CN115286234A - Copper high-temperature-resistant antibacterial agent, antibacterial ceramic and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of novel inorganic antibacterial materials, in particular to a copper high-temperature-resistant antibacterial agent, antibacterial ceramic and a preparation method thereof. The invention utilizes the principles of electrostatic adsorption and hydroxyl function to convert Cu into Cu ²⁺ Loading the mixture to the outer surface of the tubular halloysite to obtain the copper high-temperature-resistant antibacterial agent, and further obtaining the corresponding antibacterial glaze and antibacterial ceramic. The copper high-temperature resistant antibacterial agent has strong antibacterial and broad-spectrum antibacterial effects, the antibacterial rate of the copper high-temperature resistant antibacterial agent on strains such as escherichia coli and staphylococcus aureus is higher than 99% through detection, and the antibacterial rate of the copper high-temperature resistant antibacterial agent is still higher than 99% after high-temperature calcination (higher than 1100 ℃). In addition, the antibacterial ceramic has excellent antibacterial performance, is not easy to discolor, is not limited by illumination conditions, has good stability of antibacterial active elements, and can exert the antibacterial effect for a long time. At the same time, the raw materials of the process of the invention do not require any treatmentAnd the preparation process is simple, the cost is low, the preparation method is safe and environment-friendly, large-scale industrial production is easy, and the market prospect is wide.

Description

A copper-based high temperature resistant antibacterial agent, antibacterial ceramics and preparation method thereof

technical field

The invention relates to the technical field of new inorganic antibacterial materials, in particular to a copper-based high-temperature-resistant antibacterial agent, antibacterial ceramics and a preparation method thereof.

Background technique

According to statistics, as many as 20 million people die every year due to pathogenic microbial infections in the world, accounting for about one-third of the global mortality rate. Therefore, bacterial or viral infection has brought huge loss to people's life and social development.

An important way to prevent bacterial infection is to cut off the transmission of germs or viruses. The use of antibacterial ceramics is an effective measure to inhibit the growth and reproduction of bacteria and reduce the invasion of pathogenic microorganisms. Therefore, it has become a research hotspot to develop a long-acting, broad-spectrum and strong antibacterial ceramic to block the spread of bacteria.

In order to obtain antibacterial ceramics with long-term broad-spectrum and strong antibacterial properties, researchers have proposed many preparation methods in this regard. At present, the preparation methods of antibacterial ceramics that have been reported can be mainly divided into the following categories: [Patent 1: An antibacterial and environmentally friendly daily-use ceramics and its preparation method, publication number: CN110015884A; Patent 2: A load-modified zinc oxide Antibacterial ceramics and its preparation method and application, publication number: CN111269026A; patent 3: a rare earth antibacterial ceramics and its preparation method, publication number: CN111454045A; patent 4: a high-temperature reduction antibacterial ceramics and its preparation process, publication number: CN111792841A ; Patent 5: A kind of antibacterial ceramic glaze based on boron mud and its preparation method and application; publication number: CN112250305A], namely a). Add Ag antibacterial agent or photosensitive antibacterial agent (such as Zn0, Ti0 etc.) or Rare earth antibacterial agent or composite antibacterial agent to realize the antibacterial function of ceramics; b). In order to prevent the loss of antibacterial agent at high temperature, the preparation of antibacterial ceramics is realized by low temperature glaze or segmental firing or secondary firing process; although these The method has made great progress, but there are still some problems: such as the high cost of Ag-based antibacterial agents, easy discoloration, and poor long-term effect; the efficacy of photosensitive antibacterial agents is greatly affected by light conditions, poor high temperature stability, and when the temperature T> 500 ℃ The antibacterial effect will be lost; the rare earth antibacterial agent needs to use rare earth as a raw material, the cost and process requirements are relatively high, and resources are wasted. In addition, the process of segmental sintering or secondary sintering is complicated, and the molding temperature of segmental sintering is relatively high, and the energy consumption is high, which is not conducive to industrial production. Therefore, to provide a kind of antibacterial ceramics with simple raw materials and preparation process, low cost, safety and environmental protection, good high temperature stability, not easy to change color, not limited by light conditions, long-term broad-spectrum and strong antibacterial effect is an urgent need to realize the industrialization of antibacterial ceramics. problem to be solved.

