A compound disinfectant and a preparation method thereof

Abstract

The application discloses a kind of compound disinfectant and preparation method thereof, the compound disinfectant includes the following component raw materials by mass percentage: 0.1%~0.5% quaternary ammonium salt mixture, nonionic surfactant 0.02%~0.05%, antifungal agent and chitosan modified nanoparticle 0.02%~0.05%, humectant 0.1%~0.3%, the balance is water.The compound disinfectant system of the application has good bactericidal performance, antifungal agent and chitosan modified nanoparticle can reduce the influence of foam and improve the bactericidal activity, the presence of nonionic surfactant makes the sterilization more rapid, and the quaternary ammonium salt mixture is more stable.The compound disinfectant of the application can kill escherichia coli, staphylococcus aureus, candida albicans, has little irritation and little corrosivity, and is suitable for general object surface disinfection and public place disinfection with human contact.

Description

Technical Field

[0001] This invention relates to the field of disinfectant technology, and in particular to a compound disinfectant and its preparation method. Background Technology

[0002] Disinfection is a method of eliminating pathogenic microorganisms in the external environment and controlling other microorganisms that cause economic losses through physical, chemical, or biological means, so as to achieve harmless treatment. Drugs with disinfecting effects are called disinfectants. With the increasing resistance of microorganisms to existing disinfection products and the continuous improvement of human awareness of health and environmental protection, the development of new, highly effective, and low-toxicity disinfectants is increasingly in line with contemporary trends.

[0003] Currently, widely used disinfectants include chlorine-based disinfectants, alcohol-based disinfectants, peroxide-based disinfectants, aldehyde-based disinfectants, quaternary ammonium salt disinfectants, iodine-based disinfectants, phenolic disinfectants, and guanidine-based disinfectants. Among these, quaternary ammonium salt and guanidine-based disinfectants have attracted widespread attention due to their low corrosivity to metals, low toxicity, and minimal impact on the ecological environment. Some existing technologies also provide high-performance compound quaternary ammonium disinfectants. For example, CN113383775A discloses a low-temperature compound quaternary ammonium salt disinfectant that uses a mixture of single-chain, double-chain, and heterocyclic quaternary ammonium salts to significantly enhance its antibacterial effect. CN112088879A discloses a quaternary ammonium salt compound disinfectant, the components of which are: benzalkonium chloride 0.1%, polyhexamethylene biguanide 0.02%, coconut oil fatty acid diethanolamide 0.2%, glycerol 0.2%, and deionized water as the balance. This quaternary ammonium salt compound disinfectant has the advantages of readily available raw materials, easy preparation process, low production cost, non-corrosive to people and object surfaces, odorless, non-toxic, environmentally friendly, and convenient to use.

[0004] Existing compound quaternary ammonium salt disinfectants mainly utilize quaternary ammonium salts or other bactericidal components to enhance bactericidal performance. Some nanomaterials are not only low in toxicity or non-toxic, but also have good bactericidal properties. Combining quaternary ammonium salts with nanomaterials that have bactericidal properties is expected to prepare compound disinfectants with excellent performance. Summary of the Invention

[0005] To address the technical problems existing in the prior art, the present invention provides a compound disinfectant comprising the following raw materials by mass percentage: 0.1%~0.5% quaternary ammonium salt mixture, 0.02%~0.05% nonionic surfactant, 0.02%~0.05% antifungal agent and chitosan modified nanoparticles, 0.1%~0.3% humectant, balance water.

[0006] The disinfectant of this invention mainly comprises quaternary ammonium salt bactericides and other adjuvants. Quaternary ammonium salts are typically not only bactericides but also surfactants. The bactericidal mechanism of quaternary ammonium salts is as follows: after hydrolysis in water, they become positively charged, adsorb onto the surface of microorganisms, forming ionic microclusters. These microclusters gradually penetrate the lipid and protein layers of the cytoplasm, thereby altering cell membrane permeability, causing cell contents to leak out, leading to cell death. Simultaneously, they coagulate cell proteins, denature enzymes and their structural proteins, disrupt microbial metabolism, and precipitate cytoplasmic proteins and cell membranes, ultimately killing the microorganisms. Quaternary ammonium salt bactericides are effective at low concentrations, exhibiting extremely low toxicity, safety, colorlessness, odorlessness, non-irritation, and stability, making them ideal bactericides. The nonionic surfactant in the system does not degrade the quaternary ammonium salt. Instead, it effectively reduces surface tension, allowing the quaternary ammonium salt to distribute more quickly and evenly on the contact surface, enhancing its bactericidal performance. The antifungal agent and chitosan-modified nanoparticles contain antifungal components. Based on the foaming properties of the surfactant, the unevenness at the edges of the nanoparticles helps to defoam, further enhancing the bactericidal and disinfecting performance of the compound disinfectant. The presence of a humectant reduces the adverse effects when the compound disinfectant is applied to humans or other animals.

