JPH11292725A - Antimicrobial agent, its production and antimicrobial treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial agent having high resistance to a sulfide, having both an immediate effect and a residual effect on sterilization and deodorization by including both an oxidizing agent and silver ion. SOLUTION: This antimicrobial agent is obtained by dissolving >=0.05 mg/L silver ion as a chlorine complex in an aqueous solution of a chloride and dissolving an oxidizing agent such as sodium hypochlorite or sodium chlorite in the solution. The antimicrobial agent has a sterilizing and an antimicrobial effects of immediate and residual properties on wide kinds of bacteria and molds and shows instant deodorization by treating an objective with the antimicrobial agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antibacterial agent used for treating sterilization, deodorization, fungicide, etc. of dwellings, hospitals, public facilities, industrial products, industrial wastes, etc., a method for producing the same, and an antibacterial agent. It relates to the antibacterial treatment method used.

[0002]

2. Description of the Related Art In recent years, infections in hospitals such as MRSA and infections such as pathogenic Escherichia coli O-157 in public facilities have become a serious social problem, and measures to prevent them are strongly desired. In addition, as the number of highly airtight dwellings such as condominiums has increased, the demand for fungicides especially in places with high humidity such as bathrooms has been increasing.

Conventionally, disinfection for preventing infection in hospitals and disinfection in dwellings include chlorine-based disinfectants such as sodium hypochlorite, sodium chlorite, sodium dichloroisocyanurate and sodium trichloroisocyanurate; A quaternary ammonium salt such as benzalkonium chloride has often been used.

[0004] In particular, chlorine-based germicides have a bactericidal effect against fungi and bacteria other than Mycobacterium tuberculosis, and have the property of having a broad spectrum such as inactivating viruses,
It has the most common properties, such as being instantly effective, not producing resistant bacteria, not only sterilizing but also being able to oxidize and decompose odor components at the same time, and after decomposition it becomes safe salt or urea etc. It is a fungicide that is commonly used.

However, chlorine-based disinfectants have no residual effect,
When microorganisms newly fly from the outside after the treatment, there is a disadvantage that the growth cannot be suppressed, and the treatment has to be repeated frequently. Also,
Although quaternary ammonium salts have similar germicidal properties to chlorine-based germicides, they cannot decompose odor components, react with anionic surfactants commonly used in the art, and become ineffective. There was a problem that the use was limited as compared with the system bactericide.

On the other hand, as an antibacterial agent having a long-lasting effect, ions of heavy metals such as zinc, silver and copper are generally used. Heavy metal ions exhibit a broad bactericidal spectrum, and have characteristics such as a high bactericidal effect, particularly a long-lasting antibacterial effect against bacteria, and the resistance to resistant bacteria. As a type of heavy metal ion, silver ion is particularly excellent in terms of safety and has been widely used in recent years.

[0007] However, silver ions are insufficient in bactericidal and deodorizing powers immediately after processing as compared with oxidizing agents such as chlorine-based germicides, and in order to exhibit fungicidal properties, silver ions are required for bacteria. It requires a higher concentration of silver ions. Furthermore, when sulfide coexists in the object to be treated,
Since silver ions are converted into sulfides unnecessary for water, the antibacterial effect is significantly reduced thereafter.

[0008]

Therefore, the present inventors show a broad bactericidal spectrum by combining an oxidizing agent having an immediate effect and a silver ion having a residual effect, and resistant bacteria are hardly generated. We studied the development of an antibacterial agent which has high efficacy, exhibits immediate effect and residual effect on sterilization and deodorization, and has high resistance to sulfide.

When combined with an oxidizing agent, silver ions are desirably present in the form of an aqueous solution. As a method for keeping silver ions in a solution, a method of converting silver into a complex salt of thiosulfuric acid or thiocyanic acid, a method of converting silver into amino acid silver, and the like are widely known. However, thiosulfuric acid, thiocyanic acid, and amino acids are decomposed by the oxidizing power of the oxidizing agent, and silver ions, which are active ingredients, are precipitated. Therefore, silver thiosulfate complex, silver thiocyanate complex,
The amino acid silver could not be mixed with the oxidizing agent.

The present invention has been made in view of such a conventional situation,
Oxidizing agent and silver ion coexist, show wide bactericidal spectrum, resistant bacteria are hard to be generated, high safety, high resistance to sulfide, and immediate effect for sterilization and deodorization It is an object of the present invention to provide an antimicrobial agent having both antibacterial and residual effects and a method for producing the same, and a method for treating the same with the antimicrobial agent.

