An antibacterial glass with stable silver ion release and its preparation method

Abstract

The present invention discloses an antibacterial glass capable of stably releasing silver ions and a preparation method thereof. The antibacterial glass capable of stably releasing silver ions is composed of component A and component B in a mass ratio of 1:3 - 3:1. Component A contains 9 - 10 wt% Ag2O, 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% Ag2O, and the silver ion solubility of component B is 0.010 - 0.030 mg / (g×L×24Hrs×30°C). By adjusting the composition of the glass formula, especially by utilizing the hydrolysis resistance of zirconia and controlling the specific ratio of network modifiers such as alkali metals and alkaline earth metals in the glass, a new type of antibacterial glass with a high silver content and capable of stably releasing silver ions in the long term is achieved.

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 multiplying 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 after a long time. To meet related requirements, various measures are taken, 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 lower than at the beginning. There are currently 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 initial 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 particularly 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, the same silver ion hydrolysis rate can be achieved, and at the same time, the problem of silver ion coloring does not occur.

[0005] The patent with the application number CN201480023325.X discloses an antibacterial glass which can be housed in a narrow housing space of an antibacterial water unit for supplying antibacterial water to the washing tub of a washing machine, can effectively inhibit the generation of Cladosporium cladosporioides, etc. in the washing tub, and can inhibit the coloring of the objects to be washed while enabling effective antibacterial action. For the antibacterial glass of the present invention which directly contacts water and releases silver ions to exert antibacterial effect, when the total amount is 100% by weight, the content of Ag2O is a value in the range of more than 5% by weight and 10% by weight or less, the contents of P2O5 and CaO are values within the specified ranges, the content of ZnO is a value less than 10% by weight, the contents of K2O, Al2O3 and MgO are values within the specified ranges, and the shape of the antibacterial glass is tablet-shaped. However, judging from the data disclosed therein, 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 and provide a glass antibacterial agent capable of stably releasing silver ions for a long time, the applicant adjusted the composition of the glass formula, especially utilized the hydrolysis resistance of zirconia to regulate the specific ratios of network modifiers such as alkali metals and alkaline earth metals in the glass, and achieved a new type of antibacterial glass with long-term stable release of silver ions at a high silver content. The specific technical solution of the present invention is as follows:

[0007] An antibacterial glass with stable silver ion release, which is composed of component A and component B in a mass ratio of 1:3 - 3:1. Component A contains 9 - 10 wt% Ag2O, 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% Ag2O, and the silver ion solubility of component B is 0.010 - 0.030 mg / (g×L×24Hrs×30°C).

[0008] 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.

[0009] The silver ion solubility of the 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.

[0010] 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.

[0011] Further, the finished antibacterial glass is in granular form, about 0.5 - 1 g / granule, and has a density of 2.2 - 2.8 g / cm³.

[0012] Further, after 280 days, the silver ion release amount is more than 95% of the reference release amount. Specifically, the reference release amount here refers to the silver ion solubility (dissolution amount) 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 amounts of the antibacterial glass prepared at different days. After 280 days, the silver ion release amount of the antibacterial glass prepared by the present invention is more than 95% of the reference release amount.

[0013] 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 L 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.

[0014] 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.

[0015] The component A is one or more of component A1, component A2, and component A3. The specific composition of component A1 is: 2 wt% Al2O3, 8 wt% B2O3, 2 wt% ZnO2, 25 wt% CaO, 0.7 wt% Na2O, 0.5 wt% K2O, 42 wt% P2O5, 9 wt% Ag2O, 6.2 wt% ZrO2, 4.2 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A2 is: 2.4 wt% Al2O3, 7 wt% B2O3, 1.5 wt% MgO, 26 wt% CaO, 0.8 wt% Na2O, 0.4 wt% K2O, 41 wt% P2O5, 10 wt% Ag2O, 7 wt% ZrO2, 3.5 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A3 is: 1.5 wt% Al2O3, 9 wt% B2O3, 1 wt% MgO, 1.5 wt% ZnO2, 25.6 wt% CaO, 0.6 wt% Na2O, 0.4 wt% K2O, 40 wt% P2O5, 9.5 wt% Ag2O, 6.5 wt% ZrO2, 4 wt% SiO2, and 0.4 wt% CeO2.

