KR102735673B1 - Salt compound and biocide composition comprising the same - Google Patents

Abstract

A salt compound having a wide antibacterial spectrum, bactericidal power, and human safety against microorganisms harmful to human skin is provided. One embodiment of the present invention provides a salt compound in which a cation represented by the general formula 1 and an anion represented by the general formula 2-1 or 2-2 are combined.

Description

{SALT COMPOUND AND BIOCIDE COMPOSITION COMPRISING THE SAME}

The present invention relates to salt compounds, and more particularly, to salt compounds and biocidal compositions containing the same.

As people's awareness of personal hygiene management increases, the market for wet tissues with cleansing power and convenience is gradually expanding. Since wet tissues were classified as cosmetics in 2015, the industry has stopped using existing preservatives that had harmful issues and is focusing on developing products that focus on safety in line with the marketing trend of the cosmetics industry.

Although products using preservative substitutes or natural extracts have been developed to replace preservatives, their practical use has been difficult due to their low microbial inhibition efficacy, low solubility, and specific odor, which results in poor product miscibility. Ethyl lauroyl arginate hydrochloride (Ethyl Lauroyl Arginate HCl), which can solve these problems, has been used as a sterilizing preservative in many countries, including Korea, due to its high human safety and wide antibacterial and antiviral spectrum. However, commercialization has been difficult due to its high price and relatively low antifungal activity. Therefore, there is a need to develop a biocide that has high safety and preservative power as well as solubility and economic feasibility.

The purpose of the present invention is to provide a salt compound capable of implementing a wide antibacterial spectrum and bactericidal power against microorganisms harmful to human skin.

Another object of the present invention is to provide a salt compound which has excellent human safety and can solve miscibility problems due to low solubility and specific odor.

Another object of the present invention is to provide a biocidal composition comprising the salt compound.

The purposes of the present invention are not limited to the purposes mentioned above, and other purposes and advantages of the present invention which are not mentioned can be understood by the following description, and will be more clearly understood by the embodiments of the present invention. In addition, it will be easily understood that the purposes and advantages of the present invention can be realized by the means and combinations thereof indicated in the claims.

One embodiment of the present invention to achieve the above object provides a salt compound in which a cation represented by the following general formula 1 and an anion represented by the following general formula 2-1 or 2-2 are combined.

[General formula 1]

[General formula 2-1]

[General formula 2-2]

In the above general formula 1,

R ₁ is an alkyl group linking group having 1 to 5 carbon atoms; or an aryl group linking group having 6 to 20 carbon atoms;

R ₂ is each independently a hydrogen atom; a linear or branched alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;

R ₅ is a linear or branched alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;

R ₆ is a linear or branched alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;

In the above general formula 2-1,

R ₃ is an electron donating group (EDG) with a negative charge,

_R4 is an electron withdrawing group (EWG),

X is a substituent substituted 1 to 4 times on a benzene ring, each independently a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;

In the above general formula 2-2,

R ₇ is a ketone group having 3 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

Specifically, the salt compound is any one of the compounds represented by the following chemical formulas 1 to 3.

Another embodiment of the present invention to achieve the above object can provide a biocidal composition comprising the salt compound.

According to another embodiment of the present invention, a biocidal composition may be provided that further comprises purified water. Specifically, the content of the purified water may exceed 0.05 wt% based on the total weight of the biocidal composition.

According to another embodiment of the present invention, a biocidal composition further comprising an oil can be provided. Specifically, the content of the oil can be from 0.0001% to 20% by weight based on the total weight of the biocidal composition. Specifically, the content of the oil can be from 0.001% to 10% by weight.

The above-mentioned solution to the problem does not enumerate all the features of the present invention. The various features of the present invention and the advantages and effects thereof can be understood in more detail by referring to the specific examples below.

According to one aspect of the present invention, a salt compound having a high antibacterial activity at a low concentration in a formulation containing a large amount of water and exhibiting a broad antibacterial spectrum and having the property of being rapidly biodegraded when absorbed by the human body can be provided, thereby exhibiting excellent safety in the human body.

According to another aspect of the present invention, a salt compound having excellent human safety and solving miscibility problems due to low solubility and specific odor can be provided. When such a salt compound is applied to a wet tissue, an antibacterial and/or antifungal effect can be effectively implemented in the fabric included in the wet tissue that is easily contaminated.

In addition to the effects described above, the specific effects of the present invention are described below together with the specific contents for carrying out the invention.

Figure 1a shows the ^1H -NMR analysis results of Example 1, Figure 1b shows the mass analysis results of ethyl lauroyl alginate of Example 1, and Figure 1c shows the mass analysis results of levulinate.
Figure 2a shows the ^1H -NMR analysis results of Example 2, Figure 2b shows the mass analysis results of ethyl lauroyl alginate of Example 2, and Figure 2c shows the mass analysis results of P-anisate.
Figure 3a shows the ^1H -NMR analysis results of Example 3, Figure 3b shows the mass analysis results of ethyl lauroyl alginate of Example 3, and Figure 3c shows the mass analysis results of 4-acetoyl phenoxide.

