A silver-loaded glass antibacterial agent, its preparation method and product

Abstract

The present invention discloses a silver-loaded glass antibacterial agent, a preparation method thereof, and a product. The silver oxide in the silver-loaded glass antibacterial agent accounts for 5-8 wt% of the silver-loaded glass antibacterial agent with a surface thickness of 0-50 nm, and accounts for [[r 3 -(r - 0.05) 3 / r 3 ×W of the overall silver-loaded glass antibacterial agent. By introducing specific contents of alumina and alkali metal ions sodium oxide and potassium oxide, the present invention prepares a matrix glass without Ag2O, and then through ion exchange, while maintaining a high Ag2O content on the surface, the aging yellowing of the resin caused by Ag2O is inhibited. The preparation of an antibacterial glass containing Ag2O with lower cost is realized, and when added to the resin, the addition amount required to achieve the same antibacterial effect is lower, and the influence on the aging yellowing of the resin is smaller.

Description

Technical Field

[0001] The present invention belongs to the technical field of antibacterial materials, and particularly relates to a silver-loaded glass antibacterial agent, a preparation method thereof, and a product thereof. Background Art

[0002] In the existing silver-loaded glass antibacterial agents, generally, Ag2O is directly added during the preparation of glass and then ground into powders of the required particle size. On the one hand, the content of Ag2O on the surface and inside of the glass particles is the same, and the actually effective one is mainly the Ag2O on the surface. However, Ag2O has a high cost, which limits the addition in resins and other materials to reach a minimum addition amount. At the same time, through experimental research, it is found that when silver-containing glass powder is added to resins, with the increase of time, the aging yellowing phenomenon of plastics will gradually accelerate, affecting the performance and aesthetics of the materials.

[0003] The patent with the application number CN2024110821056 discloses a silver-loaded glass antibacterial agent for high-transparency AS resin. The present invention relates to the field of antibacterial materials and provides a silver-loaded glass antibacterial agent for high-transparency AS resin. Calculated by weight percentage of oxides, the silver-loaded glass antibacterial agent is composed of the following components: 50-60 wt% of B2O3, 3-10 wt% of P2O5, 0.1-3 wt% of SiO2, 5-10 wt% of Al2O3, 25-35 wt% of MgO, 0.8-2 wt% of Ag2O, 0.001-0.03 wt% of CuO, 0.003-0.05 wt% of Co2O3; and the glass is formed by a blowing process; for the high-transparency antibacterial AS resin material prepared with the silver-loaded glass antibacterial agent of the present invention, the haze value increase of a 3-mm-thick sample is less than 5%, and the light transmittance reduction value is less than 3%. Summary of the Invention

[0004] In order to overcome the following deficiencies in the prior art: 1. In the prior art, the content of Ag2O on the surface and inside of the manufactured glass particles is the same, resulting in a high use cost; 2. When glass powder containing Ag2O is added to resins, with the increase of time, the aging yellowing phenomenon of plastics will gradually accelerate. This solution introduces specific contents of alumina and alkali metal ions sodium oxide and potassium oxide to prepare a matrix glass without Ag2O. After grinding it into powders of the required particle size, ion exchange is carried out. The first ion exchange introduces Ag2O with a high surface content. Preferably, a second ion exchange is also included to appropriately increase the content of alkali metal K2O on the surface of the high-content Ag2O, so as to maintain a high Ag2O content on the surface while inhibiting the aging yellowing of the resin caused by Ag2O. The preparation of a silver-loaded antibacterial glass with a lower cost is realized. At the same time, when added to resins, the addition amount required to achieve the same antibacterial effect is lower, and the impact on the aging yellowing of the resin is smaller. The specific technical solution of the present invention is as follows:

[0005] The first technical solution provided by the present invention is: a silver-loaded glass antibacterial agent, wherein the silver oxide content in the silver-loaded glass antibacterial agent accounts for 5-8 wt% of the silver-loaded glass antibacterial agent with a surface thickness of 0-50 nm, and accounts for [[r 3 -(r - 0.05) 3 / r 3 ×W, where r is the radius of the silver-loaded glass antibacterial agent, and W is the mass percentage of silver oxide content in the silver-loaded glass antibacterial agent with a surface thickness of 0-50 nm. The silver-loaded glass antibacterial agent is in powder form, and the average powder particle size is 4-6 µm. Taking a glass antibacterial agent with a powder particle size of 4 µm and a radius of 2 µm as an example, when the silver oxide content in the glass antibacterial agent with a surface layer thickness of 0-50 nm is 5 wt%, the proportion in the overall mass fraction = (2 3 -1.95 3 ) / 2 3 ×5 wt% = 0.366 wt%; when the silver oxide content in the glass antibacterial agent with a surface layer thickness of 0-50 nm is 6 wt%, the proportion in the overall mass fraction = (2 3 -1.95 3 ) / 2 3 ×6 wt% = 0.439 wt%; when the silver oxide content in the glass antibacterial agent with a thickness of 0-50 nm is 7.5 wt%, the proportion in the overall mass fraction = (2 3 -1.95 3 ) / 2 3 ×7.5 wt% = 0.549 wt%.

[0006] Furthermore, the inhibition rate of the silver-loaded glass antibacterial agent against Staphylococcus aureus and Escherichia coli is above 99.99%. Specifically, the antibacterial activity against Staphylococcus aureus is 99.99%, and the antibacterial activity against Escherichia coli is 99.9999%.

[0007] Even further, the raw material composition of the silver-loaded glass antibacterial agent is: 1-10 wt% of Al2O3, 11-12 wt% of B2O3, 8-15 wt% of ZnO, 3-5 wt% of CaO, 11-12 wt% of Na2O, 0.1-0.5 wt% of K2O, 50-55 wt% of P2O5, 2-3 wt% of SiO2, and 0.2-0.5 wt% of CeO2.

