High-performance ceramic glaze for bacteriostatic domestic porcelain and preparation method thereof

Abstract

The application relates to the technical field of glazes, and discloses a high-performance ceramic glaze for antibacterial daily-use porcelain and a preparation method. The high-performance ceramic glaze for antibacterial daily-use porcelain is prepared from the following raw materials in parts by weight: 5-15 parts of sodium feldspar, 20-30 parts of potassium feldspar, 10-30 parts of kaolin, 13-26 parts of quartz, 0.3-7 parts of talc, 5-10 parts of limestone, 2-5 parts of boron-magnesium-iron ore, 0.5-1 part of rare earth, 2-5 parts of silver-loaded flower-like CuS, 1-3 parts of modified polysiloxane, 0.1-0.5 parts of sodium tripolyphosphate, and 0.1-0.3 parts of carboxymethyl cellulose. The high-performance ceramic glaze for antibacterial daily-use porcelain prepared by the application has good long-acting antibacterial performance and high strength.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of glazes, in particular to a high-performance ceramic glaze for antibacterial daily-use porcelain and a preparation method. BACKGROUND

[0002] Daily-use porcelain is a kind of porcelain utensil designed for daily life, which is mainly applied to the fields of tableware, tea set, coffee set and storage container, etc. However, pathogenic bacteria such as Escherichia coli and Staphylococcus aureus will inevitably breed in the daily use process, causing damage to people's life and property. Moreover, with the improvement of people's health consciousness, the existing traditional daily-use porcelain cannot meet people's needs.

[0003] As an inorganic antibacterial agent, copper-based antibacterial agent has the advantages of high melting point, low cost, safety, environmental protection and good high-temperature stability. However, in ceramics, copper-based antibacterial agent has poor dispersibility after high-temperature calcination, and has the problem of loss, which weakens its antibacterial type and limits its application in antibacterial ceramics.

[0004] Patent with the authorized announcement number CN 108892473 B discloses an antibacterial daily-use porcelain, which is prepared from kaolin, mullite, albite, zirconium phosphate / sodium alginate modified attapulgite composite silver-loaded antibacterial agent as raw materials, and has good antibacterial performance. SUMMARY

[0005] (I) Technical problems solved

[0006] In view of the deficiencies of the prior art, the application provides a high-performance ceramic glaze for antibacterial daily-use porcelain and a preparation method. The prepared ceramic glaze has the advantages of long-acting antibacterial property and high strength.

[0007] (II) Technical solutions

[0008] A high-performance ceramic glaze for antibacterial daily-use porcelain is prepared from the following raw materials in parts by weight: 5-15 parts of albite, 20-30 parts of potassium feldspar, 10-30 parts of kaolin, 13-26 parts of quartz, 0.3-7 parts of talc, 5-10 parts of limestone, 2-5 parts of boron-magnesium-iron ore, 0.5-1 part of rare earth oxide, 2-5 parts of silver-loaded flower-like CuS, 1-3 parts of modified polysiloxane, 0.1-0.5 parts of sodium tripolyphosphate, and 0.1-0.3 parts of carboxymethyl cellulose.

[0009] Preferably, the preparation method is as follows:

[0010] Sodium feldspar, potassium feldspar, kaolin, quartz, talc, limestone, boron-magnesium-iron ore, rare earth oxide, silver-loaded flower-like CuS, modified polysiloxane, sodium tripolyphosphate, carboxymethyl cellulose are added into a ball mill tank, zirconium oxide balls are used as the ball milling medium, deionized water is used as the solvent, and ball milling is carried out for 24 h at a ratio of material: ball: water = 1:2:1, and then the mixture is sieved through a 250-mesh screen to obtain a high-performance ceramic glaze for bacteriostatic daily-use porcelain.