Hereinafter, each component of the present invention will be described in more detail so that a person with ordinary skill in the art can easily implement the present invention. However, this is only an example, and the scope of the rights of the present invention is not limited by the following contents.

In describing the present invention, the meaning of 'substituted' is defined as at least one hydrogen atom being replaced by any one selected from the group consisting of an alkylthiol group, an alkoxy group, an ether group, an acetal group, a linear or branched alkyl group, a linear or branched alkenyl group, a cycloalkyl group, a heterocycloalkyl group, an allyl group, a benzyl group, an aryl group, a heteroaryl group, derivatives thereof, and combinations thereof.

In describing the present invention, 'biocide' means a substance that has the function of eliminating, rendering harmless, or inhibiting the growth of harmful organisms (bacteria, fungi, etc.).

One embodiment of the present invention provides a salt compound in which a cation represented by the following general formula 1 is combined with an anion represented by the following general formula 2-1 or 2-2.

[General formula 1]

[General formula 2-1]

[General formula 2-2]

In the general formula 1 above, R ₁ is an alkyl group linking group having 1 to 5 carbon atoms; or an aryl group linking group having 6 to 20 carbon atoms; and R ₂ is each independently a hydrogen atom; a linear or branched alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; and R ₅ is a linear or branched alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; and R ₆ is a linear or branched alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; and

In the general formula 2-1, R ₃ is an electron donating group (EDG) having a negative charge, R ₄ is an electron withdrawing group (EWG), X is a substituent substituted 1 to 4 times on a benzene ring, each independently a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; and in the general formula 2-2, R ₇ is a ketone group having 3 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

According to one aspect of the present invention, a salt compound can be provided which has a high antibacterial activity at a low concentration in a formulation containing a large amount of water, exhibits a broad antibacterial spectrum, and has the characteristic of being rapidly biodegraded when absorbed by the human body, thereby exhibiting excellent safety in the human body. According to another aspect of the present invention, a salt compound can be provided which has excellent safety in the human body and solves the problem of miscibility due to low solubility and specific odor. When such a salt compound is applied as a preservative to wet tissues, an antibacterial and/or antifungal effect can be effectively implemented in the fabric of wet tissues which are easily contaminated.

Below, the composition of the present invention is described in more detail.

1. Salt compounds

The cation of the salt compound according to the present invention is represented by the following general formula 1.

[General formula 1]

In the above general formula 1, R ₁ is a divalent linking group, such as an alkyl linking group having 1 to 5 carbon atoms; or an aryl linking group having 6 to 20 carbon atoms. Specifically, the 'alkyl linking group' may mean a divalent linking group including a linear or branched alkyl group as a backbone structure, and according to an example, may be a -(CH ₂ ) _n - molecular structure (wherein n is 1 to 5). Specifically, the 'aryl linking group' may mean a divalent linking group including a substituted or unsubstituted aryl group as a backbone structure, and according to an example, may be -C ₆ H ₄ -, -C ₆ H ₁ (R ₈ ) ₃ -, -C ₆ H ₂ (R ₈ ) ₂ - _, -C ₆ H ₃ (R ₈ ) ₁ -, etc. For example, R ₈ can be a linear or branched alkyl group having 1 to 5 carbon atoms.

In the general formula 1 above, each R ₂ is independently a hydrogen atom; a linear or branched alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; and specifically, each R ₂ can be independently a hydrogen atom.

In the above general formula 1, R ₅ is a linear or branched alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In the above general formula 1, R ₆ is a linear or branched alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

The anion of the salt compound according to the present invention can be represented by the following general formula 2-1.

[General formula 2-1]

In the general formula 2-1 above, R ₃ is an electron donating group (EDG) having a negative charge, R ₄ is an electron withdrawing group (EWG), and X is a substituent substituted 1 to 4 times on a benzene ring, each independently a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

For example, the electron donating group having the negative charge may include a primary to tertiary amine group, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group, an oxygen anion (-O ^- ), or a group including a nitrogen anion (-N ^- H, or -N ^- COH).

For example, the electron-withdrawing group may include a halogen atom, a nitrile group, a nitroso group, a sulfonyl group, a group containing a nitrogen cation, a carboxyl group, a ketone group, an ester group, or an aldehyde group.

The anion of the salt compound according to the present invention can be represented by the following general formula 2-2.

[General formula 2-2]

In the above general formula 2-2, R ₇ is a ketone group having 3 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

Specifically, the salt compound may be any one of the compounds represented by the following chemical formulas 1 to 3.

