Dry granulated glaze, antibacterial ceramic tile and method for manufacturing the same

Abstract

The present application relates to the technical field of ceramic tiles, in particular to a dry particle glaze, antibacterial ceramic tile and a preparation method thereof, wherein the dry particle glaze comprises the following preparation raw materials in percentage by mass: 6-9% corundum, 9-12% fused quartz, 6-9% fused zirconium silicate, and the rest is first dry particles and second dry particles with a mass ratio of 1:(1.8-2.2). The dry particle glaze of the present application is prepared by using the first dry particles and the second dry particles with a specific formula, and is matched with corundum, fused quartz and fused zirconium silicate, so as to improve the melting temperature of the dry particle glaze, so that the initial melting temperature is above 1300 DEG C, the surface antibacterial agent is not coated, and the problem of poor wear resistance of the conventional antibacterial glaze is avoided.

Description

Technical Field

[0001] This invention relates to the field of ceramic tile technology, and in particular to a dry granule glaze, an antibacterial ceramic tile, and its preparation method. Background Technology

[0002] The production of existing antibacterial ceramic products mainly encompasses three technical approaches: coating, sintering, and sintered coating. First, the coating method involves spraying an antibacterial coating onto the ceramic surface to achieve an antibacterial effect. For example, patent application number CN202610028048.6 describes an invention that uses a fully chemically bonded approach to firmly anchor antibacterial functional groups, such as quaternary ammonium pyridine antibacterial layers, onto the ceramic surface to exert an antibacterial effect. Second, the sintering method involves adding antibacterial materials to the glaze and sintering them together, allowing the antibacterial materials to remain stably within the glaze and achieve long-lasting antibacterial effects. For example, patent application number CN202510343030.0 describes an invention that adds far-infrared ceramic powder to the base glaze and a specific hot-melt sealing glaze. Even if the surface glaze is damaged, the stability and durability of the product's performance will not be affected, thus maintaining stable and efficient antibacterial performance. Third, the sintering coating method refers to sintering an antibacterial layer onto the ceramic surface, which has both high-efficiency and long-lasting antibacterial effects. For example, the patent application number CN202511798095.0 describes an invention that combines the application of a gridded ceramic layer with carbon coating of the antibacterial agent. The two work synergistically to construct an antibacterial layer on the surface of a low-gloss matte ceramic layer without significantly increasing the gloss, thereby retaining excellent antibacterial properties.

[0003] However, current technical solutions still have shortcomings. For example, when organic antibacterial coatings are anchored to the ceramic surface via chemical bonds, the durability of organic antibacterial agents is poor. This is mainly due to two reasons: firstly, the organic antibacterial agents have poor adhesion to the ceramic slab surface; secondly, the organic antibacterial agents themselves are prone to degradation and failure. As for the solution of adding conventional antibacterial agents and far-infrared antibacterial agents to the glaze for sintering, although this solves the durability problem, the antibacterial agents may be completely encapsulated by the glaze, which greatly reduces their antibacterial performance. To achieve the same antibacterial effect, more antibacterial agents need to be added, leading to excessively high costs. The sintering coating method combines the two, but current designs are complex and not conducive to large-scale production.

[0004] It is evident that existing technologies still need improvement and enhancement. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a dry granule glaze, antibacterial ceramic brick and its preparation method, which aims to solve the technical problem in the prior art that the glaze will over-coat the antibacterial agent, resulting in a significant reduction in the antibacterial performance of the antibacterial agent.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: The first aspect of the present invention provides a dry granule glaze, comprising, by mass percentage, the following raw materials: 6% to 9% corundum, 9% to 12% fused quartz, 6% to 9% fused zirconium silicate, and the remainder being first and second dry granules in a mass ratio of 1:(1.8 to 2.2). The chemical composition of the first dry granules, by mass percentage, includes: 46%–49% SiO2, 16%–18% Al2O3, 3%–5% ZnO, 9%–11% BaO, 2%–4% CaO, 4%–6% MgO, 3%–5% K2O, 2%–4% Na2O, with the remainder being loss on ignition and impurities. The chemical composition of the second dry granules, by mass percentage, includes: 48%–53% SiO2, 16%–18% Al2O3, 5%–7% ZnO, 6%–8% BaO, 6%–8% CaO, 1%–3% MgO, 3%–5% K2O, 1%–3% Na2O, 1%–3% SrO, with the remainder being loss on ignition and impurities.

[0007] The dry granule glaze, wherein the first dry granule has a D90 ≤ 72 μm and the second dry granule has a D90 ≤ 52 μm.

[0008] The dry granule glaze, wherein the corundum has a particle size range of 500 nm to 1 μm; the fused quartz has a particle size range of 500 nm to 1 μm; and the fused zirconium silicate has a particle size range of 800 nm to 1.5 μm.

[0009] The dry granule glaze further comprises a suspending agent and water in a mass ratio of 1:(0.8-1.2); the specific gravity of the dry granule glaze is 1.40-1.50 g / cm³. 3 The application rate is 280–320 g / m³. 2 .

[0010] A second aspect of the present invention provides an antibacterial ceramic tile, comprising, from bottom to top: a body layer, a surface glaze layer, a dry granule glaze layer, and a surface antibacterial layer, wherein the raw material for preparing the dry granule glaze layer is the dry granule glaze as described above.

[0011] The antibacterial ceramic brick, wherein the raw material for preparing the surface antibacterial layer is an antibacterial agent dispersion, the raw materials for preparing the antibacterial agent dispersion include: nano zinc oxide, dispersant and water; the content of nano zinc oxide is 5% to 10% by mass percentage.

[0012] The antibacterial ceramic brick, wherein the particle size of the nano zinc oxide ranges from 10 to 30 nm.

