WO2013094927A4 - Cationic antimicrobial compound and antimicrobial composition comprising same - Google Patents

Abstract

The present invention relates to a cationic antimicrobial compound and an antimicrobial composition comprising the same. More particularly, the present invention relates to an antimicrobial compound which is prepared by a method that quaternizes ammonium alkyldimethylamine by epichlorohydrin and which may exhibit superior antimicrobial activity to eumycota including viruses. The present invention also relates to an antimicrobial composition comprising the cationic antimicrobial compound.

Description

Cationic antimicrobial compound and antimicrobial composition containing the same

The present invention relates to a cationic antimicrobial compound and an antimicrobial composition containing the antimicrobial compound. More particularly, the present invention relates to a cationic antimicrobial compound which is produced by quaternary ammoniumation of alkyldimethylamine with epichlorohydrin, And an antimicrobial composition containing the same.

Antimicrobial and fungicides are classified into oxidizing and non-oxidizing fungicides.

Halogen compounds such as chlorine, bromine and the like are mainly used as the oxidizing fungicide. They are widely used because they have a strong oxidizing power and are economical. However, they have a great influence on wood corrosion and metal corrosion and are easily released into the atmosphere, It reacts with the polysaccharide secreted before reacting with the causative microorganism in the state where the biofilm is formed, so that the microbicidal effect is substantially lowered.

On the other hand, non-oxidative fungicides include 3-isothiazolinone, quaternary ammonium compounds, formaldehyde-releasing compounds, glutaraldehyde and the like, which are mainly used singly but are described in US Pat. No. 3,282,775, US Pat. No. 4,107,312, EP 0217339 There have been exemplified a sterilizing composition in which glutaraldehyde and quaternary ammonium chloride are combined in order to impart quick-acting properties and increase sterilizing power.

Quaternary ammonium compound means that all the hydrogen present in ammonium (NH ₄ ⁺ ) is replaced with an organic molecule (such as an alkyl group). Quaternary ammonium compounds exhibit excellent antibacterial activity over a wide temperature and pH range. The quaternary ammonium compound is the main component of the cationic surfactant, which is known to have weaker detergency than the anionic surfactant but strong antimicrobial activity. Typical examples of quaternary ammonium compounds which are cationic surfactants are benzalkonium chloride and benzethonium chloride, which are harmless to the human body and have no metal corrosiveness, so they are mainly used as disinfectants for hand and appliance. In addition, various quaternary ammonium compounds such as polyoxyethylene trimethyl ammonium chloride and polyoxyalkyl trialkyl ammonium chloride are used for antibacterial and deodorization of textile products.

Quaternary ammonium compounds are known to adsorb quaternary ammonium compounds on the surface of microbial cells, and then the antimicrobial substance diffuses through the cell walls and the cytoplasmic membrane is destroyed, releasing the cytoplasmic components such as K ⁺ ions and DNA and RNA, thereby inactivating the microorganisms . This mechanism is based on the fact that the microbial cell surface is negatively charged and quaternary ammonium compounds are positive cations.

Recently, research has been conducted on the development of new quaternary ammonium compounds which are easy to apply to coatings and the like or which are more harmless to humans, or how the antimicrobial activity varies when the substituent length of the compound is changed or changed to another substituent .

Conventional quaternary ammonium salts have a disadvantage in that the instantaneous sterilizing power is excellent but the antibacterial and sterilizing performance against fungi is inferior.

Accordingly, it is an object of the present invention to provide an antimicrobial agent that solves the problems of the conventional quaternary ammonium salt antimicrobial agent as described above, is excellent in not only bacteria but also fungi, and is simple and economical to manufacture.

In order to achieve the above object, the present inventors have produced a new type of cationic antimicrobial agent which is very economical and has excellent antibacterial performance by quaternization by reacting alkyldimethylamine with epichlorohydrin.

The cationic antimicrobial compound of the present invention is very simple and economical, has excellent antimicrobial activity, and exhibits excellent antimicrobial activity against fungi.

The antimicrobial compound of the present invention is represented by the following general formula (1).

Formula 1

And in formula R 1 is the group consisting of a mixture of C ₆ linear or branched alkyl group -C _18, an alkenyl group, or they are at least one, A is _{CHCH 2 (O), CHOHCH 2} OH, CH 2 CH: CHOH, CH ₂ CHCH ₂ (O), CH ₂ CHOHCH ₂ OH, or a mixture of at least one of these. R represents an excellent antibacterial function in the range of 6 to 18 carbon atoms, and if it is out of this range, the antibacterial function is lowered.

The present inventors prepared the antibacterial compound of formula (I) by quaternarization by reacting alkyldimethylamine with epichlorohydrin. However, the antibacterial compound of the present invention is not necessarily prepared by this method.