[0016] The component B is one or more of component B1, component B2, and component B3. The specific composition of component B1 is: 13 wt% Al2O3, 2 wt% B2O3, 4 wt% MgO, 11 wt% ZnO2, 3 wt% CaO, 0.2 wt% Na2O, 0.3 wt% K2O, 40 wt% P2O5, 5 wt% Ag2O, 9 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B2 is: 14 wt% Al2O3, 2.5 wt% B2O3, 3 wt% MgO, 9 wt% ZnO2, 2 wt% CaO, 0.3 wt% Na2O, 0.2 wt% K2O, 41 wt% P2O5, 4.5 wt% Ag2O, 10 wt% ZrO2, 13 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B3 is: 13.5 wt% Al2O3, 2.9 wt% B2O3, 5 wt% MgO, 10 wt% ZnO2, 3 wt% CaO, 0.25 wt% Na2O, 0.35 wt% K2O, 39.2 wt% P2O5, 4 wt% Ag2O, 9.3 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2.

[0017] A method for the aforementioned antibacterial glass with stable silver ion release, comprising the following steps:

[0018] Step 1: Weigh the raw materials according to the proportions of component A1, component A2, component A3, component B1, component B2, and component B3 respectively, mix them evenly respectively, then place them in crucibles and melt them under the condition of 1300 - 1500 °C;

[0019] Step 2: The 6 kinds of melts obtained in Step 1 are each formed into sheets or directly water-quenched, and 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;

[0020] 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 mixed materials, and then mix evenly;

[0021] Step 4: Add the mixed materials obtained in Step 3 into a mold. The weight of the glass powder added to the mold is 0.5 - 5 g, then press and form, and then sinter at 700 - 1000 °C for 30 - 120 minutes. After sintering is completed, cool to room temperature to obtain the final product.

[0022] The specific composition of component A1 in Step 1 is: 2 wt% Al2O3, 8 wt% B2O3, 2 wt% ZnO2, 25 wt% CaO, 0.7 wt% Na2O, 0.5 wt% K2O, 42 wt% P2O5, 9 wt% Ag2O, 6.2 wt% ZrO2, 4.2 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A2 is: 2.4 wt% Al2O3, 7 wt% B2O3, 1.5 wt% MgO, 26 wt% CaO, 0.8 wt% Na2O, 0.4 wt% K2O, 41 wt% P2O5, 10 wt% Ag2O, 7 wt% ZrO2, 3.5 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A3 is: 1.5 wt% Al2O3, 9 wt% B2O3, 1 wt% MgO, 1.5 wt% ZnO2, 25.6 wt% CaO, 0.6 wt% Na2O, 0.4 wt% K2O, 40 wt% P2O5, 9.5 wt% Ag2O, 6.5 wt% ZrO2, 4 wt% SiO2, and 0.4 wt% CeO2.

[0023] The specific composition of component B1 in step 1 is as follows: 13 wt% Al2O3, 2 wt% B2O3, 4 wt% MgO, 11 wt% ZnO2, 3 wt% CaO, 0.2 wt% Na2O, 0.3 wt% K2O, 40 wt% P2O5, 5 wt% Ag2O, 9 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B2 is: 14 wt% Al2O3, 2.5 wt% B2O3, 3 wt% MgO, 9 wt% ZnO2, 2 wt% CaO, 0.3 wt% Na2O, 0.2 wt% K2O, 41 wt% P2O5, 4.5 wt% Ag2O, 10 wt% ZrO2, 13 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B3 is: 13.5 wt% Al2O3, 2.9 wt% B2O3, 5 wt% MgO, 10 wt% ZnO2, 3 wt% CaO, 0.25 wt% Na2O, 0.35 wt% K2O, 39.2 wt% P2O5, 4 wt% Ag2O, 9.3 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2.

[0024] 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 mixed materials, and then mix evenly.

[0025] Step 2: Add the mixed materials 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.

