An antimicrobial coating and methods of making and using the same

Abstract

This invention relates to an antimicrobial coating, its preparation method, and its application, belonging to the field of antibacterial materials technology. The invention involves treating the surface of a solid object with a specific activation treatment, followed by plasma treatment with ammonia or amine compounds to create a surface with a stable positive charge. This stable positive charge, which is non-quenchable, adsorbs negatively charged harmful microorganisms, including bacteria, fungi, and viruses, thereby penetrating the microbial envelope and eliminating the microorganisms. This is a purely physical mechanism for eliminating harmful microorganisms, offering stable and long-lasting effects, high efficiency, broad spectrum, safety, non-toxicity, good biocompatibility, non-sensitization, non-irritation, and no drug resistance.

Description

Technical Field

[0001] This invention relates to the field of antimicrobial materials technology, and in particular to an antimicrobial coating, its preparation method, and its application. Background Technology

[0002] Currently, the antimicrobial properties of solid antibacterial and anti-infective products mainly come from the addition of antibiotics, iodine, guanidine, heavy metals such as silver, and other drugs, reagents, or substances to the product surface or interior. Undeniably, silver is an excellent inorganic antibacterial agent, highly effective and broad-spectrum, maintaining strong antibacterial and anti-infective effects even at low concentrations, and is widely used in medical, environmental protection, and other fields. However, silver as an antibacterial agent has the following significant drawbacks: ① Excessive use of silver-containing wound dressings may lead to silver accumulation in the body, posing a risk of silver poisoning. While any heavy metal ion can be antimicrobial and is easily released, it is also prone to accumulation in the body, causing heavy metal poisoning. ② It is not suitable for patients sensitive or allergic to silver or other metals, and its biocompatibility is relatively poor; ③ It may cause slight staining of wounds; ④ It is a non-renewable resource and expensive; ⑤ It is not suitable for wounds with good healing or low risk of infection; ⑥ Its use should not be prolonged. In recent years, considering the accumulation and toxicity of silver in the human body, the development of silver-containing medical products has been restricted, regulations have become increasingly strict, and silver-containing medical products are no longer popular in some areas.

[0003] In response to the problems of silver-containing antibacterial products, such as sensitization, poor biocompatibility, and easy accumulation in the human body leading to heavy metal poisoning, there is a need for a safe, non-toxic, biocompatible, and non-sensitizing antibacterial product. Although iodine, guanidine, and other reagents or substances are still used internationally, iodine ① has a deep color, ② its antibacterial effect is affected by pH, organic matter content, and temperature, making it unstable, and ③ it is sensitive to light and heat, making it difficult to store. Guanidine, according to the updated EU CLP regulation document Commission Regulation (EU) No. 944 / 2013 (effective October 24, 2013), is classified as a CMR2 substance (Category 2 carcinogenic, mutagenic, and reproductive toxicant), and is not allowed to be used in spray products. Other commonly used antibacterial agents, such as hypochlorous acid, are highly irritating, easily decompose, and difficult to store, while organosilicon quaternary ammonium salts are unstable, volatile, and easily penetrate, leaving residual toxicity.

[0004] Therefore, there is a need to develop a new type of antibacterial product that is stable, long-lasting, highly effective, broad-spectrum, safe, non-toxic, biocompatible, non-allergenic, non-irritating, and does not induce drug resistance. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides an antimicrobial coating, its preparation method, and its application. The novel antimicrobial coating technology of this invention involves treating the surface of a solid object with a specific activation treatment, followed by treatment with amine-containing plasma to create a surface with a stable positive charge. This stable positive charge, which is non-quenchable, adsorbs negatively charged harmful microorganisms, including bacteria, fungi, and viruses, thereby penetrating the microbial membrane and eliminating the microorganisms.

[0006] This invention is achieved through the following technical solution:

[0007] The first objective of this invention is to provide a method for preparing an antimicrobial surface coating, comprising the following steps:

[0008] The material is activated by immersing it in an activator solution, and after drying, the activated material is treated in a plasma containing ammonia or amine compounds to form an antimicrobial coating on the surface of the material.

[0009] In one embodiment of the present invention, the material is selected from one or more of metals, ceramics, glass, composite materials and polymers.

[0010] In one embodiment of the present invention, the microorganism is selected from one or more of molds, Escherichia coli and Staphylococcus aureus.

[0011] In one embodiment of the present invention, the activator in the activator solution is selected from one or more of 3-methacrylamide, eprosartan mesylate, N-acetyldopamine and n-[2-(3,4-dihydroxyphenyl)ethyl]-2-propionamide (9ci).

