Antibacterial agent, method for producing the same, powder coating, product having antibacterial function, and method for producing the same

Abstract

The application relates to an antibacterial agent and a preparation method thereof, a powder coating, a product with antibacterial function and a preparation method thereof. The antibacterial agent comprises an inorganic carrier and silver ions, copper ions and third metal ions supported on the inorganic carrier; the third metal ions comprise one or more of nickel ions, titanium ions, manganese ions and zinc ions; the content of the silver ions is greater than the content of the copper ions and greater than the content of the third metal ions. In the antibacterial agent, the silver ions play a main antibacterial role, the copper ions are used for reducing the silver ions, the state of the silver ions is protected, the third metal ions increase the number of additional exchangeable cations, the release speed of the silver ions is delayed, and the copper ions are matched to improve the durability of the antibacterial effect of the silver ions.

Description

Technical Field

[0001] This application relates to the field of antibacterial agents, and in particular to an antibacterial agent and its preparation method, powder coatings, products with antibacterial functions and their preparation methods. Background Technology

[0002] Kitchen and bathroom hardware products, such as faucets and showerheads, are used in humid and complex environments, making their surfaces prone to bacterial growth and the proliferation of mold, acids, and toxic metabolites. This negatively impacts the product's appearance and quality, and can harm human health. Therefore, high antibacterial properties are essential for kitchen and bathroom hardware products. Currently, most solutions achieve good antibacterial capabilities by creating an antibacterial coating on the product surface. For example, adding antibacterial agents to powder coatings and spraying them onto the product surface enhances antibacterial performance.

[0003] Currently, antibacterial agents are broadly classified into inorganic and organic categories. The safety of organic antibacterial agents is still under investigation, and they also suffer from poor heat resistance, are prone to hydrolysis, and have a short shelf life, making widespread use difficult. While inorganic antibacterial agents, such as silver ion antibacterial agents, offer relatively high safety and good heat resistance, the antibacterial durability of the resulting coatings is poor, with the antibacterial effect significantly weakening after repeated washing. Therefore, the application of inorganic antibacterial agents in antibacterial coatings currently faces the problem of poor antibacterial durability, with the antibacterial effect greatly diminishing after repeated washing. Summary of the Invention

[0004] Based on this, some embodiments of this application provide an antibacterial agent with good durability and a method for preparing the same.

[0005] In addition, some other embodiments of this application also provide a powder coating comprising the above-mentioned antibacterial agent, a product having antibacterial function, and a method for preparing the same.

[0006] An antibacterial agent comprising an inorganic carrier and silver ions, copper ions and a third metal ion loaded on the inorganic carrier;

[0007] The third metal ion includes one or more of nickel ions, titanium ions, manganese ions, and zinc ions;

[0008] In the antibacterial agent, the content of silver ions is greater than the content of copper ions and greater than the content of the third metal ion.

[0009] Optionally, the third metal ion includes nickel ions; and / or,

[0010] The inorganic carrier includes one or more of zeolite, vermiculite, montmorillonite, mesoporous silica, and talc. Optionally, the inorganic carrier includes zeolite.

[0011] Optionally, in the antibacterial agent, the content of silver ions is 0.6 g / meq to 1.12 g / meq; and / or,

[0012] The copper ion content is 0.3 g / meq to 0.7 g / meq; and / or,

[0013] The content of the third metal ion is 0.3 g / meq to 0.5 g / meq.

[0014] A method for preparing an antibacterial agent includes the following steps:

[0015] An antibacterial agent loaded with silver ions, copper ions and a third metal ion was prepared by ion exchange between an inorganic carrier and silver ions, copper ions and a third metal ion.

[0016] The third metal ion includes one or more of nickel ions, titanium ions, manganese ions, and zinc ions; in the antibacterial agent, the content of silver ions is greater than the content of copper ions and greater than the content of the third metal ion.

[0017] Optionally, the step of ion exchange between the inorganic support and silver ions, copper ions, and a third metal ion includes:

[0018] The inorganic carrier is placed sequentially in a silver salt solution, a copper salt solution, and a salt solution containing the third metal ion, and the mixture is stirred to allow the inorganic carrier to exchange ions with the silver ions, the copper ions, and the third metal ion in sequence.

[0019] Optionally, the concentration of the silver salt solution is 0.02 mol / L to 0.06 mol / L.

[0020] Optionally, the concentration of the copper salt solution is 0.04 mol / L to 0.06 mol / L.

[0021] Optionally, the concentration of the salt solution containing the third metal ion is 0.02 mol / L to 0.05 mol / L.

[0022] Optionally, one or more of the following conditions must be met:

[0023] (1) The silver salt solution includes silver nitrate solution;

[0024] (2) The copper salt solution includes copper nitrate solution;

[0025] (3) The salt solution containing the third metal ion includes one or more of nickel nitrate solution, titanium nitrate solution, manganese nitrate solution and zinc nitrate solution. Optionally, the salt solution containing the third metal ion includes nickel nitrate solution.

[0026] (4) The reaction time for each stirring reaction is 5h~7h;

[0027] (5) The pH of each stirring reaction is 4~6;

[0028] (6) The temperature of each stirring reaction is 55℃~65℃, and it is carried out under light-protected conditions.

[0029] Optionally, before the step of ion exchange between the inorganic carrier and silver ions, copper ions and a third metal ion, the method further includes: placing the inorganic carrier in a sodium salt solution with a concentration of 0.3 mol / L to 0.6 mol / L and treating it at a pH of 11 to 12 for 2 to 3 hours.

[0030] A powder coating comprising the above-described antibacterial agent or comprising an antibacterial agent prepared by the above-described preparation method.

[0031] Optionally, by weight, the composition includes: 35 to 60 parts resin, 15 to 30 parts antibacterial agent, 10 to 20 parts pigments and fillers, 2 to 5 parts curing agent, and 0.6 to 2.5 parts additives.

[0032] Optionally, the additives include 0.4 to 1.5 parts of leveling agent and 0.2 to 1 part of benzoin.

[0033] Optionally, the average particle size of the powder coating is 1 μm to 35 μm.

[0034] A product with antibacterial function includes a substrate and an antibacterial coating disposed on the surface of the substrate, wherein the antibacterial coating is obtained by spraying and curing the above-mentioned powder coating.

[0035] Optionally, the antibacterial products include kitchen and bathroom hardware products.

[0036] A method for preparing a product with antibacterial function includes the following steps:

[0037] The above-mentioned powder coating is sprayed onto the surface of the substrate and cured to prepare the product with antibacterial function.

[0038] Optionally, the spraying process parameters include: electrostatic high voltage of 40kV~70kV, electrostatic current of 10μA~20μA, flow rate pressure of 0.3MPa~0.6MPa, atomization pressure of 0.3MPa~0.5MPa, and distance between the spray gun nozzle and the substrate of 150mm~200mm.

[0039] Optionally, the curing temperature is 150℃~200℃ and the time is 15min~30min.

