sulfuric acid of 1 g / l was treated with manganese ion and iodine ion. The compounding ratios were prepared at the respective ratios shown in Table 2. After adding sodium hydroxide to these to adjust the pH to 3.0, 50 mM phosphate buffer (pH
3.0) and subjected to a bactericidal test.

[0024]

[Table 2]

Test Example 3 (Amount of alkali added to acidic aqueous solution and bactericidal activity) An acidic aqueous solution containing 1 g / l of manganese ion and 1 g / l of iodine ion was prepared by changing the concentration of sulfuric acid. These were adjusted to pH 3.0 by adding sodium hydroxide, and then diluted with a 50 mM phosphate buffer (pH 3.0) and subjected to a bactericidal test. Table 3 shows the results. The test liquid without sodium hydroxide did not show any bactericidal activity, and the bactericidal activity increased depending on the amount of sodium hydroxide added. This result indicates that it is necessary to further add an alkali to the acidic aqueous solution containing manganese ions and iodine ions in order to generate bactericidal activity.

[0026]

[Table 3]

Test Example 4 (Type of Acid and Bactericidal Activity) The type of acid was changed, and an acidic aqueous solution containing 1 g / l of manganese ion and 1 g / l of iodine ion was prepared. These were adjusted to pH 3.0 by adding sodium hydroxide, and then diluted with a 50 mM phosphate buffer (pH 3.0) and subjected to a bactericidal test. Table 4
As is clear from the results shown in Table 1, the acidic aqueous solution used in the present invention is not limited to sulfuric acid, and other acids can be used.
When a strong inorganic acid such as sulfuric acid, nitric acid or hydrochloric acid is used, a strong bactericidal activity can be obtained.

[0028]

[Table 4]

Test Example 5 (Type of Alkali and Bactericidal Activity) An acidic aqueous solution containing 1 g / l of manganese ion and 1 g / l of iodine ion was prepared using 1 g / l of sulfuric acid as an acid. After adding various alkalis to these to adjust the pH to 3.0, 50 mM
Was diluted with a phosphate buffer solution (pH 3.0) and subjected to a bactericidal test. As is clear from the results shown in Table 5, the alkali used in the present invention is not limited to sodium hydroxide.
Other alkalis can be used.

[0030]

[Table 5]

Test Example 6 (Effect of pH on bactericidal effect) Manganese ion 1 g / l, iodine ion 1 g / l, sulfuric acid 0.6
Add sodium hydroxide to an acidic aqueous solution containing
H 3.0. 50 mM of this test solution adjusted to various pH
And diluted for bactericidal activity test. As is clear from the results shown in Table 6, the bactericide obtained according to the present invention exhibited a bactericidal effect in a wide pH range from acidic to neutral.

[0032]

[Table 6]

Example 1 (Bactericidal effect) 1 g of concentrated sulfuric acid was diluted with about 950 ml of distilled water, and 1.4 g of manganese sulfate and 1.3 g of potassium iodide were dissolved therein. Add 10 N sodium hydroxide to this acidic aqueous solution to adjust the pH.
Was adjusted to 4.0, and distilled water was added to adjust the liquid volume to 1,000 ml to produce a bactericide.

Using the strains shown in Table 7, the cultivation was carried out for 24 hours for bacteria, 48 hours for yeast, and 72 hours for mold, at the temperature shown in Table 7. After washing these cells with 8 g / l saline, the bacteria count is 10 ⁸ to 10 ⁹ cells / ml and the yeast count is 1
0 ⁶ to 10 ⁷ cells / ml, fungus count 10 ⁴ to 10 ⁵ cells / ml
Was diluted with the same saline to obtain a cell suspension. 0.2 ml of the cell suspension was mixed with 3.8 ml of a test solution obtained by serially diluting a bactericide with distilled water, and the mixture was allowed to stand at room temperature for 4 hours. After applying 0.1 ml of this treatment solution to an agar plate medium, bacteria are
Time, yeast was 48 hours, mold was 72 hours at the temperature shown in Table 7, and the presence or absence of growth was examined. In addition, bacteria are S
The CD medium “Digo” (manufactured by Nippon Pharmaceutical Co., Ltd.) and the yeast and mold used the GP medium “Digo” (manufactured by Nippon Pharmaceutical Co., Ltd.).

[0035]

[Table 7]

As shown in Table 8, the fungicide has a bactericidal effect on a wide variety of bacteria.

[0037]

[Table 8]

Example 2 (Iodine odor, effervescent) The fungicide produced in Example 1 was used. On the other hand, an iodine molecule (I ₂ ) 6 according to the Japanese Pharmacopoeia was used as a control.
0 g and 40 g of potassium iodide were dissolved in 70% by volume of ethanol to make 1,000 ml, thereby producing tincture of iodine.

The iodine ion of the control iodine tincture was 1,
A panel of 12 people compared the iodine odor of a liquid serially diluted with purified water so as to contain 2, 4, and 8 ppm, and the stock solution of this fungicide (iodine content: 1,000 ppm). Four out of twelve responded that they felt an iodine odor almost equivalent to the iodine tincture diluent containing 2 ppm of iodine ions, and eight felt that they felt an iodine odor stronger than the 2 ppm diluent but weaker than the 4 ppm diluent. In addition, this bactericide did not feel any odor other than iodine odor.

The bactericidal activity of a control solution obtained by serial dilution of iodine tincture with purified water and a solution obtained by serially diluting the present disinfectant with purified water were compared in a bactericidal activity test. The bactericidal activity of this fungicide corresponded to iodine molecules 50 ppm to 100 ppm contained in iodine tincture. From this, it was found that the present fungicide has a feature that the iodine odor is low with respect to the fungicidal activity.

No foaming was observed in the present fungicide stock solution or its diluted solution with purified water.

Example 3 (Utilization of Natural Water) As acidic water containing manganese ion and iodine ion, hot spring water springing from Yubatake, Kusatsu-machi, Agatsuma-gun, Gunma Prefecture was used. Collected in the hot spring water manganese ion is 1.5mg / l, an iodine ion was included 0. 3 mg / l. Sodium hydroxide was added to hot spring water having a pH of 2.0 to adjust the pH to 3.0. The unadjusted stock solution and the hot spring water whose pH was adjusted were subjected to a bactericidal test. A solution obtained by diluting sulfuric acid with purified water was used as a control.

As shown in Table 9, a bactericide can be produced by using natural water directly as acidic water containing manganese ion and iodine ion.

[0044]

[Table 9]

[0045]

According to the present invention, there is provided a disinfectant which has no foaming property, is easy to clean, has a low unpleasant odor of iodine molecules in a practical concentration range, and has an excellent disinfecting effect.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI A61P 17/00 101 A61P 17/00 101 (58) Investigated field (Int.Cl. ⁷ , DB name) A61K 33/18 A01N 59 / 12 A01N 59/16 A61K 33/32 A61L 2/16 A61P 17/00 101 BIOSIS (STN) CA (STN) MEDLINE (STN) EMBASE (STN)

Claims (3)

(57) [Claims] 1. An alkali solution is added to an acidic aqueous solution containing iodine ions and manganese ions, and pH 2.5 to pH 7.0 is added.
A fungicide characterized by being obtained by adjusting to 2. The fungicide according to claim 1, wherein the weight ratio of manganese ion to iodine ion is from 10: 1 to 1:30. 3. The fungicide according to claim 1, wherein the manganese ion is derived from manganese sulfate or manganese chloride, and the iodine ion is derived from an alkali metal salt.