[0011]

In order to achieve the above object, an antibacterial agent provided by the present invention comprises:
It is characterized by containing 0.05 mg / liter or more of silver ions as a chloro complex salt and containing an oxidizing agent.

In this antibacterial agent, the aqueous solution contains at least 2.5 mg / l of silver ion as a chloro complex, and the aqueous solution has a chloride ion content of at least 0.02 mol / l. Preferably, the oxidizing agent is sodium hypochlorite or sodium chlorite.

The method for producing an antibacterial agent according to the present invention comprises mixing an aqueous chloride solution with a silver compound or silver metal, dissolving 0.05 mg / l or more of silver ions as a chloro complex salt in the aqueous solution. It is characterized by dissolving an oxidizing agent.

Further, the antibacterial treatment method according to the present invention uses an aqueous chloride solution containing a chloro complex of silver ion and an oxidizing agent, or an aqueous chloride solution containing a chloro complex of silver ion and an oxidizing agent. The method is characterized by processing an object.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, silver ions are stabilized in the form of a chloro complex salt in order to coexist with an oxidizing agent. The chloro complex of silver ions is stabilized by the presence of high concentrations of chloride ions. The compound supplying chlorine ions is not particularly limited as long as it is a chloride, but, for example, in the case of coexisting with alkaline sodium hypochlorite as an oxidizing agent, it forms a hydroxide even in alkaline. Chloride which does not cause precipitation, specifically, sodium chloride, potassium chloride and the like are particularly desirable.

The chloro complex of silver ion, unlike thiocyanate or thiosulfate, or silver amino acid, is not oxidatively decomposed by sodium hypochlorite.
In addition, since the chloro complex of silver is stabilized by chloride ions, even when a chlorine-based oxidizing agent is used, silver chloride is not generated by mixed chlorine ions and precipitation does not occur.

It is generally known that silver ions change to silver sulfide in the presence of sulfur or sulfide and lose their antibacterial activity. However, in the present invention, by coexisting an oxidizing agent with silver ions, sulfur or sulfide can be oxidized, so that formation of silver sulfide can be prevented.
Therefore, the antibacterial agent of the present invention can be used for antibacterial treatment in a place where sulfur or sulfide exists, to which a conventional silver-based antibacterial agent could not be applied.

The oxidizing agent used in the present invention is not particularly limited, but it is inexpensive, colorless, and sufficiently stable for about several months in an aqueous solution, and is particularly effective immediately. Chlorite and hypochlorite are suitable because of their excellent properties. Hypochlorite is expected to be more immediate, while chlorite is pH
However, since it is near neutral, it is possible to select a wide variety of types of metal ions that can be mixed, and it is characterized by being more stable to decomposition than hypozincate.

Most of the oxidizing agents have the property of reducing their content by self-decomposition, but the chloro complex of silver does not promote the decomposition of the oxidizing agent. The stability of the agent is not impaired.

The antibacterial effect of the antibacterial agent of the present invention described above is exerted when the chloride aqueous solution contains 0.05 mg / liter or more of silver ions. However, even in the presence of an oxidizing agent, when an organic substance containing sulfur in a sulfide form is present, some silver is consumed as silver sulfide.
It is desirable to contain silver ion of 5 mg / liter or more as a chloro complex salt. That is, when the silver ion concentration is less than 2.5 mg / liter, the antibacterial effect is slightly poor.
It is desirable to use it for antibacterial treatment of objects that do not contain sulfide form of sulfur.

The chloride concentration in the above aqueous solution can be appropriately determined according to the required silver ion concentration.
For example, if the chloride ion concentration is 0.003 mol / l or more, silver can be dissolved as a chloro complex ion, but the silver ion concentration is set to 2.5 mg / l or more which is effective even in the presence of sulfide. For this purpose, the chloride ion concentration is preferably set to 0.02 mol / liter or more. Further, the concentration of the oxidizing agent in the aqueous solution can be used at an arbitrary concentration. It is desired to do.

As described above, the antibacterial agent of the present invention contains, as a main component, a chloro complex of an oxidizing agent and silver ion, and a chloride for stabilizing the chloro complex.
Surfactants, fragrances, dyes and the like can be included.