[0013] The antibacterial ceramic brick, wherein the raw materials for preparing the antibacterial agent dispersion further include gloss adjusting auxiliary materials, the content of which is 0.26% to 10% by mass percentage; the gloss adjusting auxiliary materials are selected from one or more of alumina, potassium feldspar, sodium feldspar, quartz, and barium carbonate.

[0014] A third aspect of the present invention provides an antibacterial ceramic tile, comprising, from bottom to top: a body layer, a surface glaze layer, a pattern layer, a dry granule glaze layer, and a surface antibacterial layer, wherein the raw material for preparing the dry granule glaze layer is the dry granule glaze as described above.

[0015] A fourth aspect of the present invention provides a method for preparing ceramic bricks, which is used to prepare antibacterial ceramic bricks as described above, comprising the following steps: S1. Apply a glaze to the body layer to form a glaze layer after firing; S2. Inkjet print the pattern to form a pattern layer after firing; S3. Spray dry granule glaze at a rate of 280–320 g / m³. 2 To form a dry granular glaze layer after firing; S4. Spray the antibacterial agent dispersion onto the dry granule glaze at a spraying rate of 110–125 g / m². 2 To form an antibacterial layer on the surface after firing; S5. After drying, the ceramic brick is fired at a temperature of 1180-1210℃ for a period of 40-50 minutes to obtain the antibacterial ceramic brick.

[0016] Beneficial Effects: This invention provides a dry-granule glaze, which is mainly composed of first and second dry granules. The active ingredients in the first and second dry granules are locked in a glass network, reducing the probability of reaction between the active ingredients and the antibacterial agent, thereby reducing the consumption of the antibacterial agent in the glaze. Furthermore, by limiting the potassium and sodium content in the formula and increasing the barium and strontium content, as well as adding corundum, fused zirconium silicate, and fused quartz to the formula, the melting temperature of the dry-granule glaze is increased to above 1300℃, higher than the conventional temperature of 1260℃. This ensures that the antibacterial agent on the glaze surface is not coated, and also compensates for the decrease in glaze wear resistance caused by the addition of antibacterial agents, thus comprehensively improving the antibacterial durability of the ceramic. Attached Figure Description

[0017] Figure 1 The antibacterial ceramic brick prepared in Example 1.

[0018] Figure 2 The antibacterial ceramic brick prepared as Comparative Example 10. Detailed Implementation

[0019] This invention provides a dry-granule glaze, an antibacterial ceramic tile, and a method for preparing the same. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0020] The first aspect of the present invention provides a dry granule glaze, comprising, by mass percentage, the following raw materials: 6% to 9% corundum, 9% to 12% fused quartz, 6% to 9% fused zirconium silicate, and the remainder being first and second dry granules in a mass ratio of 1:(1.8 to 2.2). The chemical composition of the first dry granules, by mass percentage, includes: 46%–49% SiO2, 16%–18% Al2O3, 3%–5% ZnO, 9%–11% BaO, 2%–4% CaO, 4%–6% MgO, 3%–5% K2O, 2%–4% Na2O, with the remainder being loss on ignition and impurities. The chemical composition of the second dry granules, by mass percentage, includes: 48%–53% SiO2, 16%–18% Al2O3, 5%–7% ZnO, 6%–8% BaO, 6%–8% CaO, 1%–3% MgO, 3%–5% K2O, 1%–3% Na2O, 1%–3% SrO, with the remainder being loss on ignition and impurities.

[0021] The dry-granule glaze of this invention, through the rational combination of first and second dry granules with corundum, fused quartz, and fused zirconium silicate, avoids the antibacterial agent being coated by the glaze layer, allowing the nano-antibacterial agent to fully exert its highly efficient antibacterial properties. The resulting antibacterial ceramic tiles exhibit antibacterial properties and antibacterial durability of over 99.9% against Escherichia coli. Furthermore, it gives the glaze excellent wear resistance. Specifically, in the dry-granule glaze formula, by limiting the potassium and sodium content in the dry granules and increasing the barium and strontium content, and by adding corundum, fused zirconium silicate, and fused quartz, the melting temperature of the glaze is increased, resulting in an initial melting temperature of over 1300℃, while the initial melting temperature of conventional glazes is generally no higher than 1260℃. This prevents the antibacterial agent from being coated during tile firing. In addition, the addition of corundum, fused zirconium silicate, and fused quartz improves the wear resistance of the glaze surface, compensating for the decrease in wear resistance caused by the addition of the antibacterial agent.

[0022] Specifically, the components used in the dry granule glaze, including the first dry granule, the second dry granule, corundum, fused quartz, and fused zirconium silicate, have all undergone a single firing process or are inherently heat-resistant, resulting in stable composition and performance. They maintain stable performance even during subsequent firing processes, which greatly reduces the consumption of antibacterial agents in the materials themselves. Furthermore, these materials have low loss on ignition, reducing glaze surface exhaust and resulting in a glaze with good transparency, a pleasant feel, and excellent wear resistance.

[0023] The first and second dry granules constitute the basic system of the dry granule glaze, ensuring its transparency and tactile feel. Pre-forming the basic glaze components into dry granules helps lock the active ingredients within the glass network, reducing the probability of reaction with antibacterial agents and thus minimizing their consumption. Corundum provides a hard framework, enhancing the glaze's scratch and abrasion resistance. Furthermore, corundum increases the melting temperature and high-temperature viscosity of the dry granule glaze, preventing the coating of antibacterial agents. The addition of molten zirconium silicate serves two purposes: first, its combination with the high-alumina glaze system further increases the melting temperature and high-temperature viscosity of the dry granule glaze, preventing the coating of antibacterial agents; second, it prevents the reaction of silica and alumina in the high-alumina glaze system with zinc oxide in the antibacterial agent to form zinc silicate and zinc-aluminum spinel, respectively, reducing the consumption of antibacterial agents and ensuring their effectiveness. Fused silica can act as a binder to connect corundum and zirconium oxide particles, thereby enhancing their strength and toughness. On the other hand, it can optimize the smoothness and feel of the glaze during the firing process.