[0011] The present application introduces charge repulsion and steric hindrance effects by using the carboxyl contained therein to adsorb sodium phosphate in sodium tripolyphosphate on the surface of solid particles, directly breaking the agglomerates between particles, and uniformly and stably dispersing them in the glaze, thereby achieving effective dispersion of the glaze.

[0012] The present application introduces boron-magnesium-iron ore to produce magnesium oxide, di boron trioxide, iron oxide and other solubilizing substances during sintering, forming a glass phase with good fluidity, and di boron trioxide can form a glass network structure with silicon dioxide and aluminum trioxide, thereby improving the hardness, wear resistance, corrosion resistance and other properties of the glaze surface.

[0013] Preferably, the preparation method of the silver-loaded flower-like CuS is as follows:

[0014] (1) 1g of copper nitrate hydrate and 0.6g of thiourea are added to a 75% mass fraction ethylene glycol aqueous solution, stirred uniformly, 0.6g of hexadecyl trimethyl ammonium bromide is added and stirred and dispersed, and then the mixture is reacted at 100℃ for 24h, after the reaction, centrifugation is performed, and the mixture is washed with deionized water and anhydrous ethanol in sequence, and then dried, and the obtained product is denoted as flower-like CuS;

[0015] (2) The flower-like CuS is added to deionized water, stirred and dispersed, 0.5mol / L of silver nitrate solution and methanol are added, the mixture is stirred in the dark for 10-20min, and then the mixture is irradiated under a 125W high-pressure mercury lamp for 12h, and then the mixture is washed with deionized water, centrifuged, and dried to obtain silver-loaded flower-like CuS;

[0016] The present application prepares a flower-like CuS, which has a flower-like structure and can pierce the cell membrane when touching bacteria, thereby achieving the purpose of sterilization and bacteriostasis, and the flower-like structure has a large specific surface area, which can load a large amount of silver to prevent the loss of silver, and the large specific surface area of the flower-like CuS is conducive to the absorption of light and effectively increases the photocatalytic antibacterial effect of CuS, and the silver ions and the flower-like CuS form a synergistic antibacterial effect.

[0017] Preferably, the preparation method of the modified polysiloxane is as follows:

[0018] A1, add aminopropyl triethoxysilane, anhydrous sodium sulfate into anhydrous ethanol, stir for 10-20min under nitrogen atmosphere, then add 2,5-dihydroxy terephthaldehyde into it, reflux for 3-5h, after the reaction is completed, filter, distill under reduced pressure, and the obtained is a bis-silane Schiff base imine ligand, wherein the molar ratio of aminopropyl triethoxysilane, anhydrous sodium sulfate and 2,5-dihydroxy terephthaldehyde is 2-2.4:2.2-2.5:1, in the reaction, the Schiff base reaction is carried out by using the amino group contained in aminopropyl triethoxysilane and the aldehyde group contained in 2,5-dihydroxy terephthaldehyde, and the bis-silane Schiff base imine ligand is obtained;

[0019] A2, under nitrogen atmosphere, add the bis-silane Schiff base imine ligand into anhydrous ethanol, then add copper nitrate into it, reflux for 10-14h, after the reaction is completed, cool to room temperature, then add ether into it, filter under negative pressure, wash with ether, and dry to obtain a silane-based Schiff base imine copper complex, wherein the molar ratio of the bis-silane Schiff base imine ligand and copper nitrate is 1:1-1.2;

[0020] A3, mix octamethylcyclotetrasiloxane, aminopropyl triethoxysilane and the silane-based Schiff base imine copper complex uniformly, then add potassium silanolate into it, heat to 105-115℃, react for 10-12h, after the reaction is completed, remove low-boiling substances under vacuum, cool to room temperature, then add isopropanol and maleic anhydride into it, heat to 70-75℃, react for 3-5h, and distill under reduced pressure to obtain a modified polysiloxane;

[0021] The application solves the problem of poor dispersibility of copper-based antibacterial agents after high-temperature calcination by introducing a Schiff base imine copper complex into polysiloxane, limiting copper ions to the network structure formed by polysiloxane, and generating silicon carbide and forming pores when polysiloxane reacts with carbon and the rearrangement of Si-O bonds and Si-C bonds during sintering, and the copper ions loaded in the polysiloxane can be uniformly dispersed in the pores formed by the polysiloxane by generating copper oxide particles, thereby improving the density and strength of the ceramic material.