The reaction is carried out using at least one of water and an organic solvent such as ethanol, isopropyl alcohol, ethyl acetate, acetone, benzene or toluene as a solvent.

The epichlorohydrin to be added to the reaction is used in an amount of 0.9 to 1.1 equivalents of alkyldimethylamine. The reaction is well performed within the above equivalence range.

The reaction temperature is 0 to 90 ° C, preferably 60 to 70 ° C, and the reaction time is 1 to 15 hours. If the temperature and time do not exceed or fall below the above range, the reaction may not occur properly or the reaction may proceed excessively, resulting in undesired by-products. The resulting compound has a solid content of 10 to 80%, and this solid content is a cationic antimicrobial agent as a final product.

The cationic antimicrobial compound thus obtained may be incorporated into various products such as a hair product such as a detergent, a fabric softener, a shampoo, a cosmetic product, a textile product or an agricultural chemical composition according to a method known to a person skilled in the art Can be used.

In addition, the present invention encompasses an antimicrobial composition comprising the compound represented by the above-mentioned formula (1).

The antimicrobial composition of the present invention may contain at least one compound represented by the formula (1) alone or in combination with 0.001 to 99% by weight of the compound represented by the formula (1) and an additive suitably selected according to the purpose of use. The present invention does not particularly limit the selective use and content of these additives, and can be appropriately adjusted according to the method of use and the formulation at the level of the experts engaged in the art. That is, the additive of the present invention may be a substance included in conventional antimicrobial agents, for example, an excipient or diluent, and examples thereof include saline, buffer solution, dextrose, isoparaffin, water, glycerol and ethanol. It is by no means limited.

The formulation of the antimicrobial agent can be suitably adjusted according to the method of use and the intended use. For example, the antimicrobial agent may be formulated into a liquid, suspension, granule, It may be a main tablet, a capsule, a cream, or a remedy.

The antimicrobial composition of the present invention can be used as a fabric softener, a detergent, a detergent, a medicine, a food additive, a fragrance, a cosmetic, and an agricultural chemical composition for inhibiting the production and growth of pathogenic bacteria, phytopathogenic bacteria and fungi. When it is used as a detergent, it can be manufactured as a spraying agent, a detergent, a shampoo, a hair conditioner, a hair conditioner, a soap, etc. The antibacterial composition may include 0.01 to 50% by weight, but is not limited thereto. When it is used as a medicine, it can be used as a disinfectant, a therapeutic agent, a prophylactic agent, etc. In this case, the dose of the antimicrobial composition may be 1 to 1000 mg per day, but is not limited thereto. When it is used as a quasi-drug, it can be manufactured as a hair growth agent, a hair dye, a depilator, a deodorant, a body odor inhibitor, a dentifrice, etc. The antimicrobial composition may include 0.01 to 50% by weight, but is not limited thereto. When it is used as a food additive, the antimicrobial composition is suitably adjusted according to the kind of the food and the method of use. For example, the antimicrobial composition may be used in an amount of 0.0001 to 10% by weight based on the weight of the food. When it is used as a fragrance, it may further contain a volatile substance, and the antimicrobial composition may be used in an amount of 0.0001 to 90% by weight. When used as a fabric softener, the antimicrobial composition may be used in an amount of 0.0001 to 30% by weight. When used as a cosmetic, the antimicrobial composition may be contained in an amount of 0.0001 to 30% by weight. When used as an agricultural chemical composition for inhibiting the growth and growth of phytopathogenic bacteria or fungi, the antimicrobial composition may be contained in an amount of 0.001 to 30% by weight.

Various antimicrobial compositions containing the antibacterial compound of the present invention as an active ingredient can be easily prepared according to conventional methods and compositions by those skilled in the art, It is not stated separately in the explanation.

Hereinafter, the configuration of the present invention will be described in more detail with reference to embodiments. It will be apparent to those skilled in the art, however, that the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Example 1

In a flask equipped with a mechanical stirrer, a thermometer and a condenser, 568 g of distilled water and 213 g of dimethyl laurylamine were added at room temperature, and 93 g of epichlorohydrin was slowly added thereto. After the addition, the flask was maintained at 80 DEG C for about 3 hours, and the reaction was terminated. The reaction was confirmed by amine and the reaction was terminated at 3 or less. At this time, the pH measured by diluting the reaction product to 5% was 8.5.

Example 2

In the same apparatus as in Example 1, 568 g of ethanol and 213 g of dimethyl laurylamine were added and mixed, and 93 g of epichlorohydrin was slowly added thereto. After the addition, the reaction mixture was maintained at 60 ° C for about 5 hours and the reaction was terminated. The reaction was confirmed by amine and the reaction was terminated at 3 or less. At this time, the pH measured by diluting the reactant to 5% was 8.3.