As a method of producing the antibacterial agent of the present invention, an aqueous chloride solution having a predetermined concentration is mixed with a silver compound or silver metal, and 0.05 mg / liter or more of silver ion is added to the aqueous chloride solution. Dissolve as chloro complex.
Furthermore, in a chloride aqueous solution containing this silver as a chloro complex salt,
An antimicrobial agent can be obtained by dissolving the oxidizing agent at a predetermined concentration.

In the antibacterial treatment method according to the present invention, an object is treated using an aqueous chloride solution containing a chloro complex of silver ion and an oxidizing agent, which is an antibacterial agent of the present invention. Alternatively, the treatment may be performed using a chloride aqueous solution containing the compound and an oxidizing agent. When the antibacterial agent of the present invention is used, it can be treated with a stock solution, but there is also a method of treating with the stock solution and washing with water, or a method of diluting the stock solution with water and then treating.

When treated with the stock solution, the oxidizing agent has immediate effect, and the chloro complex of silver ion has residual effect. In the method of washing with water after treating with an undiluted solution, the chloride ion concentration decreases at the time of washing, and the chloro complex salt of silver ion changes to insoluble silver chloride and is fixed on the surface of the object to be treated. The silver chloride produced by this method is a very fine particle, has a strong antibacterial activity for a long period of time because it is dispersed and has a large surface area, and does not cause blackening which is normally observed when silver chloride is produced.
Furthermore, in the method of processing after dilution with water, the chloro complex salt of silver ions changes to silver chloride at the time of dilution, and as in the case of washing with water after undiluted solution treatment, immediate effect by oxidizing agent and residual effect by minute silver chloride Is shown.

Although the present invention is directed to an aqueous solution of an oxidizing agent and a chloro complex of silver, similar effects can be expected for a mixture of a solid chloro complex and a solid oxidizing agent.

[0027]

EXAMPLES Example 1 [Stability of antibacterial agent solution] 35% by weight of sodium chloride
An aqueous solution containing 500 ppm of silver chloro complex salt as silver ion (solution A) and an aqueous solution of sodium hypochlorite containing approximately 137 g / l of available chlorine (solution B) are mixed at a volume ratio of 1: 1. Thus, an antimicrobial solution (solution C) was obtained.

Each of these solutions A, B, and C was stored at 30 ° C. for 50 days, and changes in available chlorine and changes in the state of the solution were investigated. The results are shown in Table 1. As a result, it was revealed that even in the presence of the silver chloro complex salt, the reduction of available chlorine was not promoted, and that the storage stability did not decrease. It was also found that mixing with sodium hypochlorite did not cause the silver chloro complex salt to become unstable and precipitate.

[0029]

TABLE 1 At the start of the study (immediately after mixing) after 30 ° C. 50 days test solution amount of chlorine (g / l) residual ratio (%) a solution state chlorine content (g / l) residual ratio (%) a solution state solution A 0 - Colorless and transparent 0-Colorless and transparent Solution B 137 100 Yellow and transparent 103 75 Yellow and transparent Solution C 67 100 Yellow and transparent 56 84 Yellow and transparent

Example 2 [Antibacterial Effect on Staphylococcus aureus] The antibacterial effect on Staphylococcus aureus was evaluated using the antibacterial agent solution of Example 1 (solution C). The same evaluation was performed using a sodium hypochlorite solution (solution B) as a control. The evaluation method is as follows.

The flooring material (linoleum) was cut into 10 × 10 cm, and boiling for 1 hour was repeated four times in water containing a neutral detergent to remove a plasticizer and the like. A solution B diluted 200 times and a solution C diluted 100 times were sprayed on these flooring materials by spraying at a rate of about 1 ml / sheet. The number of sprays was four every day, every other day, every two days, and once every six days. In each flooring, Staphylococcus aureus 10 ² CFU
/ Ml was sprayed every day about 1 ml / sheet to inoculate. For the section to be treated with the solution C, the inoculation was performed after the floor material surface was dried after the solution treatment. On the 7th day from the start of the test, the YP medium was sprayed on the flooring material, and was sprayed at 30 ° C. and 100% RH for 2 hours.
Cultured for days.

The results obtained are shown in Table 2 below. ○ in the table indicates the day on which the treatment solution was sprayed. As can be seen from Table 2, no residual effect against Staphylococcus aureus was observed in the solution B containing only sodium hypochlorite, but in the solution C diluted to contain the same amount of available chlorine, A residual effect of one day was observed.

