Antibacterial composite material and method for preparing the same

Abstract

The present application provides an antibacterial composite material and a method for preparing the antibacterial composite material. The antibacterial composite material includes a ceramic substrate and an antibacterial functional layer containing a bactericide and covering at least a portion of the surface of the ceramic substrate, where the component of the antibacterial functional layer includes a soluble antibacterial glass. The present application can improve the bactericidal efficiency and bactericidal effect of the antibacterial composite material.

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 China on December 31, 2020, with application number 202011634998.2 and entitled "Antibacterial composite material and method for preparing antibacterial composite material", the entire contents of which are incorporated herein by reference.

[0002] The present application relates to the technical field of inorganic antibacterial materials, in particular to antibacterial composite materials and methods for preparing antibacterial composite materials. [Background technology]

[0003] Antibacterial materials are functional materials with bactericidal and antibacterial properties, and they exert their antibacterial effect mainly by adding antibacterial agents. One of the drawbacks of the related technology is that the antibacterial effect of the antibacterial agents is insufficient. Summary of the Invention

[0004] The present application aims to solve at least one of the above technical problems.

[0005] Therefore, a first object of the present application is to provide an antibacterial composite material.

[0006] A second object of the present application is to provide a method for preparing an antibacterial composite material.

[0007] To achieve the first object of the present application, an embodiment of the present application provides an antibacterial composite material including a ceramic substrate and an antibacterial functional layer including a bactericide and covering at least a portion of a surface of the ceramic substrate.

[0008] This technical solution improves the antibacterial effect of the antibacterial functional layer by coating the surface of the ceramic substrate with an antibacterial functional layer containing a bactericide, thereby reducing the cost of the antibacterial composite material. Specifically, the antibacterial and bactericidal effect of the antibacterial composite material is affected by the contact area with a medium such as water or air. The larger the specific surface area of ​​the antibacterial composite material, the larger the contact area with the medium waiting for sterilization. The specific surface area is the total area per unit mass of an object. Compared to a technical solution in which an antibacterial functional component or material is directly prepared as a bulk material, this technical solution improves the specific surface area of ​​the antibacterial functional layer per unit mass by coating the surface of the ceramic substrate with an antibacterial functional layer containing a bactericide, thereby improving the antibacterial effect of the antibacterial functional layer and the antibacterial composite material having the antibacterial functional layer. In addition, taking an antibacterial material applicable to a washing machine as an example, the service life of the washing machine is about 4000 hours, and taking an antibacterial material applicable to a washing machine such as soluble antibacterial glass as an example, the service life is about 10000 hours. In other words, the service life of the antibacterial material is much longer than the service life of the washing machine, and when the user needs to discard and replace the washing machine, it will result in the waste of antibacterial materials such as soluble antibacterial glass. Similarly, in the case of products such as washing machines and air conditioners, the excessive addition of antibacterial materials will unnecessarily increase the production costs of the products. Therefore, the present technical solution applies an antibacterial functional layer to the surface of the ceramic substrate so as to match the release period of the antibacterial composite material with the service life of products such as washing machines and air conditioners, thereby avoiding the waste of the antibacterial composite material and effectively reducing the production costs of products such as washing machines and air conditioners that need to realize the sterilization function.

[0009] In addition, the technical solutions provided by the above embodiments of the present application may further have the following additional technical features:

[0010] In the above technical solution, the ceramic substrate is a porous ceramic substrate.

[0011] Since the surface and interior of the antibacterial composite material are distributed with a sparse porous structure, the antibacterial functional layer can be filled into the porous structure and tightly bonded with the ceramic substrate. In addition, since the antibacterial functional layer is filled into the porous structure, the present technical solution can use the porous structure to reasonably control the release speed of the bactericidal functional component in the antibacterial functional layer. Specifically, compared with a ceramic substrate with a smooth surface, a ceramic substrate with a porous structure can limit the release speed of the antibacterial functional layer and extend the release period of the antibacterial functional layer. From the above, the present technical solution can use the porous structure to adjust the release period of the bactericide in the antibacterial functional layer and ensure that the bactericide is stably released within a relatively long time period.

[0012] In any one of the above technical solutions, the material of the ceramic substrate is aluminum oxide.

[0013] Aluminum oxide ceramic has excellent mechanical properties, and its wear resistance, corrosion resistance and thermal stability are better, which can ensure the service life of the ceramic substrate.

