Highly stain-resistant ceramic glaze and preparation method and application thereof

Abstract

The application relates to the technical field of ceramic glazes, and particularly discloses a high-stain-resistant ceramic glaze as well as a preparation method and application thereof. The high-stain-resistant ceramic glaze comprises the following raw materials in parts by weight: 30-40 parts of potassium feldspar, 15-25 parts of quartz, 5-15 parts of talc, 7-13 parts of calcium carbonate, 12-18 parts of kaolin, 6-8 parts of a stain-resistant agent, 0.4-0.7 parts of a fluorosilane-based functional material and 0.3-0.5 parts of sodium hexametaphosphate. The stain-resistant agent is expanded kaolin loaded with nano-zinc oxide or expanded kaolin loaded with nano-zinc oxide-rare earth oxide. The application fills glaze layer pores with expanded kaolin loaded with nano-zinc oxide to block the penetration of dirt, and the nano-zinc oxide cooperates with the fluorosilane-based functional material to form a low-surface-energy hydrophobic coating on the glaze surface to reduce dirt adhesion. The kaolin guarantees the uniform dispersion of functional components, and the potassium feldspar and quartz basic components are combined to construct a dense and stable glaze layer, so that the high-stain-resistant performance of the glaze is finally achieved.

Description

Technical Field

[0001] This application relates to the field of ceramic glaze technology, and more specifically, to a highly stain-resistant ceramic glaze, its preparation method, and its application. Background Technology

[0002] Ceramics, as a material with a long history and wide application, occupies an important position in fields such as building decoration (e.g., wall tiles, floor tiles), sanitary ware (e.g., toilets, washbasins), and daily-use ceramics (e.g., tableware, teaware) due to its excellent mechanical properties, chemical stability, and decorative properties. Ceramic glaze, as a thin, glassy layer covering the surface of the ceramic body, not only determines the appearance and texture of ceramic products (e.g., gloss, color, texture), but also plays a crucial role in protecting the body and improving the product's performance. Its performance directly affects the lifespan and suitability for various applications of ceramic products.

[0003] In recent years, with the improvement of people's quality of life and the upgrading of consumption demands, the market has placed higher requirements on the stain resistance of ceramic products. Especially in high-end residences, star-rated hotels, medical facilities, food processing workshops, and other scenarios with stringent cleanliness and hygiene standards, ceramic products with excellent stain resistance have become the first choice. At the same time, under the trend of green development in the ceramic industry, reducing the amount of cleaning agents used and lowering cleaning energy consumption have also become directions of industry focus, and improving the stain resistance of glazes is a key path to achieving this goal.

[0004] Existing technologies mostly focus on optimizing glaze formulations, adjusting the proportions of basic components such as silica, alumina, and calcium oxide to reduce porosity and improve surface density after firing. Some studies have also attempted to introduce oxides such as zirconium oxide and titanium dioxide into the glaze, utilizing their properties to enhance surface hardness and chemical stability, thereby indirectly improving stain resistance. However, these formulation optimization methods have significant limitations: on the one hand, excessive pursuit of density may lead to increased glaze firing temperatures, increasing production costs and easily causing defects such as glaze cracking and deformation; on the other hand, traditional glaze surfaces remain hydrophilic, exhibiting weak resistance to the adsorption of polar pollutants, making it difficult to fundamentally solve the problem of stain adhesion. Therefore, developing a new type of highly stain-resistant ceramic glaze is of great significance to the development of ceramics. Summary of the Invention

[0005] In order to develop a novel highly stain-resistant ceramic glaze to improve the stain resistance of ceramics, this application provides a highly stain-resistant ceramic glaze, its preparation method, and its application.

[0006] In a first aspect, this application provides a highly stain-resistant ceramic glaze, employing the following technical solution:

[0007] A highly stain-resistant ceramic glaze comprises the following raw materials in parts by weight: 30-40 parts potassium feldspar, 15-25 parts quartz, 5-15 parts talc, 7-13 parts calcium carbonate, 12-18 parts kaolin, 6-8 parts stain-resistant agent, 0.4-0.7 parts fluorosilane functional material, and 0.3-0.5 parts sodium hexametaphosphate. The stain-resistant agent is expanded kaolin-supported nano-zinc oxide or expanded kaolin-supported nano-zinc oxide-rare earth oxide.

[0008] By adopting the above technical solution, on the one hand, the expansion treatment of kaolin increases the interlayer spacing, and the abundant active hydroxyl groups on its surface and between layers can firmly anchor nano-zinc oxide, forming a dual-load morphology of nano-zinc oxide on the kaolin surface and between layers, improving the dispersibility of nano-zinc oxide and avoiding rough glaze caused by agglomeration. On the other hand, the layered structure of kaolin can flow with the glass phase during the glaze firing process, actively filling the micropores of the glaze layer and adsorbing residual gases, reducing the porosity of the glaze layer, and fundamentally blocking the penetration channels of dirt such as oil and water. At the same time, expanded kaolin itself is a silicate component, which has high compatibility with the glass phase of the glaze base, without interface gaps or high-temperature decomposition defects, ensuring the stability of the glaze layer structure, and relying on its supporting role to improve the wear resistance of the hydrophobic coating. In addition, nano-zinc oxide forms chemical bonds with fluorosilanes through surface hydroxyl groups, promoting the uniform coverage of fluorocarbon groups on the glaze surface, reducing surface energy, reducing dirt adhesion and making it easy to wipe, and also releasing zinc ions to inhibit mold growth, avoiding the problems of yellowing and difficulty in cleaning the glaze surface caused by microbial contamination.

[0009] In summary, the above formulation achieves high anti-fouling performance of the glaze by using expanded kaolin loaded with nano zinc oxide to fill the pores of the glaze layer to block dirt penetration, nano zinc oxide working synergistically with fluorosilane functional materials to form a low surface energy hydrophobic coating on the glaze surface to reduce dirt adhesion, and kaolin ensuring uniform dispersion of functional components. Combined with potassium feldspar and quartz as basic components, a dense and stable glaze layer is constructed.

[0010] Preferably, the method for preparing the stain-resistant agent includes the following steps:

[0011] (1) Mix kaolin, intercalating agent and deionized water in a mass ratio of 1:(1-1.5):(8-15) to obtain suspension A; heat suspension A to 60-70℃ and stir for 4-6h. After the reaction is completed, filter, wash and dry to obtain precursor; calcine the precursor at 250-350℃ for 0.5-1.5h to obtain expanded kaolin.

