Quaternary ammonium salt disinfectant

Abstract

The embodiment of the invention discloses a quaternary ammonium salt disinfectant. The quaternary ammonium salt disinfectant comprises quaternary ammonium salt, a solvent and a pH regulator, the quaternary ammonium salt is selected from at least one of thioether ester quaternary ammonium salt and gemini quaternary ammonium salt; the pH value of the quaternary ammonium salt disinfectant is less than 7. According to the embodiment of the invention, at least one of the evomorad and the gemini quaternary ammonium salt is adopted as the disinfection component, the disinfection effect is ensured, the disinfection agent is easy to degrade and environment-friendly, and the pH regulator is adopted to regulate the pH of the quaternary ammonium salt disinfectant to be less than 7, that is, the quaternary ammonium salt disinfectant is an acidic system, the system stability is good, and the system is easy to use and store.

Description

Technical Field

[0001] The invention relates to the technical field of disinfectants, in particular to a quaternary ammonium salt disinfectant. Background Art

[0002] Quaternary ammonium salts are widely used in the field of disinfection. They are often used as environmental and surface disinfectants. They are generally used by spraying or wiping with wet wipes. There are also a small number of hand disinfectant products on the market. In recent years, single-chain quaternary ammonium salts represented by benzalkonium chloride and double-chain quaternary ammonium salts represented by didecyldimethylammonium chloride have been widely used. The most outstanding performance of these quaternary ammonium salts is good product stability. The product content remains basically unchanged during the two-year shelf life, but this characteristic will lead to the enrichment of quaternary ammonium salts in the environment after use, especially in natural water bodies. Quaternary ammonium salts that exist stably for a long time in water bodies have a continuous bactericidal effect, which will lead to persistent drug resistance of bacteria, thereby damaging the water body.

[0003] At present, new and easily degradable quaternary ammonium salts such as Efmora have also appeared. Compared with traditional single-chain quaternary ammonium salts and double-chain quaternary ammonium salts, such quaternary ammonium salts have high bactericidal efficiency and can be completely degraded in a short period of time, becoming an environmentally friendly disinfection factor with application prospects in the future. However, due to the relatively rapid degradation performance of such quaternary ammonium salts in water, they encounter product stability problems during application. At present, in order to obtain stable and easily degradable quaternary ammonium salt disinfection products, the easily degradable quaternary ammonium salt disinfection products are usually made into high-concentration, easily degradable quaternary ammonium salts and high ethanol systems, which need to be diluted before use, causing inconvenience to users; in addition, the high ethanol system is flammable, which causes certain dangers to the production, storage and use of the product. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems in the prior art. To this end, the present invention proposes a quaternary ammonium salt disinfectant to achieve the effects of environmentally friendly, easily degradable, convenient for use and storage of quaternary ammonium salt disinfection products.

[0005] Specifically, the present invention provides a quaternary ammonium salt disinfectant, which comprises: a quaternary ammonium salt, a solvent and a pH regulator;

[0006] The quaternary ammonium salt is selected from at least one of thioether ester quaternary ammonium salt and gemini quaternary ammonium salt;

[0007] The pH of the quaternary ammonium salt disinfectant is less than 7.

[0008] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the mass proportion of the quaternary ammonium salt in the quaternary ammonium salt disinfectant is 0.02% to 0.5%.

[0009] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the volume proportion of the solvent is greater than or equal to 40%.

[0010] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the solvent is an alcohol solvent.

[0011] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the alcohol solvent is selected from at least one of ethanol, isopropanol, propylene glycol, butylene glycol and glycerol.

[0012] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the mass proportion of the pH adjuster is 0-2%.

[0013] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the pH regulator is an acid regulator.

[0014] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the acid regulator is selected from at least one of lactic acid, malic acid, hydrochloric acid and phosphoric acid.

[0015] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the pH value of the quaternary ammonium salt disinfectant is 5 to 6.5.

[0016] In one embodiment of the above-mentioned quaternary ammonium salt disinfectant, the quaternary ammonium salt disinfectant also includes at least one of a chelating agent and a humectant.

[0017] One or more of the above embodiments of the present invention have at least one or more of the following beneficial effects: at least one of Efmora and gemini quaternary ammonium salts is used as a disinfectant component to ensure the disinfection effect while being easy to degrade and environmentally friendly; a pH adjuster is used to adjust the pH of the quaternary ammonium salt disinfectant to less than 7, that is, the quaternary ammonium salt disinfectant is an acidic system, the system has good stability, and is easy to use and store.