[0040] Some embodiments of this application provide an antibacterial agent comprising an inorganic carrier and silver ions, copper ions, and a third metal ion loaded on the inorganic carrier, and adjusting the content of each metal ion. Among them, silver ions play the main antibacterial role, copper ions are used to reduce the reduction of silver ions and protect the ionic state of silver, and the third metal ion increases the number of additional exchangeable cations in the carrier, slows down the release rate of silver ions, and works with copper ions to improve the durability of the antibacterial effect of silver ions. Attached Figure Description

[0041] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0042] Figure 1 This is a schematic diagram of a process flow for preparing an antibacterial agent according to some embodiments of this application;

[0043] Figure 2 The sterilization rate curves of the antibacterial coatings prepared in the various embodiments and comparative examples of this application against Escherichia coli after 5000 rubs. Detailed Implementation

[0044] To facilitate understanding of this application, a more comprehensive description of the application will be provided below in conjunction with specific embodiments. Preferred embodiments of the application are given in the specific embodiments. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0046] Unless otherwise stated or in case of conflict, the terms or phrases used in this application shall have the following meanings:

[0047] In this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" and "second" may explicitly or implicitly include at least one of those features.

[0048] In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.

[0049] In this application, "one or more" refers to any one, any two, or any two or more of the listed items. "Several" refers to any two or more.

[0050] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0051] In this document, terms such as "further," "even further," "especially," "for example," "as," "example," and "exemplary" are used for descriptive purposes to indicate a connection in the coverage of different technical solutions presented earlier and later. However, they should not be construed as limitations on the preceding technical solution or on the scope of protection of this document. Unless otherwise specified, A (as in B) indicates that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0052] In this document, "optionally," "optionally," and "optional" mean that something is optional, that is, it is selected from either "present" or "absent." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent. In this application, descriptions such as "optionally contains" and "optionally includes" indicate "contains or does not contain." "Optional component X" indicates whether component X exists or does not exist, or whether component X is contained or not.

[0053] When a numerical range is disclosed in this application, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed in this application should be understood to include any and all subranges to which they are included.

[0054] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0055] The terms "comprising" and "having," and any variations thereof, used in the embodiments of this application, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the steps or units listed, but may optionally include steps or units not listed, or may optionally include other steps or components inherent to such processes, methods, products, or devices.

[0056] In this application, the reference to "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this application can be combined with other embodiments.

[0057] This application provides an antibacterial agent and its preparation method, which has good antibacterial durability.

[0058] In a first aspect, this application provides an antibacterial agent comprising: an inorganic carrier and silver ions, copper ions and a third metal ion loaded on the inorganic carrier;

[0059] The third metal ion includes one or more of nickel ions, titanium ions, manganese ions, and zinc ions;

[0060] In antibacterial agents, the content of silver ions > the content of copper ions ≥ the content of the third metal ion.

[0061] The aforementioned antibacterial agent includes an inorganic carrier and silver ions, copper ions, and a third metal ion loaded on the inorganic carrier. The content of each metal ion is adjusted, with silver ions playing the primary antibacterial role and their content exceeding that of copper ions and the third metal ion. Copper ions reduce the reduction of silver ions, protecting their ionic state. The third metal ion increases the number of additional exchangeable cations, slowing the release rate of silver ions and, in conjunction with copper ions, improving the durability of the antibacterial effect of silver ions. Since the antibacterial effect and durability of the third metal ion are inferior to those of copper ions, if the content of the third metal ion is greater than that of copper ions, the antibacterial properties and durability of the antibacterial agent will deteriorate. Therefore, in some embodiments of this application, the content of copper ions is ≥ the content of the third metal ion.

[0062] Furthermore, traditional silver ion antibacterial agents, at high temperatures, Ag + It is easily damaged, which not only caused Ag + The loss of these elements also causes yellowing of the coating surface. In some embodiments of this application, copper ions are used to protect silver ions, improving durability while reducing yellowing of the coating.

[0063] Furthermore, traditional powder coatings containing antibacterial agents cannot achieve broad-spectrum antibacterial activity and pose a risk of antibacterial agent failure. However, in some embodiments of this application, the combination of silver ions, copper ions, and a third metal ion exhibits good antibacterial activity against various bacteria such as Escherichia coli, Staphylococcus aureus, and Candida albicans, while simultaneously reducing the risk of antibacterial agent failure.

[0064] In some embodiments, the inorganic support includes one or more of zeolite, vermiculite, montmorillonite, mesoporous silica, and talc. Optionally, the inorganic support includes zeolite. Compared with other inorganic supports, zeolite has better ion exchange performance, which is beneficial to improving the antibacterial effect and antibacterial durability of antimicrobial agents.

[0065] In some embodiments, copper ions not only protect silver ions and reduce their reduction, but also have good antibacterial properties, which helps to improve the antibacterial effect of the antibacterial agent.

[0066] In some embodiments, the third metal ion includes nickel ions. Experiments have shown that including nickel ions as the third metal ion can further improve the durability of the antibacterial agent compared to including titanium ions, manganese ions, etc.

[0067] In some embodiments, the antibacterial agent includes an inorganic carrier and silver ions, copper ions, and nickel ions loaded on the inorganic carrier; the content of silver ions > the content of copper ions ≥ the content of nickel ions. Further, the antibacterial agent includes zeolite and silver ions, copper ions, and nickel ions loaded on the zeolite; the content of silver ions > the content of copper ions > the content of nickel ions.

[0068] In some embodiments, the silver ion content in the antimicrobial agent is 0.6 g / meq to 1.12 g / meq. The copper ion content in the antimicrobial agent is 0.3 g / meq to 0.7 g / meq. The third metal ion content in the antimicrobial agent is 0.3 g / meq to 0.5 g / meq. For example, the silver ion content in the antimicrobial agent may be, but is not limited to, 0.6 g / meq, 0.7 g / meq, 0.8 g / meq, 0.9 g / meq, 1 g / meq, 1.1 g / meq, 1.12 g / meq, or a range consisting of any two of these values. The copper ion content may be, but is not limited to, 0.3 g / meq, 0.4 g / meq, 0.45 g / meq, 0.5 g / meq, 0.55 g / meq, 0.6 g / meq, 0.65 g / meq, 0.7 g / meq, or any combination of these values. The tertiary metal ion content may be, but is not limited to, 0.3 g / meq, 0.35 g / meq, 0.4 g / meq, 0.45 g / meq, 0.5 g / meq, or any combination of these values.

[0069] In some embodiments, the inorganic carrier may optionally include zeolite, and the copper ion content in the antibacterial agent is 0.4 g / meq to 0.7 g / meq.

[0070] In some embodiments, the average particle size of the antimicrobial agent is less than 50 μm, for example, less than 30 μm. In one example, the average particle size of the antimicrobial agent is 10 μm to 20 μm.