[Chemical Formula 1]

[Chemical formula 2]

[Chemical Formula 3]

Meanwhile, 4-hydroxyacetophenone, used as an anion in [chemical formula 3], is a phenolic compound that can stabilize molecules through delocalization of intermolecular electrons through electrical interaction with the guanidine group as shown in chemical formula 4 below, and thus can exhibit strong bactericidal power.

[Chemical Formula 4]

2. Biocidal composition

Another embodiment of the present invention can provide a biocidal composition comprising the salt compound.

The content of the salt compound may be 0.0001 wt% or more, specifically may exceed 0.05 wt%, or may be 0.001 to 20 wt%, more specifically 0.002 to 1 wt%, based on the total weight of the biocidal composition. When the content of the salt compound satisfies the numerical range, the properties of being stable against skin irritation, having excellent biocidal ability, and having excellent compatibility can be better implemented.

According to another embodiment of the present invention, a biocidal composition may further include an oil that makes dry skin flexible and forms a skin protective film to block evaporation of moisture. Specifically, the oil may be at least one selected from the group consisting of vegetable oil, animal oil, mineral oil, and synthetic oil, and preferably vegetable oil.

The content of the oil may be 0.0001 to 20 wt% based on the total weight of the biocidal composition, and specifically may be 0.001 to 10 wt%. When the content of the oil satisfies the numerical range, the skin protection effect of the biocidal composition may be further improved.

The above vegetable oils are extracted from the leaves, fruits, flowers, barks or roots of plants and may have the characteristics of having a good fragrance and being the least irritating to the skin. For example, the above vegetable oils may be coconut oil, olive oil, camellia oil, almond oil, avocado oil, etc.

The above animal oil may have excellent physiological activity and high skin absorption rate. For example, the animal oil may be horse oil, mink oil, sea turtle oil, etc.

The above mineral oil has a low risk of oxidation and has a strong oily feel, so it can effectively prevent moisture evaporation and protect the skin from the outside. For example, the above mineral oil can be Vaseline, mineral oil, etc.

The above synthetic oil is a chemically synthesized oil that does not easily deteriorate and can implement the characteristics of spreading well on the skin and being easy to apply. For example, the above synthetic oil can be dimethylpolysiloxane, methylphenylpolysiloxane, etc.

According to another embodiment of the present invention, a biocidal composition may further include a thickener that increases viscosity and adhesiveness and improves a feeling of use and stability. The thickener may be, for example, xanthan gum, gelatin, natural cellulose, methyl cellulose, etc. The content of the thickener may be 0.01 to 70 wt% based on the total weight of the biocidal composition. When the content of the thickener satisfies the numerical range, the feeling of use and stability of the biocidal composition may be further improved.

A biocidal composition according to another embodiment of the present invention may further include a first additive as a means for improving antibacterial or antifungal ability. Specifically, the first additive may include at least one first additive selected from the group consisting of nonionic glycol compounds, quaternary ammonium compounds, aromatic compounds, fatty acids and derivatives thereof, saccharide and derivative compounds thereof, alcohol compounds, amino acid-based antibacterial compounds, aldehyde compounds, natural extract compounds, and metal salt compounds.

The above nonionic glycol compound may be at least one compound selected from the group consisting of ethylhexylglycerin, 1,2-hexanediol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, caprylyl glycol, nonylene glycol, decylene glycol, undecylene glycol, dodecylene glycol, glyceryl caprylate and derivatives thereof, glyceryl laurate and derivatives thereof, glyceryl decylate and derivatives thereof, glyceryl caprylyl ether, glyceryl capryl ether, and glyceryl undecylinate.

The above quaternary ammonium compound may be at least one compound selected from the group consisting of benzalkonium halide, cetylpyridinium halide, cetrimonium halide, laurylpyridinium halide, lautrimonium halide, cetyltrimonium halide, decyltrimonium halide, octyltrimonium halide, chlorhexidine, hexamidine and derivatives thereof, polyquaternium, guanidine and derivatives thereof, polyhexamethyleneguanidine, methylisothiazolinone and derivatives thereof, benzisothiazolinone and derivatives thereof, and imidazolinyl urea and derivatives thereof.

The above aromatic compound may be at least one compound selected from the group consisting of phenoxyethanol and its derivatives, paraben and its derivatives, p-hydroxyaromatic acid and its salts, benzoic acid and its salts, hydroxyacetophenone and its derivatives, anisic acid and its salts, phenethyl alcohol and its derivatives, 2-phenylphenol, gallic acid and its derivatives, clivazol, pyrithione and its derivatives, butylhydroxyanisole and its derivatives, and butylhydroquinone and its derivatives.