[0018] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. DETAILED DESCRIPTION

[0019] Some embodiments of the present invention are described below. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the protection scope of the present invention.

[0020] As described in the background technology, the field of quaternary ammonium salt disinfection products is widely used and has been used on a large scale in recent years.But the quaternary ammonium salt disinfection products that are widely used at present are mostly single-chain quaternary ammonium salts represented by benzalkonium chloride and double-chain quaternary ammonium salts represented by didecyl dimethyl ammonium chloride, and the product stability of these quaternary ammonium salts is outstanding, but just because of this characteristic, after the quaternary ammonium salt disinfection products are used, this type of quaternary ammonium salt enrichment in the environment, especially in natural water bodies, can cause the persistent drug resistance of bacteria and destroy water bodies after a long time.And at present, the easily degradable new quaternary ammonium salts such as Efumo La can all be degraded in a short period of time, and are environmentally friendly, but their poor stability, in order to make up for the defect of their stability, it is necessary to make the disinfection products into high quaternary ammonium salt concentration and high ethanol concentration system, need to dilute before use, and preserve the inconvenience of dangerousness.

[0021] In order to solve the above problems, the present application creatively proposes a quaternary ammonium salt disinfectant, which uses at least one of the easily decomposable Efmora and gemini quaternary ammonium salts, adds a pH adjuster to the disinfectant system to adjust the pH of the quaternary ammonium salt disinfectant to less than 7, and adjusts the quaternary ammonium salt disinfectant system to an acidic system, so as to achieve the effect of quaternary ammonium salt disinfection products being environmentally friendly, easy to degrade, easy to use and store.

[0022] The present invention will be described in detail below through specific embodiments.

[0023] Specifically, the embodiment of the present application provides a quaternary ammonium salt disinfectant, which includes: a quaternary ammonium salt, a solvent and a pH regulator;

[0024] The quaternary ammonium salt is selected from at least one of thioether ester quaternary ammonium salt and gemini quaternary ammonium salt;

[0025] The pH of quaternary ammonium disinfectant is less than 7.

[0026] Quaternary ammonium salts, also known as quaternary ammonium salts, are compounds formed by replacing the four hydrogen atoms in the ammonium ion with hydrocarbon groups. The general formula is R4NX, where R refers to the hydrocarbon group and X represents a halogen anion or an acid radical. The four hydrocarbon groups R can be the same or different.

[0027] The term "hydrocarbon group" refers to a group containing only carbon and hydrogen atoms, which is the group remaining after the corresponding hydrocarbon loses a hydrogen atom (H). The hydrocarbon group can be straight chain, branched or cyclic, and the number of carbon atoms can be, for example, C1-C5, C1-C4, C1-C3, C1-C2, etc. For example, alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.

[0028] The halogen anion is selected from fluoride, chloride, bromide and iodide; the acid radical includes but is not limited to sulfate, acetate, nitrate, nitrite, carbonate, carboxylate, tartrate, p-toluenesulfonate, methanesulfonate, citrate and the like.

[0029] In the present application, at least one of the preferred thioether ester quaternary ammonium salt and the gemini quaternary ammonium salt of quaternary ammonium salt.Gemini quaternary ammonium salt is a quaternary ammonium salt formed by connecting two monosodium quaternary ammonium salt molecules at its hydrophilic head group or near the hydrophilic head group through a linking group, because its single molecule contains two quaternary ammonium positive ions, charge density is higher, compared with traditional monosodium quaternary ammonium salt bactericide, has stronger adsorption to bacteria, can sterilize efficiently in small quantities.Gemini quaternary ammonium salt can be a symmetrical gemini quaternary ammonium salt with ester group as hydrophobic group, can also be an asymmetric gemini quaternary ammonium salt.

