Soluble germicidal glass and method for preparing soluble germicidal glass

Abstract

The present application relates to a soluble sterilizing glass and a method for preparing the soluble sterilizing glass. The soluble sterilizing glass comprises 0.2 to 10 parts by weight of zinc oxide, 1 to 20 parts by weight of boron oxide, 10 to 30 parts by weight of calcium oxide, and 30 to 70 parts by weight of phosphorus oxide. The prepared soluble sterilizing glass improves the sustained release performance of zinc ions as a bactericide in the soluble sterilizing glass, and by sustainedly releasing zinc ions at a reasonable speed, the sterilizing efficiency and sterilizing effect of the soluble sterilizing glass can be improved.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims priority to a Chinese patent application filed with the State Intellectual Property Office of the People's Republic of China on December 31, 2020, bearing application number 202011638430.8 and entitled "Soluble germicidal glass and method for preparing soluble germicidal glass," the entire contents of which are incorporated herein by reference.

[0002] The present application relates to the technical field of inorganic antimicrobial materials, and in particular to a soluble germicidal glass and a method for preparing the soluble germicidal glass. [Background technology]

[0003] Antibacterial materials are functional materials with bactericidal and antibacterial properties, and their antibacterial action is mainly achieved by adding antibacterial agents. Antibacterial agents are mainly classified into three types: natural organisms, organic, and inorganic antibacterial agents.

[0004] Natural antibacterial agents such as chitosan and sorbic acid have been extensively studied. These agents are safe, environmentally friendly, and have excellent antibacterial properties. However, they have poor heat resistance, a short effective period, and limited production conditions, making their industrialization difficult.

[0005] Organic antibacterial agents contain organic substances such as organic acids, phenols, quaternary ammonium salts, and benzimidazoles as antibacterial ingredients, and are effective in inhibiting the growth of harmful bacteria and mold. However, they are unstable, easily decomposed, and usually highly toxic.

[0006] Inorganic antibacterial agents are mainly obtained by adding antibacterial metals or their ions to porous materials such as zeolite and silica gel, or materials such as glass. Inorganic antibacterial materials have the characteristics of longer-lasting effectiveness, broad-spectrum antibacterial properties, good heat resistance, and safety compared to organic and biological antibacterial materials.

[0007] Among many inorganic antibacterial agents, zinc is one of the antibacterial agents with relatively good performance and relatively wide use. Zinc-loaded antibacterial glass materials have excellent antibacterial effect and good safety, so extensive application research is being conducted.

[0008] However, one of the drawbacks of the conventional technology is that the sustained release performance of zinc-loaded antibacterial glass materials is insufficient. Summary of the Invention

[0009] The present application aims to solve at least one of the above technical problems.

[0010] Therefore, a first object of the present application is to provide a soluble germicidal glass.

[0011] A second object of the present application is to provide a method for preparing a soluble germicidal glass.

[0012] In order to achieve the first object of the present application, an embodiment of the present application provides a soluble sterilizing glass comprising 0.2 to 10 parts by mass of zinc oxide, 1 to 20 parts by mass of boron oxide, 10 to 30 parts by mass of calcium oxide, and 30 to 70 parts by mass of phosphorus oxide.

[0013] Zinc ions are inorganic bactericides with good bactericidal effect, stable performance and low cost. The present technical solution provides a ternary oxide soluble bactericidal glass mainly composed of boron oxide, calcium oxide and phosphorus oxide, in order to rationally control the release rate and release efficiency of zinc ions in the soluble bactericidal glass. By adding phosphorus oxide and boron oxide and controlling the proportion, zinc ions can be released in boron calcium phosphorus at a reasonable speed. Specifically, the applicant, regardless of any theory, has found in the process of realizing the present application that the addition of phosphorus oxide can increase the dissolution rate of zinc ions to promote the release of zinc ions. Conversely, the addition of boron oxide can reduce the dissolution rate of zinc ions to inhibit the release of zinc ions. Therefore, the present technical solution controls the addition amount and specific ratio of phosphorus oxide and boron oxide (i.e., the content of phosphorus oxide is 30 parts by weight to 70 parts by weight, and the content of boron oxide is 1 part by weight to 20 parts by weight). Thus, the technical solution can reasonably control the sustained release rate and sustained release efficiency of zinc ions in the soluble sterilizing glass. In addition, the addition of calcium oxide can appropriately lower the melting temperature of the soluble sterilizing glass, reduce the production cost of the soluble sterilizing glass, and improve the production efficiency of the soluble sterilizing glass. In addition, the technical solution controls the content of zinc oxide to 0.2 parts by mass to 10 parts by mass, and the above content of zinc oxide can ensure the long-term release of zinc ions in the soluble sterilizing glass and ensure the sterilizing effect of the soluble sterilizing glass.