Contents of the invention

In order to solve the above problems, the present invention proposes a copper-based high temperature resistant antibacterial agent, antibacterial ceramics and a preparation method thereof. The raw materials of the method do not need to be pre-treated, the preparation process is simple, the cost is low, the method is safe and environment-friendly, and the industrialized production can be easily realized.

The specific technical scheme is as follows:

The invention provides a copper-based high-temperature-resistant antibacterial agent, which can withstand high-temperature calcination above 1100°C, and its preparation consists of the following steps:

S1) dissolving the soluble copper salt in deionized water, stirring evenly and heating in a water bath;

S2) adding halloysite to the above solution, stirring evenly, fully reacting, and keeping the reaction temperature constant;

S3) stop heating, let stand for precipitation, pour off the supernatant, wash and centrifugally dry, and finally obtain the copper-based high-temperature-resistant antibacterial agent.

Further, S1) the soluble copper salt is one of copper sulfate and copper chloride; the heating temperature of the water bath is 60-80°C.

Further, S2) the mass ratio of halloysite and soluble copper salt is: M _halloysite :M _{copper salt} =1-20:1, preferably 2-5:1; the stirring method is manual stirring, One of mechanical stirring or magnetic stirring; the reaction time is 15-25min; the reaction temperature is 60-80°C.

Further, the cleaning in S3) is cleaning 2-5 times; the drying temperature is 70-90°C.

The present invention provides an antibacterial ceramic containing the aforementioned copper-based high-temperature-resistant antibacterial agent, including a green body and an antibacterial glaze. The raw materials of the antibacterial glaze are mainly made of the following components: basic glaze, copper-based high-temperature-resistant antibacterial Ionized water, wherein the basic glaze and copper high-temperature resistant antibacterial agent are proportioned according to the following mass fractions, basic glaze 95-99.5%, copper high-temperature resistant antibacterial agent 0.5-5%; preferably, basic glaze 97-99%, copper Class high temperature resistant antibacterial agent 1-3%.

The present invention provides a kind of preparation method of aforementioned antibacterial ceramics, it is characterized in that: comprise the following steps:

1) Add copper-based high-temperature-resistant antibacterial agent into the basic glaze, mix it with deionized water in an appropriate proportion, and then perform wet ball milling to obtain antibacterial glaze;

2) The above-mentioned antibacterial glaze is evenly coated on the surface of the green body, and after drying, it is fired in an oxidizing atmosphere to obtain antibacterial ceramics with a strong antibacterial effect.

Further, the mass ratio of the base glaze to deionized water in step (1) is: M _{base glaze} :M _{deionized water} =1:0.5-1; the ball milling time is 15-25min.

Further, the coating method in step (2) is one of flow coating, spray coating, brushing or dip coating, and the thickness of the glaze layer is required to be 1-1.2mm; the firing temperature is 1100-1250°C , preferably at 1150-1200°C; the firing time is 6-10h.

Antibacterial agents in the prior art tend to lose antibacterial ability at >500°C, and thus cannot be applied to make antibacterial ceramics. However, the antibacterial agents provided by the present invention can withstand the high temperature of ceramic calcination above 1100°C, and the antibacterial rate of the obtained antibacterial ceramics can still be high. Stay above 99%.