[0030] Exemplarily, the thioether ester quaternary ammonium salt is preferably Efmora, and the structural formula of the gemini quaternary ammonium salt is as shown in Formula I or Formula II:

[0031]

[0032] Wherein: R1 and R2 are saturated long-chain alkanes with 6 to 12 carbon atoms, X is one of chlorine, bromine and iodine, and R3 is a long-chain alkane with 4 to 8 carbon atoms, wherein the alkane may be substituted with a hydroxyl group or not, and for exemplary purposes only, R3 is any one of the following structures:

[0033]

[0034] It should be noted that the above examples are only for illustrative purposes and are not intended to limit the scope of protection of this application. Any modification / adjustment / update made under the teachings of this application is within the scope of protection of this application.

[0035] In some embodiments, the mass proportion of quaternary ammonium salt in the quaternary ammonium disinfectant is 0.02% to 0.5%. Optionally, the mass proportion of quaternary ammonium salt in the quaternary ammonium disinfectant can be 0.02%, 0.05%, 0.08%, 0.1%, 0.13%, 0.05%, 0.17%, 0.2%, 0.26%, 0.3%, 0.35%, 0.4%, 0.43%, 0.47%, 0.5%, etc., or any point value within the above numerical range.

[0036] In certain embodiments, the volume proportion of the solvent is greater than or equal to 40%. Optionally, the volume proportion of the solvent in the quaternary ammonium salt disinfectant can be 40%, 43%, 45%, 47%, 50%, 53%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, or any point value within the above numerical range. Preferably, the volume proportion of the solvent in the quaternary ammonium salt disinfectant is greater than or equal to 40%, and less than or equal to 75%.

[0037] In some embodiments, the solvent is an alcohol solvent.

[0038] In the present application, an alcohol solvent refers to a liquid organic compound having a hydroxyl group connected to a saturated sp3 hybridized carbon atom.

[0039] In some embodiments, the alcohol solvent is selected from at least one of ethanol, isopropanol, propylene glycol, butylene glycol and glycerol.

[0040] In some embodiments, the mass proportion of the pH adjuster is 0-2%. Optionally, the mass proportion of the pH adjuster in the quaternary ammonium salt disinfectant can be 0, 0.1%, 0.4%, 0.7%, 1.0%, 1.3%, 1.6%, 1.9%, 2.0%, or any point value within the above numerical range.

[0041] In some embodiments, the pH adjuster is an acid adjuster.

[0042] Specifically, the quaternary ammonium salt disinfectant system can be adjusted to an acidic system by using an acid salt or an acid regulator that completely ionizes in an aqueous solution to make the solution acidic. As an example, the acid salt can be NaHSO4, KHSO4, phosphate, etc. In the present application, an acid regulator is preferred, which is more convenient for adjusting pH.

[0043] In some embodiments, the acid regulator is selected from at least one of lactic acid, malic acid, hydrochloric acid and phosphoric acid.

[0044] In some embodiments, the pH value of the quaternary ammonium salt disinfectant is 5 to 6.5. Optionally, the pH value of the quaternary ammonium salt disinfectant can be 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.5, or any point value within the above numerical range.

[0045] Maintaining the pH value of the quaternary ammonium salt disinfectant system at 5 to 6.5 can not only maintain the stability of the quaternary ammonium salt disinfectant system, but also avoid skin irritation caused by excessive acidity of the quaternary ammonium salt disinfectant system.

[0046] In some embodiments, the quaternary ammonium disinfectant further comprises at least one of a chelating agent and a humectant.

[0047] The present application is further described in detail below in conjunction with the embodiments. It should be noted that the following embodiments are only used to illustrate the present application and are not used to limit the scope of protection claimed in the present application, and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the contents of the present application above still belong to the scope of protection of the present application.

[0048] In the following examples, the reagents, materials and instruments used are all commercially available products and can be purchased unless otherwise specified.

[0049] Example 1: Prepare 500 ml of solvent alcohol with a volume concentration of 45%; add 0.5030 g of Efmora, with a mass ratio of 0.1%, and stir to completely dissolve the Efmora; finally, add 1% hydrochloric acid to adjust the pH of the system to 5-6.5.

[0050] Example 2: The difference between this example and Example 1 is that in this example, 0.5011 g of gemini quaternary ammonium salt is added to the solvent alcohol.

[0051] Example 3: The difference between this example and Example 2 is that in this example, the volume concentration of the solvent alcohol is 75%, and the mass of the gemini quaternary ammonium salt is 0.5085g.

[0052] Example 4: The difference between this example and Example 2 is that in this example, the mass of the gemini quaternary ammonium salt is 0.2577 g, and the mass proportion is 0.05%.