[0024] Preferably, the initial melting temperature of the dry granular glaze is not lower than 1300°C.

[0025] Preferably, the first dry particle has a D90 ≤ 72 μm, and the second dry particle has a D90 ≤ 52 μm. By creating a certain gradation difference in size between the first and second dry particles, and adjusting the weight ratio between them, the feel and stain-resistant properties of the glaze system can be controlled. Single small-diameter dry particles, after melting, tend to form an overly smooth glaze surface, resulting in a monotonous, slippery feel lacking texture. The real key to improving the feel is the combination of coarse and fine particles, rather than the effect of a single particle. Large-diameter dry particles act as a framework, constructing a basic three-dimensional texture on the glaze surface, providing rich tactile layers and forming the basis for improving a monotonous feel. Fine-diameter dry particles act as fillers, filling the deep gaps between large particles, making the surface undulations smoother and more continuous, eliminating the roughness caused by isolated protrusions, and ultimately achieving a delicate and smooth feel.

[0026] The deep voids formed by the accumulation of large-diameter dry particles are "stain hiding places" where stains (such as oil and ink) can easily get stuck and penetrate. When fine particles fill the voids between the coarse particles, the glaze layer becomes denser. This is equivalent to building a dense protective layer on the glaze surface, blocking the microscopic channels through which stains penetrate into the glaze layer. The stains can only stay on the surface and are easier to clean.

[0027] Therefore, by grading dry particles of appropriate coarse and fine particle sizes, through this synergistic effect of "skeleton-filler", not only is a better, more delicate and layered feel achieved, but it also has excellent anti-fouling performance.

[0028] Preferably, the particle size range of the corundum is 500 nm to 1 μm; the particle size range of the fused silica is 500 nm to 1 μm; and the particle size range of the fused zirconium silicate is 800 nm to 1.5 μm.

[0029] Preferably, the dry granule glaze further comprises a suspending agent and water in a mass ratio of 1:(0.8-1.2); the specific gravity of the dry granule glaze is 1.40-1.50 g / cm³. 3 The application rate is 280–320 g / m³. 2 .

[0030] The suspending agent is selected from at least one of ethylene glycol, sodium carboxymethyl cellulose, and sodium methyl cellulose.

[0031] A second aspect of the present invention provides an antibacterial ceramic tile, comprising, from bottom to top: a body layer, a surface glaze layer, a dry granule glaze layer, and a surface antibacterial layer, wherein the raw material for preparing the dry granule glaze layer is the dry granule glaze as described above.

[0032] Preferably, the raw material for preparing the surface antibacterial layer is an antibacterial agent dispersion, which includes: nano zinc oxide, dispersant and water; the content of nano zinc oxide is 5% to 10% by mass percentage.

[0033] The dispersant is methylcellulose or sodium hexametaphosphate, and the amount added is 2% to 5% of the total mass of the solid material in the antibacterial dispersion.

[0034] Preferably, the particle size range of the nano zinc oxide is 10–30 nm.

[0035] Preferably, the raw materials for preparing the antibacterial agent dispersion further include gloss-adjusting auxiliary materials, and the content of the gloss-adjusting auxiliary materials is 0.26% to 10% by mass; the gloss-adjusting auxiliary materials are selected from one or more of alumina, potassium feldspar, sodium feldspar, quartz, and barium carbonate.

[0036] Adding gloss-adjusting materials to antibacterial agent dispersions can eliminate the impact of antibacterial agent addition on glaze gloss changes, and allow for adjustment within a certain gloss range to meet different market demands. The mechanism for reducing glaze gloss is to increase surface roughness by adding high-temperature materials, thereby reducing gloss. The mechanism for increasing glaze gloss is to add materials with fluxing properties or materials with lower melting temperatures, improving glaze smoothness and thus increasing gloss. It should be noted that gloss adjustment requires the ceramic tile glaze to have a gloss range of 8GU to 20GU. This is because for low-gloss glazes, the glaze layer is already fired at high temperatures, and adding high-temperature materials cannot significantly reduce gloss; similarly, for high-gloss glazes, the glaze layer is already fired at low temperatures, and adding low-temperature materials cannot significantly reduce gloss. In this technical solution, the optimal adjustment range for the gloss adjustment material is -5GU to 10GU. As an auxiliary material, its addition amount should not be too large, otherwise it will easily damage the glaze performance and reduce the effect of the antibacterial agent.

[0037] A third aspect of the present invention provides an antibacterial ceramic tile, comprising, from bottom to top: a body layer, a surface glaze layer, a pattern layer, a dry granule glaze layer, and a surface antibacterial layer, wherein the raw material for preparing the dry granule glaze layer is the dry granule glaze as described above.

[0038] A fourth aspect of the present invention provides a method for preparing ceramic bricks, which is used to prepare antibacterial ceramic bricks as described above, comprising the following steps: S1. Apply a glaze to the body layer to form a glaze layer after firing; S2. Inkjet print the pattern to form a pattern layer after firing; S3. Spray dry granule glaze at a rate of 280–320 g / m³. 2 To form a dry granular glaze layer after firing; S4. Spray the antibacterial agent dispersion onto the dry granule glaze at a spraying rate of 110–125 g / m². 2 To form an antibacterial layer on the surface after firing; S5. After drying, the ceramic brick is fired at a temperature of 1180-1210℃ for a period of 40-50 minutes to obtain the antibacterial ceramic brick.

[0039] The present invention will be further illustrated by the following examples and comparative examples.

