An antibacterial agent, its preparation method, antibacterial masterbatch, and its application.

Abstract

The application discloses an antibacterial agent and a preparation method, antibacterial master batch and application thereof. The chemical composition of the antibacterial agent is Ag x Zn y Zr z (PO4)3, wherein 0

Description

Technical Field

[0001] This invention relates to an antibacterial agent, its preparation method, antibacterial masterbatch, and its application. Background Technology

[0002] With increasing awareness of health and environmental protection, antibacterial materials are being used more and more widely in textiles, plastics, and other fields. These everyday materials often become breeding grounds for microorganisms, increasing the risk of disease transmission. Inorganic antibacterial agents are favored because they are less likely to develop drug resistance and have good heat resistance, but they generally suffer from problems such as insufficient antibacterial durability, poor stability, high required dosage leading to increased costs, and potential impact on substrate performance.

[0003] While silver-based antibacterial agents possess broad-spectrum and highly effective antibacterial properties, they also suffer from inherent drawbacks such as easy discoloration, poor dispersibility in resin-based substrates, and short shelf life due to the explosive release of silver ions. To address these shortcomings, combining silver with materials like zinc oxide is a common approach. However, existing silver-zinc composite antibacterial agents have not yet achieved ideal results in terms of long-term, controllable, and sustained release of silver ions, improved compatibility with resins, and long-term color stability, thus failing to meet the demands for highly effective and durable applications.

[0004] For example, patent CN114903053A discloses an antibacterial agent, antibacterial masterbatch, and antibacterial tableware, as well as their preparation method. This patent uses zinc-aluminum hydrotalcite as the antibacterial agent with a silver loading of not less than 1.5%, and prepares the antibacterial agent by immersing the zinc-aluminum hydrotalcite in a solution containing silver ions and then calcining it. However, this patent still has the problem that the structure and morphology of the zinc-aluminum hydrotalcite need further optimization to improve its specific surface area and antibacterial activity, and it does not solve the problem of how to maintain the long-term sustained release of silver ions. Patent CN118303425A discloses a method for preparing a nano-zinc oxide antibacterial agent doped with rare earth elements. This method involves dissolving sucrose in deionized water, adding a zinc precursor and a rare earth element precursor, adding a complex and adjusting the pH value during constant-temperature magnetic stirring, and finally obtaining the nano-zinc oxide antibacterial agent doped with rare earth elements through calcination. This method solves the problems of easy agglomeration, poor antibacterial effect, and large dosage required for pure nano-zinc oxide antibacterial agents during use. However, this patent still faces the challenge of how to further improve the efficiency of the preparation method and reduce the preparation cost.

[0005] Therefore, there is an urgent need to develop a new type of antibacterial agent that can achieve long-term and controllable sustained release of silver ions while maintaining high efficiency and broad-spectrum antibacterial properties, and fundamentally solve the problems of silver-based products being prone to discoloration and having poor compatibility with resins, thereby meeting the comprehensive requirements of high-end antibacterial materials for durability, safety and appearance stability. Summary of the Invention

[0006] The present invention provides an antibacterial agent, a preparation method thereof, an antibacterial masterbatch and an application, aiming to solve the problems of the existing antibacterial agents, such as the non-persistent silver ion slow-release effect, poor compatibility with resin substrates and easy discoloration. The antibacterial agent of the present invention can maintain excellent antibacterial performance while having excellent long-term silver ion slow-release performance and anti-discoloration performance.

[0007] The present invention solves the above technical problems through the following technical solutions.

[0008] The present invention provides an antibacterial agent with the following chemical composition: Ag

[0015] , , , , , , ,

[0014] Zn y Zr z (PO4)3, where 0 < x + y < 6, and z is 0 - 2.25 and not 0.

[0009] In the present invention, preferably, x + y satisfies 1 < x + y < 4; more preferably, x + y satisfies 1 < x + y < 3.5, for example, the value of x + y is 1.08.

[0010] Among them, x can be 0 - 4 and not 0, preferably 0.1 - 3, more preferably 0.1 - 2, for example 0.36. <​​​​​​​​​​​​​​​​​​​​

[0016] In this invention, in step S1, the concentration of silver salt in the aqueous solution containing silver salt and zinc salt can be 0.01-0.2 mol / L, preferably 0.025-0.15 mol / L, for example 0.03 mol / L, 0.035 mol / L, 0.1 mol / L or 0.11 mol / L.

[0017] In this invention, in step S1, the zinc salt may be one or more of zinc nitrate, zinc sulfate, and zinc acetate, such as zinc nitrate.