[0014] In any one of the above technical solutions, the shape of the ceramic substrate is spherical, and the diameter of the ceramic substrate is in the range of 0.1 mm to 20 mm.

[0015] The spherical or nearly spherical ceramic substrate has a large specific surface area, which is advantageous for the antibacterial functional layer on the surface to exert antibacterial and bacteriostatic effects.

[0016] In any one of the above technical solutions, the soluble antibacterial glass includes 0.1 to 10 parts by mass of an inorganic bactericide, 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.

[0017] By controlling the amount and ratio of phosphorus oxide and boron oxide, inorganic bactericides such as silver ions and zinc ions can be released at a reasonable speed in the glass material containing boron calcium phosphorus. Specifically, the applicant found that the addition of phosphorus oxide increases the dissolution rate of silver ions and promotes the release of silver ions in the process of realizing the present application. Conversely, the addition of boron oxide can reduce the dissolution rate of silver ions and inhibit the release of silver ions. Therefore, the present technical solution controls the amount and specific ratio of phosphorus oxide and boron oxide (i.e., the content of phosphorus oxide is 30 parts by mass to 70 parts by mass, and the content of boron oxide is 1 part by mass to 20 parts by mass). As a result, the present technical solution can rationally control the release rate and release efficiency of silver ions in the soluble antibacterial glass. In addition, the addition of calcium oxide can appropriately reduce the melting temperature of the soluble antibacterial glass, reduce the production cost of the soluble antibacterial glass, and improve the production efficiency of the soluble antibacterial glass.

[0018] In any one of the above technical solutions, the inorganic bactericide includes 0.1 to 5 parts by mass of silver oxide, or 0.2 to 10 parts by mass of zinc oxide.

[0019] Both silver ions and zinc ions have good bactericidal and disinfecting effects, and occupy the lattice of metal oxide glass in the form of doping, and are released steadily over time in the liquid immersion or scoured environment, realizing a long-term bactericidal effect. The use of silver oxide and zinc oxide as inorganic bactericides not only guarantees the bactericidal effect, but also ensures that the inorganic bactericide is stable for a long time and not easily decomposed.

[0020] In any one of the above technical solutions, the soluble antibacterial glass further comprises 0.0001 to 0.0008 parts by weight of a colorant, and / or 0.0001 to 0.0006 parts by weight of cerium oxide, and the colorant comprises at least one of cobalt oxide, manganese oxide, iron oxide, copper oxide, cadmium sulfide, or a combination thereof.

[0021] The purpose of adding a colorant is to adjust and control the color of the soluble antibacterial glass. The addition of cerium oxide to the boron-calcium-phosphorus ternary oxide soluble antibacterial glass can increase the proportion of high valence metal ions in the metal ions as a bactericide. Therefore, the addition of cerium oxide can improve the bactericidal effect and bactericidal efficiency of the soluble antibacterial glass according to the embodiment of the present application.

[0022] In order to achieve the second object of the present application, an embodiment of the present application provides a method for preparing an antibacterial composite material, including the steps of preparing a ceramic substrate, preparing a melt of a soluble antibacterial glass, and applying the melt of the antibacterial glass to at least a portion of a surface of the ceramic substrate.

[0023] The preparation method of the antibacterial composite material according to the examples of the present application can obtain the antibacterial composite material according to any one of the examples of the present application, and the preparation method of the antibacterial composite material according to the examples of the present application has all the beneficial effects of the antibacterial composite material according to any one of the examples of the present application, and no further mention will be made here.

[0024] In the above technical solution, the step of preparing the ceramic body includes the steps of preparing a ceramic powder material, spraying and granulating the ceramic powder material to obtain a ceramic body, and sintering the ceramic body to obtain the ceramic body.

[0025] This technical solution can obtain a ceramic body with a uniform shape by spray granulation using ceramic powder material, and can also obtain a ceramic substrate with high mechanical strength by sintering.

[0026] In the above technical solution, the step of preparing a molten liquid of soluble antibacterial glass includes the steps of: weighing and mixing raw materials in a mass ratio of silver oxide:boron oxide:calcium oxide:phosphorus oxide = (0.1-5):(1-20):(10-30):(30-70) to obtain a mixture; or 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; and melting the mixture to obtain a molten liquid of soluble antibacterial glass.