[0007] Furthermore, the method for preparing the antifungal agent and chitosan-modified nanoparticles includes, by weight, the following: Mix 0.1-0.5 parts of antifungal agent, 2-5 parts of nitrogen-phosphorus co-doped titanium dioxide, and 100-200 parts of ethanol to obtain antifungal agent modified nitrogen-phosphorus co-doped titanium dioxide; Two to five parts of antifungal agent-modified nitrogen-phosphorus co-doped titanium dioxide, 0.5 to 1 part of carboxymethyl chitosan, and 100 to 200 parts of water were stirred and mixed to obtain antifungal agent and chitosan-modified nanoparticles.

[0008] Titanium dioxide possesses excellent antibacterial properties and has been proven to kill a variety of bacteria, fungi, and viruses. This is because titanium dioxide has a high specific surface area and strong physical adsorption capacity, enabling it to effectively adsorb and immobilize on the surface of microorganisms, thereby achieving the purpose of killing them. Nitrogen and phosphorus co-doped titanium dioxide can effectively increase the reaction sites on the surface, thus enhancing its antibacterial performance. However, under ultraviolet light, titanium dioxide also exhibits good photocatalytic performance, generating superoxide radicals with strong oxidizing properties. Although it has a strong bactericidal effect, photocatalytic sterilization is extremely unstable depending on the application scenario. It may cause the decomposition of antifungal agents and quaternary ammonium salts, leading to certain side effects.

[0009] Carboxymethyl chitosan is an important water-soluble chitosan derivative with antibacterial and anti-infective properties, as well as good biocompatibility and biodegradability. Surface modification of nitrogen-phosphorus co-doped titanium dioxide with carboxymethyl chitosan can reduce the decomposition effect of nitrogen-phosphorus co-doped titanium dioxide on antifungal agents.

[0010] Furthermore, the stirring and mixing is carried out at 500~1000 rpm for 5~10 hours.

[0011] Furthermore, the antifungal agent is fluconazole.

[0012] Fluconazole is an antifungal drug used to treat deep and superficial fungal infections in various tissues. Compared to other antifungal drugs, fluconazole has the advantage of having fewer side effects.

[0013] Furthermore, the method for preparing nitrogen-phosphorus co-doped titanium dioxide includes, by weight, the following: 5-10 parts of titanate, 0.5-1 part of hexamethylenetetramine, 0.2-0.5 parts of phosphoric acid, 20-30 parts of water, and 70-80 parts of ethanol are stirred and mixed to obtain a gel. The gel is then calcined to obtain nitrogen and phosphorus co-doped titanium dioxide.

[0014] It should be noted that the titanate ester of the present invention is not strictly limited. For example, it can be at least one of ethyl titanate, n-propyl titanate, isopropyl titanate, and tetrabutyl titanate.

[0015] Furthermore, the calcination is maintained at 300~400℃ for 1~2 hours.

[0016] Furthermore, the quaternary ammonium salt mixture includes at least one of decyl dimethyl ammonium chloride, decyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, and benzalkonium chloride.

[0017] Furthermore, the nonionic surfactant is decyl glucoside.

[0018] Furthermore, the moisturizer is glycerin.

[0019] This invention also provides a method for preparing the above-mentioned compound disinfectant, characterized in that it includes, A mixture was prepared by stirring water, nonionic surfactant, antifungal agent, chitosan-modified nanoparticles, and humectant. The quaternary ammonium salt mixture is added to the mixed solution and stirred to obtain the compound disinfectant solution.

[0020] Compared with the prior art, the present invention has the following beneficial effects: The compound disinfectant system of this invention contains a quaternary ammonium salt mixture that exhibits excellent bactericidal properties. The antifungal agent and chitosan-modified nanoparticles reduce foaming and enhance bactericidal activity. The presence of nonionic surfactants makes sterilization more rapid, and the quaternary ammonium salt mixture is more stable. This compound disinfectant liquid can kill Escherichia coli, Staphylococcus aureus, and Candida albicans. It is low in irritation and corrosiveness, making it suitable for disinfecting general object surfaces that come into contact with the human body, as well as for disinfecting public places. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0022] Description of some of the raw materials used in the embodiments of this invention: Octyldecyldimethylammonium chloride, model CY-D2, purchased from Shandong Changyao New Materials Co., Ltd. Benzalkonium chloride, model LA-6Q, purchased from Shandong Li'ang New Material Technology Co., Ltd. Decyl glucoside, model ZH54549-25-6, purchased from Zhonghe Chemical (Shandong) Co., Ltd. Fluconazole, product number DF0057, was purchased from Chengdu Lemeitian Pharmaceutical Technology Co., Ltd. Carboxymethyl chitosan, model C-87, was purchased from Qingdao Bozhi Huili Biotechnology Co., Ltd.