[0018] In this invention, in step S1, the concentration of zinc salt in the aqueous solution containing silver salt and zinc salt can be 0.01-0.05 mol / L, preferably 0.015-0.03 mol / L, more preferably 0.018-0.026 mol / L, for example 0.02 mol / L, 0.025 mol / L or 0.028 mol / L.

[0019] In this invention, in step S1, the molar ratio of the silver salt to the zinc salt can be 1:(0.05-2), preferably 1:(0.1-1.5), more preferably 1:(0.15-1), for example 1:0.18, 1:0.2, 1:0.28, 1:0.67, 1:0.71 or 1:0.93.

[0020] In this invention, in step S1, the complexing agent can be ammonia.

[0021] The concentration of the ammonia water can be 25-28%, where % refers to the percentage of the mass of ammonia in the ammonia water relative to the total mass of the ammonia water.

[0022] In this invention, in step S1, the ratio of the number of moles of the complexing agent to the total number of moles of silver ions and zinc ions in the aqueous solution containing silver salt and zinc salt can be (1-3):1, for example 2:1, 2.2:1 or 2.6:1.

[0023] In this invention, in step S1, the pH value of the mixed solution before mixing can be 10-12.

[0024] In this invention, in step S1, the mixing can be carried out under stirring conditions as is common in the art; the stirring time is preferably 10-30 min, for example 10 min, 16 min or 30 min.

[0025] In this invention, in step S2, the zirconium phosphate can be used as a reaction raw material in the form of zirconium hydrogen phosphate monohydrate.

[0026] In this invention, in step S2, the solid-liquid ratio of the zirconium phosphate to the complexed ion solution can be 1g:(5-15)mL, preferably 1g:(8-10)mL, for example 1g:8.8mL or 1g:10mL.

[0027] In this invention, in step S2, the reaction can be carried out under stirring conditions. The stirring time is preferably 0.5-12 hours, more preferably 1-8 hours, for example 0.5 hours, 1 hour, or 4.5 hours.

[0028] In this invention, in step S2, the pH value of the solution during the reaction can be 10-12.

[0029] In this invention, step S2 may further include a drying step after the reaction.

[0030] The drying temperature can be 60-150℃, preferably 80-130℃, more preferably 90-120℃, and even more preferably 100-120℃, such as 100℃, 105℃ or 106℃.

[0031] The drying time can be 12-48 hours, more preferably 18-40 hours, such as 18 hours, 22 hours or 32 hours.

[0032] In this invention, in step S3, the mass ratio of the zirconium phosphate-supported zinc precursor to the zinc oxide can be 100:(5-40), for example 100:8, 100:10, 100:15, 100:16, 100:20, or 100:35. In this invention, zinc oxide acts as a crystallizing agent to aid in crystal formation.

[0033] In this invention, in step S3, the dispersant may be one or more of polyvinylpyrrolidone, polyacrylamide, and polypropylene glycol.

[0034] In this invention, in step S3, the mass percentage of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide can be 0-50%, preferably 10-45%, more preferably 15-45%, for example 15%, 32%, 40% or 50%.

[0035] In this invention, in step S3, the dispersant is preferably 15% by mass of polyacrylamide, 50% by mass of polypropylene glycol, 50% by mass of polyacrylamide, 50% by mass of polyvinylpyrrolidone, 40% by mass of polyacrylamide, or 32% by mass of polyacrylamide.

[0036] In this invention, step S3 may optionally include a crushing process before calcination.

[0037] In this invention, step S3, the calcination may include a first calcination and a second calcination.

[0038] The heating rate of the first calcination can be 2-5℃ / min, preferably 2.5-4.8℃ / min, more preferably 2.8-4.5℃ / min, for example 2.8℃ / min, 4.4℃ / min or 4.8℃ / min.

[0039] The temperature of the first calcination can be 100-500℃, preferably 200-400℃, such as 200℃, 320℃ or 350℃.

[0040] The first calcination time can be 1-5 hours, preferably 1.5-5 hours, more preferably 2-5 hours, such as 2 hours or 2.2 hours.

[0041] The heating rate of the second calcination can be 1-5℃ / min, preferably 1.5-4.5℃ / min, more preferably 2-4℃ / min, for example 3℃ / min, 3.5℃ / min or 4℃ / min.

[0042] The second calcination temperature can be 600-1200℃, preferably 700-1100℃, more preferably 750-1000℃, such as 750℃, 820℃ or 900℃.

[0043] The second calcination time can be 1-15h, preferably 3-12h, more preferably 5-12h, for example 2.5h, 5h or 11h.