[0040] Example 1 A method for preparing ceramic tiles, the method comprising the following steps: S1. Apply a glaze to the body layer to form a glaze layer after firing; The chemical composition of the green body layer, by mass percentage, includes: SiO2 68.36%, Al2O3 18.82%, Fe2O3 1.33%, TiO2 0.17%, CaO 0.38%, MgO 0.70%, K2O 3.42%, Na2O 1.74%, with the balance being loss on ignition; The chemical composition of the glaze, by mass percentage, includes: SiO2 47.88%, Al2O3 20.34%, Fe2O3 0.20%, TiO2 0.08%, CaO 3.64%, MgO 1.60%, K2O 2.69%, Na2O 4.07%, BaO 4.15%, ZrO2 6.66%, ZnO 2.53%, with the balance being loss on ignition and impurities. S2. Inkjet print the pattern to form a pattern layer after firing; S3. Spray dry granule glaze, the specific gravity of which is 1.50 g / cm³. 3 The application rate is 290 g / m 2 To form a dry granular glaze layer after firing; The dry granule glaze is composed of 33 parts of first dry granules, 67 parts of second dry granules, 10 parts of corundum (D50=500nm), 15 parts of fused silica (D50=900nm), 10 parts of fused zirconium silicate (D50=600nm), 75 parts of suspending agent, and 75 parts of water. The chemical composition of the solid phase material, by mass percentage, includes: SiO2 49.75%, Al2O3 20.40%, CaO 4.14%, MgO 1.89%, K2O 2.84%, Na2O 1.44%, BaO 6.13%, ZrO2 4.82%, ZnO 3.92%, SrO 1.05%, with the remainder being loss on ignition and impurities. The raw materials for preparing the first dry granules, by weight, include: 25 parts potassium feldspar, 3 parts calcite, 2 parts dolomite, 2 parts alumina, 12 parts calcined kaolin, 25 parts high-purity nepheline, 4 parts zinc oxide, 14 parts barium carbonate, and 13 parts calcined talc. These raw materials are mixed, calcined and melted in a furnace at a high temperature of 1400℃, and then rapidly cooled in a water bath to form a glassy texture. This is then ground and crushed until 200-mesh powder is obtained, which is the first dry granule. The chemical composition of the first dry granules includes: 47.98% SiO2, 17.03% Al2O3, 2.61% CaO, 4.51% MgO, 3.88% K2O, 2.91% Na2O, 10.88% BaO, and 3.96% ZnO. The remainder consists of loss on ignition and impurities. The D90 of the first dry granules is 70 μm. The raw materials for preparing the second dry granules, by weight, include: 38 parts potassium feldspar, 1 part sodium feldspar, 3 parts high-white nepheline, 1 part quartz, 17 parts calcined kaolin, 3 parts alumina, 6 parts zinc oxide, 3 parts strontium carbonate, 9 parts barium carbonate, 15 parts wollastonite, and 4 parts calcined talc. These raw materials are mixed, calcined in a furnace at 1400℃ until melted, and then rapidly cooled in a water bath to form a glassy powder. This powder is then ground and crushed to obtain 300-mesh powder, thus yielding the second dry granules. The chemical composition of these dry granules includes: SiO2 49.29%, Al2O3 17.65%, CaO 7.03%, MgO 1.59%, K2O 3.83%, Na2O 1.47%, BaO 6.99%, ZnO 5.94%, and SrO2. 2.11%, the remainder being loss on ignition and impurities; the D90 of the second dry particle is 50 μm. S4. Spray the antibacterial agent dispersion onto the dry granule glaze at a spraying rate of 110 g / m². 2 To form an antibacterial layer on the surface after firing; The preparation method of the antibacterial agent dispersion, by weight, is as follows: 40 parts of 20nm zinc oxide, 2 parts of aluminum oxide, and 2 parts of sodium hexametaphosphate are added sequentially to 100 parts of water. After ball milling for 5 minutes, the particle size of the slurry is measured, D50 = 2.2 μm. Water is then added to adjust the specific gravity to 1.04 g / cm³. 3 To obtain an antibacterial dispersion; S5. After drying, it is transferred to a roller kiln for firing at a temperature of 1190℃ for a firing cycle of 40 minutes. After exiting the kiln, the edges are ground and trimmed to obtain antibacterial ceramic bricks.