The above fatty acid and its derivative compounds are formic acid and its salts, acetic acid and its salts, propionic acid and its salts, butanoic acid and its salts, pentanoic acid and its salts, hexanoic acid and its salts, heptanoic acid and its salts, caprylic acid and its salts, nonanoic acid and its salts, decanoic acid and its salts, undecanoic acid and its salts, undecyleneic acid and its salts, dodecanoic acid and its salts, sorbic acid and its salts, formylhydroxamic acid, acetylhydroxamic acid, propylhydroxamic acid, butylhydroxamic acid, pentylhydroxamic acid, hexylhydroxamic acid, It may be at least one compound selected from the group consisting of heptylhydroxamic acid, caprylylhydroxamic acid, nonylhydroxamic acid, caprylhydroxamic acid, undecylhydroxamic acid, dodecylhydroxamic acid, dehydroacetic acid, and salts thereof.

The above sugar and derivative compounds may be one or more compounds selected from the group consisting of gluconolactone, sucrose, xylitol and sorbitol.

The above alcohol compound may be at least one compound selected from the group consisting of methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, and dodecyl alcohol.

The above amino acid-based antimicrobial compound may be at least one compound selected from the group consisting of capryloyl glycine, undecylenoyl glycine, ethyl lauroyl alginate and derivatives thereof, PCA cocoyl alginate, polylysine and nisin.

The above aldehyde compound may be one or more compounds selected from the group consisting of hydantoin and its derivatives, benzaldehyde, formaldehyde, and acetaldehyde.

The above natural extract compound may be at least one compound selected from the group consisting of golden extract, grapefruit seed extract, green tea extract, aroma oil, cypress extract, prickly ash extract, white rhododendron extract, moss extract, coptis extract, phellodendron extract, rosemary extract, mugwort extract, paeonium bark extract, golden chrysanthemum extract, gallnut extract, cinnamon extract, clove extract, star anise extract, red ginseng extract, ginseng extract, dragon's mantle extract, and dragon's mantle tea extract.

The above metal salt compound may be at least one compound selected from the group consisting of copper salts, silver salts, germanium salts, gold salts, titanium salts, zinc salts, and aluminum salts.

A biocidal composition according to another embodiment of the present invention may further include a second additive. The additive may be, for example, at least one selected from the group consisting of an anti-foam, a pH regulator, a stabilizer, a perfume, and a dispersant that are commonly used in the relevant technical field.

The biocidal composition according to the present invention may further contain purified water. The content of the purified water may be the content excluding the salt compound, oil, and thickener, or may be the content excluding the salt compound, oil, thickener, and additive.

For example, the strains whose growth is prevented and killed by the biocidal composition may be at least one selected from the group consisting of Escherichia coli , Staphylococcus aureus , Aspergillus niger , Pseudomonas aeruginosa , Candida albicans , Vibrio parahaemolyticus , and Salmonella typhimurium .

3. Wet tissue

Another embodiment of the present invention can provide a wet tissue comprising a fabric impregnated with the biocidal composition. The fabric can include, for example, any one selected from the group consisting of natural fibers, synthetic fibers, and combinations thereof, and specifically, can be a nonwoven fabric made of a blended fiber in which polyester fibers and polypropylene fibers are mixed. When the nonwoven fabric made of the blended fiber in which polyester fibers and polypropylene fibers are mixed is used as a fabric of a wet tissue, the mechanical properties of the wet tissue are appropriately maintained, so that damage to the fabric can be effectively prevented even when wiping human skin multiple times.

The above wet tissue may be manufactured by impregnating the above biocidal composition into fabric and then sterilizing and disinfecting it. The above wet tissue may be manufactured in various forms such as oral wet tissue, baby wet tissue for cleaning, feminine wet tissue, disposable wet tissue, and multipurpose wet tissue.

According to one aspect of the present invention, a wet tissue can be provided that has a high antibacterial activity at a low concentration in a formulation containing a large amount of water, exhibits a broad antibacterial spectrum, and has the characteristic of being rapidly biodegraded when absorbed by the human body, thereby exhibiting excellent human safety. According to another aspect of the present invention, it can also solve the problem of miscibility due to excellent human safety, low solubility, and specific odor.

Hereinafter, embodiments of the present invention will be described in detail so that a person having ordinary skill in the art to which the present invention pertains can easily implement the present invention, but this is only an example, and the scope of the rights of the present invention is not limited by the following contents.

[Synthesis Example: Synthesis of a Novel Salt Compound]

<Comparative Example 1: Preparation of ethyl lauroyl alginate hydrochloride (ELA HCl)>

Ethyl lauroyl alginate hydrochloride (ELA HCl) was obtained from Woodward Biosciences.

<Example 1: Synthesis example of compound of chemical formula 1>

In a 250 mL round-bottom flask, add 20 g (0.0475 mol) of ethyl lauroyl alginate hydrochloride and 120 mL of ethyl acetate, heat and stir at 50°C until completely dissolved. Transfer the mixed solution to a separatory funnel, maintain the temperature above 40°C, add 30 mL of saturated sodium bicarbonate aqueous solution each time, and wash the organic layer three times. Add 30 mL of saturated sodium chloride aqueous solution, and wash the organic layer twice, then add 5.24 g (0.0451 mol) of levulinic acid, dissolve completely, and age for 5 minutes. Cool to 0°C, and when crystals are formed, filter and dry to obtain 21.68 g (96%) of a white crystalline solid (ethyl lauroyl alginate levulinate).