[0012] The CAS number of the 3-methacrylamide dopamine is 471915-89-6, and the structural formula of the 3-methacrylamide is as follows:

[0013]

[0014] The CAS number for the eprosartan mesylate is 144143-96-4.

[0015] The N-acetyldopamine mentioned above has the CAS number 2494-12-4.

[0016] The n-[2-(3,4-dihydroxyphenyl)ethyl]-2-propanamide (9CI), 2-Propenamide, N-[2-(3,4-dihydroxyphenyl)ethyl]-(9CI), CAS No.: 201610-44-8.

[0017] In one embodiment of the present invention, the mass concentration of the activator solution is 1:100-5:100.

[0018] In one embodiment of the present invention, the activation time is 3 min-5 min.

[0019] In one embodiment of the present invention, the drying method is selected from one or more of air drying, oven drying, sun drying, vacuum drying and freeze drying.

[0020] In one embodiment of the invention, the amine compound is selected from one or more of methylamine, ethylamine, isopropylamine, allylamine, and trimethylamine borane. A surface coating with a stable positive charge is formed on the surface of the solid material after plasma treatment containing ammonia or an amine compound.

[0021] In one embodiment of the present invention, the plasma processing parameters of the surface coating material are as follows: power of 1W-1000W, preferably 30W-150W; activation monomer pressure of 0.5Pa-400Pa, preferably 8Pa-300Pa; and radio frequency of 13.56MHz-40.68MHz, preferably 13.56MHz-19.97MHz.

[0022] In one embodiment of the present invention, the plasma treatment time is 10 min to 30 min.

[0023] A second objective of this invention is to provide an antimicrobial coating prepared by the aforementioned method.

[0024] A third objective of this invention is to provide the application of the aforementioned antimicrobial coating in antibacterial and anti-infective applications.

[0025] This invention is primarily used for applying antimicrobial coatings to the surfaces of polymers, ceramics, glass, metals, and composite materials. The coating achieves stable and durable bonding with the material surface through three steps: first, material surface activation; second, material surface drying; and third, coating the material surface.

[0026] In one embodiment of the present invention, the solvent for the dissolving activator is selected from water and / or lower alkanols; the lower alkanols are selected from one or more of methanol, ethanol, n-propanol and isopropanol.

[0027] The technical solution of the present invention has the following advantages compared with the prior art:

[0028] This invention provides an antimicrobial coating, its preparation method, and its application. The purpose of this invention is to develop a novel broad-spectrum antimicrobial technology. The coating prepared by this invention forms a stable positive charge on the product surface. This positively charged surface adsorbs negatively charged harmful microorganisms, including bacteria, fungi, and viruses, and breaks down the microbial envelope, thereby eliminating bacteria, fungi, and viruses. The stable positive charge on the product surface prepared by this invention eliminates harmful microorganisms through a purely physical mechanism, providing stable, long-lasting, highly efficient, broad-spectrum, safe, non-toxic, biocompatible, non-sensitizing, non-irritating, and non-inducing drug resistance. Attached Figure Description

[0029] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein...

[0030] Figure 1 This is a diagram showing the bactericidal effect of the coating on microorganisms in Embodiment 1 of the present invention. Detailed Implementation

[0031] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0032] This invention first provides a method for preparing an antimicrobial surface coating, comprising the following steps:

[0033] The material is activated by immersing it in an activator solution, and after drying, the activated material is treated in a plasma containing ammonia or amine compounds to form an antimicrobial coating on the surface of the material.

[0034] Furthermore, the material is selected from one or more of metals, ceramics, glass, composite materials, and polymers.

[0035] Furthermore, the microorganism is selected from one or more of molds, Escherichia coli, and Staphylococcus aureus.

[0036] Furthermore, the activator in the activator solution is selected from one or more of 3-methacrylamide, eprosartan mesylate, N-acetyldopamine, and n-[2-(3,4-dihydroxyphenyl)ethyl]-2-propionamide (9ci).

[0037] Furthermore, the solvent for the dissolving activator is selected from water and / or lower alkanols; the lower alkanols are selected from one or more of methanol, ethanol, n-propanol and isopropanol.

[0038] The CAS number of the 3-methacrylamide dopamine is 471915-89-6, and the structural formula of the 3-methacrylamide is as follows:

[0039]

[0040] The CAS number for the eprosartan mesylate is 144143-96-4.