[0008] This solution also provides a preparation method for the silver-loaded glass antibacterial agent, which is as follows:

[0009] Step 1: After preparing the raw materials, mix them, and then place them in a crucible and melt the raw materials at 1200-1500 °C;

[0010] Step 2: Shape the melt obtained in Step 1 into sheets or directly perform water quenching;

[0011] Step 3: Grind the glass obtained in Step 2 into glass powder with D50 less than 10 µm.

[0012] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:(5 - 20), and conduct ion exchange at 380 - 480 °C for 1 - 4 hours.

[0013] Further, the composition of the raw materials in Step 1 is: 1 - 10 wt% of Al2O3, 11 - 12 wt% of B2O3, 8 - 15 wt% of ZnO, 3 - 5 wt% of CaO, 11 - 12 wt% of Na2O, 0.1 - 0.5 wt% of K2O, 50 - 55 wt% of P2O5, 2 - 3 wt% of SiO2, and 0.2 - 0.5 wt% of CeO2.

[0014] Further, the nitrate in Step 4 is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is not less than 18 wt%. The proportion of silver nitrate in the overall nitrate can be 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 98 wt%, 99 wt% or the range or sub - range between any two values.

[0015] Preferably, the molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:(0.6 - 1), and the molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:0.6 or 1:0.7 or 1:0.8 or 1:0.9 or 1:1 or the range or sub - range between any two values.

[0016] The second technical solution provided by the present invention is: a silver - loaded glass antibacterial agent. In this silver - loaded glass antibacterial agent, silver oxide accounts for 5 - 8 wt% of the glass antibacterial agent with a surface thickness of 0 - 50 nm, and accounts for [[r 3 -(r - 0.05) 3 / r 3 ×W of the overall silver - loaded glass antibacterial agent, where r is the radius of the silver - loaded glass antibacterial agent, and W is the mass percentage of silver oxide content in the silver - loaded glass antibacterial agent with a surface thickness of 0 - 50 nm; at the same time, the surface of this silver - loaded glass antibacterial agent also contains 1 - 2 wt% of K2O of the silver - loaded glass antibacterial agent with a surface thickness of 0 - 50 nm.

[0017] Furthermore, the silver-loaded glass antibacterial agent has an inhibition rate of over 99.99% against Staphylococcus aureus and Escherichia coli. Specifically, its antibacterial activity against Staphylococcus aureus is 99.99%, and against Escherichia coli is 99.9999%.

[0018] Furthermore, the raw material composition of the silver-loaded glass antibacterial agent is as follows: 1-10wt% of Al2O3, 11-12wt% of B2O3, 8-15wt% of ZnO, 3-5wt% of CaO, 11-12wt% of Na2O, 0.1-0.5wt% of K2O, 50-55wt% of P2O5, 2-3wt% of SiO2, and 0.2-0.5wt% of CeO2.

[0019] This solution also provides a preparation method for the silver-loaded glass antibacterial agent, which is as follows:

[0020] Step 1: After preparing the raw materials, mix them, and then place them in a crucible and melt the raw materials at 1200-1500 °C.

[0021] Step 2: Shape the melt obtained in Step 1 into sheets or directly perform water quenching.

[0022] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm.

[0023] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:(5-20), and perform ion exchange at 380-480 °C for 1-4 hours. The mass ratio of the glass powder to the nitrate can be 1:5, 1:10, 1:15, 1:20, or any range or sub-range between any two ratios.

[0024] Step 5: Wash the glass powder prepared in Step 4 with water to remove the nitrate, then dry it, and perform a second ion exchange. During the second ion exchange, mix the glass powder with the second nitrate in a mass ratio of 1:(2-5), perform ion exchange at 360-460 °C for 1-4 hours, and then wash and dry it to obtain the finished product.

[0025] Furthermore, the composition of the raw materials in Step 1 is as follows: 1-10wt% of Al2O3, 11-12wt% of B2O3, 8-15wt% of ZnO, 3-5wt% of CaO, 11-12wt% of Na2O, 0.1-0.5wt% of K2O, 50-55wt% of P2O5, 2-3wt% of SiO2, and 0.2-0.5wt% of CeO2.

[0026] Further, the nitrate in step 4 is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, where the proportion of silver nitrate in the overall nitrate is not less than 18 wt%; the second nitrate in step 5 is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, where the proportion of silver nitrate in the overall nitrate is 0.15 - 0.35 wt%, and the proportion of potassium nitrate in the overall second nitrate is not less than 70 wt%. The proportion of potassium nitrate in the overall second nitrate can be 80 wt%, 82 wt%, 84 wt%, 86 wt%, 88 wt%, 90 wt%, 92 wt%, 94 wt%, 96 wt%, 98 wt% or the range or sub-range between any two values.

[0027] Preferably, the molar ratio of the sodium content in the raw material to the silver content in the nitrate during the first ion exchange is 1:(0.6 - 1), and the molar ratio of the sodium content in the raw material to the silver content in the nitrate during the first ion exchange is 1:0.6 or 1:0.7 or 1:0.8 or 1:0.9 or 1:1 or the range or sub-range between any two values.

[0028] The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:(5 - 7), which can be 1:5, 1:6 or 1:7 or the range or sub-range between any two values.

[0029] Taking the example of controlling the surface silver oxide content to account for about 5 wt% of the glass antibacterial agent with a surface thickness of 0 - 50 nm, the molecular weight of silver oxide is 232, and the molecular weight of sodium oxide is 62. To reach the above surface content, if 1.4 wt% of the sodium oxide in 11 wt% of the sodium oxide in the glass antibacterial agent powder is exchanged for silver oxide, then the original 1.4 wt% of sodium oxide becomes 1.4 / 62×142 = 5.23 wt% of silver oxide.

[0030] Phosphate glass has the following advantages: 1. Low melting point: Phosphate glass has a relatively low melting point, which is convenient for processing and shaping. 2. High light transmittance: It has good light transmittance in the ultraviolet to infrared bands and is suitable for optical applications. 3. Chemical stability: It is resistant to water and chemical corrosion and is suitable for harsh environments.