[0012] (2) Expanded kaolin, deionized water and silane coupling agent in a mass ratio of 1:(15-25):(0.02-0.04) are ultrasonically dispersed to obtain suspension B; under stirring, 0.08-0.15mol / L zinc acetate solution is added dropwise to suspension B, reacted for 1h, pH is adjusted to 7.5-8.0, and the reaction continues for 2h; filtered, washed and dried to obtain composite precursor, calcined at 450-550℃ for 1.5-2.5h, cooled and ground to obtain expanded kaolin-supported nano zinc oxide; the mass-volume ratio of expanded kaolin to zinc acetate solution is 1:(10-15)g / mL.

[0013] By adopting the above technical solution, the interlayer structure of kaolin is expanded by an intercalating agent to form a porous carrier with a high specific surface area. The residual intercalating agent is removed by calcination, and the carrier structure is prevented from collapsing. Then, nano-zinc oxide is uniformly loaded in situ on the interlayer and surface of expanded kaolin, which effectively solves the problem of easy agglomeration of nanoparticles. The composite material obtained by this method has both the porous support characteristics of kaolin and the functional activity of nano-zinc oxide. The two are tightly bound by coordination bonds, which not only improves the stability of nano-zinc oxide, but also strengthens the carrier's antifouling performance.

[0014] Preferably, the intercalating agent is a mixture of urea and glycerol in a mass ratio of (2-4):1.

[0015] By adopting the above technical solution, urea, as the main intercalating agent, can effectively disrupt the tight interlayer forces by strongly binding with the hydroxyl groups between the kaolin layers through intermolecular hydrogen bonds, providing sufficient space for subsequent calcination and expansion, and ensuring the formation of a porous structure in the expanded kaolin. Glycerol, as the auxiliary intercalating agent, can enhance its affinity with the kaolin surface through its polyhydroxy structure, improve the system's dispersibility, delay the precipitation and aggregation of urea during the reaction process, and ensure that the intercalating agent penetrates evenly into the kaolin interlayers, avoiding uneven expansion caused by insufficient local intercalation. The combination of the two retains the core advantage of urea's strong intercalation ability, while the synergistic effect of glycerol compensates for the shortcomings of easy aggregation and poor dispersibility when urea is used alone for intercalation, ultimately producing expanded kaolin with a uniform pore structure.

[0016] Preferably, in step (2), expanded kaolin, deionized water, and silane coupling agent in a mass ratio of 1:(15-25):(0.03-0.07) are ultrasonically dispersed to obtain a suspension; under stirring, a mixture of 0.08-0.15 mol / L zinc acetate solution and 0.01-0.05 mol / L rare earth salt solution is added dropwise to the suspension, reacted for 1 h, the pH is adjusted to 7.5-8.0, and the reaction continues for 2 h; the mixture is filtered, washed, and dried to obtain a composite precursor; the composite precursor is calcined at 450-550℃ for 1.5-2.5 h, cooled, and ground to obtain expanded kaolin-supported nano-zinc oxide-rare earth oxide; the mass-volume ratio of expanded kaolin to zinc acetate solution is 1:(10-15) g / mL;

[0017] The mass-to-volume ratio of the expanded kaolin to the rare earth salt solution is 1:(2-4)g / mL.

[0018] By adopting the above technical solution, nano-zinc oxide and rare earth oxides are co-loaded onto expanded kaolin. On the one hand, rare earth oxides can act as active additives, enhancing the photocatalytic activity of nano-zinc oxide through their unique electronic structure, thereby enhancing the self-cleaning properties of the composite material in ceramic glazes. On the other hand, they can act as structural stabilizers, as their particles can fill some of the pores of expanded kaolin and form an interface bond with nano-zinc oxide, improving the thermal stability and mechanical properties of the composite material. In addition, by introducing rare earth oxides through in-situ doping, their loading and distribution can be flexibly controlled, and rare earth salts are easily soluble and can be completely converted into oxides after calcination, showing strong compatibility with the original preparation process.

[0019] Preferably, the rare earth salt solution is a mixed solution of lanthanum nitrate and cerium nitrate in a mass ratio of (1-3):1.

[0020] By adopting the above technical solutions, lanthanum oxide converted from lanthanum nitrate inhibits the agglomeration of nano-zinc oxide particles through steric hindrance, regulating its particle size uniformity. At the same time, relying on its high chemical inertness and thermal stability, it enhances the anti-sintering ability of the composite material in the high-temperature firing of ceramic glazes, reducing the distortion of zinc oxide crystal form or excessive reaction with glaze components. Cerium oxide converted from cerium nitrate inhibits the recombination of photogenerated electron-hole pairs in zinc oxide through valence state cycling, broadening the photoresponse range to the visible light region and improving the photocatalytic effect and reactive oxygen generation ability. When the two work synergistically, the stable framework constructed by lanthanum oxide provides a uniform dispersion environment for cerium oxide, while the activity-enhancing effect of cerium oxide compensates for the limitations of lanthanum oxide in enhancing the function of zinc oxide. The two fully exert the effect of 1+1>2.

[0021] Preferably, the fluorosilane functional material is a nanofiller-coated fluorosilane, and the preparation method of the nanofiller-coated fluorosilane includes the following steps:

[0022] Step 1: Add 25-35 parts by weight of perfluorooctyltrimethoxysilane, 0.15-0.25 parts by weight of acetic acid and 4-6 parts by weight of nonionic fluorinated surfactant to 100 parts by weight of deionized water and stir to form an emulsion;

[0023] Step 2: Under stirring, mix 35-45 parts by weight of tetraethyl orthosilicate with 100 parts by weight of deionized water to obtain a mixture. Add the mixture dropwise to the emulsion. After the addition is complete, maintain stirring for 0.5-1.5 hours, adjust the pH of the system to 9-10, raise the temperature to 45-55°C, and react for 3-5 hours. After the reaction is complete, cool the system to room temperature, centrifuge, wash, and dry to obtain nano-silica coated with fluorosilane.