[0022] Further preferably, the mass ratio of octamethylcyclotetrasiloxane, aminopropyl triethoxysilane, the silane-based Schiff base imine copper complex and maleic anhydride is 100:5-10:5-10:10-15.

[0023] Further preferably, the amount of potassium silanolate is 0.1-0.3% of the total mass of octamethylcyclotetrasiloxane, aminopropyl triethoxysilane and the silane-based Schiff base imine copper complex.

[0024] (Three) beneficial technical effects

[0025] The copper ions and silver ions contained in the glaze prepared by the application can react with the bacteria with negative charges on the surface through electrostatic action, destroy the charge distribution in the bacteria, and achieve the effect of contact sterilization and bacteriostasis; the silver ions are loaded into the flower-shaped CuS to obtain silver-loaded flower-shaped CuS, the flower-shaped CuS contains a large specific surface area, on the one hand, more silver ions are loaded, and on the other hand, the photocatalytic antibacterial effect of the flower-shaped CuS is increased, and the contact antibacterial effect of the silver ions and copper ions forms a synergistic antibacterial effect. In addition, the rare earth oxides are introduced into the glaze, on the one hand, the silver ions and copper ions are embedded in the glaze, which is difficult to be dissolved, thereby improving the long-acting antibacterial property, and on the other hand, the existence of the rare earth oxides can inhibit the grain growth, which is beneficial to form a dense structure, and improve the wear resistance and strength.

[0026] The prepared polysiloxane contains Schiff base imine copper complex, the copper ions are limited to the network structure formed by the polysiloxane, the problem of poor dispersibility of the copper-based antibacterial agent after high-temperature calcination is solved, and when the polysiloxane is sintered, silicon reacts with carbon and Si-O bonds and Si-C bonds are rearranged to generate silicon carbide and form pores, the copper ions loaded in the polysiloxane can be uniformly dispersed in the pores formed by the polysiloxane by generating copper oxide particles, thereby improving the density and strength of the ceramic material. In addition, the carboxyl structure contained therein can be used as a dispersion system with sodium tripolyphosphate, which is added to the glaze, can form dispersion of the glaze, reduce the agglomeration degree between the glaze particles, and improve the strength of the glaze. The application introduces boron-magnesium-iron ore, and the boron trioxide in the sintering process can form a glass network structure with silicon dioxide and aluminum trioxide, thereby improving the hardness, wear resistance, corrosion resistance and other properties of the glaze surface. The components used in the application complement each other, and together make the daily-use porcelain made of the glaze of the application have high mechanical properties and long-acting antibacterial properties. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is the reaction route of the bisilane Schiff base imine ligand.

[0028] Figure 2 is the SEM graph after sintering of Example 1.

[0029] Figure 3 is the SEM graph after sintering of Comparative Example 2. DETAILED DESCRIPTION

[0030] The specific embodiments of the application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the application, and are not used to limit the scope of the application.

[0031] Example 1

[0032] (1) 0.2 mol of aminopropyltriethoxysilane, 0.22 mol of anhydrous sodium sulfate were added to anhydrous ethanol, stirred for 15 min under a nitrogen atmosphere, and 0.1 mol of 2,5-dihydroxyterephthaldehyde was added thereto, and refluxed for 3 h. After the reaction was completed, it was filtered, distilled under reduced pressure, and the obtained product was designated as a bis-silane Schiff base imine ligand.