[0031] 4. Low coefficient of thermal expansion: It has good thermal stability and is suitable for environments with large temperature changes. 5. High mechanical strength, high hardness, and good wear resistance, making it suitable for high-strength applications. These advantages enable it to have wide applications in the fields of optics, biomedicine, electronics, etc. In the present invention, by designing the content of P2O5 to be 50 - 55 wt%, the content of B2O3 to be 3 - 10 wt%, the content of SiO2 to be 2 - 3 wt%, and the content of Al2O3 to be 1 - 10 wt% as the main components forming the phosphate glass network structure.

[0032] It is generally believed that the addition of alkali metal oxides will affect the melting process of glass, especially the reduction behavior of silver ions. Alkali metal oxides usually increase the alkalinity of glass and lower the redox potential of glass. Such an environment is more likely to cause the reduction of silver ions to elemental silver. The elemental silver particles in the glass will cause discoloration, usually manifested as yellow or brown, especially under high-temperature firing or extreme conditions, and this risk of discoloration will be greater. The addition of alkali metal oxides will also reduce the chemical resistance of glass, especially the water resistance. Alkali metal ions are weakly bonded to oxygen atoms in the glass network and are more easily eroded by water or other polar solvents. This reduction in water resistance will cause silver ions to be more easily leached out of the glass, thereby increasing the risk of discoloration and a decline in antibacterial performance, especially in humid or extreme environments.

[0033] In the present invention, first, a glass matrix containing alkali metals is prepared, and then through the first ion exchange, silver ions can be exchanged with sodium ions on the surface of the glass body. Then, through the second ion exchange, potassium ions with a larger ionic radius are exchanged with silver ions or sodium ions, so that silver ions can be embedded in stable positions in the glass network, thereby reducing the rate of reduction of surface high-concentration silver ions to elemental silver under long-term light irradiation, etc., and further reducing the risk of post-oxidation discoloration.

[0034] The third technical solution provided by the present invention is: a silver-loaded glass antibacterial agent product, which is composed of a resin and the silver-loaded glass antibacterial agent described in the first and second technical solutions of the present invention, and the proportion of the silver-loaded glass antibacterial agent in the product is 0.15-1 wt%. Further, the proportion of the glass antibacterial agent in the product can be 0.15 wt%, 0.3 wt%, 0.5 wt%, 0.75 wt%, 1 wt% or the range and sub-range between any two values.

[0035] Further, the resin is polystyrene (PS), styrene-acrylonitrile copolymer (AS), polypropylene (PP), polyethylene terephthalate (PET), acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC) or polyethylene (PE).

[0036] Furthermore, the resin product added with the silver-loaded glass antibacterial agent in the second solution has a good anti-yellowing effect. When continuously irradiated with ultraviolet light (light with a wavelength of 300-700 nm, 255 W / m 2 ), no yellowing occurs after 250 hours.

[0037] The present invention prepares a matrix glass without Ag2O by introducing specific contents of alumina and alkali metal ions sodium oxide and potassium oxide. After grinding it into powder of the required particle size, ion exchange is carried out. The ion exchange is carried out once or twice. The first ion exchange introduces Ag2O with a high surface content. Preferably, a second ion exchange is also included to appropriately increase the content of alkali metal K2O in the high content of Ag2O on the surface, so as to maintain a relatively high content of Ag2O on the surface while inhibiting the aging and yellowing of the resin caused by Ag2O. The preparation of the Ag2O-containing antibacterial glass with lower cost is realized. At the same time, when it is added to the resin, the addition amount required to achieve the same antibacterial effect is lower, and the influence on the aging and yellowing of the resin is smaller. Description of the Drawings

[0038] Figure 1 SEM photograph of the product prepared in Example 2 of the present invention;

[0039] Figure 2 Photograph of the resin product prepared from the product in Example 2 of the present invention after 250 hours;

[0040] Figure 3 SEM photograph of the product prepared in Comparative Example 1;

[0041] Figure 4 Photograph of the resin product prepared from the product in Comparative Example 1 after 150 hours;

[0042] Figure 5 Test result diagram of silver oxide, sodium oxide and potassium oxide on the surface of the product in Example 2 before ion exchange;

[0043] Figure 6 Test result diagram of silver oxide, sodium oxide and potassium oxide on the surface of the product in Example 2 after two ion exchanges; Detailed Embodiments

[0044] The preferred embodiments of the present invention are described in detail below.

[0045] The present document describes silver-loaded glass antibacterial agents and their preparation methods and products, including two types of silver-loaded glass antibacterial agents and their preparation methods and products. One type is the silver-loaded glass antibacterial agent, in which silver oxide accounts for 5-8 wt% of the glass antibacterial agent with a surface thickness of 0-50 nm, and accounts for [[r 3 -(r - 0.05) 3 / r 3 ×W of the overall silver-loaded glass antibacterial agent, where r is the radius of the silver-loaded glass antibacterial agent, and W is the mass percentage of silver oxide content in the silver-loaded glass antibacterial agent with a surface thickness of 0-50 nm.

[0046] Furthermore, the silver-loaded glass antibacterial agent has an inhibition rate of over 99.99% against Staphylococcus aureus and Escherichia coli.

[0047] The preparation method of the silver-loaded glass antibacterial agent is as follows:

[0048] Step 1: After preparing the raw materials, mix them, and then place them in a crucible and melt the raw materials at 1200 - 1500 °C.

[0049] Step 2: Shape the melt obtained in Step 1 into sheets or directly perform water quenching.

[0050] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm.

[0051] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:(5 - 20), and perform ion exchange at 380 - 480 °C for 1 - 4 hours.

[0052] Furthermore, the composition of the raw materials in Step 1 is: 1 - 10 wt% of Al2O3, 11 - 12 wt% of B2O3, 8 - 15 wt% of ZnO, 3 - 5 wt% of CaO, 11 - 12 wt% of Na2O, 0.1 - 0.5 wt% of K2O, 50 - 55 wt% of P2O5, 2 - 3 wt% of SiO2, and 0.2 - 0.5 wt% of CeO2.