In the prior art, there is a method of loading antibacterial ions after ore modification to obtain antibacterial agents with stable antibacterial efficiency. Usually, the introduction of surfactants, thermal modification and other modification methods are used to expand the properties of the corresponding ore components such as agglomeration, surface negativity, and slow release of guest molecules; however, the inventors discovered during the research and development process that these modification steps It will consume the hydroxyl groups on the surface of the ore components, which will lead to the weakening of the antibacterial ion loading effect and the substitution rate of the hydroxyl groups in the high temperature environment will be greatly reduced. Therefore, if it is necessary to prepare antibacterial ceramics resistant to high temperature of ceramic calcination, the requirements for the maintenance of hydroxyl groups must be considered in the selection of antibacterial ions, ore selection and its preparation process.

For the present invention, copper ions are first selected as antibacterial ions, which have a better effect than silver ions and zinc ions that cannot withstand high temperatures and cannot maintain performance. For the ore, natural tubular halloysite is selected. At room temperature, its surface is negatively charged and there are a small amount of hydroxyl groups on the outer surface defects. A large amount of Cu ²⁺ is loaded to the outer surface of halloysite through electrostatic adsorption and hydroxyl action. The inventors have found that the modification of ore is not suitable for the preparation of high temperature resistant antibacterial agents, because at high temperatures, the modification reagents will be carbonized and decomposed to cause the antibacterial ions to be coated or lost, thereby causing the antibacterial ions to lose their activity; thermal modification Activation will cause the condensation reaction of the hydroxyl group, which will lead to the loss of the hydroxyl group. Therefore, the present invention does not carry out any modification treatment to the halloysite, but obtains the high temperature resistant antibacterial agent, and its antibacterial performance is further improved after high temperature calcination, producing unexpected technical effects.

Post-analysis found that halloysite has not been treated in any way, the pores on the nanotubes will not be reduced, and there are a lot of hydroxyl groups on the inner surface of the tube and the inner surface of the interlayer. At high temperature, the originally inactive siloxane groups on the outer surface of the tube can be completely or partially replaced by hydroxyl groups, which makes the Cu ²⁺ that is weakly electrostatically removed at high temperature and then reloaded on the Eloy through the action of hydroxyl groups. Stone surface, so that Cu ²⁺ will not be lost due to electrostatic damage at high temperature.

The copper-based high-temperature-resistant antibacterial agent prepared by the method of the invention has excellent high-temperature stability, strong antibacterial and broad-spectrum antibacterial effects, and the antibacterial rates against Escherichia coli, Staphylococcus aureus and other bacterial strains are all greater than 99%. In addition, the antibacterial ceramic of the present invention has excellent antibacterial performance, is not easy to change color and is not limited by light conditions, and has good stability of antibacterial active elements, and can exert antibacterial effect for a long time.

Description of drawings

Fig. 1 is the physical figure of the copper-based high-temperature-resistant antibacterial agent prepared in Example 1.

Fig. 2 is the digital camera picture of the antibacterial effect of the copper-based high-temperature-resistant antibacterial agent prepared in Example 1.

Figure 3 is a digital camera image of the antibacterial effect of the copper-based high-temperature-resistant antibacterial agent prepared in Example 1 after being calcined at 1200°C.

Fig. 4 is the antibacterial effect digital camera picture of the antibacterial ceramic prepared in embodiment 1.

Detailed ways

The technical solution of the present invention will be described clearly and completely through the following embodiments. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

Example 1

A copper-based high-temperature-resistant antibacterial agent that can withstand high-temperature calcination above 1100°C, the preparation of which consists of the following steps:

S1) Dissolve 5g of anhydrous copper sulfate in 200ml of deionized water, stir evenly and heat in a water bath to 70°C;

S2) Add 10 g of halloysite to the above solution according to the ratio of M _halloysite :M _{copper salt} =2:1, stir evenly, fully react for 20 minutes, and keep the reaction temperature constant at 70°C;

S3) Heating was stopped, and the supernatant liquid was poured off, washed three times with deionized water, centrifuged, and dried at a drying temperature of 90° C. for a drying time of 24 hours to finally obtain a copper-based high-temperature-resistant antibacterial agent.