[0071] Secondly, this application provides a method for preparing an antibacterial agent, comprising the following steps:

[0072] An antibacterial agent loaded with silver ions, copper ions and a third metal ion was prepared by ion exchange between an inorganic carrier and silver ions, copper ions and a third metal ion.

[0073] The third metal ion includes one or more of nickel ions, titanium ions, manganese ions, and zinc ions; in antibacterial agents, the content of silver ions is greater than that of copper ions and is greater than or equal to that of the third metal ion.

[0074] In some embodiments, the step of ion exchange between the inorganic support and silver ions, copper ions, and a third metal ion includes:

[0075] The inorganic support was placed sequentially in silver salt solution, copper salt solution and salt solution containing a third metal ion, and the mixture was stirred to allow the inorganic support to exchange ions with silver ions, copper ions and the third metal ion in sequence.

[0076] Specifically, the concentration of the silver salt solution is 0.02 mol / L to 0.06 mol / L. For example, the concentration of the silver salt solution may be, but is not limited to, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, or any range of these values. Optionally, the concentration of the silver salt solution is 0.04 mol / L to 0.06 mol / L.

[0077] In one embodiment, the silver salt solution includes a silver nitrate solution.

[0078] Specifically, the concentration of the copper salt solution is 0.04 mol / L to 0.06 mol / L. For example, the concentration of the copper salt solution may be, but is not limited to, 0.04 mol / L, 0.045 mol / L, 0.05 mol / L, 0.055 mol / L, 0.06 mol / L, or any combination of these values.

[0079] In one embodiment, the copper salt solution comprises a copper nitrate solution.

[0080] Specifically, the concentration of the salt solution containing the third metal ion is 0.02 mol / L to 0.05 mol / L. For example, the concentration of the salt solution containing the third metal ion may be, but is not limited to, 0.02 mol / L, 0.025 mol / L, 0.03 mol / L, 0.035 mol / L, 0.04 mol / L, 0.045 mol / L, 0.05 mol / L, or any range of two of these values.

[0081] In one embodiment, the salt solution containing the third metal ion includes one or more of nickel nitrate solution, titanium nitrate solution, manganese nitrate solution, and zinc nitrate solution. Optionally, the salt solution containing the third metal ion includes nickel nitrate solution.

[0082] In some embodiments, the stirring reaction time is 5 to 7 hours. For example, the stirring time can be, but is not limited to, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, or any combination of these values. It is understood that the stirring reaction time can be the same or different for each reaction, and is not particularly limited.

[0083] In some embodiments, the pH of each stirring reaction is 4 to 6. For example, the pH of each stirring reaction may be, but is not limited to, 4, 4.5, 5, 5.5, 6, or any combination of these values. It is understood that the pH of each stirring reaction may be the same or different, and is not particularly limited.

[0084] In some embodiments, the temperature of each stirring reaction is 55°C to 65°C. It is understood that the temperature of each stirring reaction can be the same or different, and there is no particular limitation.

[0085] In some embodiments, each stirring reaction is carried out under light-protected conditions to prevent photo-oxidation of silver in solutions at 55°C to 65°C. For example, aluminum foil is used for shielding.

[0086] In some embodiments, after each stirring reaction step, a solid-liquid separation step is further included, in which the resulting solid is washed. For example, the solid is washed three times with deionized water.

[0087] In some embodiments, after the ion exchange step with the third metal ion, the process further includes solid-liquid separation, washing, drying, and grinding. For example, in the drying step, drying is performed at 80°C for 8 to 9 hours. In the grinding step, the average particle size is reduced to below 50 μm, for example, below 30 μm. In one example, the average particle size is 10 μm to 20 μm.

[0088] In some embodiments, prior to the step of ion exchange between the inorganic support and silver ions, copper ions, and a third metal ion, the method further includes: ion exchange between the inorganic support and sodium ions. This is achieved through Na... + To enhance the ion exchange capacity of inorganic carriers by replacing exchangeable cations in them.

[0089] Specifically, in the step of ion exchange between the inorganic carrier and sodium ions, the inorganic carrier is placed in a sodium salt solution with a concentration of 0.3 mol / L to 0.6 mol / L and treated for 2 to 3 hours at a pH of 11 to 12. Alkaline conditions are beneficial for accelerating ion exchange.

[0090] In one embodiment, the sodium salt solution includes one or more of sodium chloride, sodium sulfate, sodium carbonate, and sodium nitrate.

[0091] In some embodiments, a pretreatment step for the inorganic carrier is also included. Specifically, the pretreatment step includes grinding and washing. For example, the inorganic carrier is ground to separate inorganic carrier particles with a particle size of less than 50 μm. In the washing step, the inorganic carrier is placed in water and washed under ultrasonic and stirring conditions. Impurities are removed by washing.

[0092] In a specific example, the pretreatment steps for the inorganic carrier include: grinding and sieving the inorganic carrier to separate inorganic carriers with a particle size of less than 50 μm; placing the inorganic carrier in deionized water and subjecting it to ultrasonic and magnetic stirring at 60°C, followed by centrifugation and drying.

[0093] In some embodiments, the inorganic carrier includes one or more of zeolite, vermiculite, montmorillonite, mesoporous silica, and talc.

[0094] In some embodiments, please refer to Figure 1 The preparation method of the antibacterial agent includes the following steps:

[0095] Step S110: Place the inorganic carrier in a sodium salt solution with a concentration of 0.3 mol / L to 0.6 mol / L and treat it for 2 to 3 hours at a pH of 11 to 12.

[0096] Step S120: The inorganic carrier treated with sodium ions is placed in a silver nitrate solution with a concentration of 0.02 mol / L to 0.06 mol / L, and stirred for 5 to 7 hours under light-protected conditions at a pH of 4 to 6 and a temperature of 55°C to 65°C, so that the inorganic carrier and silver ions can exchange ions.

[0097] Step S130: Place the inorganic support after silver ion exchange in a copper nitrate solution with a concentration of 0.04 mol / L to 0.06 mol / L, and stir the reaction for 5 to 7 hours under light-protected conditions at a pH of 4 to 6 and a temperature of 55℃ to 65℃ to allow the inorganic support to exchange ions with copper ions.

[0098] Step S140: The inorganic support after silver and copper ion exchange is placed in a nickel nitrate solution with a concentration of 0.02 mol / L to 0.05 mol / L, and stirred for 5 to 7 hours under light-protected conditions at pH 4 to 6 and temperature of 55℃ to 65℃ to allow the inorganic support to exchange ions with nickel ions.

[0099] It is understandable that after each ion exchange, there are also solid-liquid separation and washing steps. After the last ion exchange step, there are also drying and grinding steps.

[0100] It should be understood that, Figure 1 This is a schematic flowchart illustrating a method for preparing an antibacterial agent according to an embodiment of this application. Figure 1 The steps in the flowchart shown are displayed sequentially according to the arrows. However, these steps are not necessarily performed in the order indicated by the arrows. Unless otherwise specified in this document, there is no strict order requirement for the execution of these steps; they can be executed in other orders. Figure 1 At least some of the steps in the process may include multiple sub-steps or multiple stages. These sub-steps or stages are not necessarily completed at the same time, but can be executed at different times. Their execution order is not necessarily sequential, but can be executed in turn or alternately with at least some of other steps or other sub-steps or stages.