[0053] Furthermore, the nitrate in Step 4 is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is not less than 18 wt%. The proportion of silver nitrate in the overall nitrate can be 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 98 wt%, 99 wt% or the range or sub-range between any two values. Preferably, the molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:(0.6 - 1).

[0054] The second type of silver-loaded glass antibacterial agent, in which silver oxide accounts for 5 - 8 wt% of the glass antibacterial agent with a surface thickness of 0 - 50 nm, and accounts for [[r 3 -(r - 0.05) 3 / r 3×W, where r is the radius of the silver-loaded glass antibacterial agent, and W is the mass percentage of silver oxide content in the silver-loaded glass antibacterial agent with a surface thickness of 0 - 50 nm; meanwhile, the surface of the silver-loaded glass antibacterial agent also contains 1 - 2 wt% of K2O based on the glass antibacterial agent with a surface thickness of 0 - 50 nm.

[0055] Furthermore, the inhibition rates of the silver-loaded glass antibacterial agent against Staphylococcus aureus and Escherichia coli are above 99.99%.

[0056] This solution also provides a preparation method of the silver-loaded glass antibacterial agent, which is as follows:

[0057] Step 1: After preparing the raw materials, mix them, and then place them in a crucible and melt the raw materials at 1200 - 1500 °C.

[0058] Step 2: Shape the melt obtained in Step 1 into sheets or directly perform water quenching.

[0059] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm.

[0060] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:(5 - 20), and perform ion exchange at 380 - 480 °C for 1 - 4 hours.

[0061] Step 5: Wash the glass powder prepared in Step 4 with water to remove nitrate, then dry it, and perform a second ion exchange after drying. During the second ion exchange, the glass powder and the second nitrate are mixed in a mass ratio of 1:(2 - 5), and ion exchange is performed at 360 - 460 °C for 1 - 4 hours, and then wash and dry to obtain the finished product.

[0062] Furthermore, the composition of the raw materials in Step 1 is: 1 - 10 wt% of Al2O3, 11 - 12 wt% of B2O3, 8 - 15 wt% of ZnO, 3 - 5 wt% of CaO, 11 - 12 wt% of Na2O, 0.1 - 0.5 wt% of K2O, 50 - 55 wt% of P2O5, 2 - 3 wt% of SiO2, and 0.2 - 0.5 wt% of CeO2.

[0063] Further, the nitrate in step 4 is a mixture of sodium nitrate, potassium nitrate and silver nitrate, wherein the proportion of silver nitrate in the overall nitrate is not less than 18 wt%, and the proportion of silver nitrate in the overall nitrate can be 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 98 wt%, 99 wt% or the range or sub-range between any two values. The second nitrate in step 5 is a mixture of sodium nitrate, potassium nitrate and silver nitrate, wherein the proportion of silver nitrate in the overall nitrate is 0.15 - 0.35 wt%, and the proportion of potassium nitrate in the overall second nitrate is not less than 70 wt%. Preferably, the molar ratio of the sodium content in the raw material to the silver content in the nitrate during the first ion exchange is 1:(0.6 - 1), and the molar ratio of the sodium content in the raw material to the silver content in the nitrate during the first ion exchange is 1:0.6 or 1:0.7 or 1:0.8 or 1:0.9 or 1:1.

[0064] The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:(5 - 7), and can be 1:5, 1:6 or 1:7.

[0065] Example 1

[0066] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0067] Step 1: Prepare the following raw materials: 9 wt% of Al2O3, 12 wt% of B2O3, 8 wt% of ZnO, 5 wt% of CaO, 12 wt% of Na2O, 0.5 wt% of K2O, 50 wt% of P2O5, 3 wt% of SiO2 and 0.5 wt% of CeO2, mix them using a V-type mixer at a rotation speed of 5 - 10 revolutions per minute, and after mixing for 10 - 30 minutes, place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0068] Step 2: Form the melt obtained in step 1 into sheets using a pair-roll forming machine or directly perform water quenching;

[0069] Step 3: Grind the glass obtained in step 2 into glass powder with D50 less than 10 µm, and the average particle size of the obtained powder is 3.4 µm;

[0070] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:5. The composition of the nitrate is NaNO3:KNO3:AgNO3 = 78.31 wt%:2.11 wt%:19.58 wt%. Conduct ion exchange at 470 °C for 1 hour, and then perform water washing and drying to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is 19.58 wt%. The molar ratio of the sodium content in the raw material to the silver content in the nitrate during ion exchange is 1:0.6.

[0071] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product. The antibacterial ability and anti-yellowing ability of resin products with different addition amounts of 0.15 - 1 wt% were studied. When the proportion of the silver-loaded glass antibacterial agent in the resin product is 1 wt%, the antibacterial effects of the product against Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively.

[0072] Example 2

[0073] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0074] Step 1: Prepare the following raw materials: 7 wt% of Al2O3, 11.4 wt% of B2O3, 10 wt% of ZnO, 4 wt% of CaO, 11.8 wt% of Na2O, 0.4 wt% of K2O, 52 wt% of P2O5, 3 wt% of SiO2, and 0.4 wt% of CeO2. Use a V-type mixer for mixing at a rotation speed of 5 - 10 revolutions per minute. After mixing for 10 - 30 minutes, place it in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0075] Step 2: Use a pair-roll forming machine to form the melt obtained in Step 1 into sheets or directly perform water quenching;

[0076] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm, and the average particle size of the obtained powder is 3.5 µm;

[0077] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:9. Conduct ion exchange at 440 °C for 2 hours, and then perform water washing and drying to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is 21.36 wt%; the molar ratio of the sodium content in the raw material to the silver content in the nitrate during the first ion exchange is 1:0.86.

[0078] Step 5: Wash the glass powder prepared in Step 4 with water to remove nitrates, then dry it. After drying, perform a second ion exchange. During the second ion exchange, the glass powder and the second nitrate are mixed at a mass ratio of 1:2, and the ion exchange is carried out at 360 - 460 °C for 1 - 4 hours. Then wash it with water and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3: KNO3:AgNO3 = 21.78 wt%:78.01 wt%:0.21 wt%. The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:6.55.