[0041] Example 2 A method for preparing ceramic tiles, the method comprising the following steps: S1. Apply a glaze to the body layer to form a glaze layer after firing; The chemical composition of the green body layer, by mass percentage, includes: SiO2 68.36%, Al2O3 18.82%, Fe2O3 1.33%, TiO2 0.17%, CaO 0.38%, MgO 0.70%, K2O 3.42%, Na2O 1.74%, with the balance being loss on ignition; The chemical composition of the glaze, by mass percentage, includes: SiO2 47.88%, Al2O3 20.34%, Fe2O3 0.20%, TiO2 0.08%, CaO 3.64%, MgO 1.60%, K2O 2.69%, Na2O 4.07%, BaO 4.15%, ZrO2 6.66%, ZnO 2.53%, with the balance being loss on ignition and impurities. S2. Inkjet print the pattern to form a pattern layer after firing; S3. Spray dry granule glaze, the specific gravity of which is 1.51 g / cm³. 3 The application rate was 291 g / m 2 To form a dry granular glaze layer after firing; The dry granule glaze is composed of 33 parts of first dry granules, 67 parts of second dry granules, 8 parts of corundum (D50=500nm), 15 parts of fused silica (D50=900nm), 10 parts of fused zirconium silicate (D50=600nm), 75 parts of suspending agent, and 75 parts of water. The chemical composition of the solid phase material, by mass percentage, includes: SiO2 49.66%, Al2O3 19.26%, CaO 4.33%, MgO 1.84%, K2O 2.77%, Na2O 1.47%, BaO 6.61%, ZrO2 4.89%, ZnO 4.22%, SrO 1.06%, with the remainder being loss on ignition and impurities. The raw materials for preparing the first dry granules, by weight, include: 24 parts potassium feldspar, 4 parts calcite, 2 parts dolomite, 3 parts alumina, 11 parts calcined kaolin, 25 parts high-purity nepheline, 5 parts zinc oxide, 14 parts barium carbonate, and 12 parts calcined talc. These raw materials are mixed, calcined and melted in a furnace at a high temperature of 1400℃, and then rapidly cooled in a water bath to form a glassy texture. This is then ground and crushed until 200-mesh powder is obtained, which is the first dry granule. The chemical composition of the first dry granule includes: 46.11% SiO2, 17.39% Al2O3, 3.15% CaO, 4.20% MgO, 3.78% K2O, 2.88% Na2O, 10.88% BaO, and 4.95% ZnO, with the remainder being loss on ignition and impurities. The D90 of the first dry granule is 71 μm. The raw materials for preparing the second dry granules, by weight, include: 36 parts potassium feldspar, 2 parts sodium feldspar, 3 parts high-white nepheline, 2 parts quartz, 15 parts calcined kaolin, 4 parts alumina, 6 parts zinc oxide, 3 parts strontium carbonate, 10 parts barium carbonate, 15 parts wollastonite, and 4 parts calcined talc. These raw materials are mixed, calcined in a furnace at 1400℃ until melted, and then rapidly cooled in a water bath to form a glassy powder. This powder is then ground and crushed to obtain 300-mesh powder, thus yielding the second dry granules. The chemical composition of these dry granules includes: SiO2 48.54%, Al2O3 17.60%, CaO 7.02%, MgO 1.59%, K2O 3.64%, Na2O 1.50%, BaO 7.77%, ZnO 5.94%, and SrO2. 2.11%, the remainder being loss on ignition and impurities; the D90 of the second dry particle is 51 μm. S4. Spray the antibacterial agent dispersion onto the dry granule glaze at a spraying rate of 110 g / m². 2 To form an antibacterial layer on the surface after firing; The preparation method of the antibacterial agent dispersion, by weight, is as follows: 40 parts of 20nm zinc oxide, 2 parts of aluminum oxide, and 2 parts of sodium hexametaphosphate are added sequentially to 100 parts of water. After ball milling for 5 minutes, the particle size of the slurry is measured, D50 = 2.1 μm. Water is then added to adjust the specific gravity to 1.04 g / cm³. 3 To obtain an antibacterial dispersion; S5. After drying, it is transferred to a roller kiln for firing at a temperature of 1180℃ for a firing cycle of 50 minutes. After exiting the kiln, the edges are ground and trimmed to obtain antibacterial ceramic bricks.

[0042] Example 3 A method for preparing ceramic tiles, the method comprising the following steps: S1. Apply a glaze to the body layer to form a glaze layer after firing; The chemical composition of the green body layer, by mass percentage, includes: SiO2 68.36%, Al2O3 18.82%, Fe2O3 1.33%, TiO2 0.17%, CaO 0.38%, MgO 0.70%, K2O 3.42%, Na2O 1.74%, with the balance being loss on ignition; The chemical composition of the glaze, by mass percentage, includes: SiO2 47.88%, Al2O3 20.34%, Fe2O3 0.20%, TiO2 0.08%, CaO 3.64%, MgO 1.60%, K2O 2.69%, Na2O 4.07%, BaO 4.15%, ZrO2 6.66%, ZnO 2.53%, with the balance being loss on ignition and impurities. S2. Inkjet print the pattern to form a pattern layer after firing; S3. Spray dry granule glaze, the specific gravity of which is 1.51 g / cm³. 3 The application rate was 291 g / m 2 To form a dry granular glaze layer after firing; The dry granule glaze is composed of 33 parts of first dry granules, 67 parts of second dry granules, 12 parts of corundum (D50=500nm), 15 parts of fused silica (D50=900nm), 10 parts of fused zirconium silicate (D50=600nm), 75 parts of suspending agent, and 75 parts of water. The chemical composition of the solid phase material, by mass percentage, includes: SiO2 48.92%, Al2O3 20.68%, CaO 4.51%, MgO 1.70%, K2O 2.80%, Na2O 1.42%, BaO 6.23%, ZrO2 4.75%, ZnO 3.62%, SrO 1.38%, with the remainder being loss on ignition and impurities. The raw materials for preparing the first dry granules, by weight, include: 23 parts potassium feldspar, 4 parts calcite, 3 parts dolomite, 2 parts alumina, 11 parts calcined kaolin, 27 parts high-purity nepheline, 5 parts zinc oxide, 13 parts barium carbonate, and 12 parts calcined talc. These raw materials are mixed, calcined and melted in a furnace at a high temperature of 1400℃, and then rapidly cooled in a water bath to form a glassy texture. This is then ground and crushed until 200-mesh powder is obtained, which is the first dry granule. The chemical composition of the first dry granules includes: 46.64% SiO2, 16.66% Al2O3, 3.47% CaO, 4.40% MgO, 3.80% K2O, 3.02% Na2O, 10.11% BaO, and 4.95% ZnO, with the remainder being loss on ignition and impurities. The D90 of the first dry granules is 71 μm. The raw materials for preparing the second dry granules, by weight, include: 39 parts potassium feldspar, 1 part sodium feldspar, 2 parts high-white nepheline, 1 part quartz, 18 parts calcined kaolin, 1 part alumina, 5 parts zinc oxide, 4 parts strontium carbonate, 10 parts barium carbonate, 16 parts wollastonite, and 3 parts calcined talc. These raw materials are mixed, calcined in a furnace at 1400℃ until melted, and then rapidly cooled in a water bath to form a glassy powder. This powder is then ground and crushed to obtain 300-mesh powder, thus yielding the second dry granules. The chemical composition of these dry granules includes: SiO2 49.73%, Al2O3 16.03%, CaO 7.48%, MgO 1.30%, K2O 3.86%, Na2O 1.41%, BaO 7.77%, ZnO 4.95%, and SrO2. 2.81%, the remainder being loss on ignition and impurities; the D90 of the second dry particle is 52 μm. S4. Spray the antibacterial agent dispersion onto the dry granule glaze at a spraying rate of 110 g / m². 2 To form an antibacterial layer on the surface after firing; The preparation method of the antibacterial agent dispersion, by weight, is as follows: 40 parts of 20nm zinc oxide, 2 parts of aluminum oxide, and 2 parts of sodium hexametaphosphate are added sequentially to 100 parts of water. After ball milling for 5 minutes, the particle size of the slurry is measured, D50 = 2.3μm. Water is then added to adjust the specific gravity to 1.04g / cm³. 3 To obtain an antibacterial dispersion; S5. After drying, it is transferred to a roller kiln for firing at a temperature of 1200℃ for a firing cycle of 40 minutes. After exiting the kiln, the edges are ground and trimmed to obtain antibacterial ceramic bricks.