[0101] Thirdly, this application provides a powder coating that includes the antibacterial agent described in the first aspect or includes an antibacterial agent prepared by the preparation method described in the second aspect.

[0102] In some embodiments, the powder coating includes an antibacterial agent, resin, pigments and fillers, a curing agent, and additives. Specifically, by weight parts, the powder coating includes: 35 to 60 parts of resin, 15 to 30 parts of antibacterial agent, 10 to 20 parts of pigments and fillers, 2 to 5 parts of curing agent, and 0.6 to 2.5 parts of additives.

[0103] Optionally, the additives include 0.4 to 1.5 parts of leveling agent and 0.2 to 1 part of benzoin.

[0104] In some embodiments, the resin includes, but is not limited to, polyester resin. Specifically, the polyester resin includes one or more of saturated polyester resin, carboxylated polyester resin, and oil-free alkyd resin. Exemplarily, the polyester resin includes one or more of NH-3295 saturated polyester resin, GH-2100 carboxylated polyester resin, 312C oil-free alkyd resin, and 335 saturated polyester resin. It is understood that in other embodiments, the resin may also be epoxy resin, etc.

[0105] For example, in powder coatings, the mass fraction of resin may be, but is not limited to, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, or any combination of these values.

[0106] For example, in powder coatings, the mass fraction of the antimicrobial agent may be, but is not limited to, 15 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, or any combination of these values.

[0107] In some embodiments, pigments and fillers include, but are not limited to, titanium dioxide. For example, pigments and fillers may also include calcium carbonate, carbon black, iron oxide red, iron oxide yellow, mica powder, etc.

[0108] For example, in powder coatings, the mass fractions of pigments and fillers may be, but are not limited to, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, or any combination of these values.

[0109] In some embodiments, the curing agent includes one or more of hexamethylene diisocyanate-based polyisocyanate (HT-100), isophorone diisocyanate (B153), triglycidyl isocyanate (TGIC), and a trimer of hexamethylene diisocyanate (HDI) (TPA 100).

[0110] For example, the mass fraction of the curing agent may be, but is not limited to, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any combination of these values.

[0111] In some embodiments, the leveling agent includes one or more of polydimethylsiloxane, polyether polyester-modified organosiloxane, and silicone oil. It is understood that only a few commonly used leveling agents are given above, and the range is not limited thereto.

[0112] For example, the mass fraction of the leveling agent may be, but is not limited to, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, or any combination of these values.

[0113] For example, in powder coatings, the mass fraction of benzoin may be, but is not limited to, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, or any combination of these values.

[0114] In one embodiment, the powder coating comprises, by weight parts: 35 to 60 parts polyester resin, 15 to 30 parts antibacterial agent, 10 to 20 parts titanium dioxide, 2 to 5 parts curing agent, 0.4 to 1.5 parts leveling agent, and 0.2 to 1 part benzoin.

[0115] In some embodiments, the average particle size of the powder coating is 1 μm to 35 μm. Optionally, the average particle size of the powder coating is 1 μm to 25 μm.

[0116] In some embodiments, the method for preparing powder coatings includes the following steps:

[0117] The raw materials are premixed and stirred, and then ultrasonically dispersed to obtain a mixture;

[0118] The mixture is melted and extruded to prepare the extrudate.

[0119] The extruded material is pressed into sheets, which are then crushed to obtain powder coating.

[0120] Specifically, the ultrasonic dispersion frequency is 20KHz~35KHz, and the time is 15min~30min.

[0121] Specifically, in the melt extrusion step, the temperature of each zone of the extruder is set as follows: Zone 1 temperature 90℃~110℃, Zone 2 temperature 130℃~300℃, and Zone 3 temperature 140℃~200℃.

[0122] In one embodiment, the method for preparing the powder coating includes the following steps:

[0123] The following raw materials are obtained by weight: 35-60 parts resin, 15-30 parts antibacterial agent, 10-20 parts pigments and fillers, 2-5 parts curing agent, and 0.6-2.5 parts additives;

[0124] The raw materials are stirred and premixed, and then dispersed at an ultrasonic frequency of 20KHz~35KHz for 15min~30min to obtain a mixture;

[0125] The mixture is added to a twin-screw extruder, and after heating, melting, mixing and extrusion, the extruded material is obtained. The temperature settings of each zone of the twin-screw extruder are: zone 1 temperature 90℃~110℃, zone 2 temperature 130℃~300℃, and zone 3 temperature 140℃~200℃.

[0126] The extruded material is pressed to obtain sheet material; the sheet material is fed into a grinding mill for pretreatment, and then conveyed to an airflow ultrafine grinding mill for further refinement and crushing to obtain powder coating with an average particle size of 1μm~35μm.

[0127] Fourthly, this application provides a product with antibacterial function, including a substrate and an antibacterial coating disposed on the surface of the substrate, wherein the antibacterial coating is obtained by spraying and curing the powder coating described in the third aspect above.

[0128] In some embodiments, the substrate is a metal substrate.

[0129] In some embodiments, products with antibacterial properties include kitchen and bathroom hardware products. For example, products with antibacterial properties include faucets, shower heads, etc.

[0130] The aforementioned products with antibacterial properties have at least the following advantages:

[0131] (1) The materials used for surface coating of the above-mentioned antibacterial products include antibacterial agents. Silver ions in the antibacterial agents play a major antibacterial role, and their content is greater than that of copper ions and third metal ions. Copper ions are used to reduce the reduction of silver ions, thus protecting the ionic state of silver. Third metal ions increase the number of additional exchangeable cations, slowing down the release rate of silver ions. Together with copper ions, they improve the durability of the antibacterial effect of silver ions. Experiments have shown that the above-mentioned antibacterial products still have excellent antibacterial properties after 5000 cycles of friction.

[0132] (2) The above-mentioned antibacterial products are not prone to yellowing and have a good appearance.

[0133] (3) The above-mentioned antibacterial products have good antibacterial properties against a variety of bacteria such as Escherichia coli, Staphylococcus aureus and Candida albicans, while reducing the risk of antibacterial agent failure.

[0134] (4) The above-mentioned antibacterial products are obtained by powder coating, without the use of solvents, which is environmentally friendly and pollution-free.

[0135] Fifthly, this application provides a method for preparing a product with antibacterial function, comprising the following steps:

[0136] The powder coating described in the third aspect is sprayed onto the surface of the substrate and cured to prepare a product with antibacterial function.

[0137] In some embodiments, the spraying process parameters include: electrostatic high voltage of 40kV~70kV, electrostatic current of 10μA~20μA, flow rate pressure of 0.3MPa~0.6MPa, atomization pressure of 0.3MPa~0.5MPa, and a distance of 150mm~200mm between the spray gun nozzle and the substrate.