[0014] In addition, the technical solutions provided by the above embodiments of the present application have the following additional technical features:

[0015] In the above technical solution, the soluble sterilizing glass further includes 0.0001 to 0.0008 parts by weight of a colorant.

[0016] The purpose of adding coloring agents is to adjust and control the color of the soluble germicidal glass to meet the various needs of users.

[0017] In any of the above technical solutions, the colorant includes at least one of cobalt oxide, manganese oxide, iron oxide, copper oxide, and cadmium sulfide, or a combination thereof.

[0018] The colorant used in this technical solution is specifically a metal oxide colorant, which has stable performance, is resistant to high temperatures, and is not easily decomposed.

[0019] In any of the above technical solutions, the soluble sterilizing glass further contains 0.0001 to 0.0006 parts by weight of cerium oxide.

[0020] The addition of cerium oxide to the soluble germicidal glass can increase the proportion of high-valent zinc ions in the zinc ions as germicide, and therefore the addition of cerium oxide can improve the germicidal effect and germicidal efficiency of the soluble germicidal glass according to the embodiment of the present application.

[0021] In any of the above technical solutions, the zinc ions in the soluble sterilizing glass include zinc ions in a tetravalent state.

[0022] Tetravalent zinc ions have a higher bactericidal effect and bactericidal efficiency than divalent zinc ions, so a soluble bactericidal glass containing tetravalent zinc ions has excellent bactericidal effect as well as sustained release effect.

[0023] In any of the above technical solutions, the soluble sterilizing glass further includes at least one of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, silicon oxide, and aluminum oxide, or a combination thereof.

[0024] Alkali metal oxides or alkaline earth metal oxides, including lithium oxide, sodium oxide, and potassium oxide, have relatively active physicochemical properties and can effectively lower the melting point of soluble sterilized glass. The addition of silicon oxide and aluminum oxide promotes the formation of glass and improves the viscosity and mechanical strength of soluble sterilized glass. Magnesium oxide increases the clarity of the molten glass and the gloss and refractive index of the soluble sterilized glass after molding.

[0025] In any of the above technical solutions, the amount of zinc ions dissolved in the soluble sterilizing glass is 1 mg zinc ions / g water to 500 mg zinc ions / g water.

[0026] This technical solution can effectively control the release concentration and speed of zinc ions in the soluble germicidal glass, and ensure that the soluble germicidal glass can achieve a long-term and effective germicidal effect.

[0027] In any of the above technical solutions, the thickness range of the soluble germicidal glass is 3mm to 5mm, and / or the length range of the soluble germicidal glass is 5mm to 8mm.

[0028] The soluble sterilized glass of the above size can meet the production and processing needs of many household appliances, and has a relatively reasonable sustained release period and good sustained release efficiency. In addition, the soluble sterilized glass of the above size can be cooled immediately under natural conditions, is not likely to explode or break into pieces, has a high yield rate during molding, has small internal stress, and has good mechanical strength and thermal stability without the need for an annealing process.

[0029] In order to achieve the second object of the present application, an embodiment of the present application provides a method for preparing a soluble sterilizing glass, including the steps of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture, melting the mixture to obtain a glass liquid, and cooling and forming the glass liquid to obtain a soluble sterilizing glass.

[0030] The preparation method of the soluble germicidal glass according to the embodiments of the present application can obtain the soluble germicidal glass according to any one of the embodiments of the present application, and the preparation method of the soluble germicidal glass according to the embodiments of the present application has all the beneficial effects of the soluble germicidal glass according to any one of the embodiments of the present application, so no further mention will be made here.

[0031] In the above technical solution, melting the mixture to obtain a glass liquid includes melting the mixture within a temperature range of 950°C to 1350°C for 0.5 to 2 hours to obtain a glass liquid.

[0032] The above temperature control ensures sufficient melting of each metal oxide and ensures that a homogeneous, clear, soluble, sterilized glass can be obtained in this embodiment.

[0033] The above technical solution further includes pre-heating the mixture before melting the mixture to obtain a glass liquid.

[0034] The purpose of the pre-heating process is to more effectively remove impurities and gases from the raw materials, prevent the glass liquid from generating excessive bubbles during the melting process, and ensure that the soluble sterilized glass material is firm and dense.

[0035] In the above technical solution, preheating the mixture includes preheating the mixture within a temperature range of 250°C to 350°C for 0.5 hours to 1.5 hours.

