Nano antibacterial ceramic glaze and preparation method thereof

Abstract

The present invention relates to the technical field of ceramic glazes, and discloses a nano-antibacterial ceramic glaze and a preparation method thereof. The ceramic glaze is made of a first glaze and a second glaze, wherein the second glaze is made of a composite antibacterial agent and a frit, and the composite antibacterial agent is made by coating silicone oil and biomass alginate on the surface of copper-loaded porous shell powder. During the calcination process of the ceramic glaze, the silicone oil and biomass alginate will generate silicon oxide, thereby effectively improving the antifouling performance of the ceramic glaze. Moreover, during the long-term use of the ceramic product, the tiny pores formed on the surface of the copper-loaded porous shell powder can continuously release the stored antibacterial material, thereby achieving a sustained-release antibacterial effect, giving the ceramic product excellent antibacterial performance, and broadening the application range of the ceramic product.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic glazes, and in particular to a nano antibacterial ceramic glaze and a preparation method thereof. Background Art

[0002] Ceramic products, such as tableware, tea sets, washbasins, toilets, and bathtubs, are an indispensable part of modern life. Ceramic glazes are a crucial component of ceramic products. They are made by applying a glaze slurry made from minerals and other raw materials to a ceramic body. After high-temperature firing, a thin, colorless or colored, glassy layer forms on the surface of the ceramic body. Glazes not only enhance the aesthetics of porcelain but also protect the surface.

[0003] In recent years, with the improvement of people's living standards and the intensification of various competitions, the functional requirements for ceramic products have become increasingly higher. Functional ceramic products are mainly achieved by preparing functional glazes. Ordinary ceramic glazes do not have antibacterial properties. In humid environments such as kitchens and bathrooms, the glaze surface of ceramic products can easily become a breeding ground for microorganisms such as bacteria and mold, forming stains and bacterial communities that are difficult to remove, posing a threat to human health. In addition, scale, food residues, soap foam and other substances are easily attached to the concave and convex parts or micropores of the glaze surface under the action of various forces, causing pollution and difficulty in cleaning, which limits the application range of ceramic products. Therefore, improving the antibacterial and anti-fouling properties of ceramic glazes is of great practical significance.

[0004] In the prior art, in order to improve the antibacterial and antifouling properties of ceramic glazes, most of the methods are to add substances with antibacterial and antifouling properties to the basic glaze, thereby giving the glaze good antibacterial and antifouling properties. For example, the invention patent with publication number CN109970341B discloses an antifouling and antibacterial ceramic glaze and a preparation method thereof. The invention adds an antibacterial agent consisting of silver-doped zirconium oxide powder and diatomaceous earth loaded with a small amount of silver to the basic glaze, so that the fired ceramic can continuously and slowly release silver ions in water, thereby achieving a continuous antibacterial effect. At the same time, an aqueous solution of phosphoric acid and an aqueous solution of yttrium nitrate are added to the glaze, so that the ceramic fired with the glaze has good hydrophobicity, thereby achieving an antifouling effect. Summary of the Invention

[0005] The purpose of the present invention is to provide a nano antibacterial ceramic glaze and a preparation method thereof, which solves the following technical problems:

[0006] (1) Solved the problem of poor antibacterial performance of ordinary ceramic glazes;

[0007] (2) Solved the problem of poor anti-fouling performance of ordinary ceramic glazes.

[0008] The purpose of the present invention can be achieved through the following technical solutions:

[0009] A method for preparing a nano antibacterial ceramic glaze comprises the following steps:

[0010] SS1: Place the first glaze and the second glaze in a sand mill and grind them thoroughly until the glaze can pass through a sieve of 800-1000 mesh to obtain a compound glaze;

[0011] SS2: The compound glaze and sodium humate are stirred and mixed, and then aged in an environment of 35 to 45° C. for 15 to 25 days to obtain an aged glaze;

[0012] SS3: Add water to the aged glaze and adjust the specific gravity to 1.6-1.8 g / cm 3 , then add methyl cellulose and stir evenly to obtain ceramic glaze;

[0013] The first glaze comprises the following raw materials in parts by weight: 25 to 35 parts of quartz, 15 to 25 parts of potassium feldspar, 8 to 12 parts of calcite, 8 to 10 parts of kaolin, 5 to 8 parts of dolomite, 4 to 6 parts of pyrophyllite, 3 to 5 parts of barium carbonate, 4 to 5 parts of borax, and 5 to 7 parts of aluminum oxide;

[0014] The second glaze comprises the following raw materials in parts by weight: 8 to 12 parts of a composite antibacterial agent and 40 to 50 parts of frit;

[0015] The composite antibacterial agent is prepared by coating silicone oil and alginic acid on the surface of copper-loaded porous shell powder.