[0027] By controlling the amount and ratio of phosphorus oxide and boron oxide added, silver ions or zinc ions can be released in boron calcium phosphorus at a reasonable speed. The addition of calcium oxide can appropriately lower the melting temperature of the soluble antibacterial glass, reduce the production cost of the soluble antibacterial glass, and improve the production efficiency of the soluble antibacterial glass.

[0028] In any one of the above technical solutions, the step of melting the mixture to obtain a molten liquid of the soluble antibacterial glass includes the step of melting the mixture at a temperature in the range of 950°C to 1350°C for 0.5 hours to 2 hours to obtain a molten liquid of the soluble antibacterial glass.

[0029] The temperature control in the melting process adopted in this technical solution ensures that each metal oxide is melted sufficiently, and in this embodiment, a homogeneous and clear melt of soluble antibacterial glass can be obtained.

[0030] In any one of the above technical solutions, the preparation method further includes a step of pre-heating the mixture before the step of melting the mixture to obtain a melt of the soluble antimicrobial glass.

[0031] 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 too many bubbles during the melting process, and ensure that the soluble antibacterial glass material is strong and dense.

[0032] In any one of the above technical solutions, the step of preheating the mixture includes a step of preheating the mixture within a temperature range of 250°C to 350°C for 0.5 hours to 1.5 hours.

[0033] In this technical solution, the mixture is preheated within the temperature range of 250℃-350℃, 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.

[0034] In any one of the above technical solutions, the step of applying the molten antibacterial glass to at least a portion of a surface of the ceramic substrate includes the steps of preheating the ceramic substrate, immersing the preheated ceramic substrate in the molten antibacterial glass, and removing the ceramic substrate from the molten antibacterial glass and cooling it.

[0035] In this technical solution, the ceramic substrate is immersed in the glass melt, so that the glass melt can be uniformly applied to the surface of the ceramic substrate.

[0036] 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]

[0037] 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:

[0038] [Figure 1] 1 is a step flow chart of a method for preparing an antibacterial composite material according to one embodiment of the present application. [Diagram 2] 1 is a step flow chart of a method for preparing an antibacterial functional layer according to one embodiment of the present application. [Diagram 3] 2 is a flow chart showing step 2 of a method for preparing an antibacterial functional layer according to an embodiment of the present application. [Figure 4]2 is a step flow chart of a method for preparing an antibacterial composite material according to one embodiment of the present application. [Diagram 5] 3 is a flow chart showing step 3 of a method for preparing an antibacterial composite material according to an embodiment of the present application. [Figure 6] 4 is a flow chart showing step 4 of a method for preparing an antibacterial composite material according to an embodiment of the present application. [Figure 7] 5 is a step flow chart of a method for preparing an antibacterial composite material according to an embodiment of the present application. [Figure 8] 6 is a flow chart showing step 6 of a method for preparing an antibacterial composite material according to an embodiment of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] 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.

[0040] 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.

[0041] Hereinafter, antibacterial composite materials and methods for preparing antibacterial composite materials according to some examples of the present application will be described with reference to FIGS.

[0042] An antibacterial composite material according to one embodiment of the present application includes a ceramic substrate and an antibacterial functional layer covering at least a portion of a surface of the ceramic substrate, the component of the antibacterial functional layer including a soluble antibacterial glass.

[0043] The purpose of the embodiment of the present application is to provide an antibacterial composite material, which is provided with an antibacterial functional layer to realize the antibacterial function, a bactericide is added to the antibacterial functional layer, and the antibacterial functional layer covers at least a part of the surface of the ceramic substrate of the antibacterial composite material. The bactericide in the antibacterial functional layer on the surface of the ceramic substrate is slowly and stably released in water or air to realize the disinfection and sterilization function.

[0044] The antibacterial composite material according to the embodiment of the present application can be applied to home appliances such as washing machines and air conditioners, and can sterilize the washing water of the washing machine and the indoor space in which the air conditioner is placed.

[0045] In particular, the embodiment of the present application coats the surface of the ceramic substrate with an antibacterial functional layer containing a bactericide, which can increase the specific surface area of ​​the antibacterial functional layer, and promote and improve the sustained release of the bactericide and the bactericidal effect.

[0046] In some embodiments of the examples of the present application, the ceramic substrate is a porous ceramic substrate. The porous structure in the ceramic substrate may be achieved by controlling the selection and ratio of raw materials, or by controlling process parameters.