[0036] The above preheating conditions can effectively remove impurities and gases in the raw material.

[0037] In the above technical solution, the step of cooling and forming the glass liquid to obtain the soluble sterilized glass includes the steps of preheating a metal mold, pouring the glass liquid into the metal mold and naturally cooling and forming the glass to obtain the soluble sterilized glass.

[0038] By pre-heating the metal mold before cooling and forming, the glass liquid can be prevented from bursting during the process of tipping and forming.

[0039] In the above technical solution, preheating the metal mold includes preheating the metal mold to a temperature range of 200℃ to 300℃.

[0040] The above-mentioned temperature control for preheating the metal mold can effectively prevent the glass from exploding during cooling and forming, and can improve the yield.

[0041] In the above technical proposal, the raw material includes a zinc source raw material including at least one of zinc nitrate, zinc chloride, zinc sulfate, and zinc oxide, or a combination thereof, and / or a boron source raw material including boric acid, and / or a calcium source raw material including at least one of calcium carbonate, calcium nitrate, calcium sulfate, calcium phosphate, calcium chloride, and calcium oxide, or a combination thereof, and / or a phosphorus source raw material including at least one of calcium phosphate, ammonium phosphate, and phosphorus oxide, or a combination thereof.

[0042] Raw materials containing zinc, boron, calcium, and phosphorus may be added directly as oxides or as salt compounds. Among these, using metal salt compounds as raw materials can improve the homogeneity and clarity of glass compared to using metal oxides as raw materials.

[0043] Additional aspects and advantages of the present application will be set forth in the description which follows, or may be learned by practice of the present application. [Brief description of the drawings]

[0044] The above and / or additional aspects and advantages of the present application will become apparent and understandable from the following detailed description of the embodiments in conjunction with the drawings, in which:

[0045] [Figure 1] 1 is a step flow chart of a method for preparing a soluble sterilizing glass according to an embodiment of the present application; [Diagram 2] 2 is a step flow chart of a method for preparing a soluble sterilizing glass according to an embodiment of the present application; [Diagram 3] 3 is a flow chart showing step 3 of a method for preparing a soluble sterilizing glass according to an embodiment of the present application; [Figure 4] 4 is a flow chart showing step 4 of a method for preparing a soluble germicidal glass according to an embodiment of the present application. [Diagram 5] 5 is a step flow chart of a method for preparing a soluble germicidal glass according to an embodiment of the present application; [Figure 6] 6 is a flow chart showing step 6 of a method for preparing a soluble germicidal glass according to an embodiment of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] In order to make the above-mentioned objects, features and advantages of the present application more clearly understandable, the present application will be described in more detail below in conjunction with the accompanying drawings and specific embodiments. It should be noted that the embodiments and features in the embodiments of the present application can be combined with each other without conflict.

[0047] In the following description, many specific details are set forth in order to fully understand the present application; however, the present application may be implemented in other ways different from the description, and therefore the scope of protection of the present application is not limited by the specific examples disclosed below.

[0048] Hereinafter, soluble germicidal glass and a method for preparing the soluble germicidal glass according to some embodiments of the present application will be described with reference to Figs. 1 to 6.

[0049] The soluble sterilizing glass of the present application includes zinc oxide (ZnO and / or ZnO2) in an amount of 0.2 to 10 parts by weight, boron oxide (B2O3) in an amount of 1 to 20 parts by weight, calcium oxide (CaO) in an amount of 10 to 30 parts by weight, and phosphorus oxide (P2O5) in an amount of 30 to 70 parts by weight.

[0050] For example, the material of the soluble germicidal glass of this embodiment specifically contains 0.2 parts by weight of zinc oxide, 19.8 parts by weight of boron oxide, 10 parts by weight of calcium oxide, and 70 parts by weight of phosphorus oxide.

[0051] Further, for example, the material of the soluble germicidal glass of this embodiment specifically contains 10 parts by mass of zinc oxide, 10 parts by mass of boron oxide, 30 parts by mass of calcium oxide, and 50 parts by mass of phosphorus oxide.

[0052] The embodiment of the present application aims to provide a soluble glass. Here, the soluble glass refers to a soluble, sterilizable glass that can slowly and stably release one or more functional ions in a liquid, such as water. The functional ions in the embodiment of the present application are specifically zinc ions (Zn 2+ and / or Zn 4+ ) Zinc ions have good bactericidal and disinfecting effects, and occupy the lattice of metal oxide glass in the form of dopants. They are steadily released over time when immersed in liquid or scoured, achieving a long-lasting bactericidal effect.