[0024] By adopting the above technical solution, on the one hand, the silica coating layer can protect the fluorosilane from volatilization during the low-temperature firing stage of the glaze. When it melts and cracks synchronously with the glass phase of the glaze during the high-temperature stage, the released fluorosilane can bond with the hydroxyl groups on the surface of expanded kaolin and the surface of nano zinc oxide, avoiding the decomposition and loss of fluorosilane at high temperature. At the same time, relying on the layered dispersion characteristics of expanded kaolin, the fluorosilane can uniformly cover the glaze surface to form a continuous low-surface hydrophobic layer. On the other hand, the fluorosilane and nano zinc oxide synergistically enhance the hydrophobic and anti-adhesion effect. After the silica coating layer melts, it will react with the alumina in the glaze to generate mullite crystals, and form a dispersion strengthening effect with nano zinc oxide, thereby improving the overall hardness and wear resistance of the glaze layer.

[0025] Preferably, in step 2: under stirring, 35-45 parts by weight of tetraethyl orthosilicate and 100 parts by weight of deionized water are mixed to obtain a mixture. The mixture is added dropwise to the emulsion. After the addition is complete, stirring is maintained for 0.5-1.5 hours, and the pH of the system is adjusted to 9-10. The temperature is raised to 45-55°C, and the reaction is carried out for 3-5 hours to obtain a reaction solution. 2-4 parts by weight of nano-zirconia dispersion is added to the reaction solution, and the reaction is carried out at 50°C for 1 hour. After the reaction is complete, the system is cooled to room temperature, centrifuged, washed, and dried to obtain nano-zirconia-nano-silica coated fluorosilane.

[0026] By adopting the above technical solution, nano-zirconium dioxide and nano-silica undergo a hydroxyl condensation reaction to form stable -Si-O-Zr- covalent bonds, which anchor the zirconium dioxide to the surface of the silica shell. At the glaze firing temperature, the two form a solid solution through lattice distortion, which reduces the porosity of the glaze layer, enhances the density, and improves the stain resistance of the glaze layer.

[0027] Preferably, the raw material further includes 0.1-0.3 parts by weight of aminosilane-grafted amphoteric carboxymethyl cellulose sodium; the amphoteric carboxymethyl cellulose sodium is prepared by a two-step method of carboxymethylation-cationization, and an amino-containing silane coupling agent is introduced in the cationization process.

[0028] By adopting the above technical solution, on the one hand, the carboxyl groups on the amphoteric carboxymethyl cellulose sodium molecular chain grafted with aminosilane can adsorb the positively charged nano-zinc oxide in the stain-resistant agent, and the quaternary ammonium salt groups and amino groups can anchor the negatively charged nano-silica coated with fluorosilane. The bidirectional adsorption combined with three-dimensional spatial steric hindrance effectively inhibits particle agglomeration and improves the uniformity of glazing. On the other hand, the silicon-oxygen bonds of the silane coupling agent can form covalent bonds with the hydroxyl groups on the surface of inorganic particles in the glaze, strengthen the interfacial bonding between organic additives and inorganic components, and reduce defects such as glaze pinholes and glaze shrinkage caused by poor interfacial compatibility during firing. At the same time, the amino groups can further enhance the adhesion of the glaze slurry to the surface of the body, avoid the glaze from flowing and exposing the base after glazing, and further improve the density and stain resistance of the glaze.

[0029] Secondly, this application provides a method for preparing a highly stain-resistant ceramic glaze, employing the following technical solution:

[0030] A method for preparing a highly stain-resistant ceramic glaze is as follows: potassium feldspar, quartz, talc, calcium carbonate, and kaolin are added to a portion of deionized water and ball-milled according to a specified ratio. Then, a stain-resistant agent and sodium hexametaphosphate are added and ball-milled again. Finally, fluorosilyl functional materials are added and ball-milled again to obtain a glaze slurry. The glaze slurry is then sieved to obtain the highly stain-resistant ceramic glaze.

[0031] By adopting the above technical solution, the preparation method is simple, and through the synergistic effect between the stain-resistant agent and fluorosilane, the prepared high stain-resistant ceramic glaze has good stain resistance.

[0032] Thirdly, this application provides an application of a highly stain-resistant ceramic glaze, employing the following technical solution:

[0033] A highly stain-resistant ceramic includes a green body and a highly stain-resistant ceramic glaze layer disposed on the upper surface of the green body, wherein the highly stain-resistant ceramic glaze layer is formed by firing the aforementioned highly stain-resistant ceramic glaze.

[0034] By adopting the above technical solution, highly stain-resistant ceramic glaze can be fired to form a glaze layer on the ceramic surface, giving the ceramic excellent stain resistance.

[0035] In summary, this application has the following beneficial effects:

[0036] 1. In this application, a stain-resistant agent is added to the glaze. After the kaolin expands, the interlayer spacing is increased, which not only facilitates the loading of nano zinc oxide, but also the loose structure formed by it better fills the micropores of the glaze layer, thereby improving the stain resistance of the glaze.

[0037] 2. This application introduces rare earth oxides into expanded kaolin-supported nano zinc oxide, which can improve the photocatalytic activity of nano zinc oxide and further improve the stain resistance of the glaze.

[0038] 3. This application improves the stain resistance of glaze by coating the surface of fluorosilane with nanofillers, so that the fluorosilane can uniformly cover the glaze surface and form a continuous low surface hydrophobic layer. Detailed Implementation

[0039] The present application will be further described in detail below with reference to preparation examples, embodiments and comparative examples. Unless otherwise specified, all raw materials involved in the present application can be obtained commercially.

[0040] Preparation Example

[0041] Preparation Examples 1-13: Stain-resistant Agents

[0042] This preparation example discloses a method for preparing a stain-resistant agent, including the following steps:

[0043] (1) 1 kg of kaolin, 1 kg of urea and 8 L of deionized water were stirred at 300 r / min to completely dissolve the solid and form suspension A. The suspension A was heated to 60 °C and stirred for 6 h. After the reaction was completed, the mixture was filtered and the filter cake was collected. The filter cake was washed three times with deionized water and placed in a vacuum drying oven. It was dried at 60 °C for 8 h to obtain expanded kaolin precursor. Then it was placed in a muffle furnace and kept at 200 °C for 0.5 h. The temperature was then raised to 350 °C and kept for 1 h. After cooling, expanded kaolin was obtained.