[0053] Comparative Example 1: The difference between this embodiment and embodiment 2 is that in this embodiment, the solvent alcohol is a compound of 18% ethanol and 2% butanediol in a volume ratio, the mass of the gemini quaternary ammonium salt is 0.5176 g, and the mass proportion is 0.1%.

[0054] Comparative Example 2: The difference between this embodiment and Comparative Example 1 is that in this embodiment, the mass of the gemini quaternary ammonium salt is 0.3779 g, and the mass proportion is 0.075%.

[0055] Comparative Example 3: The difference between this embodiment and Comparative Example 1 is that in this embodiment, the mass of the gemini quaternary ammonium salt is 0.2632 g, and the mass proportion is 0.05%.

[0056] Comparative Example 4: This comparative example provides a quaternary ammonium salt disinfectant, configured with a volume ratio of 500ml and a concentration of 35％ Add 0.5006g of Efmora (weight ratio is 0.1%) to the solvent alcohol, stir until completely dissolved, and add 1% hydrochloric acid to adjust the pH to 5-6.5.

[0057] Comparative Example 5: This comparative example provides a quaternary ammonium salt disinfectant, configured with a volume ratio of 500ml and a concentration of 35％ Add 0.5040g of gemini quaternary ammonium salt (weight ratio is 0.1%) of solvent alcohol, stir until completely dissolved, and add 1% hydrochloric acid to adjust the pH to 5-6.5.

[0058] Comparative Example 6: This comparative example provides a quaternary ammonium disinfectant, which is prepared by preparing 500 ml of solvent alcohol with a volume concentration of 45%, adding 0.5024 g of gemini quaternary ammonium salt, accounting for 0.1% by mass, stirring until completely dissolved, and adding 1% sodium hydroxide to adjust the pH to 7.5-8.5.

[0059] Comparative Example 7: This comparative example provides a quaternary ammonium salt disinfectant, which is configured with 500 ml of solvent alcohol with a volume ratio concentration of 20%. The solvent alcohol is a compound of 18% ethanol and 2% butanediol with a volume ratio concentration. 0.0751 g of gemini quaternary ammonium salt is added, with a mass ratio of 0.015%. Stir until completely dissolved, and add 1% hydrochloric acid to adjust the pH to 5-6.5.

[0060] Stability effect test:

[0061] According to the provisions of 2.2.3 of the Technical Specifications for Disinfection, the stability test was carried out by the 54°C accelerated test method, and the stability was verified by the content of active ingredients and the effect of killing microorganisms. At the same time, the changes in appearance were observed. The results are shown in Table 1:

[0062] Embodiment 1~3, after aging at 54 ℃ and 14 days, the effective ingredient content decline rate is 3.36%, 0.96%, 0.13% respectively, all <10%, and the killing logarithm value of Candida albicans is all >7 (with 45% ethanol as reference), and the appearance does not change; When the data show that the ethanol content in the system is ≥45%, Evmora and Gemini quaternary ammonium salt are stable systems. Comparative Examples 4 and Comparative Examples 5, after long-term room temperature placement or 54 ℃ and 14 days aging, the system will have turbidity, indicating that the ≤35% ethanol system is an unstable system of Evmora and Gemini quaternary ammonium salt products. Comparative Example 6 will have turbidity after aging at 54 ℃ and 14 days, indicating that the degradable quaternary ammonium salt active ingredient is easily hydrolyzed under the alkaline conditions of pH>7, and the system is unstable. For Comparative Examples 1 to 3, the systems all became turbid after being placed at room temperature for more than one month or aged at 54°C for 14 days, further proving that the 20% low alcohol system is an unstable system; however, in order to verify the bactericidal effect of the degradable quaternary ammonium salt, the influence of the alcohol solvent on the bactericidal effect must be deducted at the same time, and the method of preparing and using it immediately is adopted.