[0044] In this invention, step S3 may further include a crushing process after calcination.

[0045] The crushing process can be carried out using airflow crushing.

[0046] In this invention, the particle size D98 of the antibacterial agent can be 2-5 μm, for example 3.125 μm, 3.174 μm, 3.235 μm, 3.48 μm, 3.492 μm, 3.5 μm, 3.502 μm, 3.511 μm, 3.541 μm or 3.967 μm.

[0047] The present invention also provides an antibacterial agent, which is prepared by the above-described method for preparing antibacterial agents.

[0048] In this invention, the particle size D98 of the antibacterial agent can be 2-5 μm, for example 3.125 μm, 3.174 μm, 3.235 μm, 3.48 μm, 3.492 μm, 3.5 μm, 3.502 μm, 3.511 μm, 3.541 μm or 3.967 μm.

[0049] The present invention also provides an antibacterial masterbatch, the components of which include the above-mentioned antibacterial agent.

[0050] In this invention, the antibacterial agent accounts for 5-15% of the mass of the antibacterial masterbatch, for example, 10%.

[0051] The present invention also provides the application of the above-mentioned antibacterial agent or the above-mentioned antibacterial masterbatch in the preparation of antibacterial materials.

[0052] In this invention, the antibacterial material may be an antibacterial pipe or an antibacterial sample.

[0053] In this invention, the amount of antibacterial masterbatch added to the antibacterial material can be 1-5%, for example 2%.

[0054] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0055] The reagents and raw materials used in this invention are all commercially available.

[0056] The positive and progressive effects of this invention are as follows: 1. The antibacterial agent of this invention has high antibacterial efficiency and long-lasting safety: the antibacterial rate against Escherichia coli and Staphylococcus aureus reaches over 99.9%. Zinc ions, as a release buffer, structural stabilizer, and environmental regulator, synergistically achieve long-lasting sustained release of silver ions and significantly reduce the amount of silver ion leaching (as low as 0.7 ppb), thus improving safety in use.

[0057] 2. The antibacterial agent of this invention has excellent color stability: by stabilizing the ions within a dense crystal structure, the product fundamentally solves the problem of easy discoloration and yellowing of silver-based antibacterial agents. The resulting antibacterial agent is pure white, and the yellow index (YI value) of the prepared masterbatch is significantly reduced (as low as 2.67). It has good compatibility in resin and can maintain the aesthetic appearance of the product for a long time.

[0058] 3. The antibacterial agent of the present invention has a stable carrier structure and high stability: Ag + With Zn 2+ Firmly fixed within a NASICON-type zirconium phosphate lattice, it forms a dense, non-porous microstructure. This not only fundamentally cuts off the free migration channels of ions, reducing dissolution, but also endows the material with excellent chemical stability and durability, extending its service life.

[0059] 4. The preparation method of the present invention can effectively reduce the amount of precious metal silver while ensuring high performance, and at the same time ensure that the silver ion utilization rate reaches more than 99%, thereby reducing raw material costs and reducing wastewater pollution to the environment; the one-step process simplifies the production process and is more environmentally friendly and economical. Attached Figure Description

[0060] Figure 1 The image shows the XRD pattern of the antibacterial agent prepared in Example 8.

[0061] Figure 2 for Figure 1 A magnified view of 2θ in the 11°-64° region. Detailed Implementation

[0062] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0063] Example 1

[0064] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 10 min to obtain a complex ion solution.

[0065] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.03 mol / L AgNO3 and 0.028 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia in the ammonia solution relative to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2:1.

[0066] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 1h to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 100℃ for 18h to obtain the zirconium phosphate silver zinc precursor.

[0067] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:10, add 15% by mass of polyacrylamide (dispersant), where % refers to the mass percentage of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide; after coarsely crushing into powder, heat to 350℃ in air at a heating rate of 2.8℃ / min and hold for 2 hours; then continue heating to 750℃ at a heating rate of 3.5℃ / min and hold for 5 hours, and allow to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0068] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0069] Example 2

[0070] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 10 min to obtain a complex ion solution.

[0071] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.1 mol / L AgNO3 and 0.028 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia mass in the ammonia solution to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2:1.

[0072] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 1h to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 100℃ for 18h to obtain the zirconium phosphate silver zinc precursor.

[0073] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:10, and add 50% by mass of polypropylene glycol (dispersant). The percentage refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide. After coarsely crushing into powder, heat the mixture to 350℃ in air at a heating rate of 2.8℃ / min and hold for 2 hours. Then, continue heating to 750℃ at a heating rate of 3.5℃ / min and hold for 5 hours. Allow it to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0074] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0075] Example 3

[0076] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 10 min to obtain a complex ion solution.