[0044] (2) 1 kg of expanded kaolin was added to 15 L of deionized water and 20 g of KH-550 silane coupling agent was added and ultrasonically dispersed for 30 min to obtain suspension B; 10 L of 0.08 mol / L zinc acetate solution was added dropwise to the above suspension B at a stirring speed of 400 r / min at a dropping rate of 2 L / h, and stirred at room temperature for 1 h; 10% ammonium bicarbonate solution was added dropwise to adjust the pH of the system to 7.5, and stirring was continued for 2 h; after the reaction was completed, the filter cake was collected by suction filtration, washed with deionized water until neutral, washed once with anhydrous ethanol, and dried at 60 °C to constant weight to obtain the composite precursor; the composite precursor was transferred to a muffle furnace and heated to 450 °C at a heating rate of 5 °C / min, calcined for 2.5 h, naturally cooled to room temperature, and ground through a 200 mesh sieve to obtain expanded kaolin-supported nano zinc oxide; thermogravimetric analysis showed that the loading of expanded kaolin-supported nano zinc oxide was 5.9%.

[0045] Preparation Example 2

[0046] This preparation example discloses a method for preparing a stain-resistant agent, including the following steps:

[0047] (1) 1 kg of kaolin, 1.2 kg of urea and 12 L of deionized water were stirred at 300 r / min to completely dissolve the solid and form suspension A. The suspension A was heated to 65 °C and stirred for 5 h. After the reaction was completed, the mixture was filtered and the filter cake was collected. The filter cake was washed three times with deionized water and placed in a vacuum drying oven. It was dried at 60 °C for 8 h to obtain expanded kaolin precursor. Then it was placed in a muffle furnace and kept at 200 °C for 1 h. The temperature was then increased to 300 °C and kept for 1 h. After cooling, expanded kaolin was obtained.

[0048] (2) 1 kg of expanded kaolin was added to 20 L of deionized water and 30 g of KH-550 silane coupling agent was added and ultrasonically dispersed for 30 min to obtain suspension B; 12 L of 0.1 mol / L zinc acetate solution was added dropwise to the above suspension B at a stirring speed of 400 r / min at a rate of 2 L / h, and stirred at room temperature for 1 h; 10% ammonium bicarbonate solution was added dropwise to adjust the pH of the system to 8, and stirring was continued for 2 h; after the reaction was completed, the filter cake was collected by suction filtration, washed with deionized water until neutral, washed once with anhydrous ethanol, and dried at 60 °C to constant weight to obtain the composite precursor; the composite precursor was transferred to a muffle furnace and heated to 500 °C at a heating rate of 5 °C / min, calcined for 2 h, naturally cooled to room temperature, and ground through a 200 mesh sieve to obtain expanded kaolin-supported nano zinc oxide; thermogravimetric analysis showed that the loading of expanded kaolin-supported nano zinc oxide was 8.1%.

[0049] Preparation Example 3

[0050] This preparation example discloses a method for preparing a stain-resistant agent, including the following steps:

[0051] (1) 1 kg of kaolin, 1 kg of urea and 15 L of deionized water were stirred at 300 r / min to completely dissolve the solid and form suspension A. The suspension A was heated to 70 °C and stirred for 6 h. After the reaction was completed, the mixture was filtered and the filter cake was collected. The filter cake was washed three times with deionized water and placed in a vacuum drying oven. It was dried at 60 °C for 8 h to obtain expanded kaolin precursor. Then it was placed in a muffle furnace and kept at 200 °C for 1 h. The temperature was then increased to 250 °C and kept for 1.5 h. After cooling, expanded kaolin was obtained.

[0052] (2) 1 kg of expanded kaolin was added to 25 L of deionized water and 40 g of KH-550 silane coupling agent was added and ultrasonically dispersed for 30 min to obtain suspension B; 15 L of 0.15 mol / L zinc acetate solution was added dropwise to the above suspension B at a stirring speed of 400 r / min at a dropping rate of 2 L / h, and stirred at room temperature for 1 h; 10% ammonium bicarbonate solution was added dropwise to adjust the pH of the system to 8, and stirring was continued for 2 h; after the reaction was completed, the filter cake was collected by suction filtration, washed with deionized water until neutral, washed once with anhydrous ethanol, and dried at 60 °C to constant weight to obtain the composite precursor; the composite precursor was transferred to a muffle furnace and heated to 550 °C at a heating rate of 5 °C / min, calcined for 2 h, naturally cooled to room temperature, and ground through a 200 mesh sieve to obtain expanded kaolin-supported nano zinc oxide; thermogravimetric analysis showed that the loading of expanded kaolin-supported nano zinc oxide was 11.0%.

[0053] Preparation Example 4

[0054] This preparation example is basically the same as preparation example 2, except that the 1.2 kg urea in step (1) is replaced with 0.8 kg urea and 0.4 kg glycerol. Thermogravimetric analysis shows that the loading of expanded kaolin loaded with nano zinc oxide is 8.4%.

[0055] Preparation Example 5

[0056] This preparation example is basically the same as preparation example 2, except that the 1.2 kg urea in step (1) is replaced with 0.9 kg urea and 0.3 kg glycerol. Thermogravimetric analysis shows that the loading of expanded kaolin loaded with nano zinc oxide is 8.6%.

[0057] Preparation Example 6

[0058] This preparation example is basically the same as preparation example 2, except that the 1.2 kg urea in step (1) is replaced with 0.96 kg urea and 0.24 kg glycerol. Thermogravimetric analysis shows that the loading of expanded kaolin loaded with nano zinc oxide is 8.5%.

[0059] Preparation Example 7

[0060] This preparation example is basically the same as Preparation Example 5, except that in step (2), 1 kg of expanded kaolin is added to 20 L of deionized water and 30 g of KH-550 silane coupling agent is added and ultrasonically dispersed for 30 min to obtain suspension B; under a stirring speed of 400 r / min, 12 L of 0.1 mol / L zinc acetate solution and 2 L of 0.1 mol / L lanthanum nitrate solution are mixed and then added dropwise to the above suspension B at a dropping rate of 2 L / h, and stirred at room temperature for 1 h; 10% ammonium bicarbonate solution is added dropwise to adjust the volume. The pH was adjusted to 8, and stirring was continued for 2 hours. After the reaction was completed, the filter cake was collected by vacuum filtration, washed with deionized water until neutral, and then washed once with anhydrous ethanol. It was dried at 60°C to constant weight to obtain the composite precursor. The composite precursor was transferred to a muffle furnace and heated to 500°C at a heating rate of 5°C / min. It was calcined for 2 hours, naturally cooled to room temperature, and ground through a 200-mesh sieve to obtain expanded kaolin-supported nano-zinc oxide-lanthanum oxide. Thermogravimetric analysis showed that the loading of expanded kaolin-supported nano-zinc oxide-lanthanum oxide was 9.0%.