[0023] Other raw materials not mentioned are all common raw materials. The above content is only for the purpose of illustrating the present invention and should not be construed as a strict limitation of the present invention. Those skilled in the art can directly purchase the same / similar raw materials from the market or prepare them themselves.

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] Example 1 A method for preparing a compound disinfectant solution, comprising the following steps: S1. Weigh out 0.1% octyldecyl dimethyl ammonium chloride, 0.2% benzalkonium chloride, 0.03% decyl glucoside, 0.02% antifungal agent and chitosan-modified nanoparticles, 0.2% glycerol, and the remainder is water, calculated as a percentage by mass of the product. S2. Water, decyl glucoside, antifungal agent, chitosan-modified nanoparticles, and glycerol were stirred at 300 rpm for 30 min to obtain a mixture; S3. Add octyldecyl dimethyl ammonium chloride and benzalkonium chloride to the mixture and stir at 500 rpm for 30 min to obtain the compound disinfectant solution.

[0026] The preparation method of the antifungal agent and chitosan-modified nanoparticles is as follows: T1. 6g tetrabutyl titanate, 1g hexamethylenetetramine, 0.5g phosphoric acid (85% by mass), 20g water and 80g ethanol were stirred at 650rpm for 6h to obtain a gel. The gel was dried in a constant temperature oven at 120℃ for 12h and then transferred to a muffle furnace at 350℃ and calcined in air atmosphere for 1h to obtain nitrogen and phosphorus co-doped titanium dioxide. T2. 0.3g fluconazole, 5g nitrogen-phosphorus co-doped titanium dioxide and 200g ethanol were stirred at 800rpm for 6h. The insoluble matter was then collected by filtration, washed three times with water and three times with ethanol, and dried in an oven at 80℃ for 12h to obtain antifungal agent modified nitrogen-phosphorus co-doped titanium dioxide. T3. 5g of antifungal agent-modified nitrogen-phosphorus co-doped titanium dioxide, 1g of carboxymethyl chitosan, and 200g of water were stirred at 500rpm for 5h. The insoluble matter was then collected by filtration, washed three times each with water and ethanol, and dried in an oven at 80℃ for 12h to obtain antifungal agent and chitosan-modified nanoparticles.

[0027] Examples 2 to 6 Please refer to the formulation components in Table 1 and the preparation method of Example 1 to prepare the compound disinfectant solutions of Examples 2 to 6.

[0028] Table 1 Formulation Components

[0029] Comparative Example 1 A method for preparing a compound disinfectant solution, comprising the following steps: S1. Weigh out 0.1% octyldecyl dimethyl ammonium chloride, 0.2% benzalkonium chloride, 0.03% decyl glucoside, 0.03% chitosan-modified nanoparticles, 0.2% glycerol, and the remainder is water, calculated as a percentage by mass of the product. S2. Mix water, decyl glucoside, chitosan-modified nanoparticles, and glycerol at 300 rpm for 30 min to obtain a mixture; S3. Add octyldecyl dimethyl ammonium chloride and benzalkonium chloride to the mixture and stir at 500 rpm for 30 min to obtain the compound disinfectant solution.

[0030] The preparation method of chitosan-modified nanoparticles is as follows: T1. 6g tetrabutyl titanate, 1g hexamethylenetetramine, 0.5g phosphoric acid (85% by mass), 20g water and 80g ethanol were stirred at 650rpm for 6h to obtain a gel. The gel was dried in a constant temperature oven at 120℃ for 12h and then transferred to a muffle furnace at 350℃ and calcined in air atmosphere for 1h to obtain nitrogen and phosphorus co-doped titanium dioxide. T2, 5g of nitrogen-phosphorus co-doped titanium dioxide, 1g of carboxymethyl chitosan, and 200g of water were stirred at 800rpm for 6h. The insoluble matter was then collected by filtration, washed three times each with water and ethanol, and dried in an oven at 80℃ for 12h to obtain chitosan-modified nanoparticles.