[0077] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.1 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia mass in the ammonia solution to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2:1.

[0078] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 1h to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 100℃ for 18h to obtain the zirconium phosphate silver zinc precursor.

[0079] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:10, add 50% by mass of polyacrylamide (dispersant), where % refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide; after coarsely crushing into powder, heat to 350℃ in air at a heating rate of 2.8℃ / min and hold for 2 hours; continue heating to 750℃ at a heating rate of 3.5℃ / min and hold for 5 hours, then allow to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0080] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0081] Example 4

[0082] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 10 min to obtain a complex ion solution.

[0083] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.03 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia in the ammonia solution relative to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2:1.

[0084] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 1h to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 100℃ for 18h to obtain the zirconium phosphate silver zinc precursor.

[0085] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:10, and add 50% by mass of polyvinylpyrrolidone (dispersant). The percentage refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide. After coarsely crushing into powder, heat the mixture to 350℃ in air at a heating rate of 2.8℃ / min and hold for 2 hours. Continue heating the mixture to 750℃ at a heating rate of 3℃ / min and hold for 5 hours. Allow it to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0086] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0087] Example 5

[0088] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 10 min to obtain a complex ion solution.

[0089] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.1 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia mass in the ammonia solution to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2:1.

[0090] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 1h to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 100℃ for 18h to obtain the zirconium phosphate silver zinc precursor.

[0091] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:35, add 40% by mass of polyacrylamide (dispersant), where % refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide; after coarsely crushing into powder, heat to 350℃ in air at a heating rate of 2.8℃ / min and hold for 2 hours; continue heating to 750℃ at a heating rate of 3℃ / min and hold for 5 hours, then allow to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0092] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0093] Example 6

[0094] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 10 min to obtain a complex ion solution.

[0095] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.1 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia mass in the ammonia solution to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2:1.

[0096] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 1h to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 100℃ for 18h to obtain the zirconium phosphate silver zinc precursor.

[0097] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:8, add 40% by mass of polyacrylamide (dispersant), where % refers to the mass percentage of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide; after coarsely crushing into powder, heat to 350℃ in air at a heating rate of 2.8℃ / min and hold for 2 hours; continue heating to 750℃ at a heating rate of 3℃ / min and hold for 5 hours, then allow to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0098] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0099] Example 7

[0100] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 10 min to obtain a complex ion solution.

[0101] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.1 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia mass in the ammonia solution to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2:1.

[0102] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 1h to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 100℃ for 18h to obtain the zirconium phosphate silver zinc precursor.

[0103] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:20, and add 50% by mass of polypropylene glycol (dispersant). The percentage refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide. After coarsely crushing into powder, heat the mixture to 350℃ in air at a heating rate of 2.8℃ / min and hold for 2 hours. Continue heating the mixture to 750℃ at a heating rate of 3℃ / min and hold for 5 hours. Allow it to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0104] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0105] Example 8

[0106] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, stir for 30 min to obtain a complex ion solution.

[0107] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.035 mol / L AgNO3 and 0.025 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia mass in the ammonia solution to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2.2:1.

[0108] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:10mL, control the pH between 10 and 12, stir for 30min to obtain a mixed solution; filter the mixed solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 105℃ for 32h to obtain the zirconium phosphate silver zinc precursor.

[0109] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:15, and add 50% by mass of polyvinylpyrrolidone (dispersant). The percentage refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide. After coarsely crushing into powder, heat the mixture to 200℃ in air at a heating rate of 4.8℃ / min and hold for 2.2h. Continue heating the mixture to 820℃ at a heating rate of 4℃ / min and hold for 11h. Allow it to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0110] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0111] Example 9

[0112] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, and stir for 16 min to obtain a complex ion solution.

[0113] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.11 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia in the ammonia solution relative to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2.6:1.

[0114] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:8.8mL, control the pH between 10 and 12, stir for 4.5h to obtain a mixed solution; filter the product solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 106℃ for 22h to obtain the zirconium phosphate silver zinc precursor.

[0115] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:16, add 32% by mass of polyacrylamide (dispersant), where % refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide; after coarsely crushing into powder, heat to 320℃ in air at a heating rate of 4.4℃ / min and hold for 2h; continue heating to 900℃ at a heating rate of 4℃ / min and hold for 2.5h, then allow to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0116] Zirconium phosphate loaded with silver and zinc was subjected to air jet milling to control its particle size D98 to around 3.5 μm.