[0047] For example, in the embodiment of the present application, aluminum oxide (Al2O3) is used as the raw material, and raw materials containing aluminum oxide are uniformly ground and mixed, and then sintered at high temperature, so that the raw materials undergo a solid-phase reaction at high temperature to form a porous ceramic substrate.

[0048] Further, for example, in the embodiment of the present application, a pore-forming agent may be added to the raw material of the porous ceramic, and the raw material containing the pore-forming agent may be sintered at high temperature. Specific examples of the pore-forming agent include low molecular weight organic substances containing carbon and oxygen elements, such as chitosan and glucose. The carbon-containing low molecular weight organic substances are decomposed at high temperatures, which further increases the porosity in the ceramic substrate.

[0049] Since a sparse porous structure is distributed on the surface and inside of the ceramic substrate, the antibacterial functional layer not only penetrates and fills the porous structure and is tightly bonded to the ceramic substrate, but also the porous structure can adjust the sustained release period of the bactericide in the antibacterial functional layer, thereby ensuring stable release of the bactericide over a long period of time.

[0050] In some embodiments of the examples of the present application, the material of the ceramic substrate is aluminum oxide (Al2O3).

[0051] Aluminum oxide ceramic has excellent mechanical properties, and its wear resistance, corrosion resistance and thermal stability are better, which can ensure the service life of the ceramic substrate.

[0052] In some embodiments of the present application, the ceramic substrate is spherical and has a diameter ranging from 0.1 mm to 20 mm. The specific surface area of ​​a spherical or nearly spherical ceramic substrate is large, which is more advantageous for the antibacterial functional layer on the surface to exert antibacterial and bacteriostatic effects.

[0053] In some embodiments of the examples of the present application, the soluble antibacterial glass includes an inorganic germicide having an additive amount of 0.1 parts by weight to 10 parts by weight, boron oxide (B2O3) having an additive amount of 1 part by weight to 20 parts by weight, calcium oxide (CaO) having an additive amount of 10 parts by weight to 30 parts by weight, and phosphorus oxide (P2O5) having an additive amount of 30 parts by weight to 70 parts by weight.

[0054] The sustained release performance of inorganic bactericide in glass material of related art is difficult to control. Take bactericide-doped soluble antibacterial glass placed in washing machine as an example. In a certain washing procedure and washing time range, if the release speed of inorganic bactericide in soluble antibacterial glass is too fast, the inorganic bactericide will be released early, and the bactericidal effect during the later use of washing machine will be reduced, and even the bactericidal effect will be lost. If the release speed of inorganic bactericide in soluble antibacterial glass is too slow, the bactericidal effect during the whole use of 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 the inorganic bactericide is influenced by the amount of the bactericide 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 antibacterial glass mainly composed of boron oxide, calcium oxide and phosphorus oxide, in order to rationally control the release rate and release efficiency of the inorganic bactericide in the glass material. 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 controlling the addition and ratio of phosphorus oxide and boron oxide, the inorganic bactericide such as silver ion or zinc ion can be released at a reasonable speed in boron calcium phosphorus. The addition of phosphorus oxide increases the dissolution rate of silver ion to promote the release of silver ion, while the addition of boron oxide reduces the dissolution rate of silver ion to inhibit the release of silver ion. Therefore, in this embodiment, by controlling the compounding ratio between phosphorus and boron, the release rate and release efficiency of silver ions in the soluble antibacterial glass can be reasonably controlled. Also, the addition of calcium oxide can appropriately lower the melting temperature of the soluble antibacterial glass, thereby reducing the production cost of the soluble antibacterial glass and improving the production efficiency of the soluble antibacterial glass.

[0056] In some embodiments of the examples of the present application, the inorganic germicide comprises 0.1 to 5 parts by weight of silver oxide. For example, the material of the soluble antibacterial glass of this example specifically comprises 0.1 parts by weight of silver oxide, 19.9 parts by weight of boron oxide, 10 parts by weight of calcium oxide, and 70 parts by weight of phosphorus oxide. Again, for example, the material of the soluble antibacterial glass of this example specifically comprises 5 parts by weight of silver oxide, 20 parts by weight of boron oxide, 30 parts by weight of calcium oxide, and 45 parts by weight of phosphorus oxide.

[0057] In some embodiments of the examples of the present application, the inorganic germicide comprises 0.2 to 10 parts by weight of zinc oxide. For example, the material of the soluble antibacterial glass of this example specifically comprises 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. Again, for example, the material of the soluble antibacterial glass of this example specifically comprises 10 parts by weight of zinc oxide, 10 parts by weight of boron oxide, 30 parts by weight of calcium oxide, and 50 parts by weight of phosphorus oxide.

