KR102413384B1 - Germicidal Sterilizer Composition for hypochlrous acid solution and method for manufacturing sterilized water using the same - Google Patents

Abstract

The present invention is a hypochlorous acid water-based natural product sterilizing agent and a method for producing the same, and more specifically, hypochlorous acid water-based natural product sterilization comprising 99 to 99.9% by weight of hypochlorous acid water and 0.1 to 1% by weight of lactic acid bacteria fermentation extract It relates to a disinfectant and a method for manufacturing the same.

Description

Hypochlorous acid-based natural product disinfectant and manufacturing method {Germicidal Sterilizer Composition for hypochlrous acid solution and method for manufacturing sterilized water using the same}

The present invention is a hypochlorous acid water-based natural product sterilizing agent and a method for producing the same, and more specifically, hypochlorous acid water-based natural product sterilization comprising 99 to 99.9% by weight of hypochlorous acid water and 0.1 to 1% by weight of lactic acid bacteria fermentation extract It relates to a disinfectant and a method for manufacturing the same.

Disinfectants based on hypochlorous acid (hypochlorous acid, HOCl) are known. It also shows a remarkably improved disinfecting effect against hypochlorite (OCl-). In order to prepare disinfectants based on hypochlorous acid/hypochlorite, electrochemical activation methods are known, which are mainly used for the purpose of disinfecting water. In this method, an electrolyte, in particular sodium chloride (NaCl) or a diluted solution of a neutralizing salt such as sodium chloride, potassium chloride (KCl), etc., is converted in an electrolysis reactor into an active state suitable for disinfection by applying a voltage to the electrodes of the reactor, such as The active state is very generally metastable and can persist over a relatively longer period of time depending on the type of water and set method parameters. Such an electrochemical activation (ECA) method is described, for example, in International Patent Application No. PCT/EP2007/001265. The electrolysis reactor used in the method comprises a cathode chamber having one or more cathodes and an anode chamber having one or more anodes, wherein the anode chamber and the cathode chamber are water-/ In order to suppress the mixing of the electrolyte solution, they are spatially separated from each other by a diaphragm that is conductive - in particular conductive to ions - or by a membrane having the above-mentioned properties.

Electrolysis, such as chlor-alkali-electrolysis, typically uses a highly concentrated electrolyte solution to maximize the yield of chlorine gas - when sodium chloride solution is used, chlorine gas (Cl2) and sodium hydroxide (NaOH) solutions are produced In the case of using potassium chloride solution, chlorine gas and potassium hydroxide (KOH) solution are produced - aiming for a practical complete conversion of the extract used, whereas in electrochemical activation the water-/electrolyte solution is this solution in a much more diluted form, generally at most about 20 g/l, preferably at most about It is provided to the electrolysis reactor in a concentration of 10 g/l, in particular 0.1 g/l to 10 g/l or 0.1 g/l to 5 g/l or only 0.1 g/l to 5 g/l, where it is decomposed only at a very low rate, whereby This results in a disinfecting effect. Correspondingly, the reaction conditions such as pressure, temperature, electrode current, etc., in electrochemical activation, are usually above all else in the chlor-alkali-electrolysis carried out at elevated temperatures in the range of 50°C to 90°C. The electrochemical activation can be carried out at room temperature, while generally chosen to be more moderated than the case. The advantage in electrochemical activation is that substances generated during electrochemical activation, that is, substances that are also permitted according to German Drinking Water Regulations (TrinkwV) and act as disinfectants, have excellent health-friendliness and environmental friendliness in terms of their respective concentrations. It represents Mars.

As in the case of electrolysis, in the case of electrochemical activation, oxidation occurs at the anode (ie, positively charged electrode), while reduction occurs at the cathode (ie, negatively charged electrode). In the case of using a diluted neutralized salt solution, such as sodium chloride solution, hydrogen is generated in particular at the cathode according to the following reaction equation (1):

2 H2O + 2 e- ---> H2 + 2 OH- (1),

Hydrogen is withdrawn, for example, from the cathode chamber of the reactor after gassing from the solution. Furthermore, the diluted water-/electrolyte solution becomes alkaline by the formation of hydroxide ions in the cathode chamber of the electrolysis reactor.