[0033]

[Table 2] Spraying frequency of treatment solution Treatment solution 1 day 2 days 3 days 4 days 5 days 6 days No growth of bacteria ------+ + Solution B ○ ○ ○ ○ ○ ○ + Solution B ○-○- ○ − + Solution B ○ − − ○ − − + Solution B ○ − − − − − ++ Solution A ○ ○ ○ ○ ○ ○ − Solution A ○ − ○ − ○ − − Solution A ○ − − ○ − − − Solution A ○ − − − − − + (Note) The indication of the column of bacterial growth is as follows. ++; several hundred colonies / sheet, +; tens of colonies / sheet,-; no colony

Example 3 [Comparison of growth rates] 35 g of calcium chloride and 0.3 g of silver chloride were used.
05 g was dissolved in 100 ml of water to prepare a silver chloro complex salt solution (solution a). Further, a 4.3% sodium chlorite solution equivalent to 3 volumes was added to 7 volumes of the solution a to prepare an antibacterial agent solution (solution b).

Next, Trypto-Soya Brot
h After adjusting the “Nisui” (TSB) medium (manufactured by Nissui Pharmaceutical Co., Ltd.) to pH 7.2, sterilize at 121 ° C. for 15 minutes,
Divided. The solution a or the solution b is added to each TBS medium.
Was added so as to be 0.1% (solution a was 0.5 mg / l and solution b was 0.35 mg / l in terms of Ag concentration).

Each TB to which the above solution a or solution b was added
In the S medium, a bacterial solution of the pre-cultured E. coli (species: Esche
(Richia coli MC1061) was diluted 100-fold, inoculated in an amount of 20 μl, and cultured at 37 ° C. for 28 hours. Meanwhile, a spectrophotometer (Shimadzu SP-2)
Using OA), the absorbance at 660 nm was measured every 60 minutes to obtain the growth curve of FIG. As a control, a culture medium not inoculated with the strain was used, and cultivation was performed in the same manner as described above.

The TBS medium is a medium in which proteins containing sulfur in the form of sulfide, such as peptone and soy peptone, are present. As can be seen from FIG. The growth of the bacteria was suppressed up to 8 hours after the addition of a, and until 19 hours after the addition of the solution b.

Example 4 [Minimum growth inhibitory concentration] Solution a or solution b of Example 3 above
Was used to examine the minimum growth inhibitory concentration against E. coli as in Example 3. That is, Nutrien
t Broth (NB) medium (manufactured by DIFCO) at pH 7.
After adjusting to 2, the mixture was heat-sterilized at 121 ° C. for 15 minutes. Solution a or solution b was added to these mediums so that the concentration of the solution in each medium was as shown in Table 1 below.

Thereafter, a precultured bacterial solution (species: E. coli MC1061) was diluted 100-fold and inoculated in an amount of 20 μl to each medium, and cultured at 37 ° C. for 24 hours. The absorbance of the medium after the cultivation was measured in the same manner as in Example 1. The case where the absorbance was 0.05 or more was defined as "+" (with growth), and the value below "-" (without growth), as shown in Table 3 below. Was.

[0040]

TABLE 3 E. coli growth inhibitory concentration (%) solution a solution b control ++ 0.08 ++ 0.1 ++ 0.2 ++ 0.3 ++ 0.4 ++ 0.5 + -0.6 + -0.7 + -0.8--0.9-- 1.0 − −

As can be seen from Table 3, for a typical gram-negative bacterium E. coli, solution a had a concentration of 0.8%.
(Ag concentration of 4.0 mg / l) or more shows antibacterial activity, whereas solution b further containing oxidizing agent chlorite has a concentration of 0.0
The antibacterial activity was exhibited at 5% (Ag concentration 2.5 mg / l). From this result, it can be seen that the solution b containing the oxidizing agent together with the silver ions has an antibacterial action at a lower concentration than the solution a, even in a medium containing sulfur.

Next, in place of the above E. coli, Staphylococcus Staphyloc, a typical Gram-positive bacterium, was used.
The same test as above was performed using occus aureus IF03183, and the absorbance was measured in the same manner. The results are shown in Table 4 below. From the results shown in Table 4 below, the antibacterial activity against the representative gram-positive bacteria S. aureus was as follows:
Is not less than 1.0% (Ag concentration 5.0 mg / l) or more, whereas solution b has a concentration of 0.5% (Ag concentration 2.5 mg / l).
1), which indicates that the solution b exhibits antibacterial activity at a low concentration.