[0079] The SEM photograph of the prepared silver-loaded glass antibacterial agent is as Figure 1 shown. The prepared silver-loaded glass antibacterial agent is mixed with resin to make a product. The antibacterial ability and anti-yellowing ability of resin products with different addition amounts of 0.15 - 1 wt% are studied. When the proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%, the antibacterial effects of the product on Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively.

[0080] The overall silver content of the silver-loaded glass antibacterial agent is tested with reference to "GB / T 11066.11 - 2021 Methods for chemical analysis of gold - Part 11: Determination of magnesium, chromium, manganese, iron, nickel, copper, palladium, silver, tin, antimony, lead and bismuth contents - Inductively coupled plasma mass spectrometry method", and the silver content on the surface of 0 - 50 nm is tested with reference to "GB / T 24575 - 2009 Secondary ion mass spectrometry detection method for Na, Al, K and Fe on the surface of silicon and epitaxial wafers".

[0081] Figure 5 This is the test result diagram of silver oxide, sodium oxide and potassium oxide on the surface of the glass powder prepared in Step 3 of this example. Figure 6 This is the test result diagram of silver oxide, potassium oxide and sodium oxide on the surface of the finally prepared silver-loaded glass antibacterial agent. From Figure 5 and Figure 6 it can be seen that before ion exchange, the content of sodium oxide on the surface of the glass powder is the highest and does not contain silver oxide. After ion exchange, the content of sodium oxide decreases, while the contents of silver oxide and potassium oxide both increase, proving that silver enters the surface of the glass powder and can thus play an antibacterial role. And from Figure 6 it can be seen that after the surface thickness of the glass antibacterial agent exceeds 50 nm, the content of silver oxide drops sharply, proving that this application has successfully developed a silver oxide-containing glass antibacterial agent that accumulates on the surface of the glass powder.

[0082] Example 3

[0083] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0084] Step 1: Prepare the following raw materials: 5 wt% of Al2O3, 11.6 wt% of B2O3, 11.2 wt% of ZnO, 3.5 wt% of CaO, 11.9 wt% of Na2O, 0.5 wt% of K2O, 53 wt% of P2O5, 2.8 wt% of SiO2, and 0.5 wt% of CeO2. Mix them using a V-type mixer at a rotation speed of 5 - 10 revolutions per minute for 10 - 30 minutes, and then place them in a platinum crucible to melt the raw materials at 1200 - 1500 °C for 2 - 8 hours.

[0085] Step 2: Shape the melt obtained in Step 1 into sheets using a pair-roll forming machine or directly perform water quenching.

[0086] Step 3: Grind the glass obtained in Step 2 into glass powder with D50 less than 10 µm, and the average particle size of the prepared powder is 3.2 µm.

[0087] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:20, perform ion exchange at 450 °C for 3 hours, and then wash and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is 24.48 wt%. The molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:0.76.

[0088] Step 5: Wash the glass powder prepared in Step 4 to remove nitrate, then dry it, and perform a second ion exchange after drying. During the second ion exchange, the glass powder and the second nitrate are mixed in a mass ratio of 1:3, perform ion exchange at 360 - 460 °C for 1 - 4 hours, and then wash and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3: KNO3:AgNO3 = 19.04 wt%:80.72 wt%:0.24 wt%. The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:5.57.

[0089] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product, and study the antibacterial ability and anti-yellowing ability of resin products with different addition amounts of 0.15 - 1 wt%. The proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%, and the antibacterial effects of this product against Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively.

[0090] Example 4

[0091] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0092] Step 1: Prepare the following raw materials: 3 wt% of Al2O3, 11.5 wt% of B2O3, 13 wt% of ZnO, 4.5 wt% of CaO, 12 wt% of Na2O, 0.5 wt% of K2O, 52 wt% of P2O5, 3 wt% of SiO2, and 0.5 wt% of CeO2. Mix them using a V-type mixer at a rotation speed of 5 - 10 revolutions per minute for 10 - 30 minutes, and then place them in a platinum crucible to melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0093] Step 2: Form the melt obtained in Step 1 into sheets using a pair-roll forming machine or directly perform water quenching;

[0094] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm, and the average particle size of the obtained powder is 3.8 µm;

[0095] Step 4: Mix the glass powder obtained in Step 3 with nitrate in a mass ratio of 1:17, perform ion exchange at 380 - 480 °C for 1 - 4 hours, and then wash and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, where the proportion of silver nitrate in the overall nitrate is 27.5 wt%; the molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:0.87.

[0096] Step 5: Wash the glass powder obtained in Step 4 to remove nitrate, then dry it, and perform a second ion exchange after drying. During the second ion exchange, the glass powder and the second nitrate are mixed in a mass ratio of 1:4, perform ion exchange at 360 - 460 °C for 1 - 4 hours, and then wash and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3: KNO3:AgNO3 = 15.42 wt%:84.28 wt%:0.29 wt%. The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:5.13.

[0097] Mix the obtained silver-loaded glass antibacterial agent with resin to make a product, and study the antibacterial ability and anti-yellowing ability of resin products with different addition amounts of 0.15 - 1 wt%. The proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%, and the antibacterial effects of the product against Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively.

[0098] Example 5

[0099] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0100] Step 1: Prepare the following raw materials: 1.3 wt% of Al2O3, 11.5 wt% of B2O3, 15 wt% of ZnO, 4 wt% of CaO, 11.7 wt% of Na2O, 0.4 wt% of K2O, 53 wt% of P2O5, 2.6 wt% of SiO2 and 0.5 wt% of CeO2. Mix them using a V-type mixer at a rotation speed of 5 - 10 revolutions per minute for 10 - 30 minutes, and then place them in a platinum crucible to melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0101] Step 2: Form the melt obtained in Step 1 into sheets using a pair-roll forming machine or directly perform water quenching;

[0102] Step 3: Grind the glass obtained in Step 2 into glass powder with D50 less than 10 µm, and the average particle size of the obtained powder is 4.1 µm;

[0103] Step 4: Mix the glass powder obtained in Step 3 with nitrate in a mass ratio of 1:20, perform ion exchange at 380 - 480 °C for 1 - 4 hours, and then wash and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate and silver nitrate, and the proportion of silver nitrate in the overall nitrate is 30.41 wt%; the molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:1.