An antibacterial ceramic, including a green body and an antibacterial glaze. The raw materials of the antibacterial glaze are mainly made of the following components: basic glaze, copper-based high-temperature resistant antibacterial agent, deionized water, wherein the basic glaze and copper-based high-temperature resistant The antibacterial agent is proportioned according to the following mass fractions, 99% of the base glaze, and 1% of the copper-based high-temperature-resistant antibacterial agent. Wherein, the copper-based high-temperature-resistant antibacterial agent is the above-mentioned copper-based high-temperature-resistant antibacterial agent.

The preparation method of described antibacterial ceramics comprises the following specific steps:

1) Weigh 99g of basic glaze and 1g of copper-based high-temperature-resistant antibacterial agent, mix them with 50ml of deionized water, and then carry out wet ball milling and sieving to obtain antibacterial glaze;

2) Evenly dip-coat the above-mentioned antibacterial glaze onto the surface of the green body, the thickness of the glaze layer is 1mm, and after drying, it is fired under an oxidizing atmosphere at a firing temperature of 1200°C and a firing time of 6 hours to obtain an antibacterial agent with a strong antibacterial effect. ceramics.

Example 2

A copper-based high-temperature-resistant antibacterial agent that can withstand high-temperature calcination above 1100°C, the preparation of which consists of the following steps:

S1) Dissolve 5g of anhydrous copper sulfate in 200ml of deionized water, stir evenly and heat in a water bath to 90°C;

S2) Add 10 g of halloysite to the above solution according to the ratio of M _halloysite :M _{copper salt} =2:1, stir evenly, fully react for 20 minutes, and keep the reaction temperature constant at 90°C;

S3) Heating was stopped, and the supernatant liquid was poured off, washed three times with deionized water, centrifuged, and dried at a drying temperature of 90° C. for a drying time of 24 hours to finally obtain a copper-based high-temperature-resistant antibacterial agent.

An antibacterial ceramic, including a green body and an antibacterial glaze. The raw materials of the antibacterial glaze are mainly made of the following components: basic glaze, copper-based high-temperature resistant antibacterial agent, deionized water, wherein the basic glaze and copper-based high-temperature resistant The antibacterial agent is proportioned according to the following mass fractions, 99% of the base glaze, and 1% of the copper-based high-temperature-resistant antibacterial agent. Wherein, the copper-based high-temperature-resistant antibacterial agent is the above-mentioned copper-based high-temperature-resistant antibacterial agent.

The preparation method of described antibacterial ceramics comprises the following specific steps:

1) Weigh 99g of basic glaze and 1g of copper-based high-temperature-resistant antibacterial agent, mix them with 50ml of deionized water, and then carry out wet ball milling and sieving to obtain antibacterial glaze;

2) Dip-coat the above-mentioned antibacterial glaze evenly on the surface of the green body, the thickness of the glaze layer is 1mm, and after drying, it is fired under an oxidizing atmosphere. ceramics.

Example 3

A copper-based high-temperature-resistant antibacterial agent that can withstand high-temperature calcination above 1100°C, the preparation of which consists of the following steps:

S1) Dissolve 3g of anhydrous copper sulfate in 200ml of deionized water, stir evenly and heat in a water bath to 70°C;

S2) Add 15g of halloysite to the above solution according to the ratio of M _halloysite :M _{copper salt} =5:1, stir evenly, fully react for 20 minutes, and keep the reaction temperature constant at 70°C;

S3) Heating was stopped, and the supernatant liquid was poured off, washed three times with deionized water, centrifuged, and dried at a drying temperature of 90° C. for a drying time of 24 hours to finally obtain a copper-based high-temperature-resistant antibacterial agent.

An antibacterial ceramic, including a green body and an antibacterial glaze. The raw materials of the antibacterial glaze are mainly made of the following components: basic glaze, copper-based high-temperature resistant antibacterial agent, deionized water, wherein the basic glaze and copper-based high-temperature resistant The antibacterial agent is proportioned according to the following mass fractions, 98% of the base glaze, and 2% of the copper-based high-temperature-resistant antibacterial agent. Wherein, the copper-based high-temperature-resistant antibacterial agent is the above-mentioned copper-based high-temperature-resistant antibacterial agent.