[0016] Furthermore, in step SS1, the weight percentage of the second glaze in the compound glaze is 15-20%.

[0017] Furthermore, the preparation method of the first glaze comprises the following steps:

[0018] S1: adding quartz, potassium feldspar, calcite, kaolin, dolomite, pyrophyllite, barium carbonate, borax, and alumina into a pool furnace. The temperature of the pool furnace is 1000-1200°C, and the sintering time is 3-5 hours. The sintered materials are drained into a water pool through a pipe and crushed into particles by water flow. The water flow temperature is controlled at 20-50°C to obtain a composite material.

[0019] S2: Add the composite material into the ball mill for ball milling. After ball milling, pass it through a 400-600 mesh sieve, and then add water to adjust the specific gravity to 1.75-1.85 g / cm 3 , and obtain the first glaze.

[0020] Furthermore, in step S2, during the ball milling process, the mass ratio of the composite material, balls and water is 1:2-3:0.4-0.7, the ball milling speed is 400-600 rpm, and the ball milling time is 5-10 h.

[0021] Furthermore, the preparation method of the second glaze comprises the following steps:

[0022] Add the composite antibacterial agent and frit into the ball mill and mill for 20-40 minutes, then add water to adjust the specific gravity to 1.2-1.6 g / cm 3 , continue ball milling until the slurry can all pass through the 100-200 mesh sieve to obtain the second glaze.

[0023] Furthermore, the preparation method of the composite antibacterial agent comprises the following steps:

[0024] Ⅰ: treating the porous shell powder with an alkali solution to obtain a pretreated porous shell powder;

[0025] II: Disperse the copper salt in deionized water, add the pretreated porous shell powder under stirring at 60-70°C, act with ultrasound for 20-40 minutes, soak for 15-25 hours, and discharge to obtain copper-loaded porous shell powder;

[0026] III: Under the action of tetrabutylammonium bromide, copper-loaded porous shell powder and epoxy-terminated silicone oil are added to dimethyl sulfoxide solution, ultrasonically dispersed for 20-30 minutes, the system temperature is raised to 60-70°C, kept warm for 4-8 hours, and the solid material is separated by filtration to obtain the intermediate material;

[0027] IV: Add the intermediate material, alginic acid and N,N-dimethylformamide into the reactor, stir mechanically until uniform, then add p-toluenesulfonic acid, keep stirring at 90-110°C for 3-6 hours, and discharge the material to obtain a composite antibacterial agent.

[0028] Furthermore, in step I, the alkali solution is any one of sodium hydroxide solution, calcium hydroxide solution or sodium hypochlorite solution.

[0029] Furthermore, in step II, the copper salt is any one of copper sulfate, copper nitrate or copper chloride.

[0030] Furthermore, in step III, the epoxy value of the epoxy-terminated silicone oil is 0.15 to 0.25 mol / 100 g.

[0031] A nano antibacterial ceramic glaze is prepared by adopting the above preparation method.

[0032] Beneficial effects of the present invention: The present invention prepares a composite antibacterial agent by using porous shell powder as a matrix, copper as an antibacterial material, silicone oil and biomass alginate as antifouling materials. On the one hand, the copper-loaded porous shell powder is coated with silicone oil and biomass alginate, which can effectively prevent copper ions from escaping from the pores during the preparation of ceramic products, resulting in waste of raw materials and reduced antibacterial performance. On the other hand, during the calcination process of ceramic glaze, silicone oil is used as a source of silicon element, and biomass alginate is used to provide the required oxygen source. The two react at high temperature to generate silicon oxygen. The low surface energy silicon oxide has good hydrophobic properties, making it difficult for water molecules to approach its surface and penetrate into the interior, thereby effectively improving the anti-fouling performance of the ceramic glaze. In addition, after calcination, a tiny pore structure is formed on the surface of the copper-loaded porous shell powder. During the long-term use of ceramic products, the antibacterial material stored in the pores can be continuously released to achieve a slow-release antibacterial effect, thereby giving the ceramic products excellent antibacterial properties, avoiding the growth of bacteria, mold and other microorganisms on the ceramic glaze, posing a threat to human health, and broadening the application range of ceramic products.