[0043]

TABLE 4 S. aureus growth inhibitory concentration (%) solution a solution b control ++ 0.08 ++ 0.1 ++ 0.2 ++ 0.3 ++ 0.4 ++ 0.5 + -0.6 + -0.7 + -0.8 + -0.9 +- 1.0 − −

A test similar to that described above was carried out using the E. coli E.
oli MC1061 and Staphylococcus aureus S. aureus
The minimum growth inhibitory concentration (MIC) of the solution b was summarized by performing the test on IFO3183 (both the medium was changed), other bacteria, yeasts, and molds (fungi). The medium used in this test was Escherichia coli E. coli MC1061.
In the dezoxycholate medium, S. aureu
s IFO3183 used MSA medium, other bacteria used NB medium, yeast used SABOURAUD medium, and filamentous fungi used PDA medium. In addition, the culture period was 25 days at 25 ° C. for bacteria for 1 day, yeast for 3 days, and filamentous fungi for 7 days.

As a result, E. coli MC10
61 and S. aureus IFO3183,
MIC 0.5% with the same result as when using the NB medium
Met. In other bacteria, Pseudomonas
fluorescens IAM12022 is MIC
0.5%, Bacillus subtilis 301
3 is MIC 0.3%, Streptococcus la
ctis 12546 had an MIC of 0.4%. In yeast, Pnichia membranaefacien
s IAM4911 and Debaryomyces ha
senii IAM12209 was both MIC 0.3%. In addition, aspergillus (fungi), Aspergill
us oryzae IFO4296 and Penicil
liumcitrinum IFO both MIC 0.5%
Met.

Thus, the solution b, which is the antibacterial agent of the present invention,
Has a concentration similar to that of bacteria (1.1% in Ag concentration), even for yeasts and molds whose growth is more difficult to suppress than bacteria.
(About 5 to 2.5 mg / l), an effect of suppressing the growth was recognized.

Example 5 [Deodorizing Test] An instant deodorizing test was carried out using the solution b of Example 3 above. First, 100 g of soybean cake “okara”, which is a by-product of the tofu production process, is spread on two Petri dishes, and about 1 g of the solution b is evenly sprayed on one of the dishes. No treatment (no solution added)
It was left open at ℃.

As a result, the untreated sample clearly felt odor in 3 hours and gradually turned brown, but the sample sprayed with the solution b was odorless even after 4 weeks, and no coloring was observed. Was.

[0049]

According to the present invention, the present invention comprises a chloride aqueous solution in which an oxidizing agent and silver ions coexist, has both immediate and residual effects on disinfection and deodorization, exhibits a wide disinfection spectrum, It is resistant to bacteria and has high safety. It also has sufficient stability in medium and environment where sulfides coexist, is practical in terms of price, and has excellent deodorizing action and antibacterial and antifungal action. And an antibacterial agent, a method for producing the same, and an antibacterial treatment method using the antibacterial agent.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between culture time and bacterial growth (expressed by absorbance) in a growth test of Escherichia coli in a sulfide-containing medium in Example 3.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuichi Yokozawa 4-10-13 Higashi-Ryoke, Kawaguchi City, Saitama Prefecture Yokozawa Metal Industry Co., Ltd. (72) Inventor Yasutaka Soeda 5-1 Sokaicho, Niihama-shi, Ehime Pref. Materials Co., Ltd.

Claims (6)

[Claims] 1. An antibacterial agent comprising an aqueous chloride solution containing 0.05 mg / liter or more of silver ions as a chloro complex salt and containing an oxidizing agent. 2. The antibacterial agent according to claim 1, wherein the aqueous solution contains 2.5 mg / liter or more of silver ions as a chloro complex salt. 3. The method according to claim 1, wherein the content of chloride ions in the aqueous solution is 0.02 mol / L or more.
The antibacterial agent according to claim 1. 4. The antibacterial agent according to claim 1, wherein the oxidizing agent is sodium hypochlorite or sodium chlorite. 5. A method comprising mixing an aqueous chloride solution with a silver compound or silver metal, dissolving 0.05 mg / l or more of silver ions as a chloro complex salt in the aqueous solution, and further dissolving an oxidizing agent. Manufacturing method of antibacterial agent. 6. An object is treated using an aqueous chloride solution containing a chloro complex of silver ion and an oxidizing agent, or using an aqueous chloride solution and an oxidizing agent containing a chloro complex of silver ion. Antibacterial treatment method.