[0033] (2) 0.05 mol of the bis-silane Schiff base imine ligand was added to anhydrous ethanol under a nitrogen atmosphere, and 0.05 mol of copper nitrate was added thereto, and refluxed for 12 h. After the reaction was completed, it was cooled to room temperature, and diethyl ether was added thereto, and filtered under a negative pressure, washed with diethyl ether, and dried. The obtained product was designated as a silane-based Schiff base imine copper complex.

[0034] (3) 10 g of octamethylcyclotetrasiloxane, 1 g of aminopropyltriethoxysilane, and 0.5 g of the silane-based Schiff base imine copper complex were uniformly mixed, and 0.01 g of potassium silanolate was added thereto, and heated to 105°C, and reacted for 12 h. After the reaction was completed, low-boiling substances were removed under vacuum, and cooled to room temperature. Thereafter, isopropyl alcohol and 1.5 g of maleic anhydride were added thereto, and heated to 70°C, and reacted for 4 h. After the reaction was completed, it was distilled under reduced pressure, and the obtained product was designated as a modified polysiloxane.

[0035] (4) 1 g of copper nitrate hydrate and 0.6 g of thiourea were added to a 75% by mass aqueous ethylene glycol solution, and stirred to be uniform. Thereafter, 0.6 g of cetyltrimethylammonium bromide was added thereto, and stirred to be dispersed. The mixture was reacted at 100°C for 24 h. After the reaction was completed, it was centrifuged, and sequentially washed with deionized water and anhydrous ethanol, and dried. The obtained product was designated as a flower-like CuS.

[0036] (5) 0.5 g of the flower-like CuS was added to deionized water, and stirred to be dispersed. Thereafter, 0.5 mol / L of a silver nitrate solution and 15 mL of methanol were added thereto, and stirred for 10 min in the dark. Thereafter, it was irradiated with light for 12 h under a 125 W high-pressure mercury lamp. After the reaction was completed, it was washed with deionized water, and centrifuged, and dried. The obtained product was designated as a silver-loaded flower-like CuS.

[0037] (6) 15 g of sodium feldspar, 25 g of potassium feldspar, 30 g of kaolin, 13 g of quartz, 0.5 g of talc, 10 g of limestone, 3 g of boro-magnesio-fermite, 0.5 g of yttrium oxide, 2 g of the silver-loaded flower-like CuS, 1 g of the modified polysiloxane, 0.5 g of sodium tripolyphosphate, and 0.3 g of carboxymethyl cellulose were added to a ball mill pot, and deionized water was used as a solvent, and the mixture was ball-milled for 24 h at a ratio of 1:2:1 of the material: the ball: the water, using zirconia balls as a ball mill medium. Thereafter, it was passed through a 250-mesh screen, and a high-performance ceramic glaze for antibacterial domestic porcelain was obtained.

[0038] Example 2

[0039] (1) 0.24 mol of aminopropyltriethoxysilane, 0.25 mol of anhydrous sodium sulfate were added to anhydrous ethanol, stirred for 10 min under a nitrogen atmosphere, and 0.1 mol of 2,5-dihydroxyterephthaldehyde was added thereto, and refluxed for 5 h. After the completion of the reaction, it was filtered, distilled under reduced pressure, and the obtained product was designated as a bis-silane Schiff base imine ligand.

[0040] (2) 0.05 mol of the bis-silane Schiff base imine ligand was added to anhydrous ethanol under a nitrogen atmosphere, and 0.05 mol of copper nitrate was added thereto, and refluxed for 12 h. After the completion of the reaction, it was cooled to room temperature, and diethyl ether was added thereto, and filtered under a negative pressure, and washed with diethyl ether, and dried, and the obtained product was designated as a silane-based Schiff base imine copper complex.

[0041] (3) 10 g of octamethylcyclotetrasiloxane, 0.6 g of aminopropyltriethoxysilane, and 0.6 g of the silane-based Schiff base imine copper complex were uniformly mixed, and 0.03 g of potassium silanolate was added thereto, and heated to 115°C, and reacted for 10 h. After the completion of the reaction, low-boiling substances were removed under vacuum, and cooled to room temperature, and isopropanol was added thereto, and 1 g of maleic anhydride was added thereto, and heated to 75°C, and reacted for 3 h. After the completion of the reaction, it was distilled under reduced pressure, and the obtained product was designated as a modified polysiloxane.