[0033] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0035] Figure 1 This is the infrared spectrum test diagram of the intermediate material and the composite antibacterial agent of the present invention. DETAILED DESCRIPTION

[0036] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0037] The preparation methods of the composite antibacterial agents in the following examples and comparative examples of the present invention are as follows:

[0038] Preparation of composite antibacterial agents

[0039] I: 5 g of porous shell powder was placed in a 4% sodium hydroxide solution and soaked for 24 hours, the material was filtered, a solid sample was collected, washed, and dried to obtain a pretreated porous shell powder;

[0040] II: Disperse 2g of copper sulfate in deionized water, add 5g of pretreated porous shell powder under stirring at 65℃, act with ultrasound for 30min, soak for 20h, discharge, wash and dry to obtain copper-loaded porous shell powder;

[0041] The copper content in the copper-loaded porous shell powder was tested using a Z-5000 atomic absorption spectrometer (AAS). The test showed that the mass fraction of copper in the prepared copper-loaded porous shell powder was 5.16%.

[0042] III: Under nitrogen protection, 5g of copper-loaded porous shell powder was added to a dimethyl sulfoxide solution and ultrasonically dispersed for 25min. 2.6g of epoxy-terminated silicone oil with an epoxy value of 0.2mol / 100g and 0.1g of tetrabutylammonium bromide were added. The system temperature was raised to 65°C under stirring and kept warm for 6h. The solid material was separated by filtration, washed and vacuum-dried to obtain an intermediate material.

[0043] IV: Add 5 g of the intermediate material and N,N-dimethylformamide to a nitrogen-protected reactor, stir mechanically until uniform, then add 2.8 g of alginic acid and 0.1 g of p-toluenesulfonic acid, turn on the heating until the temperature in the reactor reaches 100°C, keep stirring for 5 hours, wait for the material to cool naturally, centrifuge to separate the solid material, wash the solid material, and vacuum dry to obtain a composite antibacterial agent.

[0044] The intermediate materials and the composite antimicrobial agent were analyzed by infrared spectroscopy using a Vertex 70 Fourier transform infrared spectrometer produced by Bruker, Germany. The analysis results are shown in Figure 1 ,Depend on Figure 1 It can be seen that in the infrared spectrum of the intermediate material, 3285cm -1 The absorption peak of hydroxyl group OH appears at 1346 cm -1 The absorption peak of CN appears at 3421cm -1 The absorption peak of NH appears at 1020 cm -1 The absorption peak of Si-O appears at 1759cm -1 The absorption peak of the ester group C=O appears at 1350cm -1 The absorption peak of CN appears at 3410 cm -1 The absorption peak of NH appears at 1025cm -1 The Si-O absorption peak appears at

[0045] It can be inferred that the principle of the above scheme is: use sodium hydroxide solution to remove the stratum corneum of porous shell powder to obtain pretreated porous shell powder, and under the action of ultrasound, copper ions interact with porous shell powder, and copper ions will flow into the pores of shell powder. At the same time, water is used as the medium and copper-loaded porous shell powder is prepared by immersion exchange method. Then, under the action of tetrabutylammonium bromide, the active groups in the copper-loaded porous shell powder can react with the epoxy groups in the end epoxy silicone oil structure to undergo a ring-opening reaction, thereby introducing active hydroxyl groups produced by the ring-opening reaction into the copper-loaded porous shell powder to obtain an intermediate material. Under the action of p-toluenesulfonic acid, the active hydroxyl groups in the intermediate material structure can react with the carboxyl groups in the alginate structure to obtain a composite antibacterial agent.

[0046] Example 1

[0047] Step 1: Preparation of the first glaze

[0048] S1: 25 g of quartz, 15 g of potassium feldspar, 8 g of calcite, 8 g of kaolin, 5 g of dolomite, 4 g of pyrophyllite, 3 g of barium carbonate, 4 g of borax, and 5 g of alumina were added to a pool furnace. The temperature of the pool furnace was 1000° C. and the sintering time was 3 h. The sintered material was drained into a water pool through a pipe and crushed into particles by water flow. The water temperature was controlled at 20° C. to obtain a composite material.