The preparation method of described antibacterial ceramics comprises the following specific steps:

1) Weigh 98g of basic glaze and 2g of copper-based high-temperature-resistant antibacterial agent, mix with 50ml of deionized water, and carry out wet ball milling and sieving to obtain antibacterial glaze;

2) Dip-coat the above-mentioned antibacterial glaze evenly on the surface of the green body, the thickness of the glaze layer is 1mm, and after drying, it is fired under an oxidizing atmosphere at a firing temperature of 1200°C and a firing time of 7 hours to obtain an antibacterial agent with a strong antibacterial effect. ceramics.

Example 4

A copper-based high-temperature-resistant antibacterial agent that can withstand high-temperature calcination above 1100°C, the preparation of which consists of the following steps:

S1) Dissolve 5g of anhydrous copper sulfate in 200ml of deionized water, stir evenly and heat in a water bath to 60°C;

S2) Add 15 g of halloysite to the above solution according to the ratio of M _halloysite : M _{copper salt} = 3:1, stir evenly, fully react for 25 minutes, and keep the reaction temperature constant at 60°C;

S3) Heating was stopped, and the supernatant liquid was poured off, washed three times with deionized water, centrifuged, and dried at a drying temperature of 90° C. for a drying time of 24 hours to finally obtain a copper-based high-temperature-resistant antibacterial agent.

An antibacterial ceramic, including a green body and an antibacterial glaze. The raw materials of the antibacterial glaze are mainly made of the following components: basic glaze, copper-based high-temperature resistant antibacterial agent, deionized water, wherein the basic glaze and copper-based high-temperature resistant The antibacterial agent is proportioned according to the following mass fractions, 98.5% of the base glaze, and 1.5% of the copper-based high-temperature-resistant antibacterial agent. Wherein, the copper-based high-temperature-resistant antibacterial agent is the above-mentioned copper-based high-temperature-resistant antibacterial agent.

The preparation method of described antibacterial ceramics comprises the following specific steps:

1) Weigh 98.5g of basic glaze and 1.5g of copper-based high-temperature-resistant antibacterial agent, mix with 50ml of deionized water, and carry out wet ball milling and sieving to obtain antibacterial glaze;

2) Evenly dip-coat the above antibacterial glaze onto the surface of the green body, the thickness of the glaze layer is 1.2mm, and after drying, it is fired in an oxidizing atmosphere at a firing temperature of 1180°C and a firing time of 8 hours to obtain a strong antibacterial effect Antibacterial ceramics.

Comparative example 1

The difference between Comparative Example 1 and Example 1 is that the anhydrous copper sulfate is replaced by zinc sulfate heptahydrate, and the others are the same.

Comparative example 2

The difference between Comparative Example 2 and Example 1 is that anhydrous copper sulfate is replaced by silver nitrate, and everything else is the same. Comparative example 3

The difference between Comparative Example 3 and Example 1 is that the antibacterial ceramics described in Comparative Example 3 do not contain the copper-based high-temperature-resistant antibacterial agent for antibacterial ceramics, and everything else is the same.

Comparative example 4

The difference between Comparative Example 4 and Example 1 is that the copper-based high-temperature-resistant antibacterial agent described in Comparative Example 4 does not contain halloysite, only a single anhydrous copper sulfate, and the others are the same.

Comparative example 5

The difference between Comparative Example 5 and Example 1 is that the antibacterial agent described in Comparative Example 5 does not contain anhydrous copper sulfate, only a single halloysite, and the others are the same.

Comparative example 6

The difference between Comparative Example 6 and Example 1 is that the halloysite described in Comparative Example 6 is organosilane-modified halloysite, and everything else is the same.

