Antibacterial agent and preparation method thereof, powder coating, product with antibacterial function and preparation method thereof

Abstract

The invention relates to an antibacterial agent and a preparation method thereof, a powder coating, a product with an antibacterial function and a preparation method of the product. The antibacterial agent comprises an inorganic carrier, and silver ions, copper ions and third metal ions which are loaded on the inorganic carrier; wherein the third metal ions comprise one or more of nickel ions, titanium ions, manganese ions and zinc ions; the content of the silver ions > the content of the copper ions > = 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 reduction of the silver ions, so that the ionic state of silver is protected, the third metal ions increase the number of additional exchangeable cations, the release speed of the silver ions is delayed, and the durability of the antibacterial effect of the silver ions is improved through the cooperation of the third metal ions and the copper ions.

Description

Technical Field

[0001] The present application relates to the antibacterial field, and in particular to an antibacterial agent and a preparation method thereof, a powder coating, a product with antibacterial function and a preparation method thereof. Background Art

[0002] Kitchen and bathroom hardware products such as faucets and showers are used in a humid and complex environment. Bacteria are easily attached to the surface of the products, which breeds various metabolites of mold, acid and toxins, thus affecting the appearance and quality of the products and endangering human health. Therefore, there are high requirements for the antibacterial properties of kitchen and bathroom hardware products. At present, most of them have good antibacterial ability by constructing antibacterial coatings on the surface of products, such as adding some antibacterial agents to powder coatings and spraying them on the surface of products to improve the antibacterial properties.

[0003] At present, antimicrobial agents are divided into two categories: inorganic and organic. The safety of organic antimicrobial agents is still under study, and organic antimicrobial agents have poor heat resistance, are easily hydrolyzed, have a short effective period, and are difficult to promote and use. Although inorganic antimicrobial agents such as silver ion antimicrobial agents are safer and have good heat resistance, the antimicrobial durability of the prepared coating is poor, and the antimicrobial effect is greatly weakened after repeated water washing. Therefore, the current inorganic antimicrobial agents used in antimicrobial coatings still have the problem of poor antimicrobial durability, and the antimicrobial effect is greatly weakened after repeated water washing. Summary of the invention

[0004] Based on this, some embodiments of the present application provide an antibacterial agent with good durability and a preparation method thereof.

[0005] In addition, other embodiments of the present application also provide a powder coating comprising the above-mentioned antibacterial agent, a product with antibacterial function and a preparation method thereof.

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

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

[0008] In the antibacterial agent, the content of the silver ions>the content of the copper ions≥the content of the third metal ions.

[0009] Optionally, the third metal ion comprises nickel ion; 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 content of the copper ion 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~0.5 g / meq.

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

[0015] The inorganic carrier is subjected to ion exchange with the silver ions, copper ions and the third metal ions to prepare an antibacterial agent loaded with the silver ions, copper ions and the third metal ions;

[0016] Wherein, the third metal ion includes one or more of nickel ion, titanium ion, manganese ion and zinc ion; in the antibacterial agent, the content of the silver ion> the content of the copper ion≥ the content of the third metal ion.

[0017] Optionally, the step of ion exchanging the inorganic carrier with the silver ions, the copper ions and the third metal ions comprises:

[0018] The inorganic carrier is sequentially placed in a silver salt solution, a copper salt solution and a salt solution containing the third metal ion, and stirred for reaction, so that the inorganic carrier sequentially performs ion exchange with the silver ion, the copper ion and the third metal ion.

[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 are met:

[0023] (1) The silver salt solution includes a 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 a nickel nitrate solution, a titanium nitrate solution, a manganese nitrate solution and a zinc nitrate solution. Optionally, the salt solution containing the third metal ion includes a nickel nitrate solution;

[0026] (4) Each stirring reaction time is 5h~7h;

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

[0028] (6) Each stirring reaction is carried out at a temperature of 55°C to 65°C in a dark environment.

[0029] Optionally, before the step of exchanging the inorganic carrier with silver ions, copper ions and the third metal ions, 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 the solution at a pH of 11 to 12 for 2 h to 3 h.

[0030] A powder coating comprises the above antibacterial agent or the antibacterial agent prepared by the above preparation method.

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

[0032] Optionally, the auxiliary agent includes 0.4 to 1.5 parts of a 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, comprising a substrate and an antibacterial coating arranged on the surface of the substrate, wherein the antibacterial coating is obtained by spraying and curing the above-mentioned powder coating;

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

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

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

[0038] Optionally, the process parameters of spraying 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 the distance between the spray gun nozzle and the substrate is 150mm~200mm.

[0039] Optionally, the curing temperature is 150° C. to 200° C., and the curing time is 15 min to 30 min.