[Chemical Formula 1]

<Example 2: Synthesis example of compound of chemical formula 2>

In a 250 mL round-bottom flask, add 20 g (0.0475 mol) of ethyl lauroyl alginate hydrochloride and 120 mL of ethyl acetate, heat and stir at 50°C until completely dissolved. Transfer the mixed solution to a separatory funnel, maintain the temperature above 40°C, add 30 mL of saturated sodium bicarbonate aqueous solution each time, and wash the organic layer three times. Add 30 mL of saturated sodium chloride aqueous solution, and wash the organic layer twice, then add 6.87 g (0.0451 mol) of p -anisic acid and dissolve completely. Age for 5 minutes. Cool to 0°C, and when crystals are formed, filter and dry to obtain 25.3 g (93%) of a white crystalline solid (ethyl lauroyl alginate p-anisate).

[Chemical formula 2]

<Example 3: Synthesis example of compound of chemical formula 3>

In a 250 mL round-bottom flask, add 20 g (0.0475 mol) of ethyl lauroyl alginate hydrochloride and 120 mL of ethyl acetate, heat and stir at 50°C until completely dissolved. Transfer the mixed solution to a separatory funnel, maintain the temperature above 40°C, add 30 mL of saturated sodium bicarbonate aqueous solution each time, and wash the organic layer three times. Add 30 mL of saturated sodium chloride aqueous solution, and wash the organic layer twice, then add 6.14 g (0.0451 mol) of 4-hydroxyacetophenone and dissolve completely. Age for 5 minutes. Cool to 0°C, and when crystals are formed, filter and dry to obtain 21.60 g (92%) of a white crystalline solid (ethyl lauroyl arginate piceolate).

[Chemical Formula 3]

[Experimental Example 1: Analysis results of a novel salt compound]

Example 1: Ethyl lauroyl alginate levulinate

Figure 1a shows the ^1H -NMR analysis results of Example 1, Figure 1b shows the mass analysis results of ethyl lauroyl alginate of Example 1, and Figure 1c shows the mass analysis results of levulinate.

NMR analysis results

^1H NMR (400 MHz, DMSO-d6) δ 8.25-8.23 (d, 1H), 8.08 (t, 1H), 4.19-4.14 (m, 1H), 4.01-4.03 (m, 2H), 3.08-3.07 ( m, 2H), 2.64-2.61 (t, 2H), 2.37-2.33 (t, 2H), 2.13-2.09 (t, 1H), 2.08 (s, 3H)1.74-1.67 (m, 1H), 1.65-1.55 (m, 1H), 1.53- 1.47 (m, 4H), 1.28-1.22 (m, 16H), 1.18-1.14 (t, 3H), 0.86-0.82 (t, 3H).

Mass Spectrometry Results

Ethyl lauroyl arginate: ESI (m/z) [M-H]- calcd for: [C20H40N4O3] (M-H)- 383.31004, found 383.30312

Levulinic acid: ESI (m/z) [M-H]- calcd for: [C5H8O3] (M-H)- 115.04734, found 115.03891

Example 2: Ethyl lauroyl alginate p-anisate

Figure 2a shows the ^1H -NMR analysis results of Example 2, Figure 2b shows the mass analysis results of ethyl lauroyl alginate of Example 2, and Figure 2c shows the mass analysis results of P-anisate.

NMR analysis results

^1H NMR (400 MHz, DMSO-d6) δ 8.26-8.24 (d, 1H), 8.05-8.02 (t, 1H), 7.88-7.86 (d, 2H), 6.98-6.96 (d, 2H), 4.19- 4.17 (m, 1H), 4.09-4.01 (m, 2H), 3.79 (s, 3H), 3.10-3.08 (d, 2H), 2.12-2.08 (t, 2H), 1.76-1.66 (m, 1H), 1.63-1.56 (m, 1H) ), 1.54-1.46 (m, 4H), 1.65-1.55 (m, 1H), 1.20 (m, 16H), 1.17-1.13 (t, 3H), 0.84-0.81 (t, 3H).

Mass Spectrometry Results

Ethyl lauroyl arginate, ESI (m/z) [MH]- calcd for: [C ₂₀ H ₄₀ N ₄ O ₃ ] (MH)- 383.31004, found 383.30303

p-Anisic acid, ESI (m/z) [MH]- calcd for: [C ₈ H ₈ O3] (MH)- 151.04734, found 151.03919

Example 3: Ethyl lauroyl alginate picoleate

Figure 3a shows the ^1H -NMR analysis results of Example 3, Figure 3b shows the mass analysis results of ethyl lauroyl alginate of Example 3, and Figure 3c shows the mass analysis results of piceonate.