[0104] Step 5: Wash the glass powder obtained in Step 4 to remove nitrate, then dry it, and perform a second ion exchange after drying. During the second ion exchange, the glass powder is mixed with the second nitrate in a mass ratio of 1:5, perform ion exchange at 360 - 460 °C for 1 - 4 hours, and then wash and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3: KNO3:AgNO3 = 7.5 wt%:92.16 wt%:0.34 wt%. The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:5.06.

[0105] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product, and study the antibacterial ability and anti-yellowing ability of resin products with different addition amounts of 0.15 - 1 wt%. When the proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%, the antibacterial effects of the product against Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively.

[0106] Comparative Example 1

[0107] Prepare an antibacterial glass agent according to the following steps:

[0108] Step 1: Prepare the following raw materials: 5wt% Al2O3, 4wt% AgO2, 12wt% B2O3, 8wt% ZnO, 5wt% CaO, 12wt% Na2O, 0.5wt% K2O, 50wt% P2O5, 3wt% SiO2, and 0.5wt% CeO2. Mix them using a V-type mixer at a rotation speed of 5 - 10 revolutions per minute for 10 - 30 minutes. Then place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours.

[0109] Step 2: Shape the melt obtained in Step 1 into sheets using a pair-roll forming machine or directly perform water quenching.

[0110] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm, and the average particle size of the prepared powder is 3.6 µm.

[0111] The SEM photograph of the prepared silver-loaded glass antibacterial agent is as Figure 3 shown. Mix the prepared silver-loaded glass antibacterial agent with resin to make a product. The proportion of the silver-loaded glass antibacterial agent in the resin product is 1wt%. The antibacterial effects of the product against Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively. Conduct a yellowing test on the product. As Figure 4 shown, when its addition amount in PS resin is 1wt%, yellowing occurs after 150 hours under the test conditions.

[0112] Comparative Example 2

[0113] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0114] Step 1: Prepare the following raw materials: 10wt% B2O3, 30wt% ZnO, 4.5wt% CaO, 2wt% Na2O, 50wt% P2O5, 3wt% AgO, and 0.5wt% CeO2. Mix them using a V-type mixer at a rotation speed of 5 - 10 revolutions per minute for 10 - 30 minutes. Then place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours.

[0115] Step 2: Shape the melt obtained in Step 1 into sheets using a pair-roll forming machine or directly perform water quenching.

[0116] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm.

[0117] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:20, conduct ion exchange at 450 °C for 3 hours, and then wash and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, where the proportion of silver nitrate in the overall nitrate is 24.68 wt%;

[0118] Step 5: Wash the glass powder prepared in Step 4 to remove nitrate, then dry it. After drying, conduct a second ion exchange. During the second ion exchange, the glass powder and the second nitrate are mixed in a mass ratio of 1:3, conduct ion exchange at 360 - 460 °C for 1 - 4 hours, and then wash and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3: KNO3:AgNO3 = 7.5 wt%:92.16 wt%:0.34 wt%.

[0119] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product. When the proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%, the antibacterial effects of the product against Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively. Conduct a yellowing test on the product. When its addition amount in ABS resin is 1 wt%, yellowing occurs after 200 hours under the test conditions.

[0120] Comparative Example 3

[0121] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0122] Step 1: Prepare the following raw materials: 5 wt% of Al2O3, 10 wt% of B2O3, 27 wt% of ZnO, 4.5 wt% of CaO, 50 wt% of P2O5, 3 wt% of SiO2, and 0.5 wt% of CeO2. Use a V-type mixer to mix them at a rotation speed of 5 - 10 revolutions per minute. After mixing for 10 - 30 minutes, place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0123] Step 2: Use a pair-roll forming machine to form the melt obtained in Step 1 into sheets or directly conduct water quenching;

[0124] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm, and the average particle size of the glass powder is 1.5 µm;

[0125] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:20, conduct ion exchange at 450 °C for 3 hours, and then wash and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, where the proportion of silver nitrate in the overall nitrate is 25.36 wt%;

[0126] Step 5: Wash the glass powder prepared in Step 4 to remove nitrate, then dry it. After drying, conduct a second ion exchange. During the second ion exchange, mix the glass powder with the second nitrate in a mass ratio of 1:3, conduct ion exchange at 360 - 460 °C for 1 - 4 hours, and then wash and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3:KNO3:AgNO3 = 7.5 wt%:92.16 wt%:0.34 wt%.

[0127] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product. The proportion of the silver-loaded glass antibacterial agent in the resin product is 0.15 wt%, and the antibacterial effects of this product against Staphylococcus aureus and Escherichia coli are 40% and 39.8% respectively.

[0128] Comparative Example 4

[0129] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0130] Step 1: Prepare the following raw materials: 5 wt% of Al2O3, 10 wt% of B2O3, 14.5 wt% of ZnO, 5.5 wt% of CaO, 11 wt% of K2O, 0.5 wt% of Na2O, 50 wt% of P2O5, 3 wt% of SiO2, and 0.5 wt% of CeO2. Use a V-type mixer to mix them at a rotation speed of 5 - 10 revolutions per minute. After mixing for 10 - 30 minutes, place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0131] Step 2: Use a pair-roll forming machine to form the melt obtained in Step 1 into sheets or directly conduct water quenching;

[0132] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm;

[0133] Step 4: Mix the glass powder prepared in Step 3 with nitrate in a mass ratio of 1:20, conduct ion exchange at 450 °C for 3 hours, and then wash and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, where the proportion of silver nitrate in the overall nitrate is 28.26 wt%;

[0134] Step 5: Wash the glass powder obtained in Step 4 with water to remove nitrates, then dry it. After drying, perform a second ion exchange. During the second ion exchange, the glass powder and the second nitrate are mixed at a mass ratio of 1:3, and the ion exchange is carried out at 360 - 460 °C for 1 - 4 hours. Then, wash it with water and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3: KNO3:AgNO3 = 7.5 wt%: 92.16 wt%: 0.34 wt%.