[0058] Both silver ions and zinc ions have good bactericidal and disinfecting effects, and occupy the lattice of metal oxide glass in the form of a dope. When immersed in liquid or washed in an environment, they are steadily released over time, achieving a long-lasting bactericidal effect.

[0059] The use of silver oxide or zinc oxide as an inorganic bactericide not only ensures the bactericidal effect, but also ensures that the bactericide is stable over the long term and not easily decomposed.

[0060] In some embodiments of the present application, the soluble antimicrobial glass further comprises a colorant in an amount of 0.0001 to 0.0008 parts by weight, the colorant comprising at least one of cobalt oxide, manganese oxide, iron oxide, copper oxide, cadmium sulfide, or a combination thereof. For example, the content of the colorant in the soluble antimicrobial glass of the present application may be 0.0001 parts by weight, 0.0004 parts by weight, or 0.0008 parts by weight.

[0061] The purpose of adding the colorant is to adjust and control the color of the soluble antibacterial glass. Here, those skilled in the art can flexibly select and adjust the amount and specific type of the colorant to be added within the above range. The colorant can be added and mixed together with the substrate raw materials such as boron oxide, calcium oxide, phosphorus oxide, etc. during the raw material blending process, so that the colorant can be uniformly distributed in the molten glass liquid during the melting and heating process of the soluble antibacterial glass, and a soluble antibacterial glass with a uniform color can be obtained after melting and cooling.

[0062] In some embodiments of the present application, the colorant includes at least one of cobalt oxide (Co2O3), manganese oxide (MnO2), iron oxide (Fe2O3 and / or Fe3O4), copper oxide (CuO), and cadmium sulfide (CdS), or a combination thereof. The colorant of this embodiment is specifically a metal oxide colorant. The metal oxide colorant has stable performance, is resistant to high temperatures, and is not easily decomposed.

[0063] In some embodiments of the present application, the soluble antibacterial glass further includes cerium oxide in an amount of 0.0001 to 0.0006 parts by weight. For example, the content of cerium oxide in the soluble antibacterial glass of the present embodiment may be 0.0001 parts by weight, 0.0003 parts by weight, or 0.0006 parts by weight. The cerium oxide 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 antibacterial glass, the proportion of high valence silver ions (i.e., divalent silver ions or trivalent silver ions) in the silver ions as the bactericide can be increased, or the proportion of high valence zinc ions (i.e., tetravalent zinc ions) in the zinc ions as the bactericide can be increased. Therefore, the addition of cerium oxide can improve the bactericidal effect and bactericidal efficiency of the soluble antibacterial glass according to the examples of the present application.

[0064] As shown in FIG. 1, the method for preparing the antibacterial composite material according to the embodiment of the present application includes: A step S102 of preparing a ceramic substrate; A step S104 of preparing a melt of a soluble antibacterial glass; and applying the antibacterial glass melt to at least a portion of the surface of the ceramic substrate (S106).

[0065] The molten liquid of the soluble antibacterial glass can be applied to the surface of the ceramic substrate by painting, spraying, etc. For example, in the embodiments of the present application, the ceramic substrate may be immersed in the molten liquid of the soluble antibacterial glass, or the soluble antibacterial glass may be ground into glass powder, and the glass powder may be attached to the surface of the ceramic substrate via a material such as an adhesive, and the ceramic substrate may be heat-treated to melt or partially melt the glass powder, thereby coating at least a portion of the surface of the ceramic substrate.

[0066] The preparation method of the antibacterial composite material according to the embodiment of the present application can obtain the antibacterial composite material according to any one of the embodiments of the present application, and the antibacterial functional layer on the surface of the antibacterial composite material is doped with a bactericide with excellent sustained release performance and reasonably controllable sustained release efficiency. The preparation method of the antibacterial composite material according to the embodiment of the present application has all the beneficial effects of the antibacterial composite material according to any one of the embodiments of the present application, and no further description is made here.

[0067] As shown in FIG. 7, in some embodiments of this example, the step of preparing the ceramic substrate includes: A step S702 of preparing a ceramic powder material; Step S704 of spraying and granulating the ceramic powder material to obtain a ceramic body; and Step S706 of sintering the ceramic body to obtain a ceramic substrate.