[0040] Some embodiments of the present application provide an antibacterial agent, including an inorganic carrier and silver ions, copper ions and a third metal ion loaded on the inorganic carrier, and the content of each metal ion is adjusted, wherein the silver ions play a major antibacterial role, the copper ions are used to reduce the reduction of the silver ions so that the ionic state of the silver is protected, and the third metal ions increase the number of additional exchangeable cations in the carrier, slow down the release rate of the silver ions, and cooperate with the copper ions to improve the durability of the antibacterial effect of the silver ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0042] Figure 1 A schematic diagram of a process flow of a method for preparing an antibacterial agent according to some embodiments of the present application;

[0043] Figure 2 This is the sterilization rate curve of Escherichia coli of the antibacterial coating prepared in each embodiment and comparative example of the present application after 5000 frictions. DETAILED DESCRIPTION

[0044] In order to facilitate the understanding of the present application, the present application will be described more comprehensively below in conjunction with the specific embodiments. The preferred embodiments of the present application are provided in the specific embodiments. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present application belongs. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0046] Unless otherwise specified or there is a contradiction, the terms and phrases used in this application have the following meanings:

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

[0048] In the description of the present application, “plurality” means at least two, for example, two, three, etc., unless otherwise clearly and specifically defined.

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

[0050] In this application, the percentage concentration involved, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0051] In this document, "further", "further", "particularly", "for example", "such as", "example", "for example", etc. are used for descriptive purposes, indicating that the previous and subsequent technical solutions are related in terms of the content covered, but should not be understood as a limitation on the previous technical solution, nor can it be understood as a limitation on the protection scope of this document. In this document, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0052] Herein, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel schemes of "yes" or "no". If multiple "optional" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" item is independent of each other. In this application, descriptions such as "optionally contain", "optionally include", etc. mean "contain or not contain". "Optional component X" means that component X exists or does not exist, or means that component X is contained or not contained.

[0053] When a numerical range is disclosed in this application, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed in this application should be understood to include any and all subranges included therein.

[0054] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

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

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

[0057] The present application provides an antibacterial agent and a preparation method thereof, which have good antibacterial durability.

[0058] In a first aspect, the present 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] Wherein, the third metal ion includes one or more of nickel ion, titanium ion, manganese ion and zinc ion;

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

[0061] The above-mentioned 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. The silver ion plays a major antibacterial role, and its content is greater than the copper ion content and the third metal ion content. The copper ion is used to reduce the reduction of the silver ion, so that the ionic state of the silver is protected. The third metal ion increases the number of additional exchangeable cations, slows down the release rate of the silver ions, and cooperates with the copper ions to improve the durability of the antibacterial effect of the silver ion. Since the antibacterial effect and durability of the third metal ion are not as good as those of the copper ion, if the content of the third metal ion is greater than the content of the copper ion, the antibacterial property and durability of the antibacterial agent will be deteriorated. Therefore, in some embodiments of the present application, the content of the copper ion is ≥ the content of the third metal ion.

[0062] In addition, the traditional silver ion antibacterial agent Ag + It is easy to be destroyed, which not only causes Ag + The loss of copper ions also causes yellowing of the coating surface. In some embodiments of the present application, copper ions are used to protect silver ions, which improves durability and reduces yellowing of the coating.

[0063] In addition, conventional powder coatings containing antimicrobial agents cannot achieve broad-spectrum antibacterial properties when used, and there is a risk of antimicrobial agent failure. In some embodiments of the present application, silver ions, copper ions and third metal ions are combined to have good antibacterial properties against a variety of bacteria such as Escherichia coli, Staphylococcus aureus and Candida albicans, while reducing the risk of antimicrobial agent failure.

[0064] In some embodiments, the inorganic carrier includes one or more of zeolite, vermiculite, montmorillonite, mesoporous silica and talc. Optionally, the inorganic carrier includes zeolite. Zeolite has better ion exchange performance than other inorganic carriers, which is beneficial to improve the antibacterial effect and antibacterial durability of the antibacterial agent.

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

[0066] In some embodiments, the third metal ion includes nickel ion. Experiments have shown that the third metal ion including nickel ion can further improve the durability of the antibacterial agent compared with the third metal ion including titanium ion, manganese ion, 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, in the antibacterial agent, the content of silver ions is 0.6 g / meq to 1.12 g / meq. In the antibacterial agent, the content of copper ions is 0.3 g / meq to 0.7 g / meq. In the antibacterial agent, the content of the third metal ion is 0.3 g / meq to 0.5 g / meq. For example, in the antibacterial agent, the content of silver ions can 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 content of copper ion can 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 a range consisting of any two of these values. The content of the third metal ion can 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 a range consisting of any two of these values.

