Antibacterial glass capable of stably releasing silver ions and preparation method thereof

Abstract

The invention discloses antibacterial glass capable of stably releasing silver ions and a preparation method thereof.The antibacterial glass capable of stably releasing the silver ions is composed of a component A and a component B according to the mass ratio of 1: 3-3: 1, the component A contains 9-10 wt% of Ag2O, and the silver ion solubility of the component A is 0.020-0.060 mg / (g * L * 24Hrs * 30 DEG C); the component B contains 4 to 5 weight percent of Ag2O, and the silver ion solubility of the component B is 0.010 to 0.030 mg / (g * L * 24Hrs * 30 DEG C). The novel antibacterial glass with high silver content and long-term stable release of silver ions is realized by adjusting the composition of the glass formula, especially by utilizing the hydrolysis resistance of zirconium oxide and regulating and controlling the specific proportion of alkali metal, alkaline earth metal and the like outside a network in the glass.

Description

Technical Field

[0001] The present invention belongs to the field of antibacterial glass, and particularly relates to an antibacterial glass capable of stably releasing silver ions. Background Art

[0002] In the prior art, in order to prevent bacteria, molds, etc. from breeding in water stored in a water storage tank, a drain pan of an air conditioner, etc., antibacterial glass that is directly in contact with water and releases silver ions in water to exert an antibacterial effect is commonly used. For antibacterial glass used in related applications, it is necessary to maintain a specified silver ion release amount even after a long time. To meet the related requirements, various measures are adopted, such as adjusting the composition and size of the antibacterial glass to a specified range, or using multiple antibacterial glasses with different characteristics in combination to suppress the pH change of water.

[0003] The water-soluble antibacterial glass used in washing machines, air conditioners, dishwashers, humidifiers, floor sweepers, etc. has good use effects. Although the dissolution rate per unit weight is basically the same before and after, as the use time increases, the volume of the antibacterial glass continuously decreases, and the surface area continuously decreases. At this time, the amount of silver ions dissolved is significantly reduced compared with the starting time. Currently, there are several improvement methods. One is to increase the overall (per unit weight) silver ion dissolution amount to ensure that the silver ion concentration still reaches the effective antibacterial concentration in the later stage of use. However, the starting dissolution concentration is relatively high, and there are disadvantages such as increased cost and silver ion staining. The other is to add new antibacterial glass during use. However, the antibacterial modules in general equipment are inside the equipment, and it requires professional personnel of the manufacturer to add them. Moreover, the use conditions and frequencies of each equipment are different, making it difficult to achieve precise addition, and the increased labor cost, etc. is relatively high. Therefore, it is necessary to develop a product in which the amount of silver ions dissolved remains stable from the beginning to the end of use.

[0004] At the same time, with the further miniaturization of equipment using water-soluble antibacterial glass such as washing machines, humidifiers, dishwashers, and air conditioners, it is urgent to develop an antibacterial glass with a higher silver content per unit weight and the same silver ion hydrolysis rate as the current one. In this way, the weight of the antibacterial glass used in a single device can be reduced, and the same silver ion hydrolysis rate can be achieved without causing silver ion coloring problems.

[0005] The patent application No. CN201480023325.X discloses an antibacterial glass that can be accommodated in a narrow accommodation space of an antibacterial water unit for supplying antibacterial water to a washing tank of a washing machine, and can effectively inhibit the generation of Cladosporium cladosporioides, etc. in the washing tank, and can inhibit the coloring of the object to be washed while making it effectively antibacterial. For the antibacterial glass of the present invention that is directly in contact with water and releases silver ions to exert an antibacterial effect, when the total amount is 100% by weight, the content of Ag 2 O is a value in the range of more than 5% by weight and 10% by weight or less, P 2O 5 The content of CaO is a value within a specified range, the content of ZnO is a value less than 10% by weight, and K 2 O, Al 2 O 3 The content of MgO is a value within a specified range, and the shape of the antibacterial glass is tablet-shaped. However, from the data disclosed, the silver ion release amounts after 7 days and 14 days are only 62% and 47% of the reference silver ions respectively. SUMMARY OF THE INVENTION

[0006] In order to overcome the deficiencies in the prior art, an antibacterial glass capable of stably releasing silver ions for a long time is provided. The applicant adjusted the composition of the glass formula, especially by utilizing the hydrolysis resistance of zirconia, and regulated the specific ratios of network modifiers such as alkali metals and alkaline earth metals in the glass, thus achieving a new type of antibacterial glass with a long-term stable release of silver ions at a high silver content. The specific technical solutions of the present invention are as follows: An antibacterial glass for stably releasing silver ions, which is composed of component A and component B in a mass ratio of 1:3 - 3:1. Component A contains 9 - 10 wt% Ag 2 O, and the silver ion solubility of component A is 0.020 - 0.060 mg / (g×L×24Hrs×30°C); component B contains 4 - 5 wt% Ag 2 O, and the silver ion solubility of component B is 0.010 - 0.030 mg / (g×L×24Hrs×30°C).