[0042] (4) 1 g of copper nitrate hydrate and 0.6 g of thiourea were added to a 75 wt% ethylene glycol aqueous solution, and stirred to be uniform, and 0.6 g of cetyltrimethylammonium bromide was added thereto, and stirred to be dispersed, and reacted for 24 h at 100°C. After the completion of the reaction, it was centrifuged, and sequentially washed with deionized water and anhydrous ethanol, and dried, and the obtained product was designated as a flower-like CuS.

[0043] (5) 0.5 g of the flower-like CuS was added to deionized water, and stirred to be dispersed, and 0.5 mol / L of a silver nitrate solution and 15 mL of methanol were added thereto, and stirred for 15 min in the dark, and irradiated with light for 12 h under a 125 W high-pressure mercury lamp. After the completion of the reaction, it was washed with deionized water, and centrifuged, and dried, and the obtained product was designated as a silver-loaded flower-like CuS.

[0044] (6) 5 g of sodium feldspar, 30 g of potassium feldspar, 20 g of kaolin, 26 g of quartz, 0.3 g of talc, 8 g of limestone, 2 g of boro-magnesio-iron ore, 0.5 g of yttrium oxide, 0.5 g of cerium oxide, 3 g of the silver-loaded flower-like CuS, 1.5 g of the modified polysiloxane, 0.3 g of sodium tripolyphosphate, and 0.1 g of carboxymethyl cellulose were added to a ball mill pot, and zirconia balls were used as a ball mill medium, and deionized water was used as a solvent, and ball-milled for 24 h at a ratio of 1:2:1 of material:ball:water. After the completion of the ball-milling, it was passed through a 250-mesh screen, and the obtained product was designated as a high-performance ceramic glaze for antibacterial domestic porcelain.

[0045] Example 3

[0046] (1) 0.22 mol of aminopropyltriethoxysilane and 0.24 mol of anhydrous sodium sulfate were added to anhydrous ethanol, stirred for 20 min under a nitrogen atmosphere, and then 0.1 mol of 2,5-dihydroxyterephthaldehyde was added thereto and refluxed for 4 h. After the reaction was completed, it was filtered, distilled under reduced pressure, and the obtained product was designated as a bis-silane Schiff base imine ligand.

[0047] (2) 0.05 mol of the bis-silane Schiff base imine ligand was added to anhydrous ethanol under a nitrogen atmosphere, and then 0.06 mol of copper nitrate was added thereto and refluxed for 10 h. After the reaction was completed, it was cooled to room temperature, and then diethyl ether was added thereto, filtered under a negative pressure, washed with diethyl ether, and dried to obtain a silane-based Schiff base imine copper complex.

[0048] (3) 10 g of octamethylcyclotetrasiloxane, 0.5 g of aminopropyltriethoxysilane, and 0.8 g of the silane-based Schiff base imine copper complex were uniformly mixed, and then 0.02 g of potassium silanolate was added thereto, heated to 110°C, and reacted for 11 h. After the reaction was completed, low-boiling substances were removed under vacuum, and then it was cooled to room temperature, and 1.2 g of maleic anhydride was added thereto, heated to 70°C, and reacted for 5 h. After the reaction was completed, it was distilled under reduced pressure to obtain a modified polysiloxane.

[0049] (4) 1 g of copper nitrate hydrate and 0.6 g of thiourea were added to a 75 wt% ethylene glycol aqueous solution, uniformly stirred, and then 0.6 g of cetyltrimethylammonium bromide was added thereto, uniformly dispersed, and reacted at 100°C for 24 h. After the reaction was completed, it was centrifuged, sequentially washed with deionized water and anhydrous ethanol, and dried to obtain a flower-like CuS.