[0117] Comparative Example 1

[0118] S1. Add ammonia to an aqueous solution of AgNO3, control the pH of the solution to 10-12, and stir for 16 minutes to obtain a complex ion solution.

[0119] The concentration of AgNO3 in the aqueous solution is 0.11 mol / L; the concentration of ammonia is 25-28% (% refers to the percentage of ammonia in the ammonia solution relative to the total mass of the ammonia solution); and the ratio of the number of moles of ammonia to the number of moles of silver ions in the ammonia solution is 2.6:1.

[0120] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:8.8mL, control the pH between 10 and 12, stir for 4.5h to obtain a mixed solution; filter the product solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 106℃ for 22h to obtain the zirconium phosphate silver zinc precursor.

[0121] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:16, add 32% by mass of polyacrylamide (dispersant), where % refers to the mass percentage of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide; after coarsely crushing into powder, heat to 320℃ in air at a heating rate of 4.4℃ / min and hold for 2 hours; continue heating to 900℃ at a heating rate of 4℃ / min and hold for 2.5 hours, then allow to cool naturally to room temperature to obtain the product.

[0122] The product was subjected to airflow crushing to control its particle size D98 to around 3.5 μm.

[0123] Comparative Example 2

[0124] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, and stir for 16 min to obtain a complex ion solution.

[0125] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.11 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia in the ammonia solution relative to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2.6:1.

[0126] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:8.8mL, control the pH between 10 and 12, stir for 4.5h to obtain a mixed solution; filter the product solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 106℃ for 22h to obtain the zirconium phosphate silver zinc precursor.

[0127] S3. Add 32% by mass of polyacrylamide (dispersant) to the zirconium phosphate silver-zinc precursor. The percentage refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor. After coarsely crushing into powder, heat to 320℃ in air at a heating rate of 4.4℃ / min and hold for 2 hours. Continue heating to 900℃ at a heating rate of 4℃ / min and hold for 2.5 hours. Allow to cool naturally to room temperature to obtain the product.

[0128] The product was subjected to airflow crushing to control its particle size D98 to around 3.5 μm.

[0129] Comparative Example 3

[0130] S1. Add ammonia to an aqueous solution of AgNO3 and Zn(NO3)2, control the pH of the solution to 10-12, and stir for 16 min to obtain a complex ion solution.

[0131] The aqueous solution of AgNO3 and Zn(NO3)2 contains 0.11 mol / L AgNO3 and 0.02 mol / L Zn(NO3)2. The concentration of ammonia is 25-28% (% refers to the percentage of ammonia in the ammonia solution relative to the total mass of the ammonia solution), and the ratio of the number of moles of ammonia in the ammonia solution to the total number of moles of silver and zinc ions is 2.6:1.

[0132] S2. Add Zr(HPO4)2·H2O to the complexed ion solution at a solid-liquid ratio of 1g:8.8mL, control the pH between 10 and 12, stir for 4.5h to obtain a mixed solution; filter the product solution to obtain a filter cake, wash it three times with deionized water, filter it again, and dry it at 106℃ for 22h to obtain the zirconium phosphate silver zinc precursor.

[0133] S3. Mix the zirconium phosphate silver-zinc precursor with ZnO at a mass ratio of 100:50, add 32% by mass of polyacrylamide (dispersant), where % refers to the mass of the dispersant relative to the total mass of the zirconium phosphate silver-zinc precursor and zinc oxide; after coarsely crushing into powder, heat to 320℃ in air at a heating rate of 4.4℃ / min and hold for 2h; continue heating to 900℃ at a heating rate of 4℃ / min and hold for 2.5h, then allow to cool naturally to room temperature to obtain zirconium phosphate silver-zinc.

[0134] Comparative Example 4

[0135] S1. Take 5g of zirconium phosphate powder, add 150mL of 0.04N silver nitrate solution, stir at room temperature, and slowly adjust the pH of the system to ≥10 with sodium hydroxide solution, and continue stirring for 4h.

[0136] S2. Wash the filter cake with deionized water until Ag is free. + The filtrate was tested with dilute hydrochloric acid and no white precipitate was found. After drying at 60°C, the silver zirconium phosphate precursor was obtained.

[0137] S3. Add 5-10 wt% of the zirconium silver phosphate precursor to a polyolefin (molecular weight 6000-10000), grind and mix thoroughly. Transfer the mixture to an alumina crucible, place it in a muffle furnace, heat to 1000℃ at 5℃ / min, hold for 2-3 hours, and then allow to cool naturally to room temperature to obtain a white powdery product, which is a flaky crystal. Its average particle size is less than 2μm, the silver ion weight content is about 5%, and the zirconium phosphate content is about 95%.