[0049] S2: The composite material was added to the ball mill for ball milling. During the ball milling process, the mass ratio of the composite material, balls and water was 1:2:0.4, the ball milling speed was 400 rpm, and the ball milling time was 5 h. After ball milling, the composite material was passed through a 400-mesh sieve, and then water was added to adjust the specific gravity to 1.75 g / cm 3 , obtaining a first glaze;

[0050] Step 2: Preparation of the second glaze

[0051] 8g of composite antibacterial agent and 40g of frit were added to the ball mill and milled for 20min. Then water was added to adjust the specific gravity to 1.2g / cm 3 , continue ball milling until the slurry can all pass through a 100-mesh sieve to obtain the second glaze;

[0052] Step 3: Preparation of ceramic glaze

[0053] SS1: The first glaze and the second glaze are placed in a sand mill and ground thoroughly until the glazes can pass through an 800-mesh sieve to obtain a compound glaze, wherein the weight percentage of the second glaze in the compound glaze is 15%;

[0054] SS2: mixing the compound glaze and sodium humate, wherein the amount of sodium humate added is 0.13% of the solid mass of the compound glaze, and then aging at 35° C. for 15 days to obtain an aged glaze;

[0055] SS3: Add water to the aged glaze and adjust the specific gravity to 1.6g / cm 3 , and then add methyl cellulose, wherein the amount of methyl cellulose added is 0.04% of the solid mass of the aged glaze, and stir evenly to obtain a ceramic glaze.

[0056] Example 2

[0057] Step 1: Preparation of the first glaze

[0058] S1: 30 g of quartz, 20 g of potassium feldspar, 10 g of calcite, 9 g of kaolin, 7 g of dolomite, 5 g of pyrophyllite, 4 g of barium carbonate, 4.5 g of borax, and 6 g of alumina were added to a pool furnace. The temperature of the pool furnace was 1100° C. and the sintering time was 4 h. The sintered material was drained into a water pool through a pipe and crushed into particles by water flow. The water temperature was controlled at 35° C. to obtain a composite material.

[0059] S2: The composite material was added to the ball mill for ball milling. During the ball milling process, the mass ratio of the composite material, balls and water was 1:2.5:0.5, the ball milling speed was 500 rpm, and the ball milling time was 8 hours. After ball milling, the composite material was passed through a 500-mesh sieve, and then water was added to adjust the specific gravity to 1.8 g / cm 3 , obtaining a first glaze;

[0060] Step 2: Preparation of the second glaze

[0061] Add 10g of composite antibacterial agent and 45g of frit into the ball mill and mill for 30min. Then add water to adjust the specific gravity to 1.4g / cm 3 , continue ball milling until the slurry can all pass through a 150-mesh sieve to obtain the second glaze;

[0062] Step 3: Preparation of ceramic glaze

[0063] SS1: The first glaze and the second glaze are placed in a sand mill and ground thoroughly until the glazes can pass through a 900-mesh sieve to obtain a compound glaze, wherein the weight percentage of the second glaze in the compound glaze is 18%;

[0064] SS2: mixing the compound glaze and sodium humate, wherein the amount of sodium humate added is 0.14% of the solid mass of the compound glaze, and then aging the mixture at 40° C. for 20 days to obtain an aged glaze;

[0065] SS3: Add water to the aged glaze and adjust the specific gravity to 1.7g / cm 3 , and then add methyl cellulose, wherein the amount of methyl cellulose added is 0.05% of the solid mass of the aged glaze, and stir evenly to obtain a ceramic glaze.

[0066] Example 3

[0067] Step 1: Preparation of the first glaze

[0068] S1: 35 g of quartz, 25 g of potassium feldspar, 12 g of calcite, 10 g of kaolin, 8 g of dolomite, 6 g of pyrophyllite, 5 g of barium carbonate, 5 g of borax, and 7 g of alumina were added to a pool furnace. The temperature of the pool furnace was 1200° C. and the sintering time was 5 h. The sintered material was drained into a water pool through a pipe and crushed into particles by water flow. The water flow temperature was controlled at 50° C. to obtain a composite material.