[0007] The silver ion solubility of the said component A is 0.02 mg / (g×L×24Hrs×30°C), 0.03 mg / (g×L×24Hrs×30°C), 0.04 mg / (g×L×24Hrs×30°C), 0.05 mg / (g×L×24Hrs×30°C), 0.06 mg / (g×L×24Hrs×30°C) or the range and sub-ranges between any two values.

[0008] The silver ion solubility of the said component B is 0.01 mg / (g×L×24Hrs×30°C), 0.015 mg / (g×L×24Hrs×30°C), 0.02 mg / (g×L×24Hrs×30°C), 0.025 mg / (g×L×24Hrs×30°C), 0.03 mg / (g×L×24Hrs×30°C) or the range and sub-ranges between any two values.

[0009] The silver content of the antibacterial glass is 5.25 - 8.75 wt%. Further, the silver content of the antibacterial glass is 5.25 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 8.75 wt% or the range and sub-ranges between any two values.

[0010] Further, the finished antibacterial glass is in granular form, about 0.5 - 1 g / granule, and the density is 2.2 - 2.8 g / cm³.

[0011] Further, after 280 days, the release amount of silver ions is more than 95% of the reference release amount. Specifically, the reference release amount here refers to the solubility (dissolution amount) of silver ions measured on the first day (24 hours), with the unit of g×L×24Hrs×30°C; the ability of the antibacterial glass to stably release silver ions is evaluated by testing the release amount of the antibacterial glass after different days. After 280 days, the release amount of silver ions of the antibacterial glass prepared by the present invention is more than 95% of the reference release amount.

[0012] Even further, the silver ion dissolution amount in the aforementioned antibacterial glass is measured under the following measurement conditions: 30 g of the antibacterial glass to be measured is immersed in 1 liter of purified water (30°C, pH = 6.5 - 7), and the measurement is carried out after placing it in a closed system for 24 hours - 280 days while maintaining the temperature.

[0013] Even further, the specific surface area of the antibacterial glass that stably releases silver ions is 3 - 5 cm 2 / g. Further, the specific surface area of the antibacterial glass is 3 cm 2 / g, 3.5 cm 2 / g, 4 cm 2 / g, 4.5 cm 2 / g, 5 cm 2 / g or the range and sub-ranges between any two values.

[0014] The component A is one or more of component A1, component A2, and component A3. The specific composition of component A1 is: 2 wt% Al 2 O 3 、8 wt% B 2 O 3 、2 wt% ZnO 2 、25 wt% CaO、0.7 wt% Na 2 O、0.5 wt% K 2 O、42 wt% P 2 O 5 、9 wt% Ag 2 O、6.2 wt% ZrO 2, 4.2 wt% SiO 2 and 0.4 wt% CeO 2 ; The specific composition of component A2 is: 2.4 wt% Al 2 O 3 , 7 wt% B 2 O 3 , 1.5 wt% Mg 2 O, 26 wt% CaO, 0.8 wt% Na 2 O, 0.4 wt% K 2 O, 41 wt% P 2 O 5 , 10 wt% Ag 2 O, 7 wt% ZrO 2 , 3.5 wt% SiO 2 and 0.4 wt% CeO 2 ; The specific composition of component A3 is: 1.5 wt% Al 2 O 3 , 9 wt% B 2 O 3 , 1 wt% Mg 2 O, 1.5 wt% ZnO 2 , 25.6 wt% CaO, 0.6 wt% Na 2 O, 0.4 wt% K 2 O, 40 wt% P 2 O 5 , 9.5 wt% Ag 2 O, 6.5 wt% ZrO 2 , 4 wt% SiO 2 and 0.4 wt% CeO 2 .