Oxygen (O2) and chlorine (Cl2), which are chemical oxidizing agents, are generated in the anode according to the following Reaction Formulas (2) and (3), and the oxygen and chlorine are effective in terms of water disinfection as is known. It is also noteworthy that the dilute water-/electrolyte solution becomes acidic in the anode chamber of the electrolysis reactor due to the formation of H3O+- ions:

6 H2O ---> O2 + 4 H3O+ + 4 e- (2),

2 Cl- ---> Cl2 + 2 e- (3).

Chlorine is again decomposed into hypochlorite ions (OCl-) and chlorine ions (Cl-) in water according to the following balanced reaction equation (4), and the hypochlorite ions (OCl-) and chlorine ions (Cl-) are again A suitable cation, for example Na+ or protons or H3O+-ions selected from the electrolyte, reacts with the corresponding (sodium) salt or the corresponding acid, ie hypochlorous acid (HClO) or - with the cations present in the water-/electrolyte solution After agglomeration together - hypochlorite and hydrogen chloride or dilute hydrochloric acid (HCl) can be formed:

Cl2 + 3 H2O <===> 2 H3O+ + OCl- + Cl- (4).

For example, when the pH-value and the oxidation/reduction potential are appropriately controlled as described in detail in the above-mentioned PCT/EP2007/001265, the balance is shifted in order to obtain hypochlorous acid, which is the most desired component, This makes it possible to obtain a disinfectant that already produces the maximum effect even at very low concentrations. In addition, from the above-mentioned substances formed at the anode, additional substances can be formed in a relatively small amount by a secondary reaction, and the additional substances also show an effect in relation to water disinfection as is known as well. In this case, in particular hydrogen peroxide (H2O2, Scheme (5)), ozone (O3, Scheme (6)), chlorine dioxide (ClO2, Scheme (7)), chlorate (ClO3-, Scheme (8)) and various radicals (Scheme (9) and (10)) are addressed.

4 H2O ---> H2O2 + 2 H3O+ + 2 e- (5),

O2 + 3 H2O ---> O3 + 2 H3O+ + 2 e- (6),

Cl- + 4 OH- ---> ClO2 + 2 H2O + 5 e- (7),

3 OCl- ---> ClO3- + 2 Cl- (8),

5 H2O ---> HO2·+ 3 H3O+ + 3 e- (9),

H2O2 + H2O ---> HO2· + H3O+ + e- (10).

One disadvantage of disinfectants prepared by electrochemical activation is that they very generally only have limited durability or storage potential. As already disclosed, the durability of the disinfectant is extended to a period of about half a year to a year, in particular by suitable control or regulation, such as in the manner according to the aforementioned International Patent Application No. PCT/EP2007/001265, but in this case the disinfectant is particularly It is preserved in an old reservoir and cooled in a suitable manner. On the other hand, in particular, when the surface of the disinfectant is relatively large by ambient air, the neutralization reaction of the disinfectant, which occurs relatively quickly, must be actually suppressed. The reason is that an equilibrium is established between the dissolved chlorine (Cl2) and hypochlorous acid or between their salts according to the above reaction equation (4), in which case chlorine is outgassed from the solution, thereby reducing the proportion of chlorine and in particular the disinfection action. The proportion of hypochlorous acid or their salts, that is, hypochlorite, is also continuously reduced because the reaction forms chlorine gas - this chlorine gas is again volatilized from the solution - the equilibrium shifts to obtain OCl - ions because it does Furthermore, hypochlorous acid tends to dislodge its protons, forming the corresponding hypochlorite, especially when the pH-value is increased, which hypochlorite has only reduced disinfection compared to undecomposed hypochlorous acid as described above. it only works

Hypochlorous acid and hypochlorite ions are called free chlorine, and chlorine, hypochlorous acid, and hypochlorite ions remaining in water are called free residual chlorine. Free residual chlorine can cause generator oxygen in water, and chlorine itself has no sterilizing power, but it is known to cause a bactericidal effect by generator oxygen.

Since hypochlorous acid has 80 times higher sterilizing power than hypochlorite ion for bacteria (US EPA guideline 1999 edition), it can be said that the higher the hypochlorous acid concentration, the higher the sterilizing power. It is known that hypochlorous acid can kill 100% of pathogenic microorganisms within 10 minutes at about 0.2 ppm.

Free residual chlorine is present in the form of hypochlorous acid in the form of hypochlorous acid at a ratio of 95% to 100%, with the highest ratio in a weakly acidic to slightly acidic region of about pH 4.5 to 6.5. At pH 8 or higher, the concentration of sodium hypochlorite becomes stronger, and the hypochlorite ratio is only about 50% or less, so the sterilization power decreases. do.