[0061] Preparation Example 8

[0062] This preparation example is basically the same as preparation example 5, except that in step (2), lanthanum nitrate is replaced with cerium nitrate, and the final loading of expanded kaolin loaded with nano zinc oxide-cerium oxide is 9.1%.

[0063] Preparation Example 9

[0064] This preparation example is basically the same as preparation example 5, except that in step (2), 2L of 0.1mol / L lanthanum nitrate solution is replaced with 1L of 0.1mol / L lanthanum nitrate solution and 1L of 0.1mol / L cerium nitrate solution, and the final loading of expanded kaolin-supported nano zinc oxide-rare earth oxide is 9.2%.

[0065] Preparation Example 10

[0066] This preparation example is basically the same as preparation example 5, except that in step (2), 2 L of 0.1 mol / L lanthanum nitrate solution is replaced with 1.33 L of 0.1 mol / L lanthanum nitrate solution and 0.67 L of 0.1 mol / L cerium nitrate solution, and the final loading of expanded kaolin-supported nano zinc oxide-rare earth oxide is 9.3%.

[0067] Preparation Example 11

[0068] This preparation example is basically the same as preparation example 5, except that in step (2), 2 L of 0.1 mol / L lanthanum nitrate solution is replaced with 1.5 L of 0.1 mol / L lanthanum nitrate solution and 0.5 L of 0.1 mol / L cerium nitrate solution, and the final loading of expanded kaolin-supported nano zinc oxide-rare earth oxide is 9.1%.

[0069] Preparation Example 12

[0070] This preparation example is basically the same as preparation example 5, except that in step (2), 2L of 0.1mol / L lanthanum nitrate solution is replaced with 2L of 0.1mol / L lanthanum nitrate solution and 1L of 0.1mol / L cerium nitrate solution, and the final loading of expanded kaolin-supported nano zinc oxide-rare earth oxide is 9.6%.

[0071] Preparation Example 13

[0072] This preparation example is basically the same as preparation example 5, except that in step (2), 2 L of 0.1 mol / L lanthanum nitrate solution is replaced with 2.67 L of 0.1 mol / L lanthanum nitrate solution and 1.33 L of 0.1 mol / L cerium nitrate solution, and the final loading of expanded kaolin-supported nano zinc oxide-rare earth oxide is 9.5%.

[0073] Preparation Examples 14-19: Fluorosilane Functional Materials

[0074] Preparation Example 14

[0075] This preparation example discloses a method for preparing a fluorosilane functional material, including the following steps:

[0076] Step 1: Add 2.5 kg of perfluorooctyltrimethoxysilane (CAS: 85857-16-5), 0.015 kg of acetic acid and 0.4 kg of perfluorohexylethanol polyoxyethylene ether to 10 kg of deionized water, and emulsify at 30°C and 3000 r / min for 30 min to form an O / W type emulsion.

[0077] Step 2: While stirring at 800 rpm, 3.5 kg of tetraethyl orthosilicate was added dropwise to 10 kg of deionized water at a rate of 1 L / h to obtain a mixture. This mixture was then added dropwise to the emulsion at a rate of 1 L / h. After the addition was complete, stirring continued for 30 min. 25% ammonia was added dropwise to adjust the pH of the system to 9. The temperature was raised to 45°C and maintained for 5 h. After the reaction was complete, the system was cooled to room temperature and centrifuged at 8000 rpm for 15 min to collect the precipitate. The precipitate was washed three times with deionized water and once with ethanol. It was then vacuum dried at 60°C for 8 h to obtain nano-silica-coated fluorosilane. The surface potential of the nano-silica-coated fluorosilane was measured to be -36 mV using a Zeta potentiometer.

[0078] Preparation Example 15

[0079] This preparation example discloses a method for preparing a fluorosilane functional material, including the following steps:

[0080] Step 1: Add 3 kg of perfluorooctyltrimethoxysilane (CAS: 85857-16-5), 0.02 kg of acetic acid, and 0.5 kg of perfluorohexylethanol polyoxyethylene ether to 10 kg of deionized water, and emulsify at 30°C and 3000 r / min for 30 min to form an O / W type emulsion.

[0081] Step 2: While stirring at 800 rpm, 4 kg of tetraethyl orthosilicate was added dropwise to 10 kg of deionized water at a rate of 1 L / h to obtain a mixture. This mixture was then added dropwise to the emulsion at a rate of 1 L / h. After the addition was complete, stirring continued for 30 min. 25% ammonia was added dropwise to adjust the pH of the system to 9.5. The temperature was raised to 50 °C and maintained for 4 h. After the reaction was complete, the system was cooled to room temperature and centrifuged at 8000 rpm for 15 min to collect the precipitate. The precipitate was washed three times with deionized water and once with ethanol. It was then vacuum dried at 60 °C for 8 h to obtain nano-silica-coated fluorosilane. The surface potential of the nano-silica-coated fluorosilane was measured to be -42 mV using a Zeta potentiometer.

[0082] Preparation Example 16

[0083] This preparation example discloses a method for preparing a fluorosilane functional material, including the following steps:

[0084] Step 1: Add 3.5 kg of perfluorooctyltrimethoxysilane (CAS: 85857-16-5), 0.025 kg of acetic acid, and 0.6 kg of perfluorohexylethanol polyoxyethylene ether to 10 kg of deionized water, and emulsify at 30°C and 3000 r / min for 30 min to form an O / W type emulsion.

[0085] Step 2: While stirring at 800 rpm, 4.5 kg of tetraethyl orthosilicate was added dropwise to 10 kg of deionized water at a rate of 1 L / h to obtain a mixture. This mixture was then added dropwise to the emulsion at a rate of 1 L / h. After the addition was complete, stirring continued for 30 min. 25% ammonia was added dropwise to adjust the pH of the system to 10. The temperature was raised to 50 °C and maintained for 4 h. After the reaction was complete, the system was cooled to room temperature and centrifuged at 8000 rpm for 15 min to collect the precipitate. The precipitate was washed three times with deionized water and once with ethanol. It was then vacuum dried at 60 °C for 8 h to obtain nano-silica-coated fluorosilane. The surface potential of the nano-silica-coated fluorosilane was measured to be -46 mV using a Zeta potentiometer.