[0069] In some of the embodiments, optionally, the inorganic carrier comprises zeolite, and the content of copper ions 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, the average particle size of the antimicrobial agent is less than 30 μm. In one example, the average particle size of the antimicrobial agent is 10 μm to 20 μm.

[0071] In a second aspect, the present application provides a method for preparing an antibacterial agent, comprising the following steps:

[0072] The inorganic carrier is subjected to ion exchange with the silver ions, copper ions and the third metal ions to prepare an antibacterial agent loaded with the silver ions, copper ions and the third metal ions;

[0073] The third metal ion includes one or more of nickel ion, titanium ion, manganese ion and zinc ion; in the antibacterial agent, the content of silver ion> the content of copper ion≥ the content of the third metal ion.

[0074] In some embodiments, the step of ion exchanging the inorganic support with the silver ions, the copper ions and the third metal ions comprises:

[0075] The inorganic carrier is sequentially placed in a silver salt solution, a copper salt solution and a salt solution containing a third metal ion, and stirred to react, so that the inorganic carrier sequentially exchanges ions with the silver ions, the copper ions and the third metal ions.

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

[0079] In one embodiment, the copper salt solution includes 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 a range consisting of any 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 time of each stirring reaction is 5h to 7h. For example, the time of each stirring reaction can be, but is not limited to, 5h, 5.5h, 6h, 6.5h, 7h, or a range consisting of any two of these values. It is understood that the time of each stirring reaction can be the same or different, 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 can be, but is not limited to, 4, 4.5, 5, 5.5, 6, or a range consisting of any two of these values. It is understood that the pH of each stirring reaction can 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 can be understood that the temperature of each stirring reaction can be the same or different, and is not particularly limited.

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

[0086] In some embodiments, after each stirring reaction step, the step of solid-liquid separation and washing the obtained solid is further included, for example, washing with deionized water three times.

[0087] In some embodiments, after the step of ion exchange with the third metal ion, the steps of solid-liquid separation, washing, drying and grinding are also included. For example, in the drying step, the drying is performed at 80° C. for 8 h to 9 h. In the grinding step, the average particle size is less than 50 μm, for example, the average particle size is less than 30 μm. In one example, the average particle size is 10 μm to 20 μm.

[0088] In some embodiments, before the step of exchanging the inorganic support with silver ions, copper ions and the third metal ions, the step of exchanging the inorganic support with sodium ions is also included. + Replace the exchangeable cations in the inorganic carrier to enhance the ion exchange capacity of the inorganic carrier.

[0089] Specifically, in the step of exchanging the inorganic support with sodium ions, the inorganic support is placed in a sodium salt solution with a concentration of 0.3 mol / L to 0.6 mol / L and treated for 2 h to 3 h at a pH of 11 to 12. Alkaline conditions are conducive to 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 of the embodiments, the step of pre-treating the inorganic carrier is also included. Specifically, the pre-treatment step includes grinding and water washing. For example, the inorganic carrier is ground and the inorganic carrier with a particle size of less than 50 μm is screened. In the water washing step, the inorganic carrier is placed in water and washed under ultrasonic and stirring conditions. Impurities are removed by water washing.

[0092] In a specific example, the step of pre-treating the inorganic carrier includes: grinding and sieving the inorganic carrier to separate the inorganic carrier with a particle size of less than 50 μm; placing the inorganic carrier in deionized water, performing ultrasonic and magnetic stirring at 60° C., centrifugal separation, 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, see Figure 1 , the preparation method of the antibacterial agent comprises the following steps:

[0095] Step S110: 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 h to 3 h.

[0096] Step S120: placing the inorganic carrier treated with sodium ions in a silver nitrate solution with a concentration of 0.02 mol / L to 0.06 mol / L, stirring the solution for 5 h to 7 h at a pH of 4 to 6 and a temperature of 55° C. to avoid light, so that the inorganic carrier and the silver ions can undergo ion exchange.

[0097] Step S130: placing the inorganic carrier after silver ion exchange in a copper nitrate solution with a concentration of 0.04 mol / L~0.06 mol / L, stirring the reaction for 5h~7h under light-proof conditions of pH 4~6 and temperature of 55°C~65°C to exchange ions between the inorganic carrier and copper ions.

[0098] Step S140: placing the inorganic carrier after the silver ion and copper ion exchange in a nickel nitrate solution with a concentration of 0.02 mol / L~0.05 mol / L, stirring the reaction for 5h~7h under light-proof conditions of pH 4~6 and temperature of 55°C~65°C to exchange ions between the inorganic carrier and the nickel ions.