[0050] (5) 0.5 g of the flower-like CuS was added to deionized water, uniformly stirred, and then 0.5 mol / L of a silver nitrate solution and 15 mL of methanol were added thereto, stirred for 20 min in the dark, and then irradiated with light for 12 h under a 125 W high-pressure mercury lamp. After the reaction was completed, it was washed with deionized water, centrifuged, and dried to obtain a silver-loaded flower-like CuS.

[0051] (6) 10 g of sodium feldspar, 20 g of potassium feldspar, 10 g of kaolin, 20 g of quartz, 7 g of talc, 5 g of limestone, 5 g of boro-magnesite, 0.4 g of yttrium oxide, 4 g of the silver-loaded flower-like CuS, 2 g of the modified polysiloxane, 0.5 g of sodium tripolyphosphate, and 0.2 g of carboxymethyl cellulose were added to a ball mill pot, and then zirconia balls were used as a ball milling medium, and deionized water was used as a solvent. The ball milling was performed at a ratio of 1:2:1 of the material:ball:water for 24 h. After the ball milling was completed, it was passed through a 250-mesh screen to obtain a high-performance ceramic glaze for antibacterial domestic porcelain.

[0052] Example 4

[0053] (1) 0.24 mol of aminopropyltriethoxysilane and 0.25 mol of anhydrous sodium sulfate were added to anhydrous ethanol, stirred for 15 min under a nitrogen atmosphere, and 0.1 mol of 2,5-dihydroxyterephthaldehyde was added thereto, and refluxed for 5 h. After the completion of the reaction, it was filtered, distilled under reduced pressure, and the obtained product was designated as a bis-silane Schiff base imine ligand.

[0054] (2) 0.05 mol of the bis-silane Schiff base imine ligand was added to anhydrous ethanol under a nitrogen atmosphere, and 0.05 mol of copper nitrate was added thereto, and refluxed for 14 h. After the completion of the reaction, it was cooled to room temperature, and diethyl ether was added thereto, and filtered under a negative pressure, washed with diethyl ether, and dried to obtain a silane-based Schiff base imine copper complex.

[0055] (3) 10 g of octamethylcyclotetrasiloxane, 0.8 g of aminopropyltriethoxysilane, and 1 g of the silane-based Schiff base imine copper complex were uniformly mixed, and 0.035 g of potassium silanolate was added thereto, and heated to 105°C, and reacted for 11 h. After the completion of the reaction, low-boiling substances were removed under vacuum, and cooled to room temperature, and isopropanol was added thereto, and 1.4 g of maleic anhydride was added thereto, and heated to 75°C, and reacted for 4 h. After the completion of the reaction, it was distilled under reduced pressure to obtain a modified polysiloxane.

[0056] (4) 1 g of copper nitrate hydrate and 0.6 g of thiourea were added to a 75 wt% ethylene glycol aqueous solution, and stirred to be uniform, and 0.6 g of cetyltrimethylammonium bromide was added thereto, and stirred to be dispersed, and reacted for 24 h at 100°C. After the completion of the reaction, it was centrifuged, and sequentially washed with deionized water and anhydrous ethanol, and dried to obtain a flower-like CuS.

[0057] (5) 0.5 g of the flower-like CuS was added to deionized water, and stirred to be dispersed, and 0.5 mol / L of a silver nitrate solution and 15 mL of methanol were added thereto, and stirred for 10 min in the dark, and irradiated with light for 12 h under a 125 W high-pressure mercury lamp, and washed with deionized water, and centrifuged, and dried to obtain a silver-loaded flower-like CuS.