[0086] Preparation Example 17

[0087] This preparation example is basically the same as Preparation Example 16, except that in step 2: 4 kg of tetraethyl orthosilicate was added dropwise to 10 kg of deionized water at a speed of 800 r / min to obtain a mixture. The mixture was then added dropwise to the emulsion at a speed of 1 L / h. After the addition was complete, stirring was continued for 30 min. 25% ammonia was added dropwise to adjust the pH of the system to 9.5, and the temperature was raised to 50℃ and kept at that temperature for 4 h. Then, 0.2 kg of 30% nano-zirconia dispersion was added, and the reaction was continued at 50℃ for 1 h. After the reaction was complete, the system was cooled to room temperature, and the precipitate was collected by centrifugation at 8000 r / min for 15 min. The precipitate was washed three times with deionized water and once with ethanol. Subsequently, it was vacuum dried at 60℃ for 8 h to obtain nano-zirconia-nano-silica coated fluorosilane. The surface potential of nano-zirconia-nano silica-coated fluorosilane was measured to be -39mV using a Zeta potentiometer.

[0088] Preparation Example 18

[0089] This preparation example is basically the same as Preparation Example 16, except that in step 2: 4 kg of tetraethyl orthosilicate was added dropwise to 10 kg of deionized water at a speed of 800 r / min to obtain a mixture. The mixture was then added dropwise to the emulsion at a speed of 1 L / h. After the addition was complete, stirring was continued for 30 min. 25% ammonia was added dropwise to adjust the pH of the system to 9.5, and the temperature was raised to 50℃ and kept at that temperature for 4 h. Then, 0.3 kg of 30% nano-zirconia dispersion was added, and the reaction was continued at 50℃ for 1 h. After the reaction was complete, the system was cooled to room temperature, and the precipitate was collected by centrifugation at 8000 r / min for 15 min. The precipitate was washed three times with deionized water and once with ethanol. Subsequently, it was vacuum dried at 60℃ for 8 h to obtain nano-zirconia-nano-silica coated fluorosilane. The surface potential of nano-zirconia-nano silica-coated fluorosilane was measured to be -37mV using a Zeta potentiometer.

[0090] Preparation Example 19

[0091] This preparation example is basically the same as Preparation Example 16, except that in step 2: 4 kg of tetraethyl orthosilicate was added dropwise to 10 kg of deionized water at a speed of 800 r / min to obtain a mixture. The mixture was then added dropwise to the emulsion at a speed of 1 L / h. After the addition was complete, stirring was continued for 30 min. 25% ammonia was added dropwise to adjust the pH of the system to 9.5, and the temperature was raised to 50℃ and kept at that temperature for 4 h. Then, 0.4 kg of 30% nano-zirconia dispersion was added, and the reaction was continued at 50℃ for 1 h. After the reaction was complete, the system was cooled to room temperature, and the precipitate was collected by centrifugation at 8000 r / min for 15 min. The precipitate was washed three times with deionized water and once with ethanol. Subsequently, it was vacuum dried at 60℃ for 8 h to obtain nano-zirconia-nano-silica coated fluorosilane. The surface potential of nano-zirconia-nano silica-coated fluorosilane was measured to be -35mV using a Zeta potentiometer.

[0092] Example

[0093] Example 1

[0094] This embodiment discloses a highly stain-resistant ceramic glaze, comprising the following raw materials: 30 kg of potassium feldspar, 25 kg of quartz, 15 kg of talc, 7 kg of calcium carbonate, 18 kg of kaolin, 6 kg of stain-resistant agent, 0.7 kg of perfluorooctyltrimethoxysilane (CAS: 85857-16-5), and 0.3 kg of sodium hexametaphosphate. The potassium feldspar, quartz, talc, calcium carbonate, and kaolin are all obtained by grinding and passing through a 100-mesh sieve. The stain-resistant agent is obtained from preparation 1.

[0095] High stain-resistant ceramic glaze is prepared according to the following steps: Weigh potassium feldspar, quartz, talc, calcium carbonate, and kaolin according to the above-mentioned mass and add them to a ball mill jar. Add 50L of deionized water and ball mill for 2 hours with zirconium dioxide balls at a ball-to-material ratio of 3:1 and a rotation speed of 300r / min. Then add stain-resistant agent and sodium hexametaphosphate, and continue ball milling for 1 hour. Then add perfluorooctyltrimethoxysilane and ball mill for 30 minutes to obtain glaze slurry. After passing the glaze slurry through a 325-mesh sieve, let it stand at room temperature for 4 hours to obtain high stain-resistant ceramic glaze.

[0096] The high stain-resistant ceramic is prepared according to the following steps: the above-mentioned high stain-resistant ceramic glaze is applied to the green body, dried and fired. The process parameters used during firing are: heating to 600℃ at 5℃ / min and holding for 30min, then heating to 1100℃ at 8℃ / min, then heating to 1220℃ at 3℃ / min and holding for 45min, and finally cooling to room temperature at 6℃ / min.

[0097] Example 2

[0098] The difference between this embodiment and Embodiment 1 is that the high stain-resistant ceramic glaze includes the following raw materials: 40 kg of potassium feldspar, 15 kg of quartz, 5 kg of talc, 13 kg of calcium carbonate, 12 kg of kaolin, 8 kg of stain-resistant agent, 0.4 kg of perfluorooctyltrimethoxysilane (CAS: 85857-16-5), 0.5 kg of sodium hexametaphosphate, and 0.3 kg of sodium carboxymethyl cellulose. Among them, potassium feldspar, quartz, talc, calcium carbonate, and kaolin are all obtained by grinding and passing through a 100-mesh sieve, and the stain-resistant agent is the one obtained in Preparation 1.