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

[0100] It should be understood that Figure 1 This is a schematic diagram of a method for preparing an antibacterial agent according to an embodiment of the present invention. Figure 1 The steps in the flowchart are shown in sequence as indicated by the arrows, but these steps are not necessarily performed in the order indicated by the arrows. Unless otherwise specified in this document, there is no strict order restriction for the execution of these steps, and they can be performed in other orders. Figure 1 At least part of the steps may include multiple sub-steps or multiple stages. These sub-steps or stages are not necessarily executed at the same time, but can be executed at different times. The order of execution is not necessarily sequential, but can be executed in turn or alternately with other steps or at least part of other sub-steps or stages.

[0101] In a third aspect, the present application provides a powder coating, comprising the antibacterial agent of the first aspect or the antibacterial agent prepared by the preparation method of the second aspect.

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

[0103] Optionally, the auxiliary agent includes 0.4 to 1.5 parts of a 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, carboxyl polyester resin and oil-free alkyd resin. Exemplarily, the polyester resin includes one or more of NH-3295 saturated polyester resin, GH-2100 carboxyl polyester resin, 312C oil-free alkyd resin and 335 saturated polyester. It is understood that in other embodiments, the resin can also be epoxy resin, etc.

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

[0106] For example, in the powder coating, the mass fraction of the antibacterial agent can 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 a range consisting of any two of these values.

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

[0108] For example, in the powder coating, the mass fraction of the pigment and filler can be, but is not limited to, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts, 20 parts, or a range consisting of any two 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 isocyanurate (TGIC) and 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 a range consisting of any two of these values.

[0111] In some embodiments, the leveling agent includes one or more of polydimethylsiloxane, polyether polyester modified organic siloxane and silicone oil. It can be understood that only several commonly used leveling agents are given above, but they are 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 parts, 1.2 parts, 1.4 parts, 1.5 parts, or a range consisting of any two of these values.

[0113] For example, in the powder coating, the mass fraction of benzoin can 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 a range consisting of any two of these values.

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

[0117] Premixing and stirring the raw materials, and then dispersing them by ultrasonication to obtain a mixture;

[0118] Melting and extruding the mixture to prepare an extrudate;

[0119] The extrudate is pressed into sheets, which are then crushed to obtain powder coatings.

[0120] Specifically, the frequency of ultrasonic dispersion 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: the temperature of the first zone is 90°C to 110°C, the temperature of the second zone is 130°C to 300°C, and the temperature of the third zone is 140°C to 200°C.

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

[0123] The following raw materials are obtained by weight: 35 to 60 parts of resin, 15 to 30 parts of antibacterial agent, 10 to 20 parts of pigment and filler, 2 to 5 parts of curing agent and 0.6 to 2.5 parts of auxiliary agent;

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

[0125] The mixture is added into a twin-screw extruder, and the extrudate is obtained through heating, melting, mixing and extrusion. The temperature of each zone of the twin-screw extruder is set as follows: the temperature of the first zone is 90°C to 110°C, the temperature of the second zone is 130°C to 300°C, and the temperature of the third zone is 140°C to 200°C;

[0126] The extrudate is pressed to obtain a flake material; the flake material is sent to a grinder for pretreatment, and then sent to an air flow type ultrafine grinder for further refinement and crushing to obtain a powder coating with an average particle size of 1μm~35μm.

[0127] In a fourth aspect, the present application provides a product with antibacterial function, comprising a substrate and an antibacterial coating arranged on the surface of the substrate, wherein the antibacterial coating is obtained by spraying and curing the powder coating of the third aspect.

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

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

[0130] The above-mentioned products with antibacterial function have at least the following advantages:

[0131] (1) The materials used for the surface spraying of the above-mentioned products with antibacterial function include antibacterial agents. The silver ions in the antibacterial agent play a major antibacterial role. The silver ions in the antibacterial agent are greater than the copper ions and the third metal ions. The copper ions are used to reduce the reduction of silver ions, so that the ionic state of silver is protected. The third metal ions increase the number of additional exchangeable cations, slow down the release rate of silver ions, and cooperate with copper ions to improve the durability of the antibacterial effect of silver ions. Experiments have shown that the above-mentioned products with antibacterial function still have excellent antibacterial properties after 5,000 frictions.

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

[0133] (3) The above-mentioned products with antibacterial function 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 product with antibacterial function is obtained by spraying powder coating, which uses no solvent and is environmentally friendly and pollution-free.

[0135] In a fifth aspect, the present application provides a method for preparing a product with antibacterial function, comprising the following steps:

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

[0137] In some of the embodiments, the process parameters of spraying 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 the distance between the spray gun nozzle and the substrate is 150mm~200mm.