NMR analysis results

^1H NMR (400 MHz, DMSO-d ₆ ) δ 8.21-8.19 (d, 1H), 7.81-7.79 (d, 2H), 6.83-6.81 (d, 2H), 4.20-4.15 (m, 1H), 4.08 -4.04 (m, 2H), 3.08 (t, 2H), 2.45 (s, 3H), 2.12-2.09 (t, 2H), 1.72-1.67 (m, 1H), 1.63-1.58 (m, 1H), 1.54-1.47 (m, 4H), 1.22 (m, 16H), 1.18-1.15 (t, 3H), 0.86-0.82 (t, 3H).

Mass Spectrometry Results

Ethyl lauroyl arginate, ESI (m/z) [MH]- calcd for: [C ₂₀ H ₄₀ N ₄ O ₃ ] (MH)- 383.31004, found 383.30301

4-hydroxyacetophenone, ESI (m/z) [MH] ^- calcd for: [C ₈ H ₈ O ₂ ] (MH) ^- 135.05243, found 135.04405

[Experimental Example 2: Solubility Measurement of Novel Salt Compounds]

Each compound (2 g) according to Comparative Example 1 and Examples 1 to 3 was mixed with water (20°C) to prepare a mixture having a total solution volume of 1 L. After checking for turbidity and precipitation, if no turbidity or precipitation occurred, the test sample was doubled and the degree of saturation was measured.

Comparative Example 1 Example 1
(chemical formula 1) Example 2
(chemical formula 2) Example 3
(chemical formula 3) Solubility (g/L) doesn't exist. 18.5 1.0 10.5

Referring to Table 1 above, it can be confirmed that Comparative Example 1, unlike Examples 1 to 3, has very low solubility in water and does not dissolve, and when a biocide composition is implemented by mixing a salt compound and purified water, there may be a problem of significantly reduced miscibility due to undissolved salt.

[Experimental Example 3: Freezing/thawing precipitation evaluation of a novel salt compound]

An aqueous solution (100 mL) containing 0.2 wt% of the compound according to the above synthesis example was prepared, and then cooled at -18°C for 6 hours. The temperature of the cooled aqueous solution was slowly raised to 25°C to check whether precipitation occurred.

Example 1 Example 2 Example 3 Presence or absence of precipitation No precipitation No precipitation
(0.1% manufacturing solution) No precipitation

[Manufacturing Example 1: Manufacturing of Biocide Composition]

Biocide compositions were prepared according to the compositions shown in Table 3 below. Examples 4 to 6 are compositions having different contents of the compound of Example 1, Examples 7 and 8 are compositions having different contents of the compound of Example 2, and Examples 9 to 11 are compositions having different contents of the compound of Example 3.

division
Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Chemical formula 1 0.05* 0.1 0.2 0 0 0 0 0 Chemical formula 2 0 0 0 0.05 0.1 0 0 0 Chemical formula 3 0 0 0 0 0 0.05 0.1 0.2 Purified water remain** remain remain remain remain remain remain remain *Unit: weight%
**Total: 100 wt%

[Experimental Example 4: Safety Evaluation of Wet Tissues]

The clinical trial was conducted by commissioning the clinical trial commissioned to Oracle Skin Clinical Center Co., Ltd., a clinical trial commissioned institution. Specifically, the biocidal composition (20 μl) according to Manufacturing Example 1 was loaded into the IQ chamber, and the test area of 30 test subjects without skin damage was applied with a patch for 24 hours. Thereafter, the patch was removed, and the test area was washed with distilled water. Skin irritation was observed 30 minutes and 24 hours after the patch was removed, and the presence or absence of abnormal reactions was observed according to the criteria in Table 4 below, and the results of the stability evaluation are shown in Table 5 below. The skin irritation index according to the criteria in Table 4 was calculated based on the evaluation criteria of the International Contact Dermatitis Research Group (ICDRG).

Test method:

1) Test subjects: More than 30 healthy adult men and women aged 19 years or older who meet the selection criteria and do not meet the exclusion criteria.

2) Evaluation method: A 24-hour single patch test was conducted in accordance with the Ministry of Food and Drug Safety (MFDS) regulations on functional cosmetics evaluation, the Personal Care Products Council (PCPC) Safety Testing Guidelines, and the International Contact Dermatitis Research Group (ICDRG) evaluation criteria.

3) Test area: Back area

4) Reading and interpretation: Skin reactions were evaluated 30 minutes and 24 hours after patch removal 24 hours after application. Each reaction was combined to calculate the average skin reaction score and determine the irritation level.