[0053] The soluble germicidal glass containing zinc ions can be applied to home appliances such as washing machines and air conditioners to sterilize the washing water of the washing machine and the indoor space where the air conditioner is installed. However, one of the problems in the conventional technology is that the sustained release performance of zinc ions that realize the germicidal function is insufficient.

[0054] Specifically, it is difficult to control the sustained release performance of zinc ions in the soluble germicidal glass of related art. Take the zinc ion-doped soluble germicidal glass placed in a washing machine as an example, in a certain washing procedure and washing time range, if the release speed of zinc ions in the soluble germicidal glass is too fast, the zinc ions will be released early, and the germicidal effect during the later use of the washing machine will be reduced, and even the germicidal effect will be lost. If the release speed of zinc ions in the soluble germicidal glass is too slow, the germicidal effect during the entire use of the washing machine will be insufficient, making it difficult to effectively sterilize clothes and home textiles.

[0055] Regardless of any theory, the applicant has found that in the process of realizing the embodiments of the present application, the release rate of zinc ions is influenced by the amount of zinc ions added and the components and compounding ratio of the soluble glass as the base material. Therefore, the embodiments of the present application provide a ternary oxide soluble sterilizing glass mainly composed of boron oxide, calcium oxide and phosphorus oxide, in order to rationally control the release rate and efficiency of zinc ions in the soluble sterilizing glass. However, the mass ratio of boron oxide, calcium oxide and phosphorus oxide is boron oxide:calcium oxide:phosphorus oxide=(1-20):(10-30):(30-70). The raw materials of the above components and compounding ratios can be within the glass forming region. By adding and proportionally controlling phosphorus oxide and boron oxide, zinc ions can be released in boron calcium phosphorus at a reasonable speed. The addition of phosphorus oxide increases the dissolution rate of zinc ions to promote the release of zinc ions, while the addition of boron oxide reduces the dissolution rate of zinc ions to suppress the release of zinc ions. Therefore, in this embodiment, the rate and efficiency of the release of zinc ions in the soluble sterilizing glass can be reasonably controlled by controlling the compounding ratio between phosphorus and boron. In addition, the addition of calcium oxide can appropriately lower the melting temperature of the soluble sterilizing glass, reduce the manufacturing cost of the soluble sterilizing glass, and improve the production efficiency of the soluble sterilizing glass. In addition, in this embodiment, the content of zinc oxide is controlled to 0.2 parts by mass to 10 parts by mass, and the above content of zinc oxide can ensure the long-term release of zinc ions in the soluble sterilizing glass and ensure the sterilizing effect of the soluble sterilizing glass.

[0056] In some embodiments of the examples of the present application, the soluble sterilizing glass further includes a colorant with an added amount of 0.0001 to 0.0008 parts by weight. For example, the content of the colorant in the soluble sterilizing glass of this embodiment may be 0.0001 parts by weight, 0.0004 parts by weight, or 0.0008 parts by weight. The purpose of adding the colorant is to adjust and control the color of the soluble sterilizing glass. Here, those skilled in the art can flexibly select and adjust the added amount and specific type of the colorant within the above range. The colorant can be added and mixed together with the substrate raw material such as boron oxide, calcium oxide, phosphorus oxide, etc. during the raw material blending process, and the colorant can be uniformly distributed in the molten glass liquid during the process of the soluble sterilizing glass entering the melting and heating process, and a soluble sterilizing glass with a uniform color can be obtained after melting and cooling.

[0057] In some embodiments of the examples of the present application, the colorant includes any one or all of metal oxides of cobalt oxide (Co2O3), manganese oxide (MnO2), iron oxide (Fe2O3 and / or Fe3O4), copper oxide (CuO), and cadmium sulfide (CdS). The colorant of this embodiment is specifically a metal oxide colorant. Metal oxide colorants have stable performance, are resistant to high temperatures, and are not easily decomposed.

[0058] In some embodiments of the examples of the present application, the soluble sterilizing glass further contains cerium oxide in an amount of 0.0001 to 0.0006 parts by weight. For example, the content of cerium oxide in the soluble sterilizing glass of the present examples may be 0.0001 parts by weight, 0.0003 parts by weight, or 0.0006 parts by weight. The rare earth element cerium ion (Ce 3+ ) is characterized by having a rich energy level and a high valence. By adding cerium oxide to the boron-calcium-phosphorus ternary oxide soluble bactericidal glass, the proportion of high-valence zinc ions (i.e., zinc ions in a tetravalent state) in the zinc ions serving as a bactericide can be increased. Therefore, the addition of cerium oxide can improve the bactericidal effect and bactericidal efficiency of the soluble bactericidal glass according to the examples of the present application.