[0026] The specific composition of component A1 in step 1 is as follows: 2 wt% Al2O3, 8 wt% B2O3, 2 wt% ZnO2, 25 wt% CaO, 0.7 wt% Na2O, 0.5 wt% K2O, 42 wt% P2O5, 9 wt% Ag2O, 6.2 wt% ZrO2, 4.2 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A2 is: 2.4 wt% Al2O3, 7 wt% B2O3, 1.5 wt% MgO, 26 wt% CaO, 0.8 wt% Na2O, 0.4 wt% K2O, 41 wt% P2O5, 10 wt% Ag2O, 7 wt% ZrO2, 3.5 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A3 is: 1.5 wt% Al2O3, 9 wt% B2O3, 1 wt% MgO, 1.5 wt% ZnO2, 25.6 wt% CaO, 0.6 wt% Na2O, 0.4 wt% K2O, 40 wt% P2O5, 9.5 wt% Ag2O, 6.5 wt% ZrO2, 4 wt% SiO2, and 0.4 wt% CeO2.

[0027] The specific composition of component B1 in step 1 is as follows: 13 wt% Al2O3, 2 wt% B2O3, 4 wt% MgO, 11 wt% ZnO2, 3 wt% CaO, 0.2 wt% Na2O, 0.3 wt% K2O, 40 wt% P2O5, 5 wt% Ag2O, 9 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B2 is: 14 wt% Al2O3, 2.5 wt% B2O3, 3 wt% MgO, 9 wt% ZnO2, 2 wt% CaO, 0.3 wt% Na2O, 0.2 wt% K2O, 41 wt% P2O5, 4.5 wt% Ag2O, 10 wt% ZrO2, 13 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B3 is: 13.5 wt% Al2O3, 2.9 wt% B2O3, 5 wt% MgO, 10 wt% ZnO2, 3 wt% CaO, 0.25 wt% Na2O, 0.35 wt% K2O, 39.2 wt% P2O5, 4 wt% Ag2O, 9.3 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2.

[0028] Through a large number of studies, the present invention realizes a novel antibacterial glass with a high silver content that can stably dissolve silver ions for a long time by adjusting the composition of the glass formula, especially by utilizing the hydrolysis resistance of zirconia and controlling 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, etc., and making the total solubility tend to be stable.

[0029] On the other hand, the Ag+ of silver-containing antibacterial glass usually shows a coloring phenomenon after being affected by factors such as light during long-term use. 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 coloring phenomenon of silver is inhibited through these two aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a photograph of the antibacterial glass prepared in Example 1 of the present invention;

[0031] 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 DESCRIPTION OF THE EMBODIMENTS

[0032] Hereinafter, the antibacterial glass as an embodiment of the present invention will be specifically described with appropriate reference to the drawings.

[0033] Example 1

[0034] The raw materials of component A1 and component B1 are homemade or purchased directly from the market, specifically component A1: 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; component B1: 13wt% Al2O3, 2wt% B2O3, 4wt% MgO, 11wt% ZnO2, 3wt% CaO, 0.2wt% %Na2O, 0.3wt%K2O, 40wt%P2O5, 5wt%Ag2O, 9wt%ZrO2, 12wt%SiO2 and 0.5wt%CeO2, component A1 and component B1 are mixed in a mass ratio of 2:3, and mixed using the QH375 forced mixer of Wuxi Yuanfang Machinery Co., Ltd., first at a stirring speed of about 5-20rpm, mixing time 5-10 minutes, during the process, add 2-3% deionized water through the water adding device inside the mixer, and then mix at a stirring speed of 30-60rpm for 3-5 minutes. Then add it to the mold, the weight of the glass powder added to the mold is 0.5g, then press it into shape, and then sinter it at 700-1000℃ for 30-120 minutes. After sintering, cool it to room temperature to get the final product. The photo of the obtained product is as follows Figure 1 As shown,

[0035] 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.

[0036] Example 2

[0037] 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.;

[0038] Step 2: The two kinds of melts obtained in Step 1 are each formed into sheets or directly water-quenched, and the resulting glasses are respectively ball-milled to glass powders with D50 of 50 - 200 µm to obtain Component A2 and Component B2 respectively. Among them, the specific composition of Component A2 is: 2.4 wt% Al2O3, 7 wt% B2O3, 1.5 wt% MgO, 26 wt% CaO, 0.8 wt% Na2O, 0.4 wt% K2O, 41 wt% P2O5, 10 wt% Ag2O, 7 wt% ZrO2, 3.5 wt% SiO2 and 0.4 wt% CeO2; the specific composition of Component B2 is: 14 wt% Al2O3, 2.5 wt% B2O3, 3 wt% MgO, 9 wt% ZnO2, 2 wt% CaO, 0.3 wt% Na2O, 0.2 wt% K2O, 41 wt% P2O5, 4.5 wt% Ag2O, 10 wt% ZrO2, 13 wt% SiO2 and 0.5 wt% CeO2.