[0015] The said component B is one or more of component B1, component B2, and component B3. The specific composition of component B1 is: 13 wt% Al 2 O 3 , 2 wt% B 2 O 3 , 4 wt% Mg 2 O, 11 wt% ZnO 2 , 3 wt% CaO, 0.2 wt% Na 2 O, 0.3 wt% K 2 O, 40 wt% P 2 O 5 , 5 wt% Ag 2 O, 9 wt% ZrO 2 , 12 wt% SiO 2 and 0.5 wt% CeO 2 ; The specific composition of component B2 is: 14 wt% Al2 O 3 and 2.5 wt% B 2 O 3 and 3 wt% Mg 2 O, 9 wt% ZnO 2 and 2 wt% CaO, 0.3 wt% Na 2 O, 0.2 wt% K 2 O, 41 wt% P 2 O 5 and 4.5 wt% Ag 2 O, 10 wt% ZrO 2 and 13 wt% SiO 2 and 0.5 wt% CeO 2 ; The specific composition of component B3 is: 13.5 wt% Al 2 O 3 and 2.9 wt% B 2 O 3 and 5 wt% Mg 2 O, 10 wt% ZnO 2 and 3 wt% CaO, 0.25 wt% Na 2 O, 0.35 wt% K 2 O, 39.2 wt% P 2 O 5 and 4 wt% Ag 2 O, 9.3 wt% ZrO 2 and 12 wt% SiO 2 and 0.5 wt% CeO 2 .

[0016] A method for the above-mentioned antibacterial glass with stable silver ion release, comprising the following steps: Step 1: Weigh the raw materials according to the ratios of component A1, component A2, component A3, component B1, component B2, and component B3 respectively, mix them evenly respectively, then place them in crucibles respectively, and melt them at 1300 - 1500 °C; Step 2: Shape the 6 melts obtained in Step 1 into sheets or directly quench them in water. The obtained glass is then ball-milled respectively until the glass powder with D50 of 50 - 200 µm is obtained, and component A1, component A2, component A3, component B1, component B2, and component B3 are obtained respectively; Step 3: Weigh and mix one or more of component A1, component A2, and component A3 with one or more of component B1, component B2, and B3 according to a mass ratio of 1:3 - 3:1. After preliminary stirring, add 2 - 3 wt% of water based on the mass of the mixture, and then mix evenly; Step 4: Add the mixture obtained in step 3 to the mold, with the weight of glass powder added to the mold being 0.5-5g, and then press it into shape, and then sinter it at 700-1000℃ for 30-120 minutes. After sintering, cool it to room temperature to obtain the final product.

[0017] The specific composition of component A1 in step 1 is: 2wt%Al 2 O 3 、8wt%B 2 O 3 、2wt%ZnO 2 、25wt%CaO、0.7wt%Na 2 O, 0.5wt%K 2 O, 42wt%P 2 O 5 、9wt%Ag 2 O, 6.2wt% ZrO 2 、4.2wt%SiO 2 and 0.4wt%CeO 2 ; The specific composition of component A2 is: 2.4wt%Al 2 O 3 、7wt%B 2 O 3 、1.5wt%Mg 2 O, 26wt%CaO, 0.8wt%Na 2 O, 0.4wt%K 2 O, 41wt%P 2 O 5 、10wt%Ag 2 O, 7wt% ZrO 2 、3.5wt%SiO 2 and 0.4wt%CeO 2 ; The specific composition of component A3 is: 1.5wt%Al 2 O 3 、9wt%B 2 O 3 、1wt%Mg 2 O, 1.5wt% ZnO 2 、25.6wt%CaO、0.6wt%Na 2 O, 0.4wt%K 2 O, 40wt%P 2 O 5 、9.5wt%Ag 2 O, 6.5wt% ZrO 2 、4wt%SiO 2 and 0.4wt%CeO 2 .

[0018] The specific composition of component B1 in step 1 is: 13 wt% Al 2 O 3 、2 wt% B 2 O 3 、4 wt% Mg 2 O, 11 wt% ZnO 2 、3 wt% CaO, 0.2 wt% Na 2 O, 0.3 wt% K 2 O, 40 wt% P 2 O 5 、5 wt% Ag 2 O, 9 wt% ZrO 2 、12 wt% SiO 2 and 0.5 wt% CeO 2 ; The specific composition of component B2 is: 14 wt% Al 2 O 3 、2.5 wt% B 2 O 3 、3 wt% Mg 2 O, 9 wt% ZnO 2 、2 wt% CaO, 0.3 wt% Na 2 O, 0.2 wt% K 2 O, 41 wt% P 2 O 5 、4.5 wt% Ag 2 O, 10 wt% ZrO 2 、13 wt% SiO 2 and 0.5 wt% CeO 2 ; The specific composition of component B3 is: 13.5 wt% Al 2 O 3 、2.9 wt% B 2 O 3 、5 wt% Mg 2 O, 10 wt% ZnO 2 、3 wt% CaO, 0.25 wt% Na 2 O, 0.35 wt% K 2 O, 39.2 wt% P 2 O 5 、4 wt% Ag 2 O, 9.3 wt% ZrO 2 、12 wt% SiO 2 and 0.5 wt% CeO 2 .