KR 10-2010-0017772 A)

An object of the present invention is to provide a disinfectant based on an aqueous solution containing non-acidic hypochlorous acid water. Slightly acidic hypochlorous acid water refers to one with a concentration of 30 to 50 ppm.

An object of the present invention is to provide a natural product sterilizing and disinfecting agent that contains a natural product ferment extract having antibacterial and antioxidant properties in non-acidic hypochlorous acid water, and has improved sterilization and disinfection performance without irritation to the skin.

In order to achieve the above object, the present invention provides a method for producing a natural product disinfectant comprising the following steps.

A first step of preparing a fermented pear broth by mixing pears, rice bran, oligosaccharides, complex lactic acid bacteria, and purified water;

A second step of preparing garlic fermented broth by mixing garlic, rice bran, oligosaccharide, complex lactic acid bacteria, and purified water;

A third step of preparing a ginger fermentation broth by mixing ginger, rice bran, oligosaccharide, complex lactic acid bacteria, and purified water;

a fourth step of pre-culturing the fermented pear broth and the garlic fermented broth to prepare a medium;

a fifth step of preparing a lactic acid bacteria fermented extract by adding the pre-culture medium and oligosaccharides to the ginger fermentation broth and performing the main culture;

and a sixth step of preparing a disinfectant by mixing the lactic acid bacteria ferment extract and hypochlorous acid water.

In the sixth step, 99 to 99.9% by weight of hypochlorous acid water and 0.1 to 1% by weight of lactic acid fermented extract are mixed, but the lactic acid fermented extract is pre-cultured with fermented pear and fermented garlic, followed by adding fermented ginger It is preferably prepared by main culture.

The hypochlorous acid water used in the sixth step corresponds to a concentration of 30 to 50 ppm, and it is preferable to use a pH of 5.0 to 6.5.

In the finally prepared sterilizer, it is preferable that the final concentration of hypochlorous acid is 10 ppm or less. The pH is preferably 5.0 to 6.0.

The present invention has the effect of providing a natural product sterilizing and disinfecting agent with improved sterilization and disinfection performance without irritation to the skin by containing a natural product ferment extract having antibacterial and antioxidant properties in non-acidic hypochlorous acid water.

1 is a process diagram showing a method for manufacturing a natural product disinfectant according to the present invention.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples.

Example 1: Preparation of disinfectant

1.1. fermented pear

100 parts by weight of pears, 50 parts by weight of rice bran, and 15 parts by weight of oligosaccharides are mixed with 325 parts by weight of purified water, and then subjected to primary sterilization by applying ultrasonic waves. Thereafter, secondary sterilization is performed at 120° C. for 10 minutes.

After adding 10 parts by weight of the complex lactic acid bacteria, put in an incubator and incubated for 24 to 48 hours.

The complex lactic acid bacteria may have the following fermented strains. Fermentation strains are Lactobacillus sp., Monascus sp., Bifidobacterium sp., Prevotella sp., Fusobacterium sp., and Yu Bacteria genus (Eubacterium sp.) may be selected from the group consisting of strains, but is not limited thereto, and preferably may be Lactobacillus sp. strains.

The liquid fermented by mixing pear and rice bran contains physiologically active substances called polyphenol compounds that exhibit natural antibacterial and antioxidant properties.

1.2. garlic fermented broth

After mixing 100 parts by weight of garlic, 100 parts by weight of rice bran, and 30 parts by weight of oligosaccharides in 750 parts by weight of purified water, primary sterilization is performed by applying ultrasonic waves. Thereafter, secondary sterilization is performed at 120° C. for 10 minutes.

Then, 20 parts by weight of the complex lactic acid bacteria is added, put in an incubator, and incubated for 24 to 48 hours.

The complex lactic acid bacteria may have the following fermented strains. Fermentation strains are Lactobacillus sp., Monascus sp., Bifidobacterium sp., Prevotella sp., Fusobacterium sp., and Yu Bacteria genus (Eubacterium sp.) may be selected from the group consisting of strains, but is not limited thereto, and preferably may be Lactobacillus sp. strains.

The mixture of garlic and rice bran is fermented and contains physiologically active substances called polyphenol compounds that exhibit natural antibacterial and antioxidant properties.

1.3. Ginger Fermented Liquid

100 parts by weight of ginger, 50 parts by weight of rice bran, and 15 parts by weight of oligosaccharides were mixed with 325 parts by weight of purified water, followed by ultrasonication to perform primary sterilization. Thereafter, secondary sterilization is performed at 120° C. for 10 minutes.