[0069] S2: The composite material was added to the ball mill for ball milling. During the ball milling process, the mass ratio of the composite material, balls and water was 1:3:0.7, the ball milling speed was 600 rpm, and the ball milling time was 10 h. After ball milling, the composite material was passed through a 600-mesh sieve, and then water was added to adjust the specific gravity to 1.85 g / cm 3 , obtaining a first glaze;

[0070] Step 2: Preparation of the second glaze

[0071] 12g of composite antibacterial agent and 50g of frit were added to the ball mill and milled for 40min. Then water was added to adjust the specific gravity to 1.6g / cm 3 , continue ball milling until the slurry can all pass through a 200-mesh sieve to obtain the second glaze;

[0072] Step 3: Preparation of ceramic glaze

[0073] SS1: The first glaze and the second glaze are placed in a sand mill and ground thoroughly until the glazes can pass through a 1000-mesh sieve to obtain a compound glaze, wherein the weight percentage of the second glaze in the compound glaze is 20%;

[0074] SS2: mixing the compound glaze and sodium humate, wherein the amount of sodium humate added is 0.15% of the solid mass of the compound glaze, and then aging at 45° C. for 25 days to obtain an aged glaze;

[0075] SS3: Add water to the aged glaze and adjust the specific gravity to 1.8g / cm 3 , and then add methyl cellulose, wherein the amount of methyl cellulose added is 0.06% of the solid mass of the aged glaze, and stir evenly to obtain a ceramic glaze.

[0076] Comparative Example 1

[0077] Step 1: Preparation of the first glaze

[0078] S1: 30 g of quartz, 20 g of potassium feldspar, 10 g of calcite, 9 g of kaolin, 7 g of dolomite, 5 g of pyrophyllite, 4 g of barium carbonate, 4.5 g of borax, 6 g of aluminum oxide, 10 g of nano-copper oxide, and 45 g of frit were added to a pool furnace. The temperature of the pool furnace was 1100° C. and the sintering time was 4 h. The sintered material was drained into a water pool through a pipe and crushed into particles by water flow. The water flow temperature was controlled at 35° C. to obtain a composite material.

[0079] S2: The composite material was added to the ball mill for ball milling. During the ball milling process, the mass ratio of the composite material, balls and water was 1:2.5:0.5, the ball milling speed was 500 rpm, and the ball milling time was 8 hours. After ball milling, the composite material was passed through a 500-mesh sieve, and then water was added to adjust the specific gravity to 1.8 g / cm 3 , obtaining a first glaze;

[0080] Step 2: Preparation of ceramic glaze

[0081] SS1: Place the first glaze in a sand mill and grind it thoroughly until it can pass through a 900-mesh sieve to obtain the compound glaze;

[0082] SS2: mixing the compound glaze and sodium humate, wherein the amount of sodium humate added is 0.14% of the solid mass of the compound glaze, and then aging the mixture at 40° C. for 20 days to obtain an aged glaze;

[0083] SS3: Add water to the aged glaze and adjust the specific gravity to 1.7g / cm 3 , and then add methyl cellulose, wherein the amount of methyl cellulose added is 0.05% of the solid mass of the aged glaze, and stir evenly to obtain a ceramic glaze.

[0084] Performance testing:

[0085] A ceramic body of 15 cm × 15 cm × 8 mm was placed in a kiln, calcined at 700°C for 4 hours, and cooled. The ceramic glazes prepared in Examples 1 to 3 of the present invention and Comparative Example 1 were then evenly coated on the surface of the calcined ceramic body to obtain a glazed body. The glazed body was then calcined at 1300°C for 5 hours and cooled to obtain a ceramic sample.

[0086] According to JC / T 897-2014 "Antibacterial Properties of Antibacterial Ceramic Products," ceramic samples were tested for antibacterial properties, using Escherichia coli and Staphylococcus aureus as the test bacteria. Water contact angles were measured on the ceramic sample surfaces using a JC2000D4 contact angle meter to determine the antifouling properties of the ceramic samples. Specific test results are shown in the table below:

[0087]

[0088] From the test results in the above table, it can be seen that the ceramic samples prepared in Examples 1 to 3 have an antibacterial rate against Escherichia coli and Staphylococcus aureus greater than 99%, and the water contact angles are greater than 120°, so they all have good antibacterial and anti-fouling properties; the ceramic sample prepared in Comparative Example 1 only uses the first glaze with directly added nano-copper oxide to coat the surface of the ceramic embryo. Compared with the examples, the antibacterial and anti-fouling properties of the ceramic sample are poor.