[0135] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product. The proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%. The antibacterial effects of this product against Staphylococcus aureus and Escherichia coli are 80% and 75.9% respectively.

[0136] Comparative Example 5

[0137] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0138] Step 1: Prepare the following raw materials: 1.3 wt% of Al2O3, 11.5 wt% of B2O3, 15 wt% of ZnO, 4 wt% of CaO, 11 wt% of Na2O, 0.4 wt% of K2O, 53 wt% of P2O5, 2.6 wt% of SiO2, and 0.5 wt% of CeO2. Use a V-type mixer to mix them at a rotation speed of 5 - 10 revolutions per minute. After mixing for 10 - 30 minutes, place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0139] Step 2: Use a pair-roll forming machine to form the melt obtained in Step 1 into sheets or directly perform water quenching;

[0140] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm;

[0141] Step 4: Mix the glass powder obtained in Step 3 with nitrate at a mass ratio of 1:15, perform ion exchange at 500 °C for 5 hours, and then wash it with water and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is 28 wt%;

[0142] Step 5: Wash the glass powder prepared in Step 4 to remove nitrates, then dry it. After drying, perform a second ion exchange. During the second ion exchange, the glass powder and the second nitrate are mixed at a mass ratio of 1:(2 - 5), and the ion exchange is carried out at 480 °C for 5 hours. Then, wash it with water and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3:KNO3:AgNO3 = 7.5 wt%:92.16 wt%:0.34 wt%.

[0143] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product. The proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%. The antibacterial effects of this product against Staphylococcus aureus and Escherichia coli are 99.9% and 99.99% respectively. When its proportion in the resin product is 1 wt%, the anti-yellowing ability also decreases, and yellowing occurs after 250 hours.

[0144] Comparative Example 6

[0145] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0146] Step 1: Prepare the following raw materials: 5 wt% of Al2O3, 11.6 wt% of B2O3, 11.2 wt% of ZnO, 3.5 wt% of CaO, 11.9 wt% of Na2O, 0.5 wt% of K2O, 53 wt% of P2O5, 2.8 wt% of SiO2, and 0.5 wt% of CeO2. Use a V-type mixer to mix them at a rotation speed of 5 - 10 revolutions per minute. After mixing for 10 - 30 minutes, place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours;

[0147] Step 2: Use a pair-roll forming machine to form the melt obtained in Step 1 into sheets or directly perform water quenching;

[0148] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm, and the average particle size of the prepared powder is 3.2 µm;

[0149] Step 4: Mix the glass powder prepared in Step 3 with nitrate at a mass ratio of 1:10, perform ion exchange at 450 °C for 3 hours, and then wash it with water and dry it to obtain the required silver-loaded glass antibacterial agent. The composition of the nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is 16 wt%; the molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:0.52.

[0150] Step 5: Wash the glass powder prepared in Step 4 with water to remove nitrates, then dry it. After drying, perform a second ion exchange. During the second ion exchange, the glass powder and the second nitrate are mixed at a mass ratio of 1:3, and the ion exchange is carried out at 360 - 460 °C for 1 - 4 hours. Then, wash it with water and dry it to obtain the finished product. The specific composition of the second nitrate is: NaNO3:KNO3:AgNO3 = 19.04 wt%:80.72 wt%:0.24 wt%. The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:8.27.

[0151] Mix the prepared silver-loaded glass antibacterial agent with resin to make a product. The proportion of the silver-loaded glass antibacterial agent in the resin product is 0.5 wt%. The antibacterial effects of this product against Staphylococcus aureus and Escherichia coli are 85.4% and 85.2% respectively.

[0152] Comparative Example 7

[0153] Prepare the silver-loaded antibacterial glass agent according to the following steps:

[0154] Step 1: Prepare the following raw materials: 5 wt% of Al2O3, 11.6 wt% of B2O3, 11.2 wt% of ZnO, 3.5 wt% of CaO, 11.9 wt% of Na2O, 0.5 wt% of K2O, 53 wt% of P2O5, 2.8 wt% of SiO2, and 0.5 wt% of CeO2. Use a V-type mixer to mix them at a rotation speed of 5 - 10 revolutions per minute. After mixing for 10 - 30 minutes, place them in a platinum crucible and melt the raw materials at 1200 - 1500 °C for 2 - 8 hours.

[0155] Step 2: Use a pair-roll forming machine to form the melt obtained in Step 1 into sheets or directly perform water quenching.

[0156] Step 3: Grind the glass obtained in Step 2 into glass powder with a D50 less than 10 µm. The average particle size of the obtained powder is 3.2 µm.

[0157] Step 4: Mix the glass powder prepared in Step 3 with nitrate at a mass ratio of 1:20, perform ion exchange at 450 °C for 3 hours, and then wash it with water and dry it to obtain the required silver-loaded glass antibacterial agent. The nitrate is a mixture of sodium nitrate, potassium nitrate, and silver nitrate, and the proportion of silver nitrate in the overall nitrate is 24.48 wt%. The molar ratio of the sodium content in the raw materials to the silver content in the nitrate during the first ion exchange is 1:0.76.

[0158] Step 5: Wash the glass powder obtained in Step 4 to remove nitrates, then dry it. After drying, perform a second ion exchange. During the second ion exchange, the glass powder and the second nitrate are mixed at a mass ratio of 1:3, and the ion exchange is carried out at 360 - 460 °C for 1 - 4 hours. Then, wash it with water and dry it to obtain the finished product. The specific composition of the second nitrate is as follows: NaNO3: KNO3:AgNO3 = 45.57 wt%:54.25 wt%:0.18 wt%. The molar ratio of the silver content in the nitrate during the first ion exchange to the potassium content in the second nitrate is 1:3.86.