[0041] The N-acetyldopamine mentioned above has the CAS number 2494-12-4.

[0042] The n-[2-(3,4-dihydroxyphenyl)ethyl]-2-propanamide (9CI), 2-Propenamide, N-[2-(3,4-dihydroxyphenyl)ethyl]-(9CI), CAS No.: 201610-44-8.

[0043] Furthermore, the mass concentration of the activator solution is 1:100-5:100.

[0044] Furthermore, the activation time is 3-5 minutes.

[0045] Furthermore, the drying method is selected from one or more of air drying, oven drying, sun drying, vacuum drying, and freeze drying.

[0046] Further, the amine compound is selected from one or more of methylamine, ethylamine, isopropylamine, allylamine, and trimethylamine borane. A surface coating with a stable positive charge is formed on the surface of the solid material after plasma treatment containing ammonia or an amine compound.

[0047] Furthermore, the plasma processing parameters for the surface coating material are as follows: power of 1W-1000W, activation monomer pressure of 0.5Pa-400Pa, and radio frequency of 13.56MHz-40.68MHz.

[0048] Furthermore, the plasma treatment time is 10 min to 30 min.

[0049] The present invention also provides an antimicrobial coating prepared by the aforementioned preparation method.

[0050] Finally, this invention provides the application of the aforementioned antimicrobial coating in antibacterial and anti-infection applications.

[0051] This invention achieves a stable and durable coating by bonding with the material surface in three steps: first, material surface activation; second, material surface drying; and third, material surface coating.

[0052] Example 1

[0053] This embodiment provides a method for preparing an antimicrobial coating, the specific steps of which are as follows:

[0054] 1 gram of 3-methacrylamide dopamine was dissolved in 100 grams of anhydrous ethanol. A cotton sample was immersed in the solution for 5 minutes, dried, and then treated in an ammonia plasma device for 10 minutes. This resulted in an antimicrobial coating on the surface of the cotton sample, with the surface carrying a positive charge. The plasma device parameters were: power 30W, activation monomer pressure 10.5 Pa, and radio frequency 13.56 MHz.

[0055] The antimicrobial coated solid cotton material prepared in this embodiment was sent to a third-party testing institution to test its antimicrobial effect; the testing method used was GB 15979-2002. The test results for Example 1 and the uncoated cotton sample are as follows: Figure 1 As shown, by Figure 1 As can be seen, the all-cotton solid material with an antimicrobial coating prepared in this embodiment can kill microorganisms such as mold, Escherichia coli, and Staphylococcus aureus, with a sterilization rate of up to 99.99%. Therefore, the antimicrobial coating of the all-cotton solid material prepared in this embodiment has a broad-spectrum microbial killing effect.

[0056] Example 2

[0057] This embodiment provides a method for preparing an antimicrobial coating, the specific steps of which are as follows:

[0058] 5 grams of 3-methylacrylamide dopamine were dissolved in 100 grams of water, and the pH was adjusted to 4 with hydrochloric acid solution. The polyurethane sample was immersed in the solution for 3 minutes, dried, and then treated in an ethylamine (C2H5NH2) plasma device for 20 minutes. This resulted in an antimicrobial coating on the surface of the polyurethane sample, with the surface carrying a positive charge. The plasma device parameters were: power 120W, activation monomer pressure 300Pa, and radio frequency 19.97MHz.

[0059] The polyurethane material with an antimicrobial coating prepared in this embodiment was sent to a third-party testing institution to test its antimicrobial effect; the testing method used was GB 15979-2002. According to the test results, the polyurethane material with an antimicrobial coating prepared in this embodiment can kill microorganisms such as mold, Escherichia coli, and Staphylococcus aureus, with a sterilization rate of 99.99%. Therefore, the antimicrobial coating of the polyurethane material prepared in this embodiment has a broad-spectrum antimicrobial effect.

[0060] Example 3

[0061] This embodiment provides a method for preparing an antimicrobial coating, the specific steps of which are as follows:

[0062] 3 g of 3-methylacrylamide dopamine was dissolved in 100 g of anhydrous ethanol, and the pH was adjusted to 11 with sodium hydroxide aqueous solution. The hydroxyapatite sample was then immersed in the solution for 5 minutes. After drying, the sample was treated in a trimethylamine borane plasma device for 30 minutes, resulting in an antimicrobial coating on the surface of the hydroxyapatite sample, with the surface carrying a positive charge. The plasma device parameters were: power 150 W, activation monomer pressure 8 Pa, and radio frequency 15.51 MHz.