[0138] Specifically, the electrostatic high voltage is 40kV to 70kV. For example, the electrostatic high voltage may be, but is not limited to, 40kV, 45kV, 50kV, 55kV, 60kV, 65kV, 70kV, or any combination of these values.

[0139] Specifically, the electrostatic current is 10μA to 20μA. For example, the electrostatic current may be, but is not limited to, 10μA, 12μA, 14μA, 15μA, 16μA, 18μA, 20μA, or any combination of these values.

[0140] Specifically, the flow velocity pressure is 0.3 MPa to 0.6 MPa. For example, the flow velocity pressure may be, but is not limited to, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, 0.55 MPa, 0.6 MPa, or any combination of these values.

[0141] Specifically, the atomization pressure is 0.3 MPa to 0.5 MPa. For example, the atomization pressure may be, but is not limited to, 0.3 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, or any combination of these values.

[0142] Specifically, the distance between the spray gun nozzle and the substrate is 150mm to 200mm. For example, the distance between the spray gun nozzle and the substrate can be, but is not limited to, 150mm, 160mm, 170mm, 180mm, 190mm, 200mm, or any combination of these values.

[0143] It is understood that the above only provides a relatively specific spraying process, but it is not limited to this and can also include other commonly used processes in this field.

[0144] In some embodiments, the curing temperature is 150°C to 200°C, and the curing time is 15 min to 30 min. For example, the curing temperature may be, but is not limited to, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, or any combination of these values. The curing time may be, but is not limited to, 15 min, 18 min, 20 min, 22 min, 25 min, 30 min, or any combination of these values.

[0145] In some embodiments, a step of drying and dehydrating the substrate is included before spraying.

[0146] To make the objectives and advantages of this application clearer, the antibacterial agent and its effects of this application are further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only for explaining this application and should not be used to limit this application. Unless otherwise specified, the following embodiments do not include components other than unavoidable impurities. Unless otherwise specified, the drugs and instruments used in the embodiments are conventional choices in the art. Experimental methods in the embodiments that do not specify specific conditions are implemented according to conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0147] Example 1

[0148] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions, and nickel ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions, and nickel ions are 1.1 g / meq, 0.7 g / meq, and 0.5 g / meq, respectively.

[0149] The method for preparing the antibacterial agent in this embodiment includes the following steps:

[0150] 1. Pre-processing

[0151] The carrier zeolite was ground and sieved to separate samples with a particle size of less than 30 μm. Then, the carrier zeolite was added to deionized water and subjected to ultrasonic and continuous magnetic stirring at 60°C to remove impurities. Finally, it was centrifuged and dried.

[0152] 2. Preparation of antibacterial agents

[0153] (1) The pretreated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH of the solution to 11, allowing for ion exchange for 2 hours. After adjustment, excess Na... + and Cl - Removed by washing with deionized water.

[0154] (2) The dried zeolite (25g) was added to 1L of AgNO3 solution with a concentration of 0.04mol / L for ion exchange, and covered with aluminum foil. The pH value was adjusted to 4, the temperature was 60℃, and the mixture was stirred for 5h. After centrifugation, the solid was collected and washed three times with deionized water to obtain silver ion exchanged zeolite.

[0155] (3) Add the silver ion-exchanged zeolite to 1L of Cu(NO3)2 solution with a concentration of 0.04mol / L, adjust the pH value to 4.5, set the temperature to 60℃, cover with aluminum foil, stir for 5h, collect the obtained solid by centrifugation, and wash it three times with deionized water to obtain the silver ion and copper ion-exchanged zeolite.

[0156] (4) The zeolite after silver and copper ion exchange was added to 1L of 0.02mol / L Ni(NO3)2 solution, the pH was adjusted to 5, the temperature was 60℃, covered with aluminum foil, stirred for 5h, and the solid was collected by centrifugation and washed three times with deionized water. The obtained sample was dried at 80℃ for 9h and ground into particles with an average particle size of 10μm~20μm to obtain the antibacterial agent of this embodiment.

[0157] Example 2

[0158] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions, and nickel ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions, and nickel ions are 0.8 g / meq, 0.7 g / meq, and 0.5 g / meq, respectively.

[0159] The preparation steps of the antibacterial agent in this embodiment are similar to those in Example 1, except that step (2) in step 2 of the preparation of the antibacterial agent is different. In this embodiment, step (2) in step 2 of the preparation of the antibacterial agent is as follows:

[0160] (2) The dried zeolite (25g) was added to 1L of 0.02mol / L AgNO3 solution for ion exchange and covered with aluminum foil. The pH was adjusted to 4, the temperature was 60℃, and the mixture was stirred for 5h. After centrifugation, the solid was collected and washed three times with deionized water to obtain the silver ion-exchanged zeolite.

[0161] In this embodiment, steps 1 and steps 2 (1), (3), and (4) are the same as in embodiment 1, and will not be repeated here.

[0162] Example 3

[0163] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions, and nickel ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions, and nickel ions are 1.12 g / meq, 0.7 g / meq, and 0.5 g / meq, respectively.

[0164] The preparation steps of the antibacterial agent in this embodiment are similar to those in Example 1, except that step (2) in step 2 of the preparation of the antibacterial agent is different. In this embodiment, step (2) in step 2 of the preparation of the antibacterial agent is as follows:

[0165] (2) The dried zeolite (25g) was added to 1L of 0.06mol / L AgNO3 solution for ion exchange and covered with aluminum foil. The pH was adjusted to 4, the temperature was 60℃, and the mixture was stirred for 5h. After centrifugation, the solid was collected and washed three times with deionized water to obtain the silver ion-exchanged zeolite.

[0166] In this embodiment, steps 1 and steps 2 (1), (3), and (4) are the same as in embodiment 1, and will not be repeated here.

[0167] Example 4

[0168] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions, and titanium ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions, and titanium ions are 1.1 g / meq, 0.7 g / meq, and 0.5 g / meq, respectively.

[0169] The preparation steps of the antibacterial agent in this embodiment are similar to those in Example 1, except that step (4) in step 2 of the preparation of the antibacterial agent is different. In this embodiment, step (4) in step 2 of the preparation of the antibacterial agent is as follows:

[0170] (4) The zeolite after silver and copper ion exchange was added to 1L of Ti(NO3)4 solution with a concentration of 0.02mol / L, the pH was adjusted to 5, the temperature was set to 60℃, the solution was covered with aluminum foil, stirred for 5h, the solid was collected by centrifugation, and washed three times with deionized water. The obtained sample was dried at 80℃ for 9h and ground to an average particle size of 10μm~20μm, thus obtaining the antibacterial agent of this embodiment.

[0171] In this embodiment, steps 1 and steps 2 (1), (2), and (3) are the same as in embodiment 1, and will not be repeated here.

[0172] Example 5

[0173] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions, and titanium ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions, and manganese ions are 1.1 g / meq, 0.7 g / meq, and 0.5 g / meq, respectively.