[0019] The present invention also provides another method for preparing the aforementioned antibacterial glass. Step 1: Weigh and mix one or more of component A1, component A2, and component A3 with one or more of component B1, component B2, and B3 according to a mass ratio of 1:3 - 3:1. After preliminary stirring, add 2 - 3 wt% of water based on the mass of the mixture, and then mix evenly. Step 2: Add the mixture obtained in Step 1 to a mold. The weight of the glass powder added to the mold is 0.5 - 5 g. Then, press it into shape and sinter it at 700 - 1000 °C for 30 - 120 minutes. After sintering is completed, cool it to room temperature to obtain the final product.

[0020] The specific composition of component A1 in Step 1 is: 2 wt% Al 2 O 3 , 8 wt% B 2 O 3 , 2 wt% ZnO 2 , 25 wt% CaO, 0.7 wt% Na 2 O, 0.5 wt% K 2 O, 42 wt% P 2 O 5 , 9 wt% Ag 2 O, 6.2 wt% ZrO 2 , 4.2 wt% SiO 2 and 0.4 wt% CeO 2 ; The specific composition of component A2 is: 2.4 wt% Al 2 O 3 , 7 wt% B 2 O 3 , 1.5 wt% Mg 2 O, 26 wt% CaO, 0.8 wt% Na 2 O, 0.4 wt% K 2 O, 41 wt% P 2 O 5 , 10 wt% Ag 2 O, 7 wt% ZrO 2 , 3.5 wt% SiO 2 and 0.4 wt% CeO 2 ; The specific composition of component A3 is: 1.5 wt% Al 2 O 3 , 9 wt% B 2 O 3 , 1 wt% Mg 2 O, 1.5 wt% ZnO 2 , 25.6 wt% CaO, 0.6 wt% Na 2 O, 0.4 wt% K 2 O, 40 wt% P2 O 5 and 9.5 wt% Ag 2 O, 6.5 wt% ZrO 2 and 4 wt% SiO 2 and 0.4 wt% CeO 2 .

[0021] The specific composition of component B1 in step 1 is: 13 wt% Al 2 O 3 and 2 wt% B 2 O 3 and 4 wt% Mg 2 O, 11 wt% ZnO 2 and 3 wt% CaO, 0.2 wt% Na 2 O, 0.3 wt% K 2 O, 40 wt% P 2 O 5 and 5 wt% Ag 2 O, 9 wt% ZrO 2 and 12 wt% SiO 2 and 0.5 wt% CeO 2 ; The specific composition of component B2 is: 14 wt% Al 2 O 3 and 2.5 wt% B 2 O 3 and 3 wt% Mg 2 O, 9 wt% ZnO 2 and 2 wt% CaO, 0.3 wt% Na 2 O, 0.2 wt% K 2 O, 41 wt% P 2 O 5 and 4.5 wt% Ag 2 O, 10 wt% ZrO 2 and 13 wt% SiO 2 and 0.5 wt% CeO 2 ; The specific composition of component B3 is: 13.5 wt% Al 2 O 3 and 2.9 wt% B 2 O 3 and 5 wt% Mg 2 O, 10 wt% ZnO 2 and 3 wt% CaO, 0.25 wt% Na 2 O, 0.35 wt% K 2 O, 39.2 wt% P 2 O 5 and 4 wt% Ag 2 O, 9.3 wt% ZrO 2, 12 wt% SiO 2 and 0.5 wt% CeO 2 .

[0022] Through a large number of studies, the present invention realizes a novel antibacterial glass with a high silver content that can stably release silver ions for a long time by adjusting the composition of the glass formula, especially by utilizing the hydrolysis resistance of zirconia to control the specific ratio of network modifiers such as alkali metals and alkaline earth metals in the glass. There are also two components with different dissolution rates and silver contents in the antibacterial glass of the present invention. Through the combination of specific ratios, the overall release of silver ions has good stability and complementary dissolution characteristics. Specifically, for component A: Component A1, Component A2, and Component A3 contain a relatively high amount of silver oxide, and at the same time, the solubility of component A is relatively high; for component B: Component B1, Component B2, and Component B3 contain a relatively low amount of silver oxide, and at the same time, their respective solubilities are relatively low. Utilizing the large solubility of component A, with the increase of time, more is dissolved, while the solubility of component B is small and less is dissolved. Subsequently, the contact area of A with water decreases, and the contact area of B with water increases, resulting in a small difference in the dissolved silver ions and the like before and after, making the total solubility tend to be stable.