[0043] Example 4 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The formulation of dry granule glaze varies. In this embodiment, the dry granule glaze consists of 33 parts of first dry granules, 67 parts of second dry granules, 10 parts of corundum (D50=500nm), 12 parts of fused quartz (D50=900nm), 10 parts of fused zirconium silicate (D50=600nm), 75 parts of suspending agent, and 75 parts of water.

[0044] Example 5 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The formulation of dry granule glaze varies. In this embodiment, the dry granule glaze consists of 33 parts of first dry granules, 67 parts of second dry granules, 10 parts of corundum (D50=500nm), 16 parts of fused quartz (D50=900nm), 10 parts of fused zirconium silicate (D50=600nm), 75 parts of suspending agent, and 75 parts of water.

[0045] Example 6 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The formulation of dry granule glaze varies. In this embodiment, the dry granule glaze consists of 33 parts of first dry granules, 67 parts of second dry granules, 10 parts of corundum (D50=500nm), 15 parts of fused quartz (D50=900nm), 8 parts of fused zirconium silicate (D50=600nm), 75 parts of suspending agent, and 75 parts of water.

[0046] Example 7 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The formulation of dry granule glaze varies. In this embodiment, the dry granule glaze consists of 33 parts of first dry granules, 67 parts of second dry granules, 10 parts of corundum (D50=500nm), 15 parts of fused quartz (D50=900nm), 12 parts of fused zirconium silicate (D50=600nm), 75 parts of suspending agent, and 75 parts of water.

[0047] Example 8 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The antibacterial agent dispersion contains 33.6 parts of 20nm zinc oxide, 8.4 parts of sodium feldspar, and 2 parts of sodium hexametaphosphate, with a specific gravity of 1.05 g / cm³. 3 .

[0048] Example 9 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The antibacterial agent dispersion contains 21 parts of 20nm zinc oxide, 21 parts of sodium feldspar, and 2 parts of sodium hexametaphosphate, with a specific gravity of 1.08 g / cm³. 3 .

[0049] Example 10 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The spraying amount of the antibacterial agent dispersion is 100 g / m³. 2 .

[0050] Example 11 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The spraying amount of the antibacterial agent dispersion is 120 g / m³. 2 .

[0051] Comparative Example 1 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: No corundum was added to the dry granule glaze.

[0052] Comparative Example 2 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: No fused silica was added to the dry granule glaze.

[0053] Comparative Example 3 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: No molten zirconium silicate was added to the dry granule glaze.

[0054] Comparative Example 4 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The antibacterial agent dispersion contains 0 parts of 20nm zinc oxide, 42 parts of aluminum oxide, and 2 parts of sodium hexametaphosphate, with a specific gravity of 1.04 g / cm³. 3 .

[0055] Comparative Example 5 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The antibacterial agent dispersion contains 12.6 parts of 20nm zinc oxide, 29.4 parts of sodium feldspar, and 2 parts of sodium hexametaphosphate, with a specific gravity of 1.08 g / cm³. 3 .

[0056] Comparative Example 6 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The spraying amount of the antibacterial agent dispersion is 80 g / m³. 2 .

[0057] Comparative Example 7 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The spraying amount of the antibacterial agent dispersion is 150 g / m³. 2 .

[0058] Comparative Example 8 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The first dry granule dosage is 67 parts, and the second dry granule dosage is 33 parts.

[0059] Comparative Example 9 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The first dry granule dosage is 25 parts, and the second dry granule dosage is 75 parts.

[0060] Comparative Example 10 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: The raw materials for the first and second dry granules are not fired at high temperatures to form dry granules. Instead, they are directly mixed, weighed, and then mixed with corundum, fused quartz, and fused zirconium silicate to form a glaze. The specific gravity and spraying amount of this glaze are the same as those of the dry granule glaze in Example 1.

[0061] Comparative Example 11 A method for preparing ceramic tiles, the difference between this method and Example 1 is as follows: In the dry granule glaze, corundum is replaced with alumina and fused silica is replaced with quartz, with the weight percentages remaining unchanged.

[0062] Performance testing The antibacterial ceramics prepared in the above embodiments and comparative examples were tested, and the test results are detailed in Table 1. The specific test methods are as follows: 1. Gloss test: The gloss meter WGG60-Y4 (KOSIJIA Optoelectronic Instruments Co., Ltd.) was used for testing.

[0063] 2. Antibacterial performance test: The antibacterial performance and antibacterial durability of the above-mentioned antibacterial ceramic tiles were determined according to the test method of JC / T 897-2014 "Antibacterial Performance of Antibacterial Ceramic Products". After continuous wiping for 500 times, the antibacterial performance test was carried out again. The bacteria tested were Escherichia coli. The judgment criteria were that the antibacterial performance was greater than 90% qualified and the antibacterial durability was greater than 85% qualified.

[0064] 3. Abrasion resistance test: According to GB / T 3810.7—2016 "Test methods for ceramic tiles - Part 7: Determination of abrasion resistance of glazed tile surfaces", the sample is ground at different preset rotation speeds (e.g., 100, 150, 600, 750, 1500, 2100, 6000, 12000 revolutions), and visually compared with the unground sample in the observation box. The sample is divided into 1 to 5 levels according to the rotation speed corresponding to the visible wear.