[0031] Comparative Example 2 A method for preparing a compound disinfectant solution, comprising the following steps: S1. Weigh out 0.1% octyldecyl dimethyl ammonium chloride, 0.2% benzalkonium chloride, 0.03% decyl glucoside, 0.03% antifungal agent-modified nanoparticles, 0.2% glycerol, and the remainder is water, calculated as a percentage by weight of the product. S2. Water, decyl glucoside, antifungal agent-modified nanoparticles, and glycerol were stirred at 300 rpm for 30 min to obtain a mixture; S3. Add octyldecyl dimethyl ammonium chloride and benzalkonium chloride to the mixture and stir at 500 rpm for 30 min to obtain the compound disinfectant solution.

[0032] The preparation method of antifungal agent modified nanoparticles is as follows: T1. 6g tetrabutyl titanate, 1g hexamethylenetetramine, 0.5g phosphoric acid (85% by mass), 20g water and 80g ethanol were stirred at 650rpm for 6h to obtain a gel. The gel was dried in a constant temperature oven at 120℃ for 12h and then transferred to a muffle furnace at 350℃ and calcined in air atmosphere for 1h to obtain nitrogen and phosphorus co-doped titanium dioxide. T2. 0.3g fluconazole, 5g nitrogen-phosphorus co-doped titanium dioxide, and 200g ethanol were stirred at 800rpm for 6h. The insoluble matter was then collected by filtration, washed three times each with water and ethanol, and dried in an oven at 80℃ for 12h to obtain antifungal agent modified nanoparticles.

[0033] Comparative Example 3 A method for preparing a compound disinfectant solution, comprising the following steps: S1. Weigh out 0.1% octyldecyl dimethyl ammonium chloride, 0.2% benzalkonium chloride, 0.03% decyl glucoside, 0.03% antifungal agent and chitosan-modified nanoparticles, 0.2% glycerol, and the remainder is water, calculated as a percentage by mass of the product. S2. Water, decyl glucoside, antifungal agent, chitosan-modified nanoparticles, and glycerol were stirred at 300 rpm for 30 min to obtain a mixture; S3. Add octyldecyl dimethyl ammonium chloride and benzalkonium chloride to the mixture and stir at 500 rpm for 30 min to obtain the compound disinfectant solution.

[0034] The preparation method of the antifungal agent and chitosan-modified nanoparticles is as follows: T1. 6g tetrabutyl titanate, 20g water and 80g ethanol were stirred at 650rpm for 6h to obtain a gel. The gel was dried in a constant temperature oven at 120℃ for 12h, and then transferred to a muffle furnace at 350℃ and calcined in air atmosphere for 1h to obtain titanium dioxide. T2. Stir 0.3g fluconazole, 5g titanium dioxide and 200g ethanol at 800rpm for 6h, then filter and collect the insoluble matter, wash three times each with water and ethanol, and dry in an 80℃ constant temperature oven for 12h to obtain antifungal modified titanium dioxide. T3. 5g of antifungal agent-modified titanium dioxide, 1g of carboxymethyl chitosan, and 200g of water were stirred at 500rpm for 5h. The insoluble matter was then collected by filtration, washed three times each with water and ethanol, and dried in an oven at 80℃ for 12h to obtain antifungal agent and chitosan-modified nanoparticles.

[0035] Comparative Example 4 A method for preparing a compound disinfectant solution, comprising the following steps: S1. Weigh out 0.02% fluconazole, 0.01% carboxymethyl chitosan, 0.1% octyldecyl dimethyl ammonium chloride, 0.2% benzalkonium chloride, 0.03% decyl glucoside, 0.2% glycerol, and the remainder is water, calculated as a percentage by mass of the product. S2. Mix carboxymethyl chitosan, water, decyl glucoside, and glycerol at 300 rpm for 30 min to obtain a mixture; S3. Add octyldecyl dimethyl ammonium chloride, benzalkonium chloride, and fluconazole to the mixture and stir at 500 rpm for 30 minutes to obtain the compound disinfectant solution.

[0036] Test case Microbial inactivation and skin irritation tests were conducted on the disinfectants in the examples and comparative examples according to the suspension quantitative method in the national standard GB 15979-2002 "Hygienic Standard for Disposable Sanitary Products". The results of the microbial inactivation test are shown in Table 2.