[0023] On the other hand, the Ag⁺ of silver-containing antibacterial glass usually shows coloration after long-term use due to factors such as light. In the present invention, this problem is overcome by using a specific component design. Specifically, zirconia in the component, which is also a kind of nucleating agent, is used to achieve rapid nucleation, resulting in a relatively small final size of the prepared glass, and the average size of the glass grains is 15 - 20 nm. Based on the relatively high solubility of borate glass for silver ions and combined with the design of boron oxide, the coloration phenomenon of silver is inhibited through these two aspects. Brief Description of the Drawings

[0024] Figure 1 It is a photograph of the antibacterial glass prepared in Example 1 of the present invention; Figure 2 It is a comparison chart of silver ion release results of the antibacterial glasses prepared in Example 1 and Comparative Example 1 of the present invention from 24 hours to 280 days. Detailed Embodiments

[0025] Hereinafter, the antibacterial glass as an embodiment of the present invention will be specifically described with appropriate reference to the drawings.

[0026] Example 1

[0027] The raw materials of component A1 and component B1 are prepared by self-making or directly purchased from the market. Specifically, for component A1: 2 wt% Al 2 O 3 , 8 wt% B 2 O 3 , 2 wt% ZnO 2, 25 wt% CaO, 0.7 wt% Na 2 O, 0.5 wt% K 2 O, 42 wt% P 2 O 5 , 9 wt% Ag 2 O, 6.2 wt% ZrO 2 , 4.2 wt% SiO 2 and 0.4 wt% CeO 2 ; Component B1: 13 wt% Al 2 O 3 , 2 wt% B 2 O 3 , 4 wt% Mg 2 O, 11 wt% ZnO 2 , 3 wt% CaO, 0.2 wt% Na 2 O, 0.3 wt% K 2 O, 40 wt% P 2 O 5 , 5 wt% Ag 2 O, 9 wt% ZrO 2 , 12 wt% SiO 2 and 0.5 wt% CeO 2 , Mix Component A1 and Component B1 in a mass ratio of 2:3, and use the QH375 type forced mixer of Wuxi Yuanfang Machinery Co., Ltd. for mixing. First, mix at a stirring speed of about 5 - 20 rpm for 5 - 10 minutes. During the process, add 2 - 3% deionized water through the water addition device inside the mixer, and then mix at a stirring speed of 30 - 60 rpm for 3 - 5 minutes. Then add it to the mold. The weight of the glass powder added to the mold is 0.5 g, and then press it into shape, and then sinter it at 700 - 1000 °C for 30 - 120 minutes. After sintering, cool it to room temperature to obtain the final product. The photo of the obtained product is as Figure 1 shown, Immerse 30 g of the prepared antibacterial glass in 1 liter of purified water (30 °C, pH = 6.5 - 7), maintain the temperature state, and place it in a closed system for 24 hours - 280 days for measurement. Test the silver ion release or dissolution amount of the product. The silver ion release or dissolution amount on the first day is 0.046 mg / (g×L×24H×30 °C), and the silver ion release or dissolution amount on the 280th day is 0.0445 mg / (g×L×24H×30 °C).

[0028] Example 2

[0029] First, the raw materials of component A2 and component B2 are prepared by the following steps, specifically: Step 1: the raw materials are weighed according to the ratio of component A2 and component B2 respectively, and then they are mixed evenly, and then placed in a crucible respectively, and melted at 1300-1500° C.; Step 2: The two melts obtained in step 1 are formed into sheets or directly quenched by water, and the obtained glasses are respectively ball-milled to obtain glass powder with a D50 of 50-200µm, and component A2 and component B2 are obtained respectively. The specific composition of component A2 is: 2.4wt%Al 2 O 3 、7wt%B 2 O 3 、1.5wt%Mg 2 O, 26wt%CaO, 0.8wt%Na 2 O, 0.4wt%K 2 O, 41wt%P 2 O 5 、10wt%Ag 2 O, 7wt% ZrO 2 、3.5wt%SiO 2 and 0.4wt%CeO 2 ; The specific composition of component B2 is: 14wt%Al 2 O 3 、2.5wt%B 2 O 3 、3wt%Mg 2 O, 9wt% ZnO 2 、2wt%CaO、0.3wt%Na 2 O, 0.2wt%K 2 O, 41wt%P 2 O 5 、4.5wt%Ag 2 O, 10wt% ZrO 2 、13wt%SiO 2 and 0.5wt%CeO 2 , Next, component A2 and component B2 are mixed in a mass ratio of 1:1, and mixed using a QH375 forced mixer from Wuxi Yuanfang Machinery Co., Ltd., with a stirring speed of about 5-20rpm and a mixing time of 5-10 minutes. During the process, 2-3% deionized water is added through the water adding device inside the mixer, and then mixed for 3-5 minutes at a stirring speed of 30-60rpm. Then, it is added to the mold, and the weight of the glass powder added to the mold is 1g, and then pressed into shape, and then sintered at 700-1000℃ for 30-120 minutes. After sintering, it is cooled to room temperature to obtain the final product.