[0065] 4. Stain resistance test: The stain resistance level is tested according to GB / T 3810.14-2016 "Test methods for ceramic tiles - Part 14: Determination of stain resistance".

[0066] 5. Touch test: The same experimenter conducts the test, touching the sample with their hand to determine whether the touch is smooth or rough.

[0067] 6. Initial melting temperature test: The change in the projection height of the glaze as the temperature increases was measured using a visualization high-temperature furnace (Tianjin Zhonghuan Electric Furnace, equipment model TA-Z16). According to the standard QB / T 1546-2016 "Method for Determination of Melting Temperature of Ceramic Glaze", the initial melting temperature is t3 when the projection of the ceramic glaze sample forms a semicircle.

[0068] 7. Energy Dispersive Spectroscopy (EDS) Test: The surface elemental composition of the antibacterial ceramic tiles prepared in Example 1 and Comparative Example 10 was analyzed by energy dispersive spectroscopy (EDS, Hitachi Flex SEM1000II, Japan). Figure 1 As shown.

[0069] Table 1

[0070] The results above show that the antibacterial ceramic tiles prepared by the method of the present invention have both excellent antibacterial and wear-resistant properties. The antibacterial performance against Escherichia coli is over 99.99%, and the durability is over 99.9%. In addition, the antibacterial ceramic tiles prepared by the present invention can also maintain a wear resistance of level 4 at 2100 revolutions, a stain resistance of level 5, and a delicate glaze.

[0071] In Comparative Example 1, the amount of corundum added in the dry granule glaze was 0. The reduction in the alumina content of the glaze surface led to a decrease in the melting temperature of the dry granule glaze. The initial melting temperature of the glaze was 1287℃. The high-temperature viscosity decreased, which caused the antibacterial agent to be coated on the glaze surface, resulting in a decrease in the antibacterial performance of the prepared antibacterial ceramic tile. In addition, the absence of corundum particles on the glaze surface also led to a significant decrease in the wear resistance of the glaze surface.

[0072] In Comparative Example 2, the amount of fused silica added to the dry granule glaze was 0, resulting in insufficient silica content on the glaze surface. This failed to eliminate the roughness of the glaze surface caused by the addition of corundum and fused zirconium silicate, thus reducing the stain resistance and making the glaze surface feel rough.

[0073] In Comparative Example 3, the amount of molten zirconium silicate added to the dry granule glaze was 0, which led to a decrease in the glaze melting temperature. The initial melting temperature of the glaze was 1293℃. The high-temperature viscosity decreased, causing the glaze to coat the antibacterial agent. Furthermore, because the amount of molten zirconium silicate added was zero, the nano zinc oxide in the antibacterial agent reacted with the alumina and silica in the glaze to generate zinc aluminum spinel and zinc silicate, consuming a large amount of antibacterial agent. This resulted in a decrease in the antibacterial performance of the prepared antibacterial ceramic tile and a sharp increase in the glaze gloss.

[0074] In Comparative Example 4, the amount of zinc oxide added to the antibacterial agent dispersion was 0. The antibacterial ceramic prepared had an antibacterial performance and antibacterial durability of less than 50% against Escherichia coli, indicating that nano zinc oxide plays a key antibacterial role.

[0075] In Comparative Example 5, the ratio of antibacterial nano-zinc oxide to sodium feldspar in the antibacterial agent dispersion was 30:70. The antibacterial ceramic brick prepared had an antibacterial performance and antibacterial durability of less than 85% against Escherichia coli, indicating that insufficient proportion of antibacterial agent in this technical solution would lead to poor antibacterial performance.

[0076] The spraying amount of the antibacterial agent dispersion in Comparative Example 6 was only 80 g / m². 2 This results in the prepared antibacterial ceramic bricks having an antibacterial performance and antibacterial durability of less than 85% against Escherichia coli, indicating that the amount of antibacterial agent dispersion sprayed in this technical solution cannot be too low.

[0077] In Comparative Example 7, the spraying amount of the antibacterial agent dispersion was as high as 150 g / m². 2 Although the prepared antibacterial ceramic tiles have antibacterial properties and antibacterial durability greater than 99.99% against Escherichia coli, the surface of the antibacterial ceramic tiles is covered with a large number of nano zinc oxide particles, which makes the surface rough but significantly reduces the wear resistance. This indicates that the spraying amount of antibacterial agent dispersion should not be too high, otherwise the wear resistance and surface roughness will be reduced due to the accumulation of too many zinc oxide agglomerates on the glaze.

[0078] In Comparative Example 8, after adjusting the mass ratio of the first dry granules and the second dry granules to approximately 2:1, the SrO content in the dry granule glaze was 0.52%. In a low-potassium sodium glaze system, a significant decrease in SrO content would affect the glaze surface air venting, resulting in a small number of pinhole defects on the glaze surface. Furthermore, using too much of the first dry granules with a larger particle size would lead to a rough surface and a decrease in stain resistance.

[0079] In Comparative Example 9, the mass ratio of the first dry granules to the second dry granules was 1:3, and the BaO content in the dry granule glaze was 5.90%. In a low potassium sodium glaze system, the BaO content is less than 6%, which will affect the glaze surface air release and cause a small number of pinhole defects on the glaze surface. Secondly, the amount of the second dry granules with smaller particle size is too large, which will lead to an increase in the smoothness of the glaze surface, a significant increase in gloss, and a smooth feel.

[0080] In Comparative Example 10, the raw materials for preparing the first and second dry granules were directly mixed with corundum, fused quartz, and fused zirconium silicate to prepare a protective glaze. Because this protective glaze used raw materials, the reactions between all components were intensified. During the glaze firing process, the raw material components easily reacted with the antibacterial agent and partially coated it, resulting in a significant decrease in the antibacterial durability of the prepared antibacterial ceramic tiles.