[0068] Specifically, this embodiment uses cold isostatic pressing powder material containing aluminum oxide, zirconium oxide, silicon oxide, etc., crushed, sieved prefabricated seed crystals, then added to a ball mill to roll, and at least two water sprays and ceramic powder material addition operations are performed to make the ceramic powder material roll and grow to a spherical ceramic body with a diameter of 1 mm to 20 mm, and then the surface of the ceramic body can be buffed and dried. In this embodiment, the ceramic body is sintered for 2 hours at a temperature condition of 1500°C. The temperature control during the heating process in the sintering process is to heat the sintering equipment from room temperature to 1000°C at a heating rate of 100°C / h, and then heat the sintering equipment from 1000°C to the sintering temperature of 1500°C at a heating rate of 50°C / h. After sintering, in this embodiment, a ceramic base with a diameter of 0.9 mm to 18 mm can be obtained. The above steps are suitable for preparing various ceramic substrates such as aluminum oxide ceramic substrate, zirconium oxide ceramic substrate, tourmaline ceramic substrate, and maifan stone ceramic substrate. In this embodiment, a ceramic body with a uniform shape can be obtained by spray granulation using ceramic powder material. Furthermore, this technical solution can obtain a ceramic substrate with high mechanical strength by sintering.

[0069] As shown in FIG. 2, in some embodiments of the examples of the present application, the step of preparing a melt of a soluble antimicrobial glass includes: A step S202 of weighing and mixing raw materials in a mass ratio of silver oxide:boron oxide:calcium oxide:phosphorus oxide=(0.1-5):(1-20):(10-30):(30-70) to obtain a mixture; and step S204 of melting the mixture to obtain a melt of the soluble antimicrobial glass.

[0070] As shown in FIG. 3, in some embodiments of the examples of the present application, the step of preparing a melt of a soluble antimicrobial glass 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; and step S304, melting the mixture to obtain a melt of the soluble antimicrobial glass.

[0071] Silver ions (Ag + and / or Ag 2+ ) or zinc ion (Zn 2+ and / or Zn 4+ ) has good bactericidal and disinfecting effects, occupies the lattice of metal oxide glass in the form of a dope, and is released stably over time when immersed in liquid or washed away, thereby achieving a long-lasting bactericidal effect.

[0072] In the above steps, based on 100 parts by mass (100wt%) of the total mass of the soluble antibacterial glass, the content of silver oxide as a germicide is 0.1wt% to 5wt%, the content of boron oxide is 1wt% to 20wt%, the content of calcium oxide is 1wt% to 30wt%, and the content of phosphorus oxide is 30wt% to 70wt%. Alternatively, based on 100 parts by mass (100wt%) of the total mass of the soluble antibacterial glass, the content of zinc oxide as a germicide is 0.2wt% to 10wt%, the content of boron oxide is 1wt% to 20wt%, the content of calcium oxide is 10wt% to 30wt%, and the content of phosphorus oxide is 30wt% to 70wt%.

[0073] In this embodiment, the ratio relationship of each oxide in the soluble antibacterial 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 the above step. 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.

[0074] In addition, in this embodiment, in addition to the main raw materials including inorganic germicide, boron oxide, calcium oxide, and phosphorus oxide, other metal oxide secondary materials can also be added. For example, in this embodiment, the soluble antibacterial glass can be prepared using 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) 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%.

[0075] In the case of preparing a less soluble antibacterial glass, the weighing process in the embodiments 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.

[0076] When preparing a large amount of soluble antimicrobial glass in actual production, the weighing process in the embodiments of the present application can be realized by using a large platform scale, a mixing mill realizes the mixing and grinding of the raw materials, and a large equipment such as a kiln realizes the melting and cooling of the mixture.

[0077] The cooling and forming step in this embodiment may be natural cooling, furnace cooling, or cooling by a water quenching method.

[0078] The melting step in this embodiment may be carried out in an air atmosphere, a reducing atmosphere, or an inert gas atmosphere.

[0079] After cooling, the present embodiment can also carry out an annealing process to remove the internal stress of the soluble antibacterial glass. The temperature range of the annealing process is 200°C to 500°C, and the annealing period is 2 hours to 4 hours.

[0080] In some embodiments of the present application, the step of melting the mixture to obtain a molten liquid of the soluble antibacterial glass 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. As shown in FIG. 4, the antibacterial functional layer is A step S402 of preparing a ceramic substrate; Step S404 of melting the mixture at a temperature range of 950°C to 1350°C for 0.5 to 2 hours to obtain a molten liquid of antibacterial glass; and applying a molten liquid of antimicrobial glass to at least a portion of a surface of the ceramic substrate (S406).