[0099] Example 3

[0100] The difference between this embodiment and Embodiment 1 is that, in this embodiment, the high-fouling-resistant ceramic glaze includes the following raw materials: 30 kg of potassium feldspar, 25 kg of quartz, 15 kg of talc, 7 kg of calcium carbonate, 18 kg of kaolin, 6 kg of stain-resistant agent, 0.7 kg of perfluorooctyltrimethoxysilane (CAS: 85857-16-5), 0.3 kg of sodium hexametaphosphate, and 0.2 kg of amphoteric carboxymethyl cellulose sodium. The potassium feldspar, quartz, talc, calcium carbonate, and kaolin are all obtained by grinding and passing through a 100-mesh sieve. The stain-resistant agent is the one obtained in Preparation 1. The preparation method of amphoteric carboxymethyl cellulose sodium is as follows: 100 g of cellulose is dispersed in 500 mL of 80% ethanol solution, 45 g of sodium hydroxide is added, and the mixture is stirred and alkalized at 35°C for 1 hour; then 60 g of sodium chloroacetate is added. The reaction was carried out at 65℃ for 2.5 h. After the reaction was completed, the pH was adjusted to 7 with glacial acetic acid, the product was collected by vacuum filtration, washed three times with 70% ethanol, and dried at 60℃ for 2 h to obtain sodium carboxymethyl cellulose. 80 g of sodium carboxymethyl cellulose was dissolved in 600 mL of deionized water and stirred until completely dissolved. 20 g of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added. The pH was adjusted to 9 with 5% sodium hydroxide solution, and KH-550 ethanol solution (3 g of KH-550 was dissolved in 10 mL of anhydrous ethanol and stirred for 10 min) was added dropwise. The reaction was carried out at 60℃ for 3.5 h. An equal volume of ethanol was added to the reaction solution to precipitate the product. After standing for 30 min, the product was filtered, washed three times with 75% ethanol, dried under vacuum at 50℃ for 6 h, and pulverized through a 200-mesh sieve to obtain amphoteric sodium carboxymethyl cellulose.

[0101] High stain-resistant ceramic glaze is prepared according to the following steps: potassium feldspar, quartz, talc, calcium carbonate, and kaolin are weighed according to the above mass and added to a ball mill jar. 50L of deionized water is added, and the mixture is ball-milled for 2 hours at a ball-to-material ratio of 3:1 using zirconia balls and a rotation speed of 300r / min. Then, a stain-resistant agent and sodium hexametaphosphate are added, and the mixture is ball-milled for another hour. After that, perfluorooctyltrimethoxysilane and amphoteric carboxymethyl cellulose sodium are added, and the mixture is ball-milled for 30 minutes to obtain a glaze slurry. The glaze slurry is then sieved through a 325-mesh sieve and allowed to stand at room temperature for 4 hours to obtain the high stain-resistant ceramic glaze.

[0102] Example 4

[0103] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 2.

[0104] Example 5

[0105] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 3.

[0106] Example 6

[0107] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 4.

[0108] Example 7

[0109] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 5.

[0110] Example 8

[0111] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 6.

[0112] Example 9

[0113] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 7.

[0114] Example 10

[0115] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained from preparation 8.

[0116] Example 11

[0117] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained from preparation 9.

[0118] Example 12

[0119] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained from preparation 10.

[0120] Example 13

[0121] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 11.

[0122] Example 14

[0123] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 12.

[0124] Example 15

[0125] This embodiment is basically the same as embodiment 2, except that the stain-resistant agent is the one obtained in preparation 13.

[0126] Example 16

[0127] This embodiment is basically the same as Embodiment 2, except that the high stain-resistant ceramic glaze includes the following raw materials: 40 kg of potassium feldspar, 15 kg of quartz, 5 kg of talc, 13 kg of calcium carbonate, 12 kg of kaolin, 8 kg of stain-resistant agent, 0.4 kg of fluorosilane functional material, 0.6 kg of sodium hexametaphosphate, and 0.3 kg of sodium carboxymethyl cellulose. Among them, potassium feldspar, quartz, talc, calcium carbonate, and kaolin are all obtained by grinding and passing through a 100-mesh sieve. The stain-resistant agent is the one obtained in Preparation 12, and the fluorosilane functional material is the one obtained in Preparation 14.

[0128] High stain-resistant ceramic glaze is prepared according to the following steps: Weigh potassium feldspar, quartz, talc, calcium carbonate, and kaolin according to the above-mentioned mass and add them to a ball mill jar. Add 50L of deionized water and ball mill for 2 hours with zirconia balls of 3:1 ball-to-material ratio and a rotation speed of 300r / min. Then add stain-resistant agent and sodium hexametaphosphate, and continue ball milling for 1 hour. Then add fluorosilane functional material and ball mill for 30 minutes to obtain glaze slurry. After passing the glaze slurry through a 325-mesh sieve, let it stand at room temperature for 4 hours to obtain high stain-resistant ceramic glaze.

[0129] Example 17

[0130] This embodiment is basically the same as Example 16, except that the stain-resistant agent is the one obtained in Preparation 12, and the fluorosilane functional material is the one obtained in Preparation Example 15.

[0131] Example 18

[0132] This embodiment is basically the same as Example 16, except that the stain-resistant agent is the one obtained in Preparation 12, and the fluorosilane functional material is the one obtained in Preparation 16.

[0133] Example 19

[0134] This embodiment is basically the same as Example 16, except that the stain-resistant agent is the one obtained in Preparation 12, and the fluorosilane functional material is the one obtained in Preparation Example 17.

[0135] Example 20

[0136] This embodiment is basically the same as Example 16, except that the stain-resistant agent is the one obtained in Preparation 12, and the fluorosilane functional material is the one obtained in Preparation Example 18.

[0137] Example 21

[0138] This embodiment is basically the same as Example 16, except that the stain-resistant agent is the one obtained in Preparation 12, and the fluorosilane functional material is the one obtained in Preparation Example 19.

[0139] Comparative Example

[0140] Comparative Example 1

[0141] This comparative example discloses a highly stain-resistant ceramic glaze, comprising the following raw materials: 30 kg of potassium feldspar, 25 kg of quartz, 15 kg of talc, 7 kg of calcium carbonate, 18 kg of kaolin, 6 kg of stain-resistant agent, 0.7 kg of perfluorooctyltrimethoxysilane (CAS: 85857-16-5), and 0.3 kg of sodium hexametaphosphate.