[0058] (6) 10 g of sodium feldspar, 30 g of potassium feldspar, 10 g of kaolin, 20 g of quartz, 5 g of talc, 10 g of limestone, 5 g of boro-magnesio-iron ore, 0.5 g of yttrium oxide, 0.5 g of cerium oxide, 5 g of the silver-loaded flower-like CuS, 3 g of the modified polysiloxane, 0.3 g of sodium tripolyphosphate, and 0.1 g of carboxymethyl cellulose were added to a ball mill pot, and zirconia balls were used as a ball mill medium, and deionized water was used as a solvent, and ball-milled for 24 h at a ratio of 1:2:1 of material:ball:water. After the completion of the ball milling, it was passed through a 250-mesh screen to obtain a high-performance ceramic glaze for antibacterial domestic porcelain.

[0059] Comparative Example 1

[0060] The ceramic glaze and its preparation method provided in this comparative example are roughly the same as those in Example 1. The main difference is that commercially available CuS is used instead of flower-shaped CuS in step (5).

[0061] Comparative Example 2

[0062] The ceramic glaze and its preparation method provided in this comparative example are roughly the same as those in Example 1. The main difference is that step (3) does not contain silyl Schiff base imine copper complex.

[0063] Pour the glaze into a wide-mouthed container, immerse the dried body in the glaze for 60 seconds, remove it, and place it in a high-temperature box-type resistance furnace for firing. Increase the temperature to 300℃ at 5℃ / min, then to 900℃ at 3℃ / min, and then to 1200℃ at 1℃ / min. Hold the temperature for 30 minutes. After the fired sample has cooled, open the furnace and remove it to obtain the ceramic product.

[0064] The flexural strength of the specimen was tested using a computerized electronic universal testing machine.

[0065] Referring to JC / T897-2002 (Antibacterial properties of antibacterial ceramic products), the bactericidal rate of ceramics against Escherichia coli was tested at 0 hours and after 1 year of storage.

[0066] Table 1:

[0067]

[0068]

[0069] As can be seen from the table above, the strength of Comparative Example 2 is worse than that of Example 1. This is because Comparative Example 2 does not contain silyl Schiff base imine copper complex. During the sintering process, polysiloxane generates gas, and the resulting pores cannot be filled. Therefore, the density and continuity are poor, and the strength is not good.

[0070] The antibacterial properties of Comparative Examples 1 and 2 are inferior to those of Example 1. This is because Comparative Example 1 uses commercially available CuS, which has a lower silver loading capacity than flower-shaped CuS with a larger specific surface area, and its photocatalytic antibacterial effect is also affected. Therefore, its long-lasting antibacterial performance is inferior to that of Example 1. Comparative Example 2 does not contain silyl Schiff base imine copper complex, therefore, its antibacterial performance is inferior to that of Example 1.

[0071] Depend on Figure 2 and Figure 3 It can be seen that, since no silyl Schiff base imine copper complex was added, the density and continuity of Comparative Example 2 after firing were not as good as those of Example 1. Therefore, its strength and antibacterial properties were not as good as those of Example 1.

[0072] The components used in the application complement each other, and together make the daily-use porcelain made by using the glaze of the application have high mechanical properties and long-acting antibacterial properties.

[0073] The above examples are only used to illustrate the technical solutions of the application, and not to limit them; although the application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can still be modified, or some technical features can be replaced by equivalents; and these modifications or replacements will not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the application.