After adding 10 parts by weight of the complex lactic acid bacteria, put in an incubator and incubated for 24 to 48 hours.

The complex lactic acid bacteria may have the following fermented strains. Fermentation strains are Lactobacillus sp., Monascus sp., Bifidobacterium sp., Prevotella sp., Fusobacterium sp., and Yu Bacteria genus (Eubacterium sp.) may be selected from the group consisting of strains, but is not limited thereto, and preferably may be Lactobacillus sp. strains.

The mixture of ginger and rice bran is fermented and contains physiologically active substances called polyphenol compounds that exhibit natural antibacterial and antioxidant properties.

1.4. Production of lactic acid bacteria fermented extract

Each of the fermented pear broth and the garlic fermented broth is pre-cultured to prepare a pre-culture medium.

The main culture is carried out by adding 10% by weight of the pre-culture medium and 3% by weight of the oligosaccharide to 87% by weight of the ginger fermentation broth.

The final extract is produced by culturing for 24 to 48 hours so that the pH of the final lactic acid bacteria fermented extract is between 3 and 4.

The fermentation extract may have an excellent antibacterial effect due to a synergistic action between the active ingredients contained in each extract. In particular, as a natural fermented extract, the disinfectant is not only harmless to the human body, but also works with the hypochlorous acid water to significantly enhance the sterilization power of the disinfectant composition.

Since the active ingredients contained in the fermentation extract are different, antibacterial activity or other commercial properties are different depending on the mixing ratio, so the mixing ratio can be appropriately controlled within the above range.

If the content of some of the extracts is too little or too much, the synergistic effect with other extracts may not be properly implemented, so it is possible to maximize the sterilization auxiliary effect by maintaining an appropriate mixing ratio.

On the other hand, the "extract" refers to a solvent in which the active ingredient contained in the extraction raw material is transferred by contacting the solvent and the extraction material under specific conditions, and the extract may include various active ingredients contained in the natural raw material.

The fermentation refers to a process in which microorganisms decompose organic matter using their own enzymes. The strain can impart hydrophilicity to the particle surface in the process of converting the organic matter contained in the extract, and since the hydrophilicity of the active ingredient contained in the extract is increased by the fermentation, a stable colloidal state can be achieved. In addition, the antibacterial substances contained in the extract increase the solubility in hypochlorous acid water by fermentation, and the sterilization auxiliary effect by interaction can be significantly improved.

The fermented extract contains various amino acids, organic acids, and antioxidants to not only promote skin metabolism, but also decompose toxic substances such as heavy metals in the fermentation process, and side effects such as irritation or allergy to the skin can be significantly reduced.

In the main culture process, oligosaccharides have excellent antioxidant activity, and can increase fermentation efficiency and enhance sterilization and antioxidant activity of fermented extracts.

The fermentation strain is Lactobacillus sp., Monascus sp., Bifidobacterium sp., Prevotella sp., Fusobacterium sp., and One or more may be selected from the group consisting of Eubacterium sp., but the present invention is not limited thereto. Preferably, it may be a Lactobacillus sp. strain.

1.5 Manufacture of natural disinfectant

A feature of the present invention is to use hypochlorous acid water instead of purified water. Prepare hypochlorous acid water having a concentration of 30 to 50 ppm and a pH of 5.0 to 6.5.

0.1 to 1% by weight of the lactic acid bacteria extract is mixed with respect to 99 to 99.9% by weight of the hypochlorous acid water.

After mixing, the concentration of hypochlorous acid water of the final disinfectant is 0 to 10 ppm, and the pH is adjusted to 5 to 6.

The hand sanitizer composition may further include glycerin or glycerin fatty acid ester as a skin protectant. The glycerin or glycerin fatty acid ester is a colorless, transparent and viscous liquid, has strong hygroscopicity, and can homogeneously disperse the mixture. The glycerin or glycerin fatty acid ester can absorb moisture in the air, supply it to the skin, and protect the skin from external stimuli. In particular, since the skin protectant component is harmless to the human body, it can be ingested and provides a skin protection effect, so that safety and functionality can be realized at the same time.

Since the fermented extract contains active ingredients such as magnesium, calcium, vitamin B, and potassium as well as polycosanol as a main component, it is excellent in anticancer action, moisturizing action, moisture replenishment and aging skin vitality improvement effect. In addition, the ferment extract reacts with odor substances such as organic acids, flavone-based compounds, phenol-based compounds and unsaturated aldehydes to have excellent chemical deodorizing effect.