[0039] Then, Component A2 and Component B2 are mixed in a mass ratio of 1:1, and a QH375 type forced mixer of Wuxi Yuanfang Machinery Co., Ltd. is used for mixing. First, at a stirring speed of about 5 - 20 rpm for 5 - 10 minutes, during which 2 - 3% of deionized water is added through the water addition device inside the mixer, and then at a stirring speed of 30 - 60 rpm for 3 - 5 minutes. Then it is added to the mold. The weight of the glass powder added to the mold is 1 g, and then it is pressed into shape and sintered at 700 - 1000 °C for 30 - 120 minutes. After sintering is completed, it is cooled to room temperature to obtain the final product.

[0040] 30 g of the prepared antibacterial glass is immersed in 1 liter of purified water (30 °C, pH = 6.5 - 7), and while maintaining the temperature, it is placed in a closed system for 24 hours - 280 days for measurement. The silver ion release or dissolution amount of the test product is measured. 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).

[0041] Example 3

[0042] First, prepare the raw materials of Component A3 and Component B3 by the following steps. Specifically: Step 1: The raw materials are respectively weighed according to the proportions of Component A3 and Component B3 and then mixed evenly respectively, and then placed in crucibles and melted at 1300 - 1500 °C.

[0043] Step 2: The two kinds of melts obtained in Step 1 are each formed into sheets or directly water-quenched, and the resulting glasses are respectively ball-milled to glass powders with a D50 of 50 - 200 µm, obtaining Component A3 and Component B3 respectively. Among them, the specific composition of Component A3 is 1.5 wt% Al2O3, 9 wt% B2O3, 1 wt% MgO, 1.5 wt% ZnO2, 25.6 wt% CaO, 0.6 wt% Na2O, 0.4 wt% K2O, 40 wt% P2O5, 9.5 wt% Ag2O, 6.5 wt% ZrO2, 4 wt% SiO2, and 0.4 wt% CeO2; the specific composition of Component B3 is: 13.5 wt% Al2O3, 2.9 wt% B2O3, 5 wt% MgO, 10 wt% ZnO2, 3 wt% CaO, 0.25 wt% Na2O, 0.35 wt% K2O, 39.2 wt% P2O5, 4 wt% Ag2O, 9.3 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2.

[0044] Next, Component A3 and Component B3 are mixed in a mass ratio of 1:1 and mixed 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 it is pressed into shape and sintered at 700 - 1000 °C for 30 - 120 minutes. After sintering, it is cooled to room temperature to obtain the final product.

[0045] 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).

[0046] Example 4

[0047] The raw materials of components A1, A2 and B1 are made by ourselves or purchased directly from the market, specifically component A1: 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; component B1: 13wt% Al2O3, 2wt% B2O3, 4wt% MgO, 11wt% ZnO2, 3wt% CaO, 0.2wt% Na2O, 0.3wt% K2O, 40wt% P2O5, 5wt% Ag2O, 9wt% ZrO2, 12wt% SiO2 and 0.5wt% CeO2, components A1, A2 and B1 are mixed in a mass ratio of (A1+A2): B1=2:3, and mixed using a QH375 forced mixer of 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 add it to the mold, the weight of the glass powder added to the mold is 0.5g, and then press it into shape, and then sinter it at 700-1000℃ for 30-120 minutes, and cool it to room temperature after sintering to obtain the final product.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] Table 1 Composition and silver ion release or dissolution data and coloring performance of Examples 5-10

[0052] 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

[0053] The difference between Comparative Examples 1-6 and Example 1 is that the specific compositions of component A and component B are different. Table 2 lists the compositions, silver ion release or dissolution data and coloring performance of Comparative Examples 1-6.

[0054] Table 2 Composition and silver ion release or dissolution data and coloring performance of Comparative Examples 1-6

[0055] 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

[0056] The specific composition of component C1 in Comparative Example 3 is: 4wt% Al2O3, 8wt% MgO, 10wt% ZnO2, 2wt% CaO, 8wt% K2O, 62wt% P2O5 and 6wt% Ag2O.