Claims

1. A ceramic glaze for antibacterial daily-use porcelain, characterized in that, The ceramic glaze of the bacteriostatic daily-use porcelain is prepared from the following raw materials in parts by weight: 5-15 parts of sodium feldspar, 20-30 parts of potassium feldspar, 10-30 parts of kaolin, 13-26 parts of quartz, 0.3-7 parts of talc, 5-10 parts of limestone, 2-5 parts of borymagnesioferrite, 0.5-1 part of rare earth oxide, 2-5 parts of silver-loaded flower-like CuS, 1-3 parts of modified polysiloxane, 0.1-0.5 part of sodium tripolyphosphate, and 0.1-0.3 part of carboxymethyl cellulose. The preparation method of the modified polysiloxane is as follows: A1, the amino propyl triethoxysilane, anhydrous sodium sulfate is added to anhydrous ethanol, stirring under nitrogen atmosphere for 10-20 min, then 2, 5-dihydroxy terephthaldehyde is added, refluxing for 3-5 h, after the reaction, filtration, vacuum distillation, the obtained is recorded as bis-silane Schiff base imine ligand; A2, under nitrogen atmosphere, the bis-silane Schiff base imine ligand is added to anhydrous ethanol, then copper nitrate is added, refluxing for 10-14 h, after the reaction, cooling to room temperature, then adding ether, negative pressure filtration, ether washing, drying, the obtained is recorded as silane-based Schiff base imine copper complex; A3, octamethylcyclotetrasiloxane, amino propyl triethoxysilane, silane-based Schiff base imine copper complex are mixed uniformly, then potassium silanol is added, heating to 105-115℃, reacting for 10-12 h, after the reaction, vacuum removal of low boiling point substances, cooling to room temperature, then adding isopropanol and maleic anhydride, heating to 70-75℃, reacting for 3-5 h, vacuum distillation, the obtained is recorded as modified polysiloxane.

2. A bacteriostatic domestic ceramic enamel according to claim 1, characterised in that, The preparation method of the ceramic glaze of the bacteriostatic daily-use porcelain is as follows: The sodium feldspar, potassium feldspar, kaolin, quartz, talc, limestone, borymagnesioferrite, rare earth oxide, silver-loaded flower-like CuS, modified polysiloxane, sodium tripolyphosphate, and carboxymethyl cellulose are added to a ball mill tank, zirconium oxide balls are used as the ball milling medium, deionized water is used as the solvent, ball milling is carried out for 24 h at a ratio of material: ball: water = 1:2:1, then the mixture is filtered through a 250-mesh screen, and the bacteriostatic daily-use porcelain ceramic glaze is obtained.

3. A bacteriostatic domestic ceramic enamel according to claim 1 or 2, characterised in that, The preparation method of the silver-loaded flower-like CuS is as follows: (1) 1 g of copper nitrate hydrate and 0.6 g of thiourea are added to a 75% mass fraction ethylene glycol aqueous solution, stirred uniformly, then 0.6 g of hexadecyl trimethyl ammonium bromide is added, stirred and dispersed, reacted at 100℃ for 24 h, after the reaction, centrifuged, washed with deionized water and anhydrous ethanol in sequence, and dried, the obtained is recorded as flower-like CuS; (2) the flower-like CuS is added to deionized water, stirred and dispersed, then 0.5 mol / L silver nitrate solution and methanol are added, stirred in the dark for 10-20 min, then placed under a 125W high-pressure mercury lamp for light irradiation for 12 h, washed with deionized water, centrifuged, and dried, and the silver-loaded flower-like CuS is obtained.

4. The bacteriostatic domestic ceramic porcelain of claim 1, characterized in that, In A1, the molar ratio of the amino propyl triethoxysilane, anhydrous sodium sulfate, and 2, 5-dihydroxy terephthaldehyde is 2-2.4:2.2-2.5:

1.

5. The bacteriostatic domestic ceramic porcelain of claim 1, characterized in that, In A2, the molar ratio of the bis-silane Schiff base imine ligand and copper nitrate is 1:1-1.

2.

6. The bacteriostatic domestic ceramic porcelain of claim 1, characterized in that, The mass ratio of octamethylcyclotetrasiloxane, aminopropyltriethoxysilane, silane-based Schiff base imine copper complex and maleic anhydride in the A3 is 100:5-10:5-10:10-15.

7. The bacteriostatic domestic ceramic porcelain of claim 1, characterized in that, The amount of potassium silanol in the A3 is 0.1-0.3% of the total mass of octamethylcyclotetrasiloxane, aminopropyltriethoxysilane and silane-based Schiff base imine copper complex.

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