Since the ferment extract contains a large amount of amino acids constituting skin proteins such as collagen and elastin, it provides a human skin protein raw material with a deodorizing effect. can do it

If the content of the fermented extract is too small, the expected effect may not be sufficiently secured.

Samples of Examples and Comparative Examples were prepared by mixing the fermentation extract and hypochlorous acid water as shown in Table 1 below.

division Hypochlorous acid water (wt%) Fermented extract (wt%) Example 1 100 0 Example 2 99.9 0.1 Example 3 99.5 0.5 Example 4 99.0 One Example 5 98 2 Comparative Example 1 95 5 Comparative Example 2 90 10

Experimental Example 1: Measurement of antibacterial activity

After the samples of Examples and Comparative Examples were treated on paper discs, the discs were arranged at regular intervals under aseptic manipulation on a medium on which the strain was smeared, and the antibacterial activity was measured by culturing for 2 days. The antimicrobial activity of the sample was evaluated by measuring the diameter (mm) of the growth inhibition region of the bacteria generated around the paper disc.

As the test strains, Salmonella, Staphylococcus aureus and E. coli were used, and each strain was purchased from the American Type Culture Collection (ATCC, U.S.A.) and used. The strains were inoculated into a medium (Malt Extract Agar 6%, Ox-bile 2%, Tween-40 1%, Glycerol mono-oleate 0.25%) and incubated at 37 °C for 24 hours.

The cultured strains were diluted at a ratio of 1/100 and spread on a plate on the solid medium of the plate, and the growth inhibitory rings were measured 2 days after arranging the Paper discs. The growth inhibition ring measurement results are shown in Table 2 below.

division Salmonella typhimurium
Unit: mm Staphylococcus aureus
Unit: mm pathogenic E. coli
Unit: mm Example 1 18.5 18.9 12.4 Example 2 21.4 22.7 14.6 Example 3 24.5 27.2 19.4 Example 4 21.6 21.9 15.3 Example 5 19.5 19.6 14.7 Comparative Example 1 18.9 19.3 14.8 Comparative Example 2 18.9 18.7 14.2

As shown in Table 2, in Examples 2 to 4, the antibacterial activity of the disinfectant was significantly increased.

Sensory evaluation was performed for Examples and Comparative Examples containing hypochlorous acid water. For this evaluation, 100 members of the evaluation group without any health problems were arbitrarily selected.

The evaluation score was set to 5 when the unpleasant odor was the most reduced, and 1 when the unpleasant odor was the least. The evaluation results are shown in Table 3 below.

division Evaluation results Example 1 4.56 Example 2 4.47 Example 3 4.37 Example 4 4.26 Example 5 4.10 Comparative Example 1 3.98 2 in comparison 3.89

As the specific parts of the present invention have been described in detail above, it will be clear to those of ordinary skill in the art that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (4)

In the natural product disinfectant,
99 to 99.9% by weight of hypochlorous acid water;
Containing; 0.1 to 1% by weight of lactic acid bacteria fermentation extract;
The lactic acid bacteria fermented extract is prepared by pre-culturing fermented pear and garlic fermented broth, and then culturing by adding fermented ginger,
The final concentration of hypochlorous acid water of the natural product disinfectant is more than 0 to 10 ppm or less,
The natural product disinfectant has a pH of 5 to 6, characterized in that
A natural disinfectant based on hypochlorous acid. delete delete A first step of preparing a fermented pear broth by mixing pears, rice bran, oligosaccharides, complex lactic acid bacteria, and purified water;
A second step of preparing a garlic fermentation broth by mixing garlic, rice bran, oligosaccharide, complex lactic acid bacteria, and purified water;
A third step of preparing a ginger fermentation broth by mixing ginger, rice bran, oligosaccharide, complex lactic acid bacteria, and purified water;
a fourth step of pre-culturing the fermented pear broth and the garlic fermented broth to prepare a medium;
a fifth step of preparing a lactic acid bacteria fermented extract by adding the pre-culture medium and oligosaccharides to the ginger fermentation broth and performing the main culture;
A sixth step of preparing a disinfectant by mixing the lactic acid bacteria ferment extract and hypochlorous acid water,
A method for producing a natural disinfectant disinfectant based on hypochlorous acid.

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