The preparation method of the organosilane-modified halloysite is as follows: 20ml of organosilane is added to 300ml of anhydrous toluene, fully stirred evenly, and then 12g of halloysite is added to the above mixed solution to obtain a suspension. Then, the suspension was continuously stirred and heated to reflux for 24h. After fully reacting, the mixed solution was filtered and washed 5 times with anhydrous toluene, and then dried in a vacuum oven for 24 hours to obtain organosilane-modified halloysite.

Comparative example 7

The difference between Comparative Example 7 and Example 1 is that the halloysite described in Comparative Example 7 is heat-activated halloysite, and everything else is the same.

The preparation method of described heat-activated halloysite is:

Put 10g of halloysite into a crucible and calcinate in a muffle furnace at 900°C for 2h to obtain thermally activated halloysite.

In order to further prove the effect of the present invention, the following test methods are provided

1. According to national standard GB/T 21510-2008 appendix A, carry out sterilizing experiment for escherichia coli and staphylococcus aureus, after the antibacterial agent prepared in embodiment 1-4, comparative example 1-7 is cleaned with sterile deionized water After drying, weigh 0.05g of antibacterial agent and add it to 10mL of Escherichia coli and Staphylococcus aureus with a concentration of 1X10 ⁵ cfu/mL, put it in a shaker at a constant temperature of 37°C for 6 hours, and take 0.1mL of the shaken bacteria solution in the Plates were painted on agar plates, placed in a 37°C constant temperature incubator for 24 hours, and the number of colonies was counted to determine the antibacterial rate. The test results are shown in Table 1.

Table 1. Antibacterial Results for Antimicrobial Agents

2. According to the recommended standard JC/T 897-2014 in the building materials industry, a sterilization experiment was carried out for Escherichia coli and Staphylococcus aureus, and the antibacterial ceramics prepared in Examples 1-4 and Comparative Examples 1-7 were cleaned with sterile deionized water After drying, take 0.2mL of the bacteria solution of Escherichia coli and Staphylococcus aureus with a concentration of 1X10 ⁵ cfu/mL and drop it on the ceramic surface, and cover the bacteria solution with a polyethylene film with the same size as the ceramic sheet to make the bacteria solution In full contact with the ceramic surface, put it in a constant temperature incubator at 37°C for 24 hours, use 10mL of eluent to rinse the film and ceramic sheet, and then remove 0.1mL of the rinsed bacterial solution to coat the plate, and put it again in 37 Cultivate in a constant temperature incubator for 24 hours and count the number of colonies and then determine the antibacterial rate. The test results are shown in Table 2.

Table 2. Antibacterial results for antibacterial ceramics

As can be seen from the antibacterial results of Table 1, the antibacterial effect of the copper-based high-temperature-resistant antibacterial agent prepared by the inventive method is all good, and the antibacterial rate to Escherichia coli and Staphylococcus aureus is all > 99%, and high-temperature calcining (1200 ℃) After that, the antibacterial rate was still >99%. It shows that the copper-based high-temperature-resistant antibacterial agent prepared by the present invention has broad-spectrum antibacterial effect and high efficiency.

As can be seen from the antibacterial results of Table 2, the antibacterial effect of the antibacterial ceramic samples prepared by the inventive method is all good, and the antibacterial ceramic products made after high-temperature calcination are all > 99% to Escherichia coli and Staphylococcus aureus antibacterial rates , showing that the antibacterial ceramics of the present invention have good high-temperature stability, are not limited by light conditions, and have broad-spectrum antibacterial effects and high efficiency.