[0089] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a nano antibacterial ceramic glaze, characterized in that: The following steps are involved: SS1: Place the first glaze and the second glaze in a sand mill and grind them thoroughly until the glaze can pass through a sieve of 800-1000 mesh to obtain a compound glaze; SS2: The compound glaze and sodium humate are stirred and mixed, and then aged in an environment of 35 to 45° C. for 15 to 25 days to obtain an aged glaze; SS3: Add water to the aged glaze and adjust the specific gravity to 1.6-1.8 g / cm 3 , then add methyl cellulose and stir evenly to obtain ceramic glaze; The first glaze comprises the following raw materials in parts by weight: 25 to 35 parts of quartz, 15 to 25 parts of potassium feldspar, 8 to 12 parts of calcite, 8 to 10 parts of kaolin, 5 to 8 parts of dolomite, 4 to 6 parts of pyrophyllite, 3 to 5 parts of barium carbonate, 4 to 5 parts of borax, and 5 to 7 parts of aluminum oxide; The second glaze comprises the following raw materials in parts by weight: 8 to 12 parts of a composite antibacterial agent and 40 to 50 parts of frit; The composite antibacterial agent is prepared by coating silicone oil and alginic acid on the surface of copper-loaded porous shell powder.

2. The method for preparing a nano antibacterial ceramic glaze according to claim 1, characterized in that: In step SS1, the weight percentage of the second glaze in the compound glaze is 15-20%.

3. The method for preparing a nano antibacterial ceramic glaze according to claim 1, characterized in that: The preparation method of the first glaze comprises the following steps: S1: adding quartz, potassium feldspar, calcite, kaolin, dolomite, pyrophyllite, barium carbonate, borax, and alumina into a pool furnace. The temperature of the pool furnace is 1000-1200°C, and the sintering time is 3-5 hours. The sintered materials are drained into a water pool through a pipe and crushed into particles by water flow. The water flow temperature is controlled at 20-50°C to obtain a composite material. S2: Add the composite material into the ball mill for ball milling. After ball milling, pass it through a 400-600 mesh sieve, and then add water to adjust the specific gravity to 1.75-1.85 g / cm 3 , and obtain the first glaze.

4. The method for preparing a nano antibacterial ceramic glaze according to claim 3, characterized in that: In step S2, during the ball milling process, the mass ratio of the composite material, balls and water is 1:2-3:0.4-0.7, the ball milling speed is 400-600 rpm, and the ball milling time is 5-10 hours.

5. The method for preparing a nano antibacterial ceramic glaze according to claim 1, characterized in that: The preparation method of the second glaze comprises the following steps: Add the composite antibacterial agent and frit into the ball mill and mill for 20-40 minutes, then add water to adjust the specific gravity to 1.2-1.6 g / cm 3 , continue ball milling until the slurry can all pass through the 100-200 mesh sieve to obtain the second glaze.

6. The method for preparing a nano antibacterial ceramic glaze according to claim 1, characterized in that: The preparation method of the composite antibacterial agent comprises the following steps: Ⅰ: treating the porous shell powder with an alkali solution to obtain a pretreated porous shell powder; Ⅱ: Disperse copper salt in deionized water adding the pretreated porous shell powder under stirring at 60-70° C., subjecting the mixture to ultrasonic treatment for 20-40 minutes, soaking the mixture for 15-25 hours, and discharging the mixture to obtain the copper-loaded porous shell powder; III: Under the action of tetrabutylammonium bromide, copper-loaded porous shell powder and epoxy-terminated silicone oil are added to dimethyl sulfoxide solution, ultrasonically dispersed for 20-30 minutes, the system temperature is raised to 60-70°C, kept warm for 4-8 hours, and the solid material is separated by filtration to obtain the intermediate material; IV: Add the intermediate material, alginic acid and N,N-dimethylformamide into the reactor, stir mechanically until uniform, then add p-toluenesulfonic acid, keep stirring at 90-110°C for 3-6 hours, and discharge the material to obtain a composite antibacterial agent.

7. The method for preparing a nano antibacterial ceramic glaze according to claim 6, characterized in that: In step I, the alkali solution is any one of sodium hydroxide solution, calcium hydroxide solution or sodium hypochlorite solution.

8. The method for preparing a nano antibacterial ceramic glaze according to claim 6, characterized in that: In step II, the copper salt is any one of copper sulfate, copper nitrate or copper chloride.

9. The method for preparing a nano antibacterial ceramic glaze according to claim 6, characterized in that: In step III, the epoxy value of the epoxy-terminated silicone oil is 0.15 to 0.25 mol / 100 g.

10. A nano antibacterial ceramic glaze, characterized in that: The method according to claim 1 is used for preparing the present invention.

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