[0059] In some embodiments of the examples of the present application, the zinc ions in the soluble germicidal glass include zinc ions in a tetravalent state. As described above, zinc ions in a tetravalent state have a higher germicidal effect and germicidal efficiency than zinc ions in a divalent state, so the soluble germicidal glass containing zinc ions in a tetravalent state has excellent germicidal effect as well as sustained release effect.

[0060] In some embodiments of the present application, the soluble sterilized glass further comprises at least one of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, silicon oxide, and aluminum oxide, or a combination thereof. Alkali metal oxides or alkaline earth metal oxides, including lithium oxide, sodium oxide, and potassium oxide, have relatively active physicochemical properties and can effectively lower the melting point (i.e., melting temperature) of the soluble sterilized glass. The addition of silicon oxide and aluminum oxide promotes the formation of glass and improves the viscosity and mechanical strength of the soluble sterilized glass. Magnesium oxide increases the clarity of the molten glass liquid and the gloss and refractive index of the soluble sterilized glass after molding.

[0061] In some embodiments of the examples of the present application, the amount of zinc ions eluted in the soluble sterilized glass is 1 mg zinc ions / g water to 500 mg zinc ions / g water. In this embodiment, the amount of zinc ions eluted is tested by a method of preparing a measurement sample by filtering the zinc ion eluate with 5C filter paper. After preparing the measurement sample, the zinc ion concentration in the sample is measured using a test analysis device capable of measuring zinc ion concentration, such as a zinc ion meter, an atomic absorption spectrometer, or an inductively coupled plasma mass spectrometry device (ICP-MS). The amount of zinc ions eluted under a temperature condition of 30°C and a test time of 24 hours obtained in the test of this embodiment is 1 mg zinc ions / g water to 500 mg zinc ions / g water, that is, 1 (mg / (g·1L·24Hrs·30°C)) to 500 (mg / (g·1L·24Hrs·30°C)).

[0062] In some embodiments of the examples of the present application, the thickness range of the soluble sterilizing glass is 3mm to 5mm. The length range of the soluble sterilizing glass is 5mm to 8mm. The size and shape of the soluble sterilizing glass are consistent with the size and shape of the molding die employed. The soluble sterilizing glass of this embodiment may be prepared in a sheet, plate or block shape, or in a spherical or approximately spherical shape. The sustained release efficiency and sustained release period of zinc ions are affected by the size and shape of the soluble sterilizing glass. The soluble sterilizing glass manufactured using the molding die of the above size can meet the production and processing needs of many home appliances, and has a relatively reasonable sustained release period and excellent sustained release efficiency. In addition, the soluble sterilizing glass of the above size can be immediately cooled under natural conditions, is less likely to explode or separate into fragments, has a high yield during molding, has small internal stress, and has good mechanical strength and thermal stability without the need for an annealing process.

[0063] FIG. 1 is a step flow chart of a method for preparing soluble germicidal glass according to an embodiment of the present application. As shown in FIG. 1, the method for preparing soluble germicidal glass according to an embodiment of the present application includes: Step S102 of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture; Step S104 of melting the mixture to obtain a glass liquid; and step S106 of cooling and forming the glass liquid to obtain a soluble sterilized glass.

[0064] In the soluble sterilizing glass according to the examples of the present application, the content of zinc oxide as a germicide is 0.2 wt% to 10 wt%, the content of boron oxide is 1 wt% to 20 wt%, the content of calcium oxide is 10 wt% to 30 wt%, and the content of phosphorus oxide is 30 wt% to 70 wt%, based on 100 parts by mass (100 wt%) of the total mass of the soluble sterilizing glass.

[0065] In this embodiment, the ratio relationship of each oxide in the soluble sterilizing glass is limited by mass fraction. When the oxide of each element is directly used as the raw material, in this embodiment, the load bearing measurement of the raw material can be performed directly based on the proportional relationship in step S102. When the salt compound of each element is directly used as the raw material, in this embodiment, the original weighing proportion can be determined from the conversion relationship between the molar mass and mass fraction of each raw material. When a liquid raw material is used, in this embodiment, the original weighing proportion can be determined from the conversion relationship between the volume concentration and mass fraction. Those skilled in the art are familiar with the above-mentioned conversion and weighing methods, and the examples of this application do not mention them.