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

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

[0140] Specifically, the flow rate pressure is 0.3 MPa to 0.6 MPa. For example, the flow rate 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 a range consisting of any two 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 a range consisting of any two of these values.

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

[0143] It can be understood that the above only provides a more specific spraying process, but is not limited thereto, and may also be a commonly used process in the art.

[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 a range consisting of any two 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 a range consisting of any two of these values.

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

[0146] In order to make the purpose and advantages of the present application clearer, the antibacterial agent of the present application and its effect are further described in detail below in conjunction with specific examples. It should be understood that the specific examples described herein are only used to explain the present application and shall not be used to limit the present application. The following examples do not include other components except inevitable impurities unless otherwise specified. The drugs and instruments used in the examples are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the examples are implemented according to conventional conditions, such as the conditions described in the literature, books, or the methods recommended by the manufacturer.

[0147] Example 1

[0148] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and nickel ions loaded 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 preparation method of the antibacterial agent of this embodiment comprises the following steps:

[0150] 1. Pre-treatment

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

[0152] 2. Preparation of antibacterial agents

[0153] (1) The pre-treated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH value of the solution to 11, and ion exchange was performed for 2 hours. + and Cl - Remove by rinsing with deionized water.

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

[0155] (3) The silver-ion-exchanged zeolite was added to 1 L of 0.04 mol / L Cu(NO3)2 solution, the pH value was adjusted to 4.5, the temperature was 60°C, covered with aluminum foil, stirred for 5 h, and the obtained solid was collected by centrifugation and washed three times with deionized water to obtain the silver-ion and copper-ion-exchanged zeolite.

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

[0157] Example 2

[0158] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and nickel ions loaded 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 steps for preparing the antibacterial agent in this embodiment are similar to those in Embodiment 1, except that (2) in the step 2 of preparing the antibacterial agent is different. In this embodiment, (2) in the step 2 of preparing the antibacterial agent is as follows:

[0160] (2) Add the treated and dried zeolite (25 g) to 1 L of 0.02 mol / L AgNO3 solution for ion exchange and cover with aluminum foil. Adjust the pH to 4, the temperature to 60°C, stir for 5 h, collect the obtained solid by centrifugation, and wash it three times with deionized water to obtain the silver ion-exchanged zeolite.

[0161] Step 1 of this embodiment and (1), (3), and (4) in step 2 are the same as those in embodiment 1 and will not be described in detail.

[0162] Example 3

[0163] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and nickel ions loaded 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 steps for preparing the antibacterial agent in this embodiment are similar to those in Embodiment 1, except that (2) in the step 2 of preparing the antibacterial agent is different. In this embodiment, (2) in the step 2 of preparing the antibacterial agent is as follows:

[0165] (2) Add the treated and dried zeolite (25 g) to 1 L of 0.06 mol / L AgNO3 solution for ion exchange and cover with aluminum foil. Adjust the pH to 4, the temperature to 60°C, stir for 5 h, collect the obtained solid by centrifugation, and wash it three times with deionized water to obtain the silver ion-exchanged zeolite.

[0166] Step 1 of this embodiment and (1), (3), and (4) in step 2 are the same as those in embodiment 1 and will not be described in detail.

[0167] Example 4

[0168] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and titanium ions loaded 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 (4) in step 2 of the preparation of the antibacterial agent is different. In this embodiment, (4) in step 2 of the preparation of the antibacterial agent is as follows:

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

[0171] Step 1 of this embodiment and (1), (2), and (3) in step 2 are the same as those in embodiment 1 and will not be described in detail.

[0172] Example 5

[0173] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and titanium ions loaded 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 (4) in step 2 of the preparation of the antibacterial agent is different. In this embodiment, (4) in step 2 of the preparation of the antibacterial agent is as follows:

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

[0176] Step 1 of this embodiment and (1), (2), and (3) in step 2 are the same as those in embodiment 1 and will not be described in detail.

[0177] Example 6

[0178] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and nickel ions loaded 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 of this embodiment are similar to those of embodiment 1, except that step 2 of the preparation of the antibacterial agent does not contain (1), that is, zeolite is not ion-exchanged with sodium ions.

[0180] Example 7

[0181] This embodiment provides an antibacterial agent, including 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 of this embodiment are similar to those of Embodiment 1, except that the inorganic carrier is different. In this embodiment, the inorganic carrier used is vermiculite.

[0183] Example 8

[0184] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and nickel ions loaded 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 preparation method of the antibacterial agent of this embodiment comprises the following steps:

[0186] 1. Pre-treatment

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

[0188] 2. Preparation of antibacterial agents

[0189] (1) The pre-treated carrier zeolite was added to a 0.6 mol / L NaCl solution, and NaOH was added to raise the pH value of the solution to 12, and ion exchange was performed for 3 hours. + and Cl - Remove by rinsing with deionized water.