[0030] 30g of the obtained antibacterial glass was immersed in 1 liter of purified water (30℃, pH=6.5-7) to maintain the temperature, and then placed in a closed system for 24 hours to 280 days for measurement. The silver ion release or dissolution of the test product was 0.051mg / (g×L×24H×30℃) on the first day and 0.0501mg / (g×L×24H×30℃) on the 280th day.

[0031] Example 3

[0032] First, the raw materials of component A3 and component B3 are prepared by the following steps, specifically: Step 1: the raw materials are weighed according to the ratio of component A3 and component B3 respectively, and then they are mixed evenly, and then placed in a crucible respectively, and melted at 1300-1500° C.; Step 2: The two melts obtained in step 1 are formed into sheets or directly quenched by water, and the obtained glasses are respectively ball-milled to obtain glass powder with a D50 of 50-200µm, and component A3 and component B3 are obtained respectively. The specific composition of component A3 is 1.5wt%Al 2 O 3 、9wt%B 2 O 3 、1wt%Mg 2 O, 1.5wt% ZnO 2 、25.6wt%CaO、0.6wt%Na 2 O, 0.4wt%K 2 O, 40wt%P 2 O 5 、9.5wt%Ag 2 O, 6.5wt% ZrO 2 、4wt%SiO 2 and 0.4wt%CeO 2 ; The specific composition of component B3 is: 13.5wt%Al 2 O 3 、2.9wt%B 2 O 3 、5wt%Mg 2 O, 10wt% ZnO 2 、3wt%CaO、0.25wt%Na 2 O, 0.35wt%K 2 O, 39.2wt%P 2 O 5 、4wt%Ag 2 O, 9.3wt% ZrO 2 、12wt%SiO 2 and 0.5wt%CeO2 , Next, mix component A3 and component B3 in a mass ratio of 1:1 using a QH375 type forced mixer from Wuxi Yuanfang Machinery Co., Ltd. First, mix at a stirring speed of about 5 - 20 rpm for 5 - 10 minutes. During the process, add 2 - 3% deionized water through the water addition device inside the mixer, and then mix at a stirring speed of 30 - 60 rpm for 3 - 5 minutes. Then add it to the mold. The weight of the glass powder added to the mold is 1 g, and then press it into shape. Then sinter it at 700 - 1000 °C for 30 - 120 minutes. After sintering is completed, cool it to room temperature to obtain the final product.

[0033] Immerse 30 g of the prepared antibacterial glass in 1 liter of purified water (30 °C, pH = 6.5 - 7), maintain the temperature state, and place it in a closed system for 24 hours - 280 days for measurement. Test the silver ion release or dissolution amount of the product. The silver ion release or dissolution amount on the first day is 0.051 mg / (g×L×24H×30 °C), and the silver ion release or dissolution amount on the 280th day is 0.0501 mg / (g×L×24H×30 °C).

[0034] Example 4

[0035] Self - make or directly purchase the raw materials of component A1, A2 and component B1 from the market. Specifically, component A1: 2 wt% Al 2 O 3 , 8 wt% B 2 O 3 , 2 wt% ZnO 2 , 25 wt% CaO, 0.7 wt% Na 2 O, 0.5 wt% K 2 O, 42 wt% P 2 O 5 , 9 wt% Ag 2 O, 6.2 wt% ZrO 2 , 4.2 wt% SiO 2 and 0.4 wt% CeO 2 ; component B1: 13 wt% Al 2 O 3 , 2 wt% B 2 O 3 , 4 wt% Mg 2 O, 11 wt% ZnO 2 , 3 wt% CaO, 0.2 wt% Na 2 O, 0.3 wt% K 2 O, 40 wt% P 2 O 5 , 5 wt% Ag2 O, 9wt% ZrO 2 、12wt%SiO 2 and 0.5wt%CeO 2 , components A1, A2 and component B1 are mixed in a mass ratio of (A1+A2): B1=2:3, and mixed using a QH375 forced mixer from Wuxi Yuanfang Machinery Co., Ltd., first at a stirring speed of about 5-20rpm, for 5-10 minutes, during which 2-3% deionized water is added through the water adding device inside the mixer, and then mixed at a stirring speed of 30-60rpm for 3-5 minutes. Then, the mixture is added to the mold, with the weight of 0.5g of glass powder added to the mold, and then pressed into shape, and then sintered at 700-1000℃ for 30-120 minutes, and cooled to room temperature after sintering to obtain the final product.