[0066] In addition, in this embodiment, in addition to the main raw materials including zinc oxide, boron oxide, calcium oxide, and phosphorus oxide, other metal oxide secondary materials can also be added. For example, in this embodiment, silver nitrate (AgNO3), calcium phosphate (Ca(H2PO4)2), sodium phosphate (NaH2PO4), ammonium phosphate (NH4H2PO4), boric acid (H3BO3), zinc oxide (ZnO), copper oxide (CuO), cobalt oxide (Co2O3), and cerium oxide CeO2 can be used as raw materials. Here, assuming the total mass of all raw materials is 100 wt%, the mass ratio of each raw material to the total raw materials is as follows: silver nitrate occupies 3 wt%, calcium phosphate occupies 78 wt%, sodium phosphate occupies 8.7 wt%, ammonium phosphate occupies 0.9 wt%, boric acid occupies 5.9 wt%, zinc oxide occupies 2.55 wt%, copper oxide occupies 0.4 wt%, cobalt oxide occupies 0.05 wt%, and cerium oxide occupies 0.5 wt%. When preparing a less soluble sterilized glass, the weighing process in the embodiment of the present application can be realized by using an analytical balance, and the raw materials are mixed and ground in a small mixing equipment such as an agate mortar or a planetary ball mill, and the mixture placed in a platinum crucible is melted in an electric resistance furnace or a muffle furnace, and finally the glass liquid in the platinum crucible is tilted onto an aluminum plate mold or an iron plate mold for cooling and forming.

[0067] When preparing a large amount of soluble sterilizing glass in actual production, the weighing process in the embodiment of the present application can be realized by using a large platform scale, the mixing mill realizes the mixing and grinding of the raw materials, and the large equipment such as a kiln realizes the melting and cooling of the mixture.

[0068] The cooling and forming step in step S106 may be performed by natural cooling, furnace cooling, or water quenching.

[0069] The melting process in step S104 may be performed in an air atmosphere, a reducing atmosphere, or an inert gas atmosphere.

[0070] After cooling, the present embodiment can also carry out an annealing process to remove the internal stress of the soluble sterilized glass. The temperature range of the annealing process is 200°C to 500°C, and the annealing period is 2 hours to 4 hours.

[0071] The method for preparing a soluble germicidal glass according to the embodiment of the present application can obtain the soluble germicidal glass according to any one of the embodiments of the present application, which has all the beneficial effects of the soluble germicidal glass according to any one of the embodiments of the present application, and the soluble germicidal glass is doped with a zinc ion germicidal agent with excellent sustained release performance and reasonably controllable sustained release efficiency.

[0072] In some embodiments of the examples of the present application, melting the mixture to obtain a glass liquid includes melting the mixture at a temperature range of 950°C to 1350°C for 0.5 hours to 2 hours to obtain a glass liquid. Figure 2 is a step flow chart 2 of a method for preparing a soluble sterilizing glass according to one embodiment of the present application. As shown in Figure 2, the method for preparing a soluble sterilizing glass of this embodiment includes the following steps: Step S202 of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture; Step S204 of melting the mixture at a temperature range of 950° C. to 1350° C. for 0.5 to 2 hours to obtain a glass liquid; and step S206 of cooling and forming the glass liquid to obtain a soluble sterilized glass.

[0073] The temperature control in the melting process adopted in step S204 of the present embodiment ensures that each metal oxide is melted sufficiently, and that the present embodiment can obtain a homogeneous and clear soluble sterilized glass.

[0074] In some embodiments of the examples of the present application, the preparation method further includes a step of preheating the mixture before melting the mixture to obtain a glass liquid. Figure 3 is a step flow chart of a preparation method for soluble germicidal glass according to an embodiment of the present application. As shown in Figure 3, the preparation method for soluble germicidal glass of this embodiment includes: Step S302 of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture; A step S304 of preheating the mixture; Step S306 of melting the mixture to obtain a glass liquid; and step S308 of cooling and forming the glass liquid to obtain a soluble sterilized glass.

[0075] The purpose of the pre-heating process is to more effectively remove impurities and gases from the raw materials, prevent the glass liquid from generating excessive bubbles during the melting process, and ensure that the soluble sterilized glass material is firm and dense.

[0076] In some embodiments of the examples of the present application, preheating the mixture includes preheating the mixture within a temperature range of 250°C to 350°C for 0.5 hours to 1.5 hours. FIG. 4 is step 4 of a flowchart of a method for preparing a soluble germicidal glass according to an example of the present application. As shown in FIG. 4, the method for preparing a soluble germicidal glass of this embodiment includes the following steps: Step S402 of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture; Step S404 of preheating the mixture within a temperature range of 250° C. to 350° C. for 0.5 hours to 1.5 hours; Step S406 of melting the mixture to obtain a glass liquid; and step S408 of cooling and forming the glass liquid to obtain a soluble sterilized glass.