[0174] The preparation steps of the antibacterial agent in this embodiment are similar to those in Example 1, except that step (4) in step 2 of the preparation of the antibacterial agent is different. In this embodiment, step (4) in step 2 of the preparation of the antibacterial agent is as follows:

[0175] (4) The zeolite after silver and copper ion exchange was added to 1L of 0.02mol / L Mn(NO3)2 solution, the pH was adjusted to 5, the temperature was 60℃, covered with aluminum foil, stirred for 5h, and the solid was collected by centrifugation and washed three times with deionized water. The obtained sample was dried at 80℃ for 9h and ground to an average particle size of 10μm~20μm, thus obtaining the antibacterial agent of this embodiment.

[0176] In this embodiment, steps 1 and steps 2 (1), (2), and (3) are the same as in embodiment 1, and will not be repeated here.

[0177] Example 6

[0178] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions, and nickel ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions, and nickel ions are 0.8 g / meq, 0.5 g / meq, and 0.3 g / meq, respectively.

[0179] The preparation steps of the antibacterial agent in this embodiment are similar to those in Example 1. The difference is that step 2 of the preparation of the antibacterial agent does not contain (1), that is, the zeolite and sodium ions are not exchanged.

[0180] Example 7

[0181] This embodiment provides an antibacterial agent comprising vermiculite and silver ions, copper ions, and nickel ions loaded on the vermiculite. In the antibacterial agent, the contents of silver ions, copper ions, and nickel ions are 0.7 g / meq, 0.3 g / meq, and 0.3 g / meq, respectively.

[0182] The preparation steps of the antibacterial agent in this embodiment are similar to those in Example 1. The difference lies in the inorganic carrier. In this embodiment, the inorganic carrier used is vermiculite.

[0183] Example 8

[0184] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions and nickel ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions and nickel ions are 1.11 g / meq, 0.7 g / meq and 0.5 g / meq, respectively.

[0185] The method for preparing the antibacterial agent in this embodiment includes the following steps:

[0186] 1. Pre-processing

[0187] The carrier zeolite was ground and sieved to separate samples with a particle size of less than 30 μm. Then, the carrier zeolite was added to deionized water and subjected to ultrasonic and continuous magnetic stirring at 60°C to remove impurities. Finally, it was centrifuged and dried.

[0188] 2. Preparation of antibacterial agents

[0189] (1) The pretreated carrier zeolite was added to a 0.6 mol / L NaCl solution, and NaOH was added to raise the pH of the solution to 12, allowing for ion exchange for 3 hours. After adjustment, excess Na... + and Cl - It is removed by washing with deionized water.

[0190] (2) The dried zeolite (25g) was added to 1L of AgNO3 solution with a concentration of 0.04mol / L for ion exchange, and covered with aluminum foil. The pH value was adjusted to 6, the temperature was 65℃, and the mixture was stirred for 7h. After centrifugation, the solid was collected and washed three times with deionized water to obtain silver ion exchanged zeolite.

[0191] (3) Add the silver ion-exchanged zeolite to 1L of Cu(NO3)2 solution with a concentration of 0.06mol / L, adjust the pH value to 6, set the temperature to 65℃, cover with aluminum foil, stir for 7h, collect the obtained solid by centrifugation, and wash it three times with deionized water to obtain the silver ion and copper ion-exchanged zeolite.

[0192] (4) The zeolite after silver and copper ion exchange was added to 1L of 0.05mol / L Ni(NO3)2 solution, the pH was adjusted to 6, the temperature was 65℃, covered with aluminum foil, stirred for 7h, the solid was collected by centrifugation, and washed three times with deionized water. The obtained sample was dried at 80℃ for 9h and ground into particles with an average particle size of 10μm~20μm to obtain the antibacterial agent of this embodiment.

[0193] Example 9

[0194] This embodiment provides an antibacterial agent comprising zeolite and silver ions, copper ions, and nickel ions supported on the zeolite. In the antibacterial agent, the contents of silver ions, copper ions, and nickel ions are 1.1 g / meq, 0.7 g / meq, and 0.5 g / meq, respectively.

[0195] The preparation method of the antibacterial agent in this embodiment includes the following steps:

[0196] 1. Pre-processing

[0197] The carrier zeolite was ground and sieved to separate samples with a particle size of less than 30 μm. Then, the carrier zeolite was added to deionized water and subjected to ultrasonic and continuous magnetic stirring at 60°C to remove impurities. Finally, it was centrifuged and dried.

[0198] 2. Preparation of antibacterial agents

[0199] (1) The pretreated carrier zeolite was added to a 0.45 mol / L NaCl solution, and NaOH was added to raise the pH of the solution to 11.5 for ion exchange for 2.5 h. After adjustment, excess Na... + and Cl - It is removed by washing with deionized water.

[0200] (2) The dried zeolite (25g) was added to 1L of AgNO3 solution with a concentration of 0.04mol / L for ion exchange, and covered with aluminum foil. The pH value was adjusted to 5, the temperature was 55℃, and the mixture was stirred for 6h. After centrifugation, the solid was collected and washed three times with deionized water to obtain silver ion exchanged zeolite.

[0201] (3) Add the silver ion-exchanged zeolite to 1L of Cu(NO3)2 solution with a concentration of 0.05mol / L, adjust the pH value to 4, set the temperature to 55℃, cover with aluminum foil, stir for 6h, collect the obtained solid by centrifugation, and wash it three times with deionized water to obtain the silver ion and copper ion-exchanged zeolite.

[0202] (4) The zeolite after silver and copper ion exchange was added to 1L of 0.03mol / L Ni(NO3)2 solution, the pH was adjusted to 4, the temperature was 55℃, covered with aluminum foil, stirred for 6h, the solid was collected by centrifugation, and washed three times with deionized water. The obtained sample was dried at 80℃ for 9h and ground into particles with an average particle size of 10μm~20μm to obtain the antibacterial agent of this embodiment.

[0203] Comparative Example 1

[0204] Comparative Example 1 provides an antibacterial agent comprising zeolite and silver and copper ions supported on the zeolite, wherein the contents of silver ions and copper ions in the antibacterial agent are 1.1 g / meq and 0.7 g / meq, respectively.

[0205] The preparation steps of the antibacterial agent in Comparative Example 1 are similar to those in Example 1, except that step 2 of the preparation of the antibacterial agent is different. In Comparative Example 1, step 2 of the preparation of the antibacterial agent is as follows:

[0206] (1) The pretreated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH of the solution to 11. Ion exchange was carried out for 2 hours. The excess Na+ after adjustment was then removed. + and Cl - It is removed by washing with deionized water.

[0207] (2) 25g of dried zeolite was added to 1L of 0.04mol / L AgNO3 solution for ion exchange and covered with aluminum foil. The pH was adjusted to 4, the temperature was set to 60℃, and the mixture was stirred for 5h. After centrifugation, the solid was collected and washed three times with deionized water to obtain silver ion-exchanged zeolite.