[0036] 30g of the obtained antibacterial glass was immersed in 1 liter of purified water (30℃, pH=6.5-7) to maintain the temperature, and then placed in a closed system for 24 hours to 280 days for measurement. The silver ion release or dissolution of the test product was 0.046mg / (g×L×24H×30℃) on the first day and 0.0445mg / (g×L×24H×30℃) on the 280th day.

[0037] The difference between Examples 5-10 and Example 1 is that the specific compositions of component A and component B are different. Table 1 lists the compositions and silver ion release or dissolution data of Examples 5-10.

[0038] At the same time, the present invention also tests the coloring performance of the products prepared in Examples 1-10 and Comparative Examples 1-6. Take 20g of each of the products prepared in Examples 1-10 and Comparative Examples 1-6, and place them in tap water at 30°C for 24 hours to prepare 16 portions of the liquid to be tested. Add 16 portions of the liquid to be tested to 16 polystyrene plastic containers with a capacity of 100ml, respectively, and use the HAM-300 high-precision spectral haze meter of Hangzhou Yuanfang Optoelectronic Information Co., Ltd. to test the polystyrene plastic containers containing the liquid to be tested. The comparative sample is the liquid to be tested directly being tap water. By testing the color L value of the comparative sample and the liquid to be tested prepared in Examples 1-10 and Comparative Examples 1-6, the difference between the color L value of the liquid to be tested prepared in Examples 1-10 and Comparative Examples 1-6 and the color L value of the polystyrene plastic container only filled with tap water is recorded as ΔL. The greater the increase in the difference ΔL value, the more serious the coloring. In this application, a ΔL value ≤ 10 is considered to be coloring OK; a ΔL value > 10 is considered to be coloring not OK.

[0039] Table 1 Composition, silver ion release or dissolution data, and coloring performance of Examples 5 - 10 Example Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Component A A1 A1 + A3 A2 + A3 A1 + A2 + A3 A1 A1 + A2 + A3 Component B B1 + B2 B3 B2 + B3 B1 B1 + B2 + B3 B1 + B2 + B3 Mass ratio of Component A to Component B 1:1 1:2 2:1 1:1 1:3 3:1 Silver ion release or dissolution amount on the first day, mg / (g×L×24H×30℃) 0.0545 0.0371 0.0482 0.0489 0.0453 0.0441 Silver ion release or dissolution amount on the 280th day, mg / (g×L×24H×30℃) 0.0514 0.0366 0.0467 0.0476 0.0438 0.0427 Colorability OK OK OK OK OK OK The differences between Comparative Examples 1 - 6 and Example 1 lie in the specific compositions of Component A and Component B. Table 2 lists the compositions, silver ion release or dissolution data, and coloring performance of Comparative Examples 1 - 6.

[0040] Table 2 Composition, silver ion release or dissolution data, and coloring performance of Comparative Examples 1 - 6 Comparative example Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Component A A3 None C1 A1 A1 A1 + A2 + A3 Component B None B3 B1 D1 B1 B1 + B2 + B3 Mass ratio of Component A to Component B / / C1:B1 = 1:3 A1:D1 = 1:1 1：4 4：1 Silver ion release or dissolution amount on the first day, mg / (g×L×24H×30℃) 0.0761 0.0202 0.0291 0.0468 0.0752 0.0684 Silver ion release or dissolution amount on the 280th day, mg / (g×L×24H×30℃) 0.06386 0.01883 0.0271 0.0412 0.0709 0.0521 Colorability Not OK OK OK Not OK Not OK Not OK The specific composition of Component C1 in Comparative Example 3 is: 4wt% Al 2 O 3 、8wt% Mg 2 O、10wt% ZnO 2 、2wt% CaO、8wt% K 2 O、62wt% P 2 O 5 and 6wt% Ag 2 O.

[0041] The specific composition of Component D1 in Comparative Example 4 is: 2wt% Al 2 O 3 、5wt% B 2 O 3 、22wt% CaO、0.5wt% Na 2 O、0.3wt% K 2 O、67wt% P 2 O 5 、3wt% Ag 2 O and 0.5wt% CeO 2 .

[0042] The applicant also simultaneously compared the silver ion dissolution of antibacterial glasses with only the addition of A1, only the addition of B1, only the addition of A2, and only the addition of B2 after 280 days, and found that the stable silver ion dissolution effect of the antibacterial glasses of the present invention could not be achieved.