Comparative Example 1

As a comparative sample 1, commercially available cationic surfactant-type antimicrobial agents such as didecyldimethylammonium chloride, which is most widely used for various purposes, were selected.

Comparative Example 2

Among the commercial cationic surfactant-type antibacterial agents, a comparative sample 2 was selected as a benzalkonium chloride salt which is widely used from medical use to industrial use.

Comparative Example 3

As a comparative sample 3, polyhexamethylbiguanide which is widely used among commercial polymer type antibacterial agents was selected.

[Test Methods]

The method of microbiology guidelines of CTFA (Cosmetic, Toiletry, and Fragrance Association) and linear regression method of DS Orth were modified and measured. The test specimens were inoculated into the liquid medium at the appropriate time and cultured. The cultured test specimens were diluted in the test medium and placed in a suitable container. Each of the prepared specimens was subjected to buoyancy test at a concentration of 1 × 10 ⁶ cells / ml , And 1 × 10 ⁶ cells / ml for fungi. The inoculated product was sampled according to the elapsed time from the time immediately after inoculation until 2 weeks after the inoculation, and the number of viable cells was tested. For bacteria, the culture was incubated for 48 hours in a 37 ° C incubator and in a 25 ° C incubator for 72 hours And the number of viable cells was measured.

[Usage Strain and Medium]

Staphylococcus aureus (KCTC 1621), Staphylococcus epidermidis (KCTC 1917), Gram-positive bacteria and Escherichia coli ; KCTC 1039) and Pseudomonas aeruginosa (KCTC 2004) were used. Bacterial medium was tryptic soy agar (TSA) and tryptic soy broth (TSB) of Merck (Germany).

Antifungal activity has hyomoryu of Candida albicans (Candida albicans; KCTC 7270) medium for fungi was used Merck (Germany)'s PDA (potato dextrose agar), PDB (potato dextrose broth).

All of the above strains were purchased from the BRC.

The results of the above-mentioned antibacterial test are shown in Table 1 below. The values in Table 1 are the minimum inhibitory concentrations (MIC concentrations) and are in ppm.

Table 1

Test strain	Example 1	Example 2	Comparative Example 1	Comparative Example 2	Comparative Example 3
Staphylococcus aureus	95	90	140	180	190
Staphylococcus epidermis.	90	90	120	180	150
Escherichia coli	90	85	135	175	190
Pseudomonas aeruginosa	80	90	150	200	220
Candida albicans	120	120	350	420	250

The two kinds of cationic antimicrobials prepared in Examples 1 and 2 were tested for their antibacterial activities by using a minimum inhibitory concentration (MIC) measurement method for various strains. As a result, it was found that the antibacterial activities of Comparative Examples 1 to 3 The antibacterial activity against fungi such as Candida albicans was excellent compared with the conventional quaternary ammonium cationic antimicrobials of Comparative Example 1 and Comparative Example 2, there was.

The cationic antimicrobial compound of the present invention is very simple and economical, has excellent antimicrobial activity, and exhibits excellent antimicrobial activity against fungi. Accordingly, the cationic antimicrobial compound of the present invention can be applied to various fields such as a fabric softener, a detergent, a cleaning agent, a medicine, a food additive, a fragrance, a cosmetic, a quasi-drug or an agricultural chemical composition.

Claims (8)

1. A cationic antimicrobial compound represented by the following formula (1).

   ≪ Formula 1 >

   

   In the above formula (1), R is selected from the group consisting of C ₆ -C ₁₈ linear or branched alkyl, alkenyl and mixtures of at least one thereof, A represents CHCH ₂ (O), CHOHCH ₂ OH, CH ₂ CH ₂ CHOH, CH ₂ CHCH ₂ (O), CH ₂ CHOHCH ₂ OH, or a mixture of at least one of these.
2. The method according to claim 1,

   The antibacterial compound is prepared by reacting alkyldimethylamine with epichlorohydrin in a solvent, and the solvent is at least one selected from the group consisting of water, ethanol, isopropyl alcohol, ethyl acetate, acetone, benzene and toluene A cationic antimicrobial compound.
3. 3. The method of claim 2,

   Wherein the amount of epichlorohydrin is reacted using 0.9 to 1.1 equivalents of alkyldimethylamine.
4. 3. The method of claim 2,

   Wherein the reaction temperature is 0 to 90 ° C and the reaction time is 1 to 15 hours.
5. 3. The method of claim 2,

   Wherein the solid content of the product obtained through the reaction is 10 to 80%.
6. An antimicrobial composition comprising at least one cationic antimicrobial compound of claim 1.
7. The method according to claim 6,

   Wherein the composition is a fabric softener, a detergent, a detergent, a medicine, a food additive, a fragrance, a cosmetic, a quasi-drug or an agricultural chemical composition.
8. 8. The method of claim 7,

   Wherein the detergent is a shampoo, a soap, or a body cleanser.