[0077] In this embodiment, the mixture is preheated within the temperature range of 250°C to 350°C, and the preheating time is more than 0.5 hours and less than 1.5 hours. The above preheating conditions can effectively remove impurities and gases in the raw materials.

[0078] In some embodiments of the examples of the present application, cooling and forming the glass liquid to obtain a soluble sterilized glass includes preheating a metal mold, pouring the glass liquid into the metal mold and naturally cooling and forming it to obtain a glass liquid. Figure 5 is a step flow chart of a method for preparing a soluble sterilized glass according to an embodiment of the present application. As shown in Figure 5, the method for preparing a soluble sterilized glass of this embodiment includes: Step S502 of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture; Step S504 of melting the mixture to obtain a glass liquid; A step S506 of preheating the metal mold; and step S508 of pouring the glass liquid into a metal mold and allowing it to cool naturally to obtain a soluble sterilized glass.

[0079] The metal mold of this embodiment may be a metal mold having excellent heat resistance and thermal conductivity, such as an aluminum mold or an iron mold. The purpose of preheating the metal mold before cooling and forming is to prevent the glass liquid from falling and exploding during the forming process. Natural cooling forming refers to placing the metal mold containing the glass liquid in a room temperature environment (for example, between 20°C and 30°C) and naturally cooling it until the liquid glass liquid becomes a solid lump glass body.

[0080] In some embodiments of the examples of the present application, preheating the metal mold includes preheating the metal mold to a temperature range of 200°C to 300°C. FIG. 6 is step 6 of a flowchart of a method for preparing soluble germicidal glass according to an embodiment of the present application. As shown in FIG. 6, the method for preparing soluble germicidal glass of this embodiment includes the following steps: Step S602 of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture; Step S604 of melting the mixture to obtain a glass liquid; Step S606: preheating the metal mold to a temperature range of 200°C to 300°C; and step S608 of pouring the glass liquid into a metal mold and allowing it to cool and form naturally to obtain a soluble sterilized glass.

[0081] In this embodiment, the mold is preheated within a temperature range of 200°C to 300°C, and the preheating time is 1 hour to 2 hours. For example, in this embodiment, melting of the raw material and preheating of the metal mold can be realized by using two electric resistance furnaces, respectively. The temperature rise rate of the raw material heating and the temperature rise rate of the metal mold preheating can be selected and adjusted by those skilled in the art according to the performance of the heating equipment. However, in this embodiment, the electric resistance furnace for preheating the metal mold is opened after the raw material approaches or reaches the melting temperature so that the preheating is completed and the metal mold with the appropriate temperature can be immediately taken out and used after the mixture is melted to obtain a glass liquid.

[0082] In some embodiments of the examples of the present application, the raw material comprises a zinc source raw material, the zinc source raw material comprising at least one of zinc nitrate (ZnO), zinc chloride (ZnCl2), zinc sulfate (ZnSO4), zinc oxide (ZnO), or a combination thereof.

[0083] In some embodiments of the examples of the present application, the raw material comprises a boron source material, and the boron source material comprises boric acid (H3BO3).

[0084] In some embodiments of the examples of the present application, the raw material comprises a calcium source material, the calcium source material comprising at least one of calcium carbonate (CaCO), calcium nitrate (Ca(NO)), calcium sulfate (CaSO), calcium phosphate (Ca(HPO) or CaHPO), calcium chloride (CaCl), calcium oxide (CaO), or a combination thereof.

[0085] In some embodiments of the examples of the present application, the raw material comprises a phosphorus source raw material, the phosphorus source raw material comprises at least one of calcium phosphate (Ca(H2PO4)2 or CaHPO4), ammonium phosphate (NH4)3PO4), phosphorus oxide (PO5), or a combination thereof.

[0086] The zinc source raw material is a raw material for supplying zinc oxide. Accordingly, the boron source raw material, calcium source raw material, and phosphorus source raw material are in the order of raw material for supplying boron oxide, raw material for supplying calcium oxide, and raw material for supplying phosphorus oxide. The raw materials containing zinc, boron, calcium, and phosphorus may be added directly as oxides (i.e., zinc oxide, boron oxide, calcium oxide, and phosphorus oxide may be added directly as raw materials), or may be added as salt compounds (e.g., zinc chloride, boric acid, calcium carbonate, various phosphates, calcium phosphates, and other substances may be added as raw materials). Here, when the salt compounds are used as raw materials, the respective salt compounds containing zinc, boron, calcium, and phosphorus are oxidized under high temperature conditions to become oxides, and an oxide glass is obtained after melting. Using metal salt compounds as raw materials can improve the homogeneity and clarity of glass compared to using metal oxides as raw materials.