[0138] Example 1: Product Structure Characterization

[0139] The antibacterial agent sample prepared in Example 8 was subjected to X-ray diffraction (XRD) and X-ray fluorescence spectroscopy (XRF) tests to determine its phase composition and elemental content.

[0140] 1. X-ray diffraction (XRD) test

[0141] XRD test results are as follows Figure 1 As shown, a magnified view of 2θ in the 11°-64° region is shown below. Figure 2 As shown in the figure, the antibacterial agent sample prepared in Example 8 contains major elements such as Zn, Ag, Zr, and P. Specifically: (1) Determination of ZnO: The diffraction peaks that appear at 2θ=31.22°, 35.48°, 36.339°, 47.86°, 55.28° match the ZnO standard card well, indicating that the ZnO crystal structure is maintained and no obvious chemical changes have occurred.

[0142] (2) Evidence of the reaction between Ag and Zn: No diffraction peaks corresponding to metallic Ag (characteristic peaks at approximately 38.1° and 44.3°) or metallic Zn (characteristic peak at approximately 39°) were observed in the spectrum, indicating that both have reacted. The peak at 36.339° is more likely to be a composite diffraction peak formed by ZnO and zirconium phosphate.

[0143] (3) Interpretation of Zirconium Phosphate Phase and Peak Shift: The theoretical characteristic peaks (20.2°, 25.0°, 31.3°) of the sintered zirconium pyrophosphate are similar to the measured peak positions (20.34°, 24.86°, 31.22°) but show a shift. Among the measured peaks, 20.34°, 23.54°, and 31.22° are similar to the characteristic peaks of silver zirconium phosphate, while 20.34°, 23.54°, and 29.2° are similar to the characteristic peaks of zinc zirconium phosphate. This shift is likely due to Ag. + Zn 2+ Lattice distortion caused by entering the lattice.

[0144] 2. X-ray fluorescence spectroscopy (XRF) test

[0145] The XRF test results are shown in Table 1, which gives the mass percentage of each major oxide.

[0146] Table 1. XRF elemental analysis results Note: Other components include MnO, Fe2O3, HfO2, etc., with a total amount of less than 1 wt%.

[0147] Based on the XRF data in Table 1, the molar ratios of key elements in the sample were calculated, as shown in Table 2.

[0148] Table 2. Element molar ratios calculated from XRF data Note: The total Zn content is higher than the theoretical value because ZnO was added as an additive during the preparation process. The detected product contained an excess of free zinc oxide, which did not enter the main phase lattice but was included in the total XRF analysis.

[0149] Based on the data in Table 2, the molar ratio of metallic elements Ag, Zr, and P is: n(Ag):n(Zr):n(P) = 0.0620:0.3145:0.5188. Using phosphate (PO4)3 as a baseline (i.e., setting n(P) = 3), this ratio is normalized, and the coefficient x for Ag is calculated to be approximately 0.36, and the coefficient z for Zr is approximately 1.8. Finally, based on the charge balance principle, the chemical formula of the product is derived as Ag. 0.36 Zn 0.72 Zr 1.8 (PO4)3.

[0150] Example 2 Performance Test

[0151] 1. Yellow Index (YI value) Test

[0152] The Yellow Index (YI value) is an optical indicator used to quantitatively evaluate the degree to which a material deviates from colorless and transparent or white in the visible light range, characterizing its tendency to yellow.

[0153] Using the antibacterial agents prepared in each embodiment and comparative example as raw materials, antibacterial masterbatch with an antibacterial agent content of 10% was prepared, and its yellow index (YI value) was tested using a benchtop spectrophotometer. The results are shown in Table 3.

[0154] 2. Silver dissolution test

[0155] Silver leaching properties were tested according to the national standard GB / T 17219-1998. Using the antibacterial agents silver-zinc prepared in the various examples and comparative examples, an antibacterial masterbatch with an antibacterial agent content of 10% was first prepared. Then, this antibacterial masterbatch was used to prepare pipes (specifications: length 1m, diameter 1cm) at a mass fraction of 2%. A standard immersion leaching test was conducted on the pipes to determine the amount of silver ions leached out. The results are shown in Table 3.

[0156] 3. Antibacterial test

[0157] The antibacterial properties were tested according to JC / T 939-2004. Using the antibacterial agents prepared in the various examples and comparative examples, an antibacterial masterbatch with an antibacterial agent content of 10% was first prepared. Then, this antibacterial masterbatch was injection molded at a mass fraction of 2% to obtain plastic samples with dimensions of 5cm × 5cm. Six parallel experiments were performed on each sample, and its antibacterial rate was calculated. The average results are shown in Table 3.