In addition, from Table 1 and Table 2, it can also be concluded that:

a. Although the antibacterial agent prepared by using Ag ⁺ or Zn ²⁺ instead of Cu ²⁺ as the antibacterial ion shows a certain antibacterial effect at room temperature, the antibacterial rate of the ceramics made after high temperature calcination is all <10%, the reason The reason is that Ag ⁺ and Zn ²⁺ antibacterial ions have poor high-temperature stability. When the temperature T>500°C, the antibacterial effect will be lost, and the antibacterial ability of Zn ²⁺ is affected by light conditions.

b. The antibacterial agent prepared by treating halloysite in advance with surfactant or heat activation also shows a certain antibacterial effect at room temperature, but the antibacterial rate of ceramics made after high temperature calcination is also <10%, the reason At high temperature, the organic silane is carbonized and decomposed to cause the antibacterial ions to be coated or lost, resulting in the inactivation of the antibacterial ions; thermal modification and activation cause the condensation reaction of the hydroxyl groups, which in turn leads to the loss of the hydroxyl groups, resulting in the loss of the antibacterial ions.

The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made by using the content of the description of the present invention, or directly or indirectly used in other related technical fields, shall be the same as The theory is included in the patent protection scope of the present invention.

Claims (8)

1. a copper-type high-temperature-resistant antibacterial agent, is characterized in that: described copper-type high-temperature-resistant antibacterial agent can withstand high-temperature calcining above 1100 ℃, and its preparation is made up of following steps: S1) Dissolve the soluble copper salt in deionized water, stir evenly and heat in a water bath; S2) Add halloysite to the above solution, stir evenly, fully react, and keep the reaction temperature constant; S3) Stop heating, let it stand for precipitation, pour off the supernatant, wash and centrifugally dry, and finally obtain copper-based high-temperature-resistant antibacterial agent. 2. The copper-based high-temperature-resistant antibacterial agent according to claim 1, characterized in that: S1) the soluble copper salt is one of copper sulfate and copper chloride; the temperature heated in the water bath is 60-80°C . 3. The copper-based high-temperature-resistant antibacterial agent according to claim 1, characterized in that: S2) the mass ratio of halloysite and soluble copper salt is: M _halloysite : M _{copper salt} =1-20:1, Preferably it is 2-5:1; the stirring method is one of manual stirring, mechanical stirring or magnetic stirring; the reaction time is 15-25min; the reaction temperature is 60-80°C. 4. The copper-based high-temperature-resistant antibacterial agent according to claim 1, characterized in that: S3) the cleaning is 2-5 times of cleaning; the drying temperature is 70-90°C. 5. An antibacterial ceramic comprising the copper-based high-temperature-resistant antibacterial agent described in any one of claims 1-4, comprising a green body and an antibacterial glaze, is characterized in that: the raw material of the antibacterial glaze is mainly made of the following components: basic Glaze, copper-based high-temperature-resistant antibacterial agent, deionized water, wherein the basic glaze and copper-based high-temperature-resistant antibacterial agent are proportioned according to the following mass fractions, the basic glaze is 95-99.5%, and the copper-based high-temperature-resistant antibacterial agent is 0.5-5%; Preferably, 97-99% of the basic glaze, 1-3% of the copper-based high-temperature-resistant antibacterial agent. 6. a preparation method of the described antibacterial ceramics of claim 5, is characterized in that: comprises the following steps: 1) Add copper-based high-temperature-resistant antibacterial agent to the basic glaze, mix it with deionized water in an appropriate proportion, and then perform wet ball milling to obtain antibacterial glaze; 2) The above-mentioned antibacterial glaze is evenly coated on the surface of the green body, and after drying, it is fired in an oxidizing atmosphere to obtain antibacterial ceramics with strong antibacterial effect. 7. The preparation method according to claim 6, characterized in that: the mass ratio of the basic glaze to deionized water in step (1) is: M _{basic glaze} : M _{deionized water} = 1:0.5-1 ; The ball milling time is 15-25min. 8. The preparation method according to claim 7, characterized in that: the coating method in step (2) is one of flow coating, spray coating, brushing or dip coating, and the thickness of the glaze layer is required to be 1-1.2 mm; the firing temperature is 1100-1250°C, preferably 1150-1200°C; the firing time is 6-10h.

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