[0037] Table 2 Results of Microbial Killing Test

[0038] The test results in Table 2 show that Examples 1-4 of the present invention have superior disinfection effects and can effectively kill bacteria in a shorter time. Comparative Examples 1 and 2 showed a log kill value >5.0 against *Escherichia coli*, *Staphylococcus aureus*, and *Candida albicans* after 150 seconds. Examples 1-4 and Comparative Examples 1-2 use the same quaternary ammonium salt bactericidal component, indicating that the quaternary ammonium salt bactericidal component selected in this invention has good bactericidal performance. Simultaneously, the antifungal agent and chitosan-modified nanoparticles enhance the bactericidal effect. Fluconazole and carboxymethyl chitosan modification on the surface of nitrogen-phosphorus co-doped titanium dioxide improves dispersion stability and reduces the foaming effect of the bactericidal solution. The nitrogen-phosphorus co-doped titanium dioxide can also effectively adsorb and fix onto the surface of microorganisms, thus enabling the bactericidal solution to take effect more quickly. In particular, Example 2 showed a log kill value >5.0 against *Escherichia coli*, *Staphylococcus aureus*, and *Candida albicans* in only 30 seconds. This may be because the higher proportion of antifungal agent and chitosan-modified nanoparticles caused partial aggregation, which conversely reduced the bactericidal effect.

[0039] Skin irritation tests showed that the compound disinfectant prepared in the embodiments and comparative examples of the present invention was non-irritating to the skin.

[0040] Following the storage conditions of the accelerated test in GB / T 38499-2020 "Stability Evaluation Method for Disinfectants", the equivalent storage time was 12 months. The retention rate of quaternary ammonium salt was then tested, and the results are shown in Table 3.

[0041] Table 3 Retention rate of quaternary ammonium salts

[0042] As can be seen from the test results in Table 3, the retention rate of quaternary ammonium salt in the disinfectant of Example 2 of the present invention is as high as 93.5%. This indicates that after modifying nitrogen and phosphorus co-doped titanium dioxide with fluconazole and carboxymethyl chitosan, it can effectively inhibit the degradation of quaternary ammonium salt by titanium dioxide under potential photocatalytic action.

[0043] The corrosion performance of the compound disinfectant on carbon steel was also tested in accordance with the national standard GB / T 38498-2020 "Evaluation Method for Corrosion of Metals by Disinfectants". The results are shown in Table 4. Among them, corrosion rate R < 0.0100 mm / a is considered to be basically non-corrosive.

[0044] Table 4 Corrosion performance results of carbon steel

[0045] As can be seen from the test results in Table 4, the disinfectant of Example 2 of the present invention has the lowest corrosion rate on carbon steel.

[0046] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a compound disinfectant, characterized in that, Includes the following steps: A mixture was prepared by stirring water, nonionic surfactant, antifungal agent, chitosan-modified nanoparticles, and humectant. The quaternary ammonium salt mixture is added to the mixed solution and stirred to obtain the compound disinfectant solution; The compound disinfectant comprises the following raw materials by weight percentage: 0.1%~0.5% quaternary ammonium salt mixture, 0.02%~0.05% nonionic surfactant, 0.02%~0.05% antifungal agent and chitosan modified nanoparticles, 0.1%~0.3% humectant, balance water; The method for preparing the antifungal agent and chitosan-modified nanoparticles includes the following steps, in parts by weight: 0.1-0.5 parts of antifungal agent, 2-5 parts of nitrogen-phosphorus co-doped titanium dioxide, and 100-200 parts of ethanol are continuously stirred and mixed at 500-1000 rpm for 5-10 hours to obtain antifungal agent modified nitrogen-phosphorus co-doped titanium dioxide. 2-5 parts of antifungal agent-modified nitrogen and phosphorus co-doped titanium dioxide, 0.5-1 parts of carboxymethyl chitosan, and 100-200 parts of water are continuously stirred and mixed at 500-1000 rpm for 5-10 hours to obtain antifungal agent and chitosan-modified nanoparticles. The antifungal agent is fluconazole; The method for preparing nitrogen and phosphorus co-doped titanium dioxide, The process includes the following steps: by weight, 5-10 parts of titanate, 0.5-1 part of hexamethylenetetramine, 0.2-0.5 parts of phosphoric acid, 20-30 parts of water, and 70-80 parts of ethanol are stirred and mixed to obtain a gel, and the gel is calcined to obtain nitrogen and phosphorus co-doped titanium dioxide. The calcination is carried out at 300-400℃ for 1-2 hours; The nonionic surfactant is decyl glucoside.

2. The method for preparing the compound disinfectant according to claim 1, characterized in that, The quaternary ammonium salt mixture is at least one of decyl dimethyl ammonium chloride, octyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, and benzalkonium chloride.

3. The method for preparing the compound disinfectant according to claim 1, characterized in that, The moisturizer is glycerin.

4. A compound disinfectant, characterized in that: Prepared by the method described in any one of claims 1-3.

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