Claims

1. An antibacterial glass that stably releases silver ions, characterized in that: It consists of component A and component B in a mass ratio of 1:3-3:1, wherein component A contains 9-10wt% Ag2O, and the silver ion solubility of component A is 0.020-0.060mg / (g×L×24H×30℃); component B contains 4-5wt% Ag2O, and the silver ion solubility of component B is 0.010-0.030mg / (g×L×24H×30℃), wherein component A is one or more of component A1, component A2, and component A3, and the specific composition of component A1 is: 2wt% Al2O3, 8wt% B2O3, 2wt% ZnO2, 25wt% CaO, 0.7wt% Na2O, 0.5wt% K2O, 42wt% %P2O5, 9wt%Ag2O, 6.2wt%ZrO2, 4.2wt%SiO2 and 0.4wt%CeO2; the specific composition of component A2 is: 2.4wt%Al2O3, 7wt%B2O3, 1.5wt%Mg2O, 26wt%CaO, 0.8wt%Na2O, 0.4wt%K2O, 41wt%P2O5, 10wt%Ag2O, 7wt%ZrO2, 3.5wt%SiO2 and 0.4wt%CeO2; the specific composition of component A3 is: 1.5wt%Al2O3, 9wt%B2O3, 1wt%Mg2O, 1.5wt%ZnO2, 25.6wt%CaO, 0.6wt%Na2 O, 0.4wt% K2O, 40wt% P2O5, 9.5wt% Ag2O, 6.5wt% ZrO2, 4wt% SiO2 and 0.4wt% CeO2; component B is one or more of component B1, component B2 and component B3, and the specific composition of component B1 is: 13wt% Al2O3, 2wt% B2O3, 4wt% Mg2O, 11wt% ZnO2, 3wt% CaO, 0.2wt% Na2O, 0.3wt% K2O, 40wt% P2O5, 5wt% Ag2O, 9wt% ZrO2, 12wt% SiO2 and 0.5wt% CeO2; the specific composition of component B2 is: 14wt% Al2O3, 2.5wt% t%B2O3, 3wt%Mg2O, 9wt%ZnO2, 2wt%CaO, 0.3wt%Na2O, 0.2wt%K2O, 41wt%P2O5, 4.5wt%Ag2O, 10wt%ZrO2, 13wt%SiO2 and 0.5wt%CeO2; the specific composition of component B3 is: 13.5wt%Al2O3, 2.9wt%B2O3, 5wt%Mg2O, 10wt%ZnO2, 3wt%CaO, 0.25wt%Na2O, 0.35wt%K2O, 39.2wt%P2O5, 4wt%Ag2O, 9.3wt%ZrO2, 12wt%SiO2 and 0.5wt%CeO2.

2. The antibacterial glass for stably releasing silver ions according to claim 1, characterized in that: The antibacterial glass contains 5.25-8.75wt% silver.

3. The antibacterial glass with stable silver ion release according to claim 1, characterized in that: After 280 days, the release of silver ions was more than 95% of the initial release.

4. A method for preparing the antibacterial glass capable of stably releasing silver ions according to claim 1 or 2, characterized in that: The following steps are involved: Step 1: Weigh the raw materials according to the proportions of component A1, component A2, component A3, component B1, component B2, and component B3, mix them evenly, and then place them in crucibles and melt them at 1300-1500° C.; Step 2: The six melts obtained in step 1 are formed into sheets or directly water-quenched, and the obtained glasses are respectively ball-milled to obtain glass powders with a D50 of 50-200 µm, thereby obtaining component A1, component A2, component A3, component B1, component B2 and component B3; Step 3: Weigh and mix one or more of component A1, component A2, and component A3 with one or more of component B1, component B2, and component B3 in a mass ratio of 1:3-3:1, initially stir, then add 2-3wt% of water by mass of the mixture, and mix evenly; Step 4: Add the mixture obtained in step 3 to the mold, with the weight of glass powder added to the mold being 0.5-5g, and then press it into shape, and then sinter it at 900-1300℃ for 30-120 minutes. After sintering, cool it to room temperature to obtain the final product.

5. A method for preparing the antibacterial glass capable of stably releasing silver ions as claimed in claim 1 or 2, characterized in that: The following steps are involved: Step 1: Weigh and mix one or more of component A1, component A2, and component A3 with one or more of component B1, component B2, and component B3 in a mass ratio of 1:3-3:1, initially stir, then add 2-3wt% of water by mass of the mixture, and mix evenly; Step 2: Add the mixture obtained in step 1 to the mold, with the weight of glass powder added to the mold being 0.5-5g, and then press it into shape, and then sinter it at 700-1000℃ for 30-120 minutes. After sintering, cool it to room temperature to obtain the final product.

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