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

[0191] (3) The silver-ion-exchanged zeolite was added to 1 L of a 0.06 mol / L Cu(NO3)2 solution, the pH value was adjusted to 6, the temperature was 65°C, and the solution was covered with aluminum foil and stirred for 7 h. The solid was collected by centrifugation and washed three times with deionized water to obtain the silver-ion and copper-ion-exchanged zeolite.

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

[0193] Example 9

[0194] This embodiment provides an antibacterial agent, including zeolite and silver ions, copper ions and nickel ions loaded 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 of this embodiment comprises the following steps:

[0196] 1. Pre-treatment

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

[0198] 2. Preparation of antibacterial agents

[0199] (1) The pre-treated carrier zeolite was added to a 0.45 mol / L NaCl solution, and NaOH was added to raise the pH value of the solution to 11.5. The ion exchange was performed for 2.5 hours. + and Cl - Remove by rinsing with deionized water.

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

[0201] (3) The silver-ion-exchanged zeolite was added to 1 L of a 0.05 mol / L Cu(NO3)2 solution, the pH value was adjusted to 4, the temperature was 55°C, and the solution was covered with aluminum foil and stirred for 6 h. The solid was collected by centrifugation and washed three times with deionized water to obtain the silver-ion and copper-ion-exchanged zeolite.

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

[0203] Comparative Example 1

[0204] Comparative Example 1 provides an antibacterial agent, including zeolite and silver ions and copper ions supported on the zeolite, in which the contents of silver ions and copper ions 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 the preparation step 2 of the antibacterial agent is different. In Comparative Example 1, the preparation step 2 of the antibacterial agent is as follows:

[0206] (1) The pre-treated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH value of the solution to 11, and ion exchange was performed for 2 hours. + and Cl - Remove by rinsing with deionized water.

[0207] (2) Add 25 g of the dried zeolite to 1 L of a 0.04 mol / L AgNO3 solution for ion exchange and cover with aluminum foil. Adjust the pH to 4, set the temperature to 60°C, stir for 5 h, collect the solid by centrifugation, and wash it three times with deionized water to obtain the silver ion-exchanged zeolite.

[0208] (3) The silver ion-exchanged zeolite was added to 1 L of a 0.04 mol / L Cu(NO3)2 solution, the pH value was adjusted to 4.5, the temperature was 60°C, covered with aluminum foil, stirred for 5 h, and the obtained solid was collected by centrifugation, washed three times with deionized water, and the obtained sample was dried at 80°C for 9 h and ground into an average particle size of 10 μm to 20 μm, thereby obtaining 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 described in detail.

[0210] Comparative Example 2

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

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

[0213] (1) The pre-treated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH value of the solution to 11, and ion exchange was performed for 2 hours. + and Cl - Remove by rinsing with deionized water.

[0214] (2) Add the treated and dried zeolite (25 g) to 1 L of 0.04 mol / L AgNO3 solution for ion exchange and cover with aluminum foil. Adjust the pH to 4, the temperature to 60°C, stir for 5 h, collect the solid by centrifugation, and wash it three times with deionized water to obtain the silver ion-exchanged zeolite.

[0215] (3) The silver ion-exchanged zeolite was added to 1 L of a 0.04 mol / L Ni(NO3)2 solution, the pH value was adjusted to 4.5, the temperature was 60°C, covered with aluminum foil, stirred for 5 h, and the solid was collected by centrifugation and washed three times with deionized water. The sample was dried at 80°C for 9 h and ground into an average particle size of 10 μm to 20 μm, thereby obtaining 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 described in detail.

[0217] Comparative Example 3

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

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

[0220] (1) The pre-treated carrier zeolite was added to a 0.3 mol / L NaCl solution, and NaOH was added to raise the pH value of the solution to 11, and ion exchange was performed for 2 hours. + and Cl - Remove by rinsing with deionized water.

[0221] (2) Add 25 g of the treated and dried zeolite to 1 L of a 0.04 mol / L AgNO3 solution for ion exchange and cover with aluminum foil. Adjust the pH to 4, set the temperature to 60°C, stir for 5 h, collect the solid by centrifugation, wash three times with deionized water, dry the sample at 80°C for 9 h, grind it into an average particle size of 10 μm to 20 μm, and 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 described in detail.