Skin irritation index Skin irritation assessment 0.00~0.75 Non-stimulating 0.76~1.50 Hypoallergenic 1.51~2.50 Light stimulation 2.51~4.00 Medium stimulation 4.01~ strong stimulus

Example 6 Example 8 Example 9 Example 10 Example 11 Chemical formula and its content (wt%) Chemical formula 1 (0.2%) Chemical formula 2
(0.1%) Chemical formula 3
(0.05%) Chemical formula 3
(0.1%) Chemical formula 3
(0.2%) 30 minutes passed Non-stimulating Non-stimulating Non-stimulating Non-stimulating Non-stimulating 24 hours have passed Non-stimulating Non-stimulating Non-stimulating Non-stimulating Non-stimulating

Referring to Table 5 above, it can be confirmed that Examples 6, 8, 9, 10, and 11 all have very low skin irritation indices, indicating no skin irritation.

[Manufacturing Example 2: Manufacturing of wet tissues]

A wet tissue was manufactured by impregnating a fabric made of rayon fiber (specimen size: 18 cm X 16 cm, basis weight: 55 g/ ^m2 ) with the biocide composition according to Manufacturing Example 1.

[Experimental Example 5: Evaluation of the killing power of wet tissues]

For the wet tissue according to the above Manufacturing Example 2, the amount of living bacteria or mold was measured at regular intervals for 28 days according to the test standard ISO 11930. After that, the amount of bacteria or mold after 7 days was measured compared to the initial amount of bacteria or mold, and the rate of reduction in bacteria or mold was calculated. Specifically, the experiment was conducted according to the PCPC Technical Guidelines "M-5 methods for preservation testing of nonwoven substrate personal care products ".

1) Bacterial reduction rate

To verify the antibacterial effect of the wet tissue according to the above Manufacturing Example 2, Escherichia coli , Staphylococcus aureus , and Pseudomonas aeruginosa were mixed and inoculated as test strains, and the bacterial reduction rate is shown in Table 6 below.

2) Mold reduction rate

To verify the antifungal effect of the wet tissue according to the above Manufacturing Example 2, Aspergillus niger and Candida albicans were mixed and inoculated as test fungi, and the fungal reduction rate is shown in Table 6 below.

Psalter Example 4 Example 5 Example 6 Example 7 Example 8 Example
9 Example 10 Example 11 Chemical formula and its content (wt%) Chemical formula 1 (0.05%) Chemical formula 1
(0.1%) Chemical formula 1
(0.2%) Chemical formula 2
(0.05%) Chemical formula 2
(0.1%) Chemical formula 3
(0.05%) Chemical formula 3
(0.1%) Chemical formula 3
(0.2%) Bacterial reduction rate (%) 0% ≥9.9% ≥99.9% ≥99.9% ≥99.9% ≥99.9% ≥99.9% ≥99.9% Mold reduction rate (%) 0% ≥9.9% ≥99.9% ≥99.9% ≥99.9% ≥99.9% ≥99.9% ≥99.9%

When comparing Examples 4 to 6 in terms of the content of the compounds in Table 6 above, it can be confirmed that when the content of the compound represented by Chemical Formula 1 exceeds 0.05 wt% based on the total weight of the biocidal composition, bacteria and fungi can be removed by 99.9% or more. On the other hand, in the case of the compounds represented by Chemical Formulas 2 and 3, it can be confirmed that bacteria and fungi can be removed by 99.9% or more even when each content does not exceed 0.05 wt% based on the total weight of the biocidal composition.

[Experimental Example 6: Evaluation of Antioxidant Effect]

The antioxidant activity of ethyl lauroyl alginate piceolate synthesized in Example 3 was evaluated by measuring DPPH free radical scavenging activity, ABTS free radical scavenging activity, and total phenol content.

The test process for measuring free radical scavenging rate using DPPH is as follows.

DPPH was prepared at a concentration of 350 μM and used. 100 μL of the test substance and 100 μL of the DPPH solution were sequentially added to a 96-well plate, reacted for 30 minutes in an oven (JSOF-150, JSR, Korea) at 37°C, and the absorbance was measured at 517 nm using a Microplate reader (Epoch 2, BioTek, USA). Ethanol was used instead of the test substance as a solvent control. L-ascorbic acid was used as a positive control for comparison (Table 7).

The test process for measuring free radical scavenging rate using ABTS is as follows.

ABTSㆍ+ was produced by reacting ABTS and potassium persulfate at room temperature for 24 hours and used. 20 μL of each concentration test substance and 180 μL of ABTSㆍ+ solution were sequentially added to a 96-well plate, reacted for 1 minute, and then the absorbance was measured at 732 nm using a microplate reader. Ethanol was used instead of the test substance as a solvent control, and L-ascorbic acid was used as a positive control for comparison (Table 8).

The test procedure for measuring total phenol content is as follows.