[0158] Table 3 Results of YI value test, silver leaching test, and antibacterial test

[0159] As shown in Table 3, the antibacterial agents prepared in each embodiment of the present invention, while maintaining excellent antibacterial performance (antibacterial rate reaching 99.9%), reduced the amount of silver ion leaching, achieving excellent long-lasting and sustained-release performance of silver ions, and significantly improved the product's anti-discoloration performance (low YI value of masterbatch). Specifically: Comparative Example 1, based on Example 9, did not add Zn(NO3)2: compared to Example 9, the silver ion dissolution rate of its masterbatch increased from 0.7018 ppb to 1.594 ppb. This result directly confirms that the silver-zinc dual-ion system can effectively inhibit silver dissolution and achieve a sustained-release effect. Zinc ions in this system have three functions: acting as a release buffer to mitigate the initial burst release of silver; acting as a structural stabilizer to maintain the long-term stability of the carrier framework and ion channels; and acting as an environmental regulator, the sacrificial anode, providing a continuous and controllable release driving force for silver ions through electrochemical corrosion. This synergistically achieves long-term, controllable sustained release of silver ions, improving the safety of the material while ensuring antibacterial activity.

[0160] Comparative Example 2, based on Example 9, did not include ZnO: its product was gray in color, which contrasted sharply with the white appearance of the various embodiments of the present invention, indicating that the addition of zinc oxide is crucial to maintaining the white appearance of the product.

[0161] Comparative Example 3, based on Example 9, added an excessive amount of ZnO: the product agglomerated and could not be further processed or applied, proving that the amount of zinc oxide used needs to be controlled within a reasonable range.

[0162] Comparative Example 4 is a commercially available product: its masterbatch has a YI value as high as 8.55 and a silver ion dissolution rate of 2.0495 ppb, both significantly higher than those in the embodiments of this invention. This clearly demonstrates that this invention has outstanding advantages in controlling product color and ensuring safety in use.

[0163] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.

Claims

1. An antibacterial agent, characterized in that, Ag x Zn y Zr z (PO4)3, wherein 0 < x + y < 6, z is 0-2.25 and not 0.

2. The antiseptic agent according to claim 1, wherein x + y satisfies 1 < x + y < 4; preferably, x + y satisfies 1 < x + y < 3.5, for example, the value of x + y is 1.08; Preferably, x is from 0 to 4 and not 0, preferably from 0.1 to 3, more preferably from 0.1 to 2, for example 0.36; Preferably, y is from 0 to 2 and not 0, preferably from 0.1 to 1.2, more preferably from 0.1 to 1, for example 0.72; And / or, z is from 1 to 2, preferably from 1.5 to 2, for example 1.8; And / or, the particle size D98 of the antibacterial agent is 2 - 5 μm, for example 3.125 μm, 3.174 μm, 3.235 μm, 3.48 μm, 3.492 μm, 3.5 μm, 3.502 μm, 3.511 μm, 3.541 μm or 3.967 μm.

3. A method for preparing an antibacterial agent, characterized by, It includes the following steps: S1. Mix an aqueous solution containing silver salt and zinc salt with a complexing agent to obtain a complex ion solution; S2. React a mixed solution containing the complex ion solution and zirconium phosphate to obtain a zirconium phosphate - supported silver - zinc precursor; S3. Mix the zirconium phosphate - supported silver - zinc precursor with zinc oxide and a dispersant and then calcine to obtain an antibacterial agent; the mass ratio of the zirconium phosphate - supported silver - zinc precursor to the zinc oxide is 100:(5 - 45).