[0223] The antibacterial agents prepared in the above-mentioned embodiments and comparative examples are used to prepare powder coatings to obtain antibacterial coatings. Specifically, the antibacterial coatings are prepared by the following steps:

[0224] 1. Preparation of powder coating

[0225] (1) By weight, 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 were premixed and stirred thoroughly to obtain a premixed material, which was then sent into an ultrasonic disperser and dispersed at a frequency of 20 kHz for 20 min to obtain an ultrasonically dispersed mixture.

[0226] (2) The ultrasonically dispersed mixture is fed into a twin-screw extruder, and a molten extrudate is obtained through heating, melting, mixing and extrusion. The temperature of each zone of the twin-screw extruder is set as follows: the temperature of the first zone is 90°C, the temperature of the second zone is 110°C, and the temperature of the third zone is 200°C.

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

[0228] 2. Preparation of antibacterial coating

[0229] (1) High voltage electrostatic powder spraying

[0230] After the pre-treated substrate is baked and dehydrated, it enters the spray gun position of the dust-free powder spraying room through the conveyor chain for high-voltage electrostatic powder spraying. The high-voltage electrostatic spraying process parameters are as follows: electrostatic high voltage 50kV, electrostatic current 10μA, flow rate pressure 0.5MPa, atomization pressure 0.3MPa, and the spray gun mouth is 150mm away from the substrate.

[0231] (2) High temperature curing

[0232] After high-voltage electrostatic spraying, the substrate enters the high-temperature curing device through a conveyor chain. The temperature is set at 150°C and the baking time is 30 minutes to form an antibacterial coating on the surface of the substrate.

[0233] The following is the specific test part:

[0234] 1. Antibacterial performance test method

[0235] This experiment implements the antibacterial performance test method 1 (film method) in Appendix A of GB21551.2-2010 "Antibacterial, sterilization and purification functions of household appliances and similar electrical appliances". The sample to be tested is prepared into a sample of (50±2)×(50±2)mm. The control sample is a standard sample of sanitary high-density polyethylene (HDPE) injection molding, with a size of (50±2)mm×(50±2)mm and a thickness of no more than 5mm. Take 0.2mL of 106CFU / mL PBS test bacterial suspension of Escherichia coli, Staphylococcus aureus and Candida albicans and drop it on the sample to be tested and the control sample, cover it with polyethylene film, make the bacterial solution evenly contact each sample, and culture it for 12h at 37±1℃ and relative humidity RH>90%. Then take out each sample after co-culture, add 20mL of PBS eluent, ultrasonicate for 3min, take 0.2mL of eluent and inoculate it in nutrient agar medium, and count the viable bacteria after incubation at 37±1℃ for 24h. All samples used in the above experiments were sterilized in advance. By quantitatively inoculating bacteria on the samples to be tested and the control samples, the bacteria were evenly contacted with the samples by the film sticking method. After (24±1)h of incubation, the number of surviving bacteria in the two groups of samples was measured, and the sterilization rate of the samples to be tested was compared and calculated.

[0236] 2. Durability test method

[0237] After each sample to be tested has undergone an antibacterial test, it is immediately placed in a wet friction test machine. The wiping sponge moves at a frequency of (37±2) reciprocating times per minute, and the distance of one reciprocating stroke is 200 mm. The wet friction machine is equipped with a digital display counter, and the counter records a value of 1 for each completed reciprocating motion. The total mass of the fixture, weights, and wiping sponge is (300±10) g. An antibacterial test is performed after every 1000 cycles of friction.

[0238] The initial sterilization rate data of the antibacterial coating prepared by the antibacterial agent prepared in each embodiment and comparative example on different bacteria are shown in Table 1 below, and the durability data of the antibacterial coating on Escherichia coli are shown in Table 1 below. Figure 2 As shown. Figure 2 In the figure, the three lines at the top that are substantially overlapped show the durability of the antibacterial coatings prepared using the antibacterial agents prepared in Example 1, Example 8, and Example 9.

[0239] Table 1 Initial sterilization rate of antimicrobial coating against Escherichia coli, Staphylococcus aureus and Candida albicans

[0240]

[0241] From Table 1 and Figure 2 It can be seen that in the antibacterial agent of the embodiment, by adding Cu 2+ Reduced Ag + The reduction of the silver ion is protected, which not only reduces yellowing but also improves durability. The addition of the third metal ion increases the number of additional exchangeable cations, thereby extending the antibacterial durability and meeting the antibacterial requirements of sanitary products in special environments. However, the antibacterial coating prepared with the antibacterial agent of Comparative Examples 1 to 3 has a significantly lower sterilization rate against Escherichia coli after rubbing 5,000 times than that of the embodiment, and has poor durability.