[0063] Table 1

[0064]

[0065]

[0066] Bactericidal effect experiment:

[0067] As shown in Table 2, the contents of gemini quaternary ammonium salts in Comparative Examples 1 to 3 are approximately 0.1%, 0.075%, and 0.05%, respectively. In order to eliminate the effect of alcohol on the bactericidal effect, a low concentration 20% solvent alcohol system is used (the killing logarithm of 35% ethanol on Candida albicans in the literature is 1.41, so the effect of alcohol can be ignored). According to the provisions of GB27950-2020 "General Requirements for Hand Disinfectants", the killing logarithm of Candida albicans within 1 minute must be ≥4. The content of gemini quaternary ammonium salts in Comparative Example 3 is as low as 0.05%, and the killing logarithm of Candida albicans is also >5, which can meet the requirements of hand disinfectants. The killing logarithm of Pseudomonas aeruginosa in Comparative Examples 1 to 3 within 5 minutes is ≥5, which meets the provisions of GB27951-2021 "General Requirements for Skin Disinfectants" and can be used for skin disinfectants. In Comparative Example 7, the content of gemini quaternary ammonium salt is 0.015%, the killing logarithm value of Pseudomonas aeruginosa is less than 5, and the killing logarithm value of Candida albicans is less than 4, which cannot meet the sterilization effect requirements. However, after a period of storage, the gemini quaternary ammonium salt component in the low alcohol system used in Comparative Examples 1 to 3 is reduced, and the stability of the disinfectant system is not good. By increasing the alcohol content, the system can be stabilized and a product with satisfactory sterilization effect can be obtained.

[0068] Table 2

[0069]

[0070]

[0071] As shown in Table 3, the content of gemini quaternary ammonium salt in Example 2 is 0.1%, and the sterilization rate from the 1st to the 7th day is >90%, which meets the provisions of WS / T 650-2019 "Antibacterial and Antibacterial Effect Evaluation Method" 5.2.7 for the sterilization rate in long-term antibacterial. In Example 4, the content of gemini quaternary ammonium salt is 0.05%, and the sterilization rate for 7 days is <90%, which does not meet the requirements in the specification. Therefore, a 45% alcohol solution with a content of gemini quaternary ammonium salt ≥0.1% can be used to prepare a long-term antibacterial surface disinfectant.

[0072] Table 3

[0073]

[0074] When the pH of the disinfectant is less than 5, the acidity of the disinfectant is too strong and it is more irritating to the skin. As for the content of quaternary ammonium salts, the national standard limit for products used on hands and skin is less than 0.5%.

[0075] In summary, the preferred quaternary ammonium salt disinfectant is prepared by adding 0.02% to 0.5% of thioether ester quaternary ammonium salt and / or gemini quaternary ammonium salt to solvent alcohol with a volume concentration of ≥40%, and adjusting the pH value of the disinfectant to 5 to 6.5 using a pH adjuster.

[0076] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0077] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0078] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A quaternary ammonium salt disinfectant, characterized in that, The quaternary ammonium salt disinfectant comprises: a quaternary ammonium salt, a solvent and a pH regulator; The quaternary ammonium salt is selected from at least one of thioether ester quaternary ammonium salt and gemini quaternary ammonium salt; The pH of the quaternary ammonium salt disinfectant is less than 7.

2. The quaternary ammonium salt disinfectant according to claim 1, characterized in that The mass proportion of the quaternary ammonium salt in the quaternary ammonium salt disinfectant is 0.02% to 0.5%.

3. The quaternary ammonium salt disinfectant according to claim 1, characterized in that The volume proportion of the solvent is greater than or equal to 40%.

4. The quaternary ammonium salt disinfectant according to claim 3, characterized in that The solvent is an alcohol solvent.

5. The quaternary ammonium salt disinfectant according to claim 4, characterized in that The alcohol solvent is selected from at least one of ethanol, isopropanol, propylene glycol, butylene glycol and glycerol.

6. The quaternary ammonium salt disinfectant according to claim 1, characterized in that The mass proportion of the pH adjuster is 0-2%.

7. The quaternary ammonium salt disinfectant according to claim 1, characterized in that The pH regulator is an acid regulator.

8. The quaternary ammonium salt disinfectant according to claim 7, characterized in that The acid regulator is selected from at least one of lactic acid, malic acid, hydrochloric acid and phosphoric acid.

9. The quaternary ammonium salt disinfectant according to claim 1, characterized in that The pH value of the quaternary ammonium salt disinfectant is 5 to 6.

5.

10. The quaternary ammonium salt disinfectant according to claim 1, characterized in that The quaternary ammonium salt disinfectant also includes at least one of a chelating agent and a moisturizing agent.

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