[0159] Mix the prepared silver-loaded glass antibacterial agent with the resin to make a product. The proportion of the silver-loaded glass antibacterial agent in the resin product is 1 wt%. The antibacterial effects of this product against Staphylococcus aureus and Escherichia coli are 99.99% and 99.9999% respectively. When performing the yellowing test, it is found that the product turns yellow after 150 hours.

[0160] Perform antibacterial performance tests on the products of Examples 1 - 5 and Comparative Examples 1 - 7. The antibacterial power is tested by the ASTM E2149-13a oscillating flask method; perform yellowing performance tests on the products of Examples 1 - 5 and Comparative Examples 1 - 5. The test conditions are as follows: Continuously irradiate with ultraviolet light (light with a wavelength of 300 - 700 nm, 255 W / m 2 ), observe the yellowing situation after irradiation. In this application, whether yellowing occurs is referred to the regulations in GB / T39822-2021. When ∆YI exceeds 1, it is regarded as yellowing. The test results of antibacterial performance and yellowing performance are shown in Tables 1 - 3.

[0161] Table 1 Test results of antibacterial performance of the products of Examples 1 - 5

[0162] Sample Example 1 Example 2 Example 3 Example 4 Example 5 Average radius of antibacterial agent (µm) 3.4 3.5 3.2 3.8 4.1 Silver content in the surface 0 - 50 nm (wt%) 7.8 7.2 6.7 6.3 5.5 Resin type Polystyrene (PS) Acrylonitrile - butadiene - styrene copolymer (ABS) Polypropylene (PP) Polycarbonate (PC) Polyethylene (PE) Proportion in resin products (wt%) 0.15 0.15 0.15 0.15 0.15 Antibacterial activity against Staphylococcus aureus (%) 99.99 99.99 99.99 99.99 99.99 Antibacterial activity against Escherichia coli (%) 99.9999 99.9999 99.9999 99.9999 99.9999

[0163] Table 2 Test results of antibacterial performance of the products of Comparative Examples 1 - 7

[0164] Sample Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Average radius of antibacterial agent (µm) 3.6 3.4 3.6 3.7 4.2 3.2 3.2 Silver content in the surface 0 - 50 nm (wt%) 6.2 5.3 1.5 1.2 3.6 2.8 5.8 Resin type Polystyrene (PS) Acrylonitrile - butadiene - styrene copolymer (ABS) Polypropylene (PP) Polycarbonate (PC) Polyethylene (PE) Polycarbonate (PC) Polyethylene (PE) Proportion in resin products (wt%) 0.15 0.15 0.15 0.15 0.15 0.5 1 Antibacterial activity against Staphylococcus aureus (%) 99.99 99.99 40 67.2 96.2 85.4 99.99 Antibacterial activity against Escherichia coli (%) 99.9999 99.9999 39.8 74.3 98.5 85.2 99.9999

[0165] Table 3 Test results of yellowing tests of the products of Examples 1 - 5 and Comparative Examples 1 - 5

[0166] Sample Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Resin type Polystyrene (PS) Acrylonitrile - butadiene - styrene copolymer (ABS) Polypropylene (PP) Polycarbonate (PC) Polyethylene (PE) Polystyrene (PS) Acrylonitrile - butadiene - styrene copolymer (ABS) Polypropylene (PP) Polycarbonate (PC) Polyethylene (PE) Proportion in resin products 1 1 1 1 1 1 1 1 1 1 After irradiation for 100 hours No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred After irradiation for 150 hours No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred Yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred After irradiation for 200 hours Yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred Yellowing occurred Yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred After irradiation for 250 hours Yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred No yellowing occurred Yellowing occurred Yellowing occurred Yellowing occurred Yellowing occurred Yellowing occurred

[0167] Meanwhile, the applicant also studied the addition of different contents of antibacterial agents in the resin for comparison, specifically including the addition of 0.5wt% and 1wt% of antibacterial agents. The results showed that in Examples 1-5 of the present invention, the addition amount of the glass antibacterial agent was in the range of 0.15-1wt%, and there were excellent antibacterial performances against Staphylococcus aureus and Escherichia coli, and the color did not change after 250 hours. In the comparative examples, generally, when the addition amount reached more than 0.5wt%, a better antibacterial effect could be achieved, but yellowing usually occurred at 200 hours or even 150 hours, and it was difficult to have both antibacterial and anti-yellowing properties simultaneously.

Claims

1. A method for preparing a silver-loaded glass antibacterial agent, characterized in that: The following steps are involved: Step 1: After the raw materials are prepared in proportion, they are mixed and then placed in a crucible to melt the raw materials at 1200-1500°C; Step 2: forming the melt obtained in step 1 into sheets or directly quenching the melt in water; Step 3: Grind the glass obtained in step 2 into glass powder with a D50 of less than 10µm; Step 4: mixing the glass powder obtained in step 3 with nitrate in a mass ratio of 1:(5-20), and performing ion exchange at 380-480° C. for 1-4 hours, wherein the nitrate is a mixture of sodium nitrate, potassium nitrate and silver nitrate, and the proportion of silver nitrate in the whole nitrate is not less than 18wt%; Step 5: Wash the glass powder obtained in step 4 to remove nitrate, then dry it, and then perform a second ion exchange after drying. During the second ion exchange, the glass powder and the second nitrate are mixed in a mass ratio of 1: (2-5), and the ion exchange is performed at 360-460° C. for 1-4 hours. Then, the finished product is obtained by washing and drying, wherein the second nitrate is a mixture of sodium nitrate, potassium nitrate and silver nitrate, wherein the proportion of silver nitrate to the whole second nitrate is 0.15-0.35wt%, and the proportion of potassium nitrate to the whole second nitrate is not less than 70wt%.

2. The method for preparing a silver-loaded glass antibacterial agent according to claim 1, characterized in that: The composition of the raw materials in step 1 is: 1-10wt% Al2O3, 11-12wt% B2O3, 8-15wt% ZnO, 3-5wt% CaO, 11-12wt% Na2O, 0.1-0.5wt% K2O, 50-55wt% P2O5, 2-3wt% SiO2 and 0.2-0.5wt% CeO2.

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