[0242] Furthermore, by optimizing the third metal ion in the antimicrobial agent, it is helpful to further improve its durability. By first treating the zeolite with sodium salt, the zeolite and Ag + The ion exchange capacity of the antibacterial agent is beneficial to further improve its antibacterial property and durability. By optimizing the carrier type, it is beneficial to further improve the antibacterial property and durability of the antibacterial agent.

[0243] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. An antibacterial agent, characterized in that It comprises an inorganic carrier and silver ions, copper ions and a third metal ion loaded on the inorganic carrier; Wherein, the third metal ion includes one or more of nickel ion, titanium ion, manganese ion and zinc ion; In the antibacterial agent, the content of the silver ions>the content of the copper ions≥the content of the third metal ions.

2. The antibacterial agent according to claim 1, characterized in that The third metal ion comprises nickel ion; and / or, The inorganic carrier includes one or more of zeolite, vermiculite, montmorillonite, mesoporous silica and talc. Optionally, the inorganic carrier includes zeolite.

3. The antibacterial agent according to claim 1 or 2, characterized in that In the antibacterial agent, the content of silver ions is 0.6 g / meq to 1.12 g / meq; and / or, The content of the copper ion is 0.3 g / meq to 0.7 g / meq; and / or, The content of the third metal ion is 0.3 g / meq~0.5 g / meq.

4. A method for preparing an antibacterial agent, characterized in that: The steps include: The inorganic carrier is subjected to ion exchange with the silver ions, copper ions and the third metal ions to prepare an antibacterial agent loaded with the silver ions, copper ions and the third metal ions; Wherein, the third metal ion includes one or more of nickel ion, titanium ion, manganese ion and zinc ion; in the antibacterial agent, the content of the silver ion> the content of the copper ion≥ the content of the third metal ion.

5. The method for preparing the antibacterial agent according to claim 4, characterized in that: The step of ion exchanging the inorganic carrier with the silver ions, the copper ions and the third metal ions comprises: placing the inorganic carrier in a silver salt solution, a copper salt solution and a salt solution containing the third metal ion in sequence, stirring and reacting, so that the inorganic carrier performs ion exchange with the silver ions, the copper ions and the third metal ions in sequence; Optionally, the concentration of the silver salt solution is 0.02mol / L~0.06mol / L; Optionally, the concentration of the copper salt solution is 0.04 mol / L to 0.06 mol / L; Optionally, the concentration of the salt solution containing the third metal ion is 0.02 mol / L to 0.05 mol / L.

6. The method for preparing the antibacterial agent according to claim 5, characterized in that: Meet one or more of the following conditions: (1) The silver salt solution includes a silver nitrate solution; (2) The copper salt solution includes copper nitrate solution; (3) the salt solution containing the third metal ion includes one or more of a nickel nitrate solution, a titanium nitrate solution, a manganese nitrate solution and a zinc nitrate solution. Optionally, the salt solution containing the third metal ion includes a nickel nitrate solution; (4) Each stirring reaction time is 5h~7h; (5) The pH of each stirring reaction is 4-6; (6) Each stirring reaction is carried out at a temperature of 55°C to 65°C in a dark environment.

7. The method for preparing the antibacterial agent according to any one of claims 4 to 6, characterized in that: Before the step of exchanging the inorganic carrier with silver ions, copper ions and the third metal ions, 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 for 2 h to 3 h at a pH of 11 to 12.

8. A powder coating, characterized in that: The invention comprises the antibacterial agent according to any one of claims 1 to 3 or the antibacterial agent prepared by the preparation method according to any one of claims 4 to 7.

9. The powder coating according to claim 8, characterized in that Calculated by weight, it includes: 35 to 60 parts of resin, 15 to 30 parts of antibacterial agent, 10 to 20 parts of pigment and filler, 2 to 5 parts of curing agent and 0.6 to 2.5 parts of auxiliary agent; Optionally, the auxiliary agent includes 0.4 to 1.5 parts of a leveling agent and 0.2 to 1 part of benzoin; Optionally, the average particle size of the powder coating is 1 μm to 35 μm.

10. A product with antibacterial function, characterized in that: It comprises a substrate and an antibacterial coating arranged on the surface of the substrate, wherein the antibacterial coating is obtained by spraying and curing the powder coating according to any one of claims 8 to 9; Optionally, the products with antibacterial function include kitchen and bathroom hardware products.

11. A method for preparing a product with antibacterial function, characterized in that: The steps include: Spraying the powder coating according to any one of claims 8 to 9 on the surface of a substrate and curing the coating to prepare the product having an antibacterial function; Optionally, the process parameters of spraying 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 the distance between the spray gun nozzle and the substrate is 150mm~200mm; Optionally, the curing temperature is 150° C. to 200° C., and the curing time is 15 min to 30 min.

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