[0208] (3) Add the silver ion-exchanged zeolite to 1L of Cu(NO3)2 solution with a concentration of 0.04mol / L, adjust the pH value to 4.5, set the temperature to 60℃, cover with aluminum foil, stir for 5h, collect the obtained solid by centrifugation, wash with deionized water three times, dry the obtained sample at 80℃ for 9h, grind it into an average particle size of 10μm~20μm, and obtain the antibacterial agent of Comparative Example 1.

[0209] Step 1 of Comparative Example 1 is the same as that of Example 1, and will not be repeated here.

[0210] Comparative Example 2

[0211] Comparative Example 2 provides an antibacterial agent comprising zeolite and silver and nickel ions supported on the zeolite, wherein the contents of silver and nickel ions in the antibacterial agent are 1.1 g / meq and 0.5 g / meq, respectively.

[0212] The preparation steps of the antibacterial agent in Comparative Example 2 are similar to those in Example 1, except that step 2 of the preparation of the antibacterial agent is different. In Comparative Example 2, step 2 of the preparation of the antibacterial agent is as follows:

[0213] (1) The pretreated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH of the solution to 11, allowing for ion exchange for 2 hours. After adjustment, excess Na... + and Cl - It is removed by washing with deionized water.

[0214] (2) The dried zeolite (25g) was added to 1L of 0.04mol / L AgNO3 solution for ion exchange and covered with aluminum foil. The pH was adjusted to 4, the temperature was set to 60℃, and the mixture was stirred for 5h. After centrifugation, the solid was collected and washed three times with deionized water to obtain the silver ion-exchanged zeolite.

[0215] (3) Add the silver ion-exchanged zeolite to 1L of Ni(NO3)2 solution with a concentration of 0.04mol / L, adjust the pH value to 4.5, set the temperature to 60℃, cover with aluminum foil, stir for 5h, collect the obtained solid by centrifugation, wash with deionized water three times, dry the obtained sample at 80℃ for 9h, grind it into an average particle size of 10μm~20μm, and obtain the antibacterial agent of Comparative Example 2.

[0216] Step 1 of Comparative Example 2 is the same as that of Example 1, and will not be repeated here.

[0217] Comparative Example 3

[0218] Comparative Example 3 provides an antibacterial agent comprising zeolite and silver ions supported on the zeolite, wherein the silver ion content in the antibacterial agent is 1.1 g / meq.

[0219] The preparation steps of the antibacterial agent in Comparative Example 3 are similar to those in Example 1, except that step 2 of the preparation of the antibacterial agent is different. In Comparative Example 3, step 2 of the preparation of the antibacterial agent is as follows:

[0220] (1) The pretreated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH of the solution to 11. Ion exchange was carried out for 2 hours. The excess Na+ after adjustment was then removed. + and Cl - It is removed by washing with deionized water.

[0221] (2) 25g of dried zeolite was added to 1L of 0.04mol / L AgNO3 solution for ion exchange and covered with aluminum foil. The pH was adjusted to 4, the temperature was 60℃, and the mixture was stirred for 5h. After centrifugation, the solid was collected and washed three times with deionized water. The sample was dried at 80℃ for 9h and ground to an average particle size of 10μm~20μm to obtain the antibacterial agent of Comparative Example 3.

[0222] Step 1 of Comparative Example 3 is the same as that of Example 1, and will not be repeated here.

[0223] The antibacterial agents prepared in the above embodiments and comparative examples were used to prepare powder coatings to obtain antibacterial coatings. Specifically, the preparation was carried out through the following steps:

[0224] 1. Preparation of powder coatings

[0225] (1) By mass, 24 parts of each of the above antibacterial agents, 56 parts of polyester resin, 18 parts of titanium dioxide, 4 parts of TGIC curing agent, 1 part of benzoin and 0.4 parts of polydimethylsiloxane are premixed and thoroughly stirred to obtain a premixed material. Then, the mixture is sent to an ultrasonic disperser and dispersed at a frequency of 20KHz for 20 min to obtain an ultrasonically dispersed mixture.

[0226] (2) The ultrasonically dispersed mixture is fed into a twin-screw extruder, and after heating, melting, mixing and extrusion, the molten extruded material is obtained. The temperature of each zone of the twin-screw extruder is set as follows: Zone 1 temperature 90℃, Zone 2 temperature 110℃, Zone 3 temperature 200℃.

[0227] (3) The material obtained by melt extrusion in (2) is pressed to obtain sheet material; the sheet material is sent to a grinding mill for pretreatment, and then sent to an airflow ultrafine grinding mill for further refinement and crushing to obtain powder coating with an average particle size of 1μm~35μm.

[0228] 2. Preparation of antibacterial coating

[0229] (1) High-voltage electrostatic powder coating

[0230] After pretreatment, the substrate undergoes baking and dehydration, then it is conveyed to the dust-free powder coating booth via a conveyor chain to perform high-voltage electrostatic powder coating. The high-voltage electrostatic powder coating process parameters are as follows: electrostatic high voltage 50kV, electrostatic current 10μA, flow rate pressure 0.5MPa, atomization pressure 0.3MPa, and the distance between the spray gun nozzle and the substrate position is 150mm.

[0231] (2) High temperature curing

[0232] After being coated by high-pressure electrostatic spraying, the substrate enters the high-temperature curing device via a conveyor chain. The temperature is set at 150°C and the baking time is 30 minutes, forming an antibacterial coating on the surface of the substrate.

[0233] The following is the specific test section:

[0234] 1. Antibacterial performance test method

[0235] This experiment followed Appendix A, Test Method 1 (film application method), of GB21551.2-2010 "Antibacterial, Sterilizing and Purifying Functions of Household Appliances and Similar Electrical Appliances". The test samples were prepared as (50±2)×(50±2) mm specimens. The control sample was a standard sample made of sanitary high-density polyethylene (HDPE) injection molded with dimensions of (50±2) mm×(50±2) mm and a thickness not exceeding 5 mm. 0.2 mL of PBS suspensions of 10⁶ CFU / mL *Escherichia coli*, *Staphylococcus aureus*, and *Candida albicans* were added to the test and control samples, respectively. The samples were then covered with a polyethylene film to ensure uniform contact of the bacterial suspensions. The samples were incubated at 37±1℃ and relative humidity (RH>90%) for 12 h. Then, each sample after co-culture was removed, and 20 mL of PBS elution buffer was added. The samples were sonicated for 3 min, and 0.2 mL of the elution buffer was inoculated into nutrient agar medium. After incubation at 37±1℃ for 24 h, viable bacterial counts were performed. All samples used in the above experiments were sterilized beforehand. Bacteria were quantitatively inoculated onto the test samples and control samples, and a film was used to ensure uniform bacterial contact. After incubation for (24±1) h, the number of surviving bacteria in the two groups of samples was measured, and the sterilization rate of the test samples was calculated by comparing the results.