[0081] The temperature control in the melting process employed in this embodiment ensures that each metal oxide is melted sufficiently, and that the present embodiment can obtain a homogeneous and clear soluble antibacterial glass.

[0082] In some embodiments of the present application, the preparation method further includes a step of preheating the mixture before melting the mixture to obtain a melt of the soluble antimicrobial glass. As shown in FIG. 5, the antimicrobial functional layer is A step S502 of preparing a ceramic substrate; Step S504 of weighing and mixing the raw materials to obtain a mixture; A step S506 of preheating the mixture; Step S508: melting the mixture to obtain a melt of the soluble antimicrobial glass; and applying a molten liquid of antimicrobial glass to at least a portion of a surface of a ceramic substrate (S510).

[0083] 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 too many bubbles during the melting process, and ensure that the soluble antibacterial glass material is strong and dense.

[0084] In some embodiments of the present application, the step of preheating the mixture includes a step of preheating the mixture within a temperature range of 250° C. to 350° C. for 0.5 hours to 1.5 hours. As shown in FIG. 6, the antibacterial functional layer is A step S602 of preparing a ceramic substrate; Step S604 of weighing and mixing the raw materials to obtain a mixture; Step S606 of preheating the mixture within a temperature range of 250° C. to 350° C. for 0.5 hours to 1.5 hours; Step S608: melting the mixture to obtain a melt of the soluble antimicrobial glass; and applying a melt of antimicrobial glass to at least a portion of a surface of a ceramic substrate (step S610).

[0085] 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.

[0086] In some embodiments of the examples of the present application, the step of cooling and forming the glass liquid to obtain the glass liquid includes the steps of preheating a metal mold, and pouring the glass liquid into the metal mold and naturally cooling and forming it to obtain a soluble antibacterial glass.

[0087] 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.

[0088] In some embodiments of the present application, the step of preheating the metal mold includes preheating the metal mold to a temperature range of 200°C to 300°C.

[0089] 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.

[0090] The raw materials for preparing the antibacterial functional layer include a silver source raw material, and the silver source raw material includes at least one of silver nitrate (AgNO3), silver chloride (AgCl), silver sulfate (Ag2SO4), silver carbonate (Ag2CO3), silver bromide (AgBr), silver iodide (AgI), and silver oxide (Ag2O), or a combination thereof. The raw materials for preparing the antibacterial functional layer include a boron source raw material, and the boron source raw material includes boric acid (H3BO3). The raw materials for preparing the antibacterial functional layer include a calcium source raw material, and the calcium source raw material includes at least one of calcium carbonate (CaCO3), calcium nitrate (Ca(NO3)2), calcium sulfate (CaSO4), calcium phosphate (Ca(H2PO4)2 or CaHPO4), calcium chloride (CaCl2), and calcium oxide (CaO), or a combination thereof. The raw materials for preparing the antibacterial functional layer include a phosphorus source raw material, and the phosphorus source raw material includes at least one of calcium phosphate (Ca(H2PO4)2 or CaHPO4), ammonium phosphate ((NH4)3PO4), phosphorus oxide (P2O5), or a combination thereof.

[0091] The silver source raw material is a raw material for supplying silver 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 silver, boron, calcium, and phosphorus may be added directly as oxides (i.e., silver oxide, boron oxide, calcium oxide, and phosphorus oxide may be added directly as raw materials), or may be added as salt compounds (for example, substances such as silver chloride, boric acid, calcium carbonate, various phosphates, and calcium phosphates may be added as raw materials). Here, when salt compounds are used as raw materials, each salt compound containing silver, boron, calcium, and phosphorus is oxidized under high temperature conditions to become an oxide, and an oxide glass is obtained after melting. Among them, using metal salt compounds as raw materials can improve the homogeneity and clarity of glass compared to using metal oxides as raw materials.

[0092] As shown in FIG. 8 , in some embodiments of the present application, the step of applying the molten antimicrobial glass to at least a portion of the surface of the ceramic substrate includes: A step S802 of preheating the ceramic substrate; A step S804 of immersing the preheated ceramic substrate into a melt of antimicrobial glass; and step S806, removing the ceramic substrate from the antimicrobial glass melt and allowing it to cool.