[0081] Figure 1 The antibacterial ceramic brick prepared in Example 1 Figure 2 As a comparative example of the antibacterial ceramic tile prepared in Example 10, at the same magnification, it is obvious that the surface of the antibacterial ceramic tile prepared in Example 1 is covered with a large number of agglomerated particles. Through energy dispersive spectroscopy scanning from left to right, it can be seen that the zinc element shows a signal enhancement with the position of the agglomerated particles, indicating that the agglomerated particles are the antibacterial agent nano zinc oxide. A large amount of antibacterial agent is not coated by the glaze, thus making the prepared antibacterial ceramic tile exhibit excellent antibacterial properties and antibacterial durability. The difference between Comparative Example 10 and Example 1 is that its protective glaze is prepared by mixing raw materials. The number of agglomerated particles on the surface of the prepared antibacterial ceramic tile is significantly reduced. Energy dispersive spectroscopy (EDS) scans from left to right show that the zinc element shows an enhanced signal as the agglomerated particles appear, indicating that the agglomerated particles are antibacterial nano-zinc oxide. Compared with Example 1, the number of agglomerated particles on the surface of the antibacterial ceramic tile prepared in Comparative Example 10 is significantly reduced. The main reason is that the antibacterial agent participates in the glaze reaction, and a large amount of antibacterial agent is coated by the raw material glaze. In addition, the antibacterial ceramic tile prepared in Comparative Example 10 has more crystal grains on the surface, which is also a result of the intensified reaction between the various components in the raw material glaze.

[0082] Comparative Example 11 replaced fused quartz and corundum in the formula with conventional quartz and conventional alumina. The dry granule glaze prepared by this scheme has higher reactivity of quartz and alumina. The antibacterial agent reacts with quartz and alumina to generate zinc silicate and zinc aluminate, respectively, which leads to an increase in glaze gloss, a significant decrease in antibacterial durability, and a decrease in glaze wear resistance.

[0083] It is understood that those skilled in the art can make equivalent substitutions or modifications to the technical solution and inventive concept of the present invention, and all such substitutions or modifications should fall within the protection scope of the appended claims.

Claims

1. A dry-granule glaze, characterized in that, The raw materials, by mass percentage, include the following: 6%–9% corundum, 9%–12% fused quartz, 6%–9% fused zirconium silicate, and the remainder being first and second dry particles in a mass ratio of 1:(1.8–2.2). The chemical composition of the first dry granules, by mass percentage, includes: 46%–49% SiO2, 16%–18% Al2O3, 3%–5% ZnO, 9%–11% BaO, 2%–4% CaO, 4%–6% MgO, 3%–5% K2O, 2%–4% Na2O, with the remainder being loss on ignition and impurities. The chemical composition of the second dry granules, by mass percentage, includes: 48%–53% SiO2, 16%–18% Al2O3, 5%–7% ZnO, 6%–8% BaO, 6%–8% CaO, 1%–3% MgO, 3%–5% K2O, 1%–3% Na2O, 1%–3% SrO, with the remainder being loss on ignition and impurities.

2. The dry-granule glaze according to claim 1, characterized in that, The first dry granule has a D90 ≤ 72 μm, and the second dry granule has a D90 ≤ 52 μm.

3. The dry-granule glaze according to claim 1, characterized in that, The particle size range of the corundum is 500 nm to 1 μm; the particle size range of the fused silica is 500 nm to 1 μm; and the particle size range of the fused zirconium silicate is 800 nm to 1.5 μm.

4. The dry-granule glaze according to claim 1, characterized in that, It also includes a suspending agent and water in a mass ratio of 1:(0.8–1.2); the specific gravity of the dry granular glaze is 1.40–1.50 g / cm³. 3 The application rate is 280–320 g / m³. 2 .

5. An antibacterial ceramic tile, characterized in that, From bottom to top, it includes: a body layer, a surface glaze layer, a dry granule glaze layer, and a surface antibacterial layer, wherein the raw material for preparing the dry granule glaze layer is the dry granule glaze as described in any one of claims 1-4.

6. The antibacterial ceramic brick according to claim 5, characterized in that, The raw material for preparing the surface antibacterial layer is an antibacterial agent dispersion, which includes: nano zinc oxide, dispersant and water; the content of nano zinc oxide is 5% to 10% by mass percentage.

7. The antibacterial ceramic brick according to claim 6, characterized in that, The particle size range of the nano zinc oxide is 10–30 nm.

8. The antibacterial ceramic brick according to claim 6, characterized in that, The raw materials for preparing the antibacterial agent dispersion also include gloss-adjusting auxiliary materials, the content of which is 0.26% to 10% by mass percentage; the gloss-adjusting auxiliary materials are selected from one or more of alumina, potassium feldspar, sodium feldspar, quartz, and barium carbonate.

9. An antibacterial ceramic brick, characterized in that, From bottom to top, it includes: a body layer, a surface glaze layer, a pattern layer, a dry granule glaze layer, and a surface antibacterial layer, wherein the raw material for preparing the dry granule glaze layer is the dry granule glaze as described in any one of claims 1-4.

10. A method for preparing ceramic bricks, characterized in that, The method for preparing the antibacterial ceramic brick as described in claim 9 comprises the following steps: S1. Apply a glaze to the body layer to form a glaze layer after firing; S2. Inkjet print the pattern to form a pattern layer after firing; S3. Spray dry granule glaze at a rate of 280–320 g / m³. 2 To form a dry granular glaze layer after firing; S4. Spray the antibacterial agent dispersion onto the dry granule glaze at a spraying rate of 110–125 g / m². 2 To form an antibacterial layer on the surface after firing; S5. After drying, the ceramic brick is fired at a temperature of 1180-1210℃ for a period of 40-50 minutes to obtain the antibacterial ceramic brick.

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