4. The method for preparing an antibacterial agent according to claim 3, wherein In step S1, the silver salt is one or more of silver nitrate, silver chlorate and silver acetate; And / or, in step S1, the zinc salt is one or more of zinc nitrate, zinc sulfate and zinc acetate; And / or, in step S1, in the aqueous solution containing silver salt and zinc salt, the concentration of the silver salt is 0.01 - 0.2 mol / L, preferably 0.025 - 0.15 mol / L, for example 0.03 mol / L, 0.035 mol / L, 0.1 mol / L or 0.11 mol / L; And / or, in step S1, in the aqueous solution containing silver salt and zinc salt, the concentration of the zinc salt is 0.01 - 0.05 mol / L, preferably 0.015 - 0.03 mol / L, more preferably 0.018 - ​ 5. The method for preparing the antibacterial agent as described in claim 3, characterized in that, ​ ​ ​ And / or, in step S1, the mixing is carried out under stirring conditions; the stirring time is preferably 10-30 min, for example 10 min, 16 min or 30 min; And / or, in step S2, the zirconium phosphate is used as a reaction raw material in the form of zirconium hydrogen phosphate monohydrate; And / or, in step S2, the solid-liquid ratio of the zirconium phosphate to the complexed ion solution is 1g:(5-15)mL, preferably 1g:(8-10)mL, for example 1g:8.8mL or 1g:10mL; And / or, in step S2, the reaction is carried out under stirring conditions; the stirring time is preferably 0.5-12h, more preferably 1-8h, for example 0.5h, 1h or 4.5h; And / or, in step S2, the pH of the solution during the reaction is 10-12; And / or, in step S2, the reaction is further followed by a drying step; Preferably, the drying temperature is 60-150°C, more preferably 80-130°C, more preferably 90-120°C, and even more preferably 100-120°C, for example 100°C, 105°C, or 106°C; Preferably, the drying time is 12-48 hours, more preferably 18-40 hours, for example 18 hours, 22 hours or 32 hours.

6. The method for preparing the antibacterial agent as described in claim 3, characterized in that, In step S3, the mass ratio of the zinc zinc phosphate precursor to the zinc oxide is 100:(5-40), for example, 100:8, 100:10, 100:15, 100:16, 100:20 or 100:

35. And / or, in step S3, the dispersant is one or more of polyvinylpyrrolidone, polyacrylamide, and polypropylene glycol; And / or, in step S3, the mass percentage of the dispersant relative to the total mass of the zirconium phosphate-supported silver-zinc precursor and zinc oxide is 0-50%, preferably 10-45%, more preferably 15-45%, for example 15%, 32%, 40% or 50%; Preferably, in step S3, the dispersant is 15% by mass of polyacrylamide, 50% by mass of polypropylene glycol, 50% by mass of polyacrylamide, 50% by mass of polyvinylpyrrolidone, 40% by mass of polyacrylamide, or 32% by mass of polyacrylamide. And / or, step S3 further includes a crushing process before calcination; And / or, in step S3, the calcination includes a first calcination and a second calcination; And / or, in step S3, the calcination process further includes a crushing process; preferably, the crushing process is performed by airflow crushing. And / or, the particle size D98 of the antibacterial agent is 2-5 μm, for example 3.125 μm, 3.174 μm, 3.235 μm, 3.48 μm, 3.492 μm, 3.5 μm, 3.502 μm, 3.511 μm, 3.541 μm or 3.967 μm.

7. The method for preparing the antibacterial agent as described in claim 6, characterized in that, The heating rate of the first calcination is 2-5℃ / min, preferably 2.5-4.8℃ / min, more preferably 2.8-4.5℃ / min, for example 2.8℃ / min, 4.4℃ / min or 4.8℃ / min; And / or, the temperature of the first calcination is 100-500°C, preferably 200-400°C, for example 200°C, 320°C or 350°C; And / or, the first calcination time is 1-5 hours, preferably 1.5-5 hours, more preferably 2-5 hours, for example 2 hours or 2.2 hours; And / or, the heating rate of the second calcination is 1-5℃ / min, preferably 1.5-4.5℃ / min, more preferably 2-4℃ / min, for example 3℃ / min, 3.5℃ / min or 4℃ / min; And / or, the temperature of the second calcination is 600-1200°C, preferably 700-1100°C, more preferably 750-1000°C, for example 750°C, 820°C or 900°C; And / or, the second calcination time is 1-15h, preferably 3-12h, more preferably 5-12h, for example 2.5h, 5h or 11h.

8. An antibacterial agent, characterized in that, It is prepared by the method for preparing the antibacterial agent as described in any one of claims 3-7; Preferably, the particle size D98 of the antibacterial agent is 2-5 μm, for example 3.125 μm, 3.174 μm, 3.235 μm, 3.48 μm, 3.492 μm, 3.5 μm, 3.502 μm, 3.511 μm, 3.541 μm or 3.967 μm.

9. An antibacterial masterbatch, characterized in that, Its components include the antimicrobial agent as described in any one of claims 1, 2 and 8; Preferably, the antibacterial agent accounts for 5-15% of the mass percentage of the antibacterial masterbatch, for example, 10%.

10. The use of an antimicrobial agent as described in any one of claims 1, 2 and 8 or an antimicrobial masterbatch as described in claim 9 in the preparation of antimicrobial materials.

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