[0236] 2. Durability testing methods

[0237] After each sample underwent an antibacterial test, it was immediately placed in a wet friction test chamber. The wiping sponge was moved at a frequency of (37±2) reciprocations per minute, with each reciprocating stroke covering a distance of 200 mm. The wet friction test chamber was equipped with a digital counter, which recorded a value of 1 after each reciprocating stroke. The total mass of the fixture, weights, and wiping sponge was (300±10) g. An antibacterial test was conducted after every 1000 cycles of friction.

[0238] The initial sterilization rates of the antibacterial coatings prepared using the antibacterial agents from the various embodiments and comparative examples against different bacteria are shown in Table 1 below. The durability data of the antibacterial coatings against *Escherichia coli* are shown below. Figure 2 As shown. In Figure 2 In the middle, the three lines at the top that basically overlap represent the durability of the antimicrobial coatings prepared using the antimicrobial agents prepared in Examples 1, 8, and 9.

[0239] Table 1 Initial sterilization rates of the antibacterial coating against Escherichia coli, Staphylococcus aureus, and Candida albicans

[0240]

[0241] From Table 1 and Figure 2 As can be seen from the examples, the antibacterial agent in the embodiments, by adding Cu 2+ Reduce Ag + The reduction process protects the ionic state of silver, reducing yellowing and improving durability. Adding a third metal ion increases the number of exchangeable cations, extending antibacterial durability and meeting the antibacterial requirements of bathroom products in special environments. However, the antibacterial coatings prepared with the antibacterial agents in Comparative Examples 1-3 showed significantly lower sterilization rates against E. coli after 5000 rubs compared to the examples, indicating poorer durability.

[0242] Furthermore, optimizing the third metal ion in the antibacterial agent can further improve its durability. Treating the zeolite with sodium salt first enhances the interaction between the zeolite and Ag. + The ion exchange capacity of the carrier is beneficial for further improving its antibacterial properties and durability. Optimizing the type of carrier can further enhance the antibacterial properties and durability of the antibacterial agent.

[0243] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0244] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification and drawings can be used to interpret the content of the claims.

Claims

1. An antibacterial agent, characterized in that, Includes an inorganic carrier and silver ions, copper ions, and third metal ions loaded on the inorganic carrier; The third metal ion includes nickel ions; In the antibacterial agent, the content of silver ions is greater than the content of copper ions, which is greater than the content of the third metal ion. The content of silver ions is 0.6 g / meq to 1.12 g / meq, the content of copper ions is 0.3 g / meq to 0.7 g / meq, and the content of the third metal ion is 0.3 g / meq to 0.5 g / meq.

2. The antibacterial agent according to claim 1, characterized in that, The inorganic carrier includes one or more of zeolite, vermiculite, montmorillonite, mesoporous silica, and talc.

3. The antibacterial agent according to claim 2, characterized in that, The inorganic carrier includes zeolite.

4. The antibacterial agent according to claim 3, characterized in that, The copper ion content is 0.4 g / meq to 0.7 g / meq.

5. A method for preparing an antibacterial agent, characterized in that, Includes the following steps: An antibacterial agent loaded with silver ions, copper ions and a third metal ion was prepared by ion exchange between an inorganic carrier and silver ions, copper ions and a third metal ion. The third metal ion includes nickel ions; in the antibacterial agent, the content of silver ions is greater than the content of copper ions, which is greater than the content of the third metal ion, wherein the content of silver ions is 0.6 g / meq to 1.12 g / meq, the content of copper ions is 0.3 g / meq to 0.7 g / meq, and the content of the third metal ion is 0.3 g / meq to 0.5 g / meq.

6. The method for preparing the antibacterial agent according to claim 5, characterized in that, The steps for ion exchange between an inorganic carrier and silver ions, copper ions, and a third metal ion include: The inorganic carrier is placed sequentially in a silver salt solution, a copper salt solution, and a salt solution containing the third metal ion, and the mixture is stirred to allow the inorganic carrier to exchange ions with the silver ions, the copper ions, and the third metal ion in sequence.

7. The method for preparing the antibacterial agent according to claim 6, characterized in that, The concentration of the silver salt solution is 0.02 mol / L to 0.06 mol / L; and / or, The concentration of the copper salt solution is 0.04 mol / L to 0.06 mol / L; and / or, The concentration of the salt solution containing the third metal ion is 0.02 mol / L to 0.05 mol / L.

8. The method for preparing the antibacterial agent according to claim 7, characterized in that, One or more of the following conditions must be met: (1) The silver salt solution includes silver nitrate solution; (2) The copper salt solution includes copper nitrate solution; (3) Salt solutions containing the third metal ion include nickel nitrate solutions; (4) The reaction time for each stirring reaction is 5h~7h; (5) The pH of each stirring reaction is 4~6; (6) The temperature of each stirring reaction is 55℃~65℃, and it is carried out under light-protected conditions.

9. The method for preparing the antibacterial agent according to any one of claims 5 to 8, characterized in that, Before the step of ion exchange between the inorganic carrier and silver ions, copper ions and a third metal ion, the method further includes: placing the inorganic carrier in a sodium salt solution with a concentration of 0.3 mol / L to 0.6 mol / L and treating it at a pH of 11 to 12 for 2 to 3 hours.

10. A powder coating, characterized in that, It includes the antibacterial agent according to any one of claims 1 to 4 or the antibacterial agent prepared by the preparation method according to any one of claims 5 to 9.

11. The powder coating according to claim 10, characterized in that, By weight, it includes: 35 to 60 parts resin, 15 to 30 parts antibacterial agent, 10 to 20 parts pigments and fillers, 2 to 5 parts curing agent, and 0.6 to 2.5 parts additives.

12. The powder coating according to claim 11, characterized in that, The additives include 0.4 to 1.5 parts of leveling agent and 0.2 to 1 part of benzoin; and / or, The average particle size of the powder coating is 1μm to 35μm.

13. A product with antibacterial function, characterized in that, It includes a substrate and an antibacterial coating disposed on the surface of the substrate, the antibacterial coating being obtained by spraying and curing the powder coating as described in any one of claims 10 to 12.

14. The product with antibacterial function according to claim 13, characterized in that, The products with antibacterial function include kitchen and bathroom hardware products.

15. A method for preparing a product with antibacterial function, characterized in that, Includes the following steps: The powder coating of any one of claims 10 to 12 is sprayed onto the surface of a substrate and cured to prepare the product with antibacterial function.

16. The method for preparing a product with antibacterial function according to claim 15, characterized in that, The spraying process parameters include: electrostatic high voltage of 40kV~70kV, electrostatic current of 10μA~20μA, flow rate and pressure of 0.3MPa~0.6MPa, atomization pressure of 0.3MPa~0.5MPa, and a distance between the spray gun nozzle and the substrate of 150mm~200mm; and / or, The curing temperature is 150℃~200℃, and the time is 15min~30min.

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