[0057] The specific composition of component D1 in Comparative Example 4 is: 2wt% Al2O3, 5wt% B2O3, 22wt% CaO, 0.5wt% Na2O, 0.3wt% K2O, 67wt% P2O5, 3wt% Ag2O and 0.5wt% CeO2.

[0058] The applicant also compared the silver ion dissolution of the antibacterial glass with simple addition of A1, simple addition of B1, simple addition of A2, and simple addition of B2 after 280 days, and found that none of them could achieve the stable silver ion dissolution effect of the antibacterial glass of the present invention.

Claims

1. An antibacterial glass that stably releases silver ions, characterized in that, It is composed of component A and component B in a mass ratio of 1:3 - 3:

1. Component A contains 9 - 10 wt% Ag2O, and the silver ion solubility of component A is 0.020 - 0.060 mg / (g×L×24H×30°C); component B contains 4 - 5 wt% Ag2O, and the silver ion solubility of component B is 0.010 - 0.030 mg / (g×L×24H×30°C). Component A is one or more of component A1, component A2, and component A3. The specific composition of component A1 is: 2 wt% Al2O3, 8 wt% B2O3, 2 wt% ZnO2, 25 wt% CaO, 0.7 wt% Na2O, 0.5 wt% K2O, 42 wt% P2O5, 9 wt% Ag2O, 6.2 wt% ZrO2, 4.2 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A2 is: 2.4 wt% Al2O3, 7 wt% B2O3, 1.5 wt% MgO, 26 wt% CaO, 0.8 wt% Na2O, 0.4 wt% K2O, 41 wt% P2O5, 10 wt% Ag2O, 7 wt% ZrO2, 3.5 wt% SiO2, and 0.4 wt% CeO2; the specific composition of component A3 is: 1.5 wt% Al2O3, 9 wt% B2O3, 1 wt% MgO, 1.5 wt% ZnO2, 25.6 wt% CaO, 0.6 wt% Na2O, 0.4 wt% K2O, 40 wt% P2O5, 9.5 wt% Ag2O, 6.5 wt% ZrO2, 4 wt% SiO2, and 0.4 wt% CeO2; component B is one or more of component B1, component B2, and component B3. The specific composition of component B1 is: 13 wt% Al2O3, 2 wt% B2O3, 4 wt% MgO, 11 wt% ZnO2, 3 wt% CaO, 0.2 wt% Na2O, 0.3 wt% K2O, 40 wt% P2O5, 5 wt% Ag2O, 9 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B2 is: 14 wt% Al2O3, 2.5 wt% B2O3, 3 wt% MgO, 9 wt% ZnO2, 2 wt% CaO, 0.3 wt% Na2O, 0.2 wt% K2O, 41 wt% P2O5, 4.5 wt% Ag2O, 10 wt% ZrO2, 13 wt% SiO2, and 0.5 wt% CeO2; the specific composition of component B3 is: 13.5 wt% Al2O3, 2.9 wt% B2O3, 5 wt% MgO, 10 wt% ZnO2, 3 wt% CaO, 0.25 wt% Na2O, 0.35 wt% K2O, 39.2 wt% P2O5, 4 wt% Ag2O, 9.3 wt% ZrO2, 12 wt% SiO2, and 0.5 wt% CeO2.

2. The antibacterial glass for stably releasing silver ions according to claim 1, wherein The silver content of the antibacterial glass is 5.25 - 8.75 wt%.

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

4. A method for preparing the antibacterial glass with stable silver ion release as claimed in claim 1 or 2, characterized in that, It includes the following steps: Step 1: Weigh the raw materials respectively according to the ratios of component A1, component A2, component A3, component B1, component B2, and component B3, mix them evenly respectively, then place them in crucibles and melt them under the condition of 1300 - 1500 °C. Step 2: The 6 kinds of melts obtained in Step 1 are each formed into sheets or directly water - quenched, and the obtained glass is respectively ball - milled 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 mixed material, and then mix evenly. Step 4: Add the mixed material obtained in Step 3 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 900 - 1300 °C for 30 - 120 minutes. After sintering is completed, cool it to room temperature to obtain the final product.

5. A method for preparing the antibacterial glass with stable silver ion release as claimed in claim 1 or 2, characterized in that, It includes the following steps: 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 mixed material, and then mix evenly. Step 2: Add the mixed material 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.

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