For the primary physiological activity assay of the test substance, gallic acid was used as a standard sample, and the content of phenolic compounds was measured to confirm the antioxidant activity. The test substance was prepared to a final treatment concentration of 0.1 mg/mL and used. 15 μL of the test substance, 15 μL of 2 N Folin-ciocalteu's phenol reagent, 30 μL of 0.5 M sodium carbonate, and 90 μL of distilled water were added to a 96-well plate, and the reaction was performed at 37°C for 30 minutes. Then, the absorbance was measured at 725 nm using a microplate reader. The total phenol content was calculated using a gallic acid standard curve of 5, 10, 20, and 40 μg/mL (Table 9).

The DPPH free radical scavenging activity of ethyl lauroyl alginate piceolate was 2.45% to 5.74% at concentrations of 75 to 125 mg/mL (p<0.05), and the ABTS free radical scavenging activity was 35.19% to 92.93% at concentrations of 0.3125 to 5 mg/mL (p<0.05). The total phenol content of ethyl lauroyl alginate piceolate was 169.80±0.76 gallic acid equivalents (μg/mL), indicating that it is a substance with antioxidant activity.

Materials Concentration
(mg/mL) Scavenging activity (%) 1 ^{st 2nd 3rd} Mean Ethyl lauroyl
arginate piceolate 0 0.00 0.00 0.00 0.00±.00 25 -1.14 -0.49 -2.36 -1.33±0.95 50 1.47 -0.33 1.14 0.76±0.96 75 3.26 1.65 2.44 2.45±0.81 100 3.91 3.21 4.56 3.89±0.68 125 5.54 4.44 7.25 5.74±1.41 L-ascorbic acid 0.000 0.00 0.00 0.00 0.00±.00 0.001 4.48 6.33 5.62 5.47±0.93 0.002 8.96 10.48 10.44 9.96±0.87 0.004 19.10 20.67 20.99 20.25±1.01 0006 22.59 24.83 25.02 24.15±1.35 0.008 46.87 47.68 47.59 47.38±0.44

Materials Concentration
(mg/mL) Scavenging activity (%) 1 ^{st 2nd 3rd} Mean Ethyl lauroyl
arginate piceolate 0 0.00 0.00 0.00 0.00±.00 0.3125 36.71 33.50 35.36 35.19±1.61 0.625 55.75 56.29 56.95 56.33±0.60 1.25 83.44 83.44 83.62 83.50±0.11 2.5 88.75 88.92 88.59 88.75±0.17 5 93.08 92.53 93.18 92.93±0.35 L-ascorbic acid 0.000 0.00 0.00 0.00 0.00±.00 0.001 10.98 11.98 12.35 11.77±0.71 0.002 20.92 21.61 21.59 21.37±0.40 0.004 43.27 43.36 43.43 43.35±0.08 0006 64.44 64.71 65.02 64.73±0.29 0.008 91.90 91.93 91.81 91.88±0.06

Materials Total phenolic contents
(Gallic acid equivalents, μg/mL) 1 ^{st 2nd 3rd} Mean Ethyl lauroyl
arginate piceolate 172.04 176.06 161.31 169.80±7.62

[Experimental Example 7: Minimum Inhibitory Concentration (MIC) Experiment]

The concentration at which microbial growth is inhibited by the ethyl lauroyl alginate piceolate synthesized in the above Example 3 was evaluated. 8 ㎍/mL, 32 ㎍/mL, and 128 ㎍/mL samples of ethyl lauroyl alginate piceolate dissolved in sterile water were inoculated into cultures of five strains ( Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Candida albicans, Aspergillus brasiliensis, and Cutibacterium acnes ), and the number of microorganisms was measured after 24 hours, which is shown in Table 10.

Through these results, it was confirmed that the growth inhibition effect of the test strain by ethyl lauroyl alginate piceolate was confirmed, and it was confirmed that the salt compound of the present invention has sufficient potential to be used as a substance for improving the preservative power of cosmetics.

Microorganism CFU/mL Control 8㎍/mL 32㎍/mL 128㎍/mL E. coli 1.79 x 10 ⁹ 1.02 x 10 ⁹ ND ND S. aureus, 1.27 x 10 ⁹ ND ND ND P. aeruginosa, 4.39 x 10 ⁹ 3.41 x 10 ⁹ ND ND C.albicans, , 3.24 x 10 ⁷ 2.03 x 10 ⁷ ND ND A. brasiliensis 1.06 x 10 ⁴ 1.12 x 10 ⁴ ND ND C. acnes 3.14 x 10 ⁶ 29 ND ND

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

Claims (5)

delete delete Containing a salt compound represented by the following chemical formula 2 or 3 in an amount exceeding 0.05 wt% and not more than 0.1 wt%
Biocidal composition.
[Chemical formula 2]

[Chemical Formula 3]
In the third paragraph,
The remaining purified water; further comprising,
Biocidal composition. delete