[0063] The hydroxyapatite material with an antimicrobial coating prepared in this embodiment was sent to a third-party testing institution to test its antimicrobial effect; the testing method used was GB 15979-2002. According to the test results, the polyurethane material with an antimicrobial coating prepared in this embodiment can kill molds, Escherichia coli, Staphylococcus aureus, and other microorganisms, with a sterilization rate of 99.99%. Therefore, the antimicrobial coating of the hydroxyapatite material prepared in this embodiment has a broad-spectrum antimicrobial effect.

[0064] Example 4

[0065] This embodiment provides a method for preparing an antimicrobial coating, the specific steps of which are as follows:

[0066] 2 g of n-[2-(3,4-dihydroxyphenyl)ethyl]-2-propanamide (9ci) was dissolved in 100 g of anhydrous ethanol. A stainless steel sample was immersed in the solution for 5 minutes, dried, and then treated in an allylamine plasma device for 30 minutes. This resulted in an antimicrobial coating on the surface of the stainless steel sample, with the surface carrying a positive charge. The plasma device parameters were: power 150 W, activation monomer pressure 200 Pa, and radio frequency 18.38 MHz.

[0067] The stainless steel material with antimicrobial coating prepared in this embodiment was sent to a third-party testing institution to test its antimicrobial effect; the testing method used was GB 15979-2002. According to the test results, the stainless steel material with antimicrobial coating prepared in this embodiment can kill mold, Escherichia coli, Staphylococcus aureus, and other microorganisms, with a sterilization rate of 99.99%. Therefore, the antimicrobial coating on the stainless steel material prepared in this embodiment has a broad-spectrum antimicrobial effect.

[0068] Example 5

[0069] This embodiment provides a method for preparing an antimicrobial coating, the specific steps of which are as follows:

[0070] 4 grams of 3-methacrylamide dopamine were dissolved in 100 grams of anhydrous ethanol. A calcium alginate sample was immersed in the solution for 5 minutes, dried, and then treated in an ammonia plasma apparatus for 20 minutes. This resulted in an antimicrobial coating on the surface of the calcium alginate sample, with the surface carrying a positive charge. The plasma apparatus parameters were: power 120W, activation monomer pressure 250Pa, and radio frequency 19.5MHz.

[0071] The calcium alginate material with an antimicrobial coating prepared in this embodiment was sent to a third-party testing institution to test its antimicrobial effect; the testing method used was AATCC TM100-2019. The bacteria used for testing were the most difficult to remove Aspergillus niger (ATCC 16404), with the sample without antimicrobial coating serving as a control. After inoculation, the samples were inoculated with 1 mL of nutrient solution (10% fetal bovine serum + 90% PBS) daily. The test results are shown in Table 1 below:

[0072] Table 1

[0073]

[0074] As shown in the table, the number of Aspergillus niger colonies in the control group increased to 4.4 × 10⁻⁶ after 7 days of culture. 7 The antimicrobial coating prepared by this invention has a significant removal effect on Aspergillus niger, with the colony count on the sample less than 100 CFU / tablet after a 7-day incubation period. This demonstrates that the antimicrobial coating prepared by this invention can effectively remove Aspergillus niger over a long period.

[0075] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing an antimicrobial coating, characterized in that, Includes the following steps: The material is activated by immersing it in an activator solution, and after drying, the activated material is treated in a plasma containing ammonia or amine compounds to form an antimicrobial coating on the surface of the material. The activator in the activator solution is selected from one or more of 3-methacrylamide, N-acetyldopamine, and n-[2-(3,4-dihydroxyphenyl)ethyl]-2-propionamide; The mass concentration of the activator solution is 1:100-5:100; The amine compound is selected from one or more of methylamine, ethylamine, isopropylamine, allylamine, and trimethylamineborane; The plasma processing parameters are: power of 30 W-150 W, activation monomer pressure of 8 Pa-250 Pa, and radio frequency of 13.56 MHz-19.97 MHz.

2. The preparation method according to claim 1, characterized in that, The material is selected from one or more of the following: metals, ceramics, glass, composite materials, and polymers.

3. The preparation method according to claim 1, characterized in that, The activation time is 3 min-5 min.

4. The preparation method according to claim 1, characterized in that, The plasma treatment time is 10 min-30 min.

5. The antimicrobial coating prepared by the preparation method according to any one of claims 1-4.

6. The application of the antimicrobial coating according to claim 5 in antibacterial and anti-infection applications.

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