[0087] From the above, the beneficial effects of the embodiments of the present application are as follows:

[0088] 1. In the embodiments of the present application, by selecting the materials of the soluble germicidal glass and adjusting the compounding ratio, the release concentration and speed of zinc ions in the soluble germicidal glass can be effectively controlled, so as to ensure that the soluble germicidal glass can achieve a long-term and effective germicidal effect.

[0089] 2. In the embodiments of the present application, by adjusting the processing steps of the soluble germicidal glass, a soluble germicidal glass with high mechanical strength, high clarity and high zinc ion loading can be obtained.

[0090] In the description herein, the term "one embodiment," "some embodiments," "specific embodiments," and the like means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, general expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0091] The above is only a preferred embodiment of the present application, and does not limit the present application. Those skilled in the art can make various modifications and variations to the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A zinc ion doped soluble germicidal glass comprising: The material of the soluble germicidal glass is 0.2 parts by mass to 10 parts by mass of zinc oxide, 1 part by mass to 20 parts by mass of boron oxide, 10 parts by mass to 30 parts by mass of calcium oxide, 30 parts by mass to 70 parts by mass of phosphorus oxide, containing 0.0001 to 0.0006 parts by mass of cerium oxide; The zinc ions in the soluble germicidal glass include zinc ions in the tetravalent state.

1. A zinc ion doped soluble germicidal glass comprising:

2. Further containing 0.0001 to 0.0008 parts by weight of a colorant 2. The zinc ion doped soluble germicidal glass of claim 1.

3. The colorant includes at least one of cobalt oxide, manganese oxide, iron oxide, copper oxide, cadmium sulfide, or a combination thereof.

2. The zinc ion doped soluble germicidal glass of claim 1.

4. Further comprising at least one of lithium oxide, sodium oxide, potassium oxide, magnesium oxide, silicon oxide, aluminum oxide, or a combination thereof.

2. The zinc ion doped soluble germicidal glass of claim 1.

5. The amount of zinc ions dissolved in the soluble sterilizing glass is 1 mg zinc ion / g water to 500 mg zinc ion / g water.

5. A zinc ion doped soluble germicidal glass according to claim 1.

6. the thickness range of said soluble germicidal glass is between 3 mm and 5 mm; and / or The length of the soluble germicidal glass ranges from 5 mm to 8 mm.

5. A zinc ion doped soluble germicidal glass according to claim 1.

7. A method for preparing a zinc ion doped soluble germicidal glass comprising the steps of: A step of weighing and mixing raw materials in a mass ratio of zinc oxide:boron oxide:calcium oxide:phosphorus oxide=(0.2-10):(1-20):(10-30):(30-70) to obtain a mixture; melting the mixture to obtain a glass liquid; and cooling and forming the glass liquid to obtain the soluble sterilized glass. The zinc ions in the soluble germicidal glass include zinc ions in a tetravalent state; The raw material is a zinc source material comprising at least one or a combination of zinc nitrate, zinc chloride, zinc sulfate, zinc oxide, and / or a boron source material comprising boric acid; and / or a calcium source material comprising at least one of calcium carbonate, calcium nitrate, calcium sulfate, calcium phosphate, calcium chloride, calcium oxide, or a combination thereof; and / or The phosphorus source material includes at least one of calcium phosphate, ammonium phosphate, phosphorus oxide, or a combination thereof.

1. A method for preparing a zinc ion-doped soluble germicidal glass, comprising:

8. The step of melting the mixture to obtain a glass liquid includes: The mixture is melted at a temperature in the range of 950° C. to 1350° C. for 0.5 to 2 hours to obtain the glass liquid.

8. A method for preparing zinc ion doped soluble germicidal glass according to claim 7.

9. The method further includes a step of preheating the mixture before melting the mixture to obtain a glass liquid.

8. A method for preparing zinc ion doped soluble germicidal glass according to claim 7.

10. The step of preheating the mixture includes preheating the mixture within a temperature range of 250° C. to 350° C. for 0.5 hours to 1.5 hours.

10. A method for preparing zinc ion doped soluble germicidal glass according to claim 9.

11. The step of cooling and forming the glass liquid to obtain a soluble sterilized glass comprises: preheating a metal mold; and pouring the glass liquid into the metal mold and allowing it to cool naturally to obtain a soluble sterilized glass.

8. A method for preparing zinc ion doped soluble germicidal glass according to claim 7.

12. The step of preheating the metal mold includes preheating the metal mold to a temperature range of 200° C. to 300° C.

12. A method for preparing zinc ion doped soluble germicidal glass according to claim 11.

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