[0093] In this embodiment, the ceramic substrate is preheated before the immersion operation in step S804, so that the ceramic substrate is not suddenly heated and surface defects such as microcracks are prevented from occurring. In step S806, after the ceramic substrate is removed from the antibacterial glass melt, the ceramic substrate may be directly cooled naturally, or may be cooled after an annealing treatment. In this embodiment, the ceramic substrate is immersed in the glass melt. The glass melt can be applied uniformly to the surface of the ceramic substrate.

[0094] In conclusion, the embodiment of the present application has the beneficial effect of coating the surface of the ceramic substrate with an antibacterial functional layer containing a bactericide, which can increase the specific surface area of ​​the antibacterial functional layer, and promote and improve the sustained release of the bactericide and the bactericidal effect.

[0095] 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.

[0096] 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. An antibacterial composite material, comprising: A ceramic substrate; an antimicrobial functional layer comprising a soluble antimicrobial glass and covering at least a portion of a surface of the ceramic substrate; the ceramic substrate is a porous ceramic substrate; The shape of the ceramic substrate is spherical, and the diameter of the ceramic substrate ranges from 0.1 mm to 20 mm; The soluble antibacterial glass contains, based on 100 parts by mass of the soluble antibacterial glass, 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, 30 to 70 parts by mass of phosphorus oxide, and 0.0001 to 0.0006 parts by mass of cerium oxide. Antibacterial composite material.

2. The material of the ceramic substrate is aluminum oxide. The antibacterial composite material according to claim 1.

3. The soluble antibacterial glass has a content of: Further comprising 0.0001 parts by weight to 0.0008 parts by weight of a colorant; The colorant comprises at least one of cobalt oxide, manganese oxide, iron oxide, copper oxide, cadmium sulfide, or a combination thereof; The antibacterial composite material according to claim 1.

4. A method for preparing an antibacterial composite material, comprising the steps of: Preparing a ceramic substrate; preparing a melt of a soluble antimicrobial glass; applying the antimicrobial glass melt to at least a portion of a surface of the ceramic substrate; the ceramic substrate is a porous ceramic substrate; The shape of the ceramic substrate is spherical, and the diameter of the ceramic substrate ranges from 0.1 mm to 20 mm; The step of applying the antimicrobial glass melt to at least a portion of a surface of the ceramic substrate includes: preheating the ceramic substrate; immersing the preheated ceramic substrate into a melt of the antimicrobial glass; removing the ceramic substrate from the antimicrobial glass melt and allowing it to cool. Method for preparing antibacterial composite material.

5. The step of preparing the ceramic substrate comprises: Preparing a ceramic powder material; spraying and granulating the ceramic powder material to obtain a ceramic body; and sintering the ceramic body to obtain the ceramic substrate. A method for preparing the antibacterial composite material according to claim 4.

6. The step of preparing a melt of the soluble antimicrobial glass comprises: a step of weighing and mixing raw materials in a mass ratio of silver oxide: boron oxide: calcium oxide: phosphorus oxide = (0.1 to 5): (1 to 20): (10 to 30): (30 to 70) to obtain a mixture, or a step of weighing and mixing raw materials in a mass ratio of zinc oxide: boron oxide: calcium oxide: phosphorus oxide = (0.2 to 10): (1 to 20): (10 to 30): (30 to 70) to obtain a mixture; and melting the mixture to obtain a melt of the soluble antimicrobial glass. A method for preparing the antibacterial composite material according to claim 4.

7. The step of melting the mixture to obtain a melt of the soluble antimicrobial glass includes: The mixture is melted at a temperature range of 950°C to 1350°C for 0.5 hours to 2 hours to obtain a melt of the soluble antibacterial glass. A method for preparing the antibacterial composite material according to claim 6.

8. The method includes, prior to the step of melting the mixture to obtain a melt of the soluble antimicrobial glass, further comprising the step of preheating the mixture. A method for preparing the antibacterial composite material according to claim 6.

9. The step of preheating the mixture comprises: preheating the mixture within a temperature range of 250°C to 350°C for 0.5 hours to 1.5 hours; A method for preparing the antibacterial composite material according to claim 8.

10. The step of preparing the ceramic substrate comprises: adding a pore-forming agent to a raw material for a porous ceramic and sintering the raw material containing the pore-forming agent at high temperature. A method for preparing the antibacterial composite material according to any one of claims 4 to 9.

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