[0142] Among them, potassium feldspar, quartz, talc, calcium carbonate, and kaolin were all obtained by grinding and passing through a 100-mesh sieve. The preparation method of the stain-resistant agent is as follows: 1 kg of kaolin was added to 20 L of deionized water and 30 g of KH-550 silane coupling agent was added and ultrasonically dispersed for 30 min to obtain suspension B; under a stirring speed of 400 r / min, 12 L of 0.1 mol / L zinc acetate solution was added dropwise to the above suspension B at a dropping rate of 2 L / h, and stirred at room temperature for 1 h; 10% ammonium bicarbonate solution was added dropwise. The pH of the liquid system was adjusted to 8, and stirring was continued for 2 hours. After the reaction was completed, the filter cake was collected by suction filtration, washed with deionized water until neutral, and then washed once with anhydrous ethanol. It was dried at 60°C to constant weight to obtain the composite precursor. The composite precursor was transferred to a muffle furnace and heated to 500°C at a heating rate of 5°C / min. It was calcined for 2 hours, cooled naturally to room temperature, and ground through a 200-mesh sieve to obtain expanded kaolin-supported nano-zinc oxide. Thermogravimetric analysis showed that the loading of kaolin-supported nano-zinc oxide was 0.61%.

[0143] High stain-resistant ceramic glaze is prepared according to the following steps: potassium feldspar, quartz, talc, calcium carbonate, and kaolin are weighed according to the above mass and added to a ball mill jar. 50L of deionized water is added, and the mixture is ball-milled for 2 hours at a ball-to-material ratio of 3:1 using zirconia balls and a rotation speed of 300r / min. Then, a stain-resistant agent and sodium hexametaphosphate are added, and the mixture is ball-milled for another hour. Finally, fluorosilane and 0.1kg of sodium carboxymethyl cellulose are added, and the mixture is ball-milled for 30 minutes to obtain a glaze slurry. The glaze slurry is then sieved through a 325-mesh sieve and allowed to stand at room temperature for 4 hours to obtain the high stain-resistant ceramic glaze.

[0144] The high stain-resistant ceramic is prepared according to the following steps: the above-mentioned high stain-resistant ceramic glaze is applied to the green body, dried and fired. The process parameters used during firing are: heating to 600℃ at 5℃ / min and holding for 30min, then heating to 1100℃ at 8℃ / min, then heating to 1220℃ at 3℃ / min and holding for 45min, and finally cooling to room temperature at 6℃ / min.

[0145] Performance testing methods

[0146] The high stain-resistant ceramic samples prepared in Examples 1-21 and Comparative Example 1 were subjected to stain resistance and abrasion resistance tests. The stain resistance was tested according to GB / T 3810.14-2016 "Ceramic Tile Test Methods Part 14: Determination of Stain Resistance"; the abrasion resistance was tested according to GB / T3810.7-2016 "Determination of Abrasion Resistance of Glazed Ceramic Tile Surface". The test results are shown in Table 1.

[0147] Table 1 Performance test data of Examples 1-21 and Comparative Example 1

[0148]

[0149] Combining Example 1 and Comparative Example 1 with reference to Table 1, it can be seen that the stain resistance and abrasion resistance of Example 1 are superior to those of Comparative Example 1. This indicates that by expanding the kaolin, this application can not only increase the loading of nano zinc oxide on it, but also facilitate its layered structure to flow with the glass phase during the glaze firing process, thereby filling the micropores of the glaze layer, reducing the porosity of the glaze layer, blocking the oil penetration channels, and thus improving the stain resistance and abrasion resistance of the glaze layer.

[0150] Combined with Examples 7 and 9-13 and referring to Table 1, it can be seen that this application introduces rare earth oxides into expanded kaolin-loaded nano zinc oxide. The rare earth oxides can enhance the photocatalytic activity of nano zinc oxide through their unique electronic structure, thereby enhancing the self-cleaning properties of the composite material in ceramic glaze. Furthermore, the rare earth oxides can fill some of the pores of expanded kaolin and form an interface bond with nano zinc oxide, thereby improving the stain resistance and wear resistance of the product.

[0151] Combined with Examples 14 and 16-18 and referring to Table 1, it can be seen that this application coats the surface of fluorosilane with nano-silica, which allows the fluorosilane to uniformly cover the glaze surface, forming a continuous low-surface-hydrophobic layer and improving the stain resistance of the glaze. At the same time, after the silica coating melts, it forms a dispersion strengthening effect with nano-zinc oxide, improving the wear resistance of the glaze.

[0152] Combined with Examples 17 and 19-21 and referring to Table 1, it can be seen that this application introduces nano-zirconium dioxide into silica-coated fluorosilane. The nano-zirconium dioxide and nano-silica undergo a hydroxyl condensation reaction to form stable -Si-O-Zr- covalent bonds, which anchor the zirconium dioxide to the surface of the silica shell. At the glaze firing temperature, the two form a solid solution through lattice distortion, which reduces the porosity of the glaze layer, enhances the density, and improves the stain resistance and wear resistance of the glaze layer.

[0153] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A highly stain-resistant ceramic glaze, characterized in that, The raw materials include the following parts by weight: 30-40 parts potassium feldspar, 15-25 parts quartz, 5-15 parts talc, 7-13 parts calcium carbonate, 12-18 parts kaolin, 6-8 parts stain resistant agent, 0.4-0.7 parts fluorosilane functional material, and 0.3-0.5 parts sodium hexametaphosphate. The stain resistant agent is expanded kaolin-supported nano zinc oxide or expanded kaolin-supported nano zinc oxide-rare earth oxide. The preparation method of expanded kaolin loaded with nano-zinc oxide includes the following steps: (1) Mix kaolin, intercalating agent and deionized water in a mass ratio of 1:(1-1.5):(8-15) to obtain suspension A; heat suspension A to 60-70℃ and stir for 4-6h. After the reaction is completed, filter, wash and dry to obtain precursor; calcine the precursor at 250-350℃ for 0.5-1.5h to obtain expanded kaolin. (2) Expanded kaolin, deionized water and silane coupling agent in a mass ratio of 1:(15-25):(0.02-0.04) are ultrasonically dispersed to obtain suspension B; under stirring, 0.08-0.15mol / L zinc acetate solution is added dropwise to suspension B, reacted for 1h, pH is adjusted to 7.5-8.0, and the reaction continues for 2h; filtered, washed and dried to obtain composite precursor, calcined at 450-550℃ for 1.5-2.5h, cooled and ground to obtain expanded kaolin-supported nano zinc oxide; the mass-volume ratio of expanded kaolin to zinc acetate solution is 1:(10-15)g / mL; The preparation method of the expanded kaolin supported nano-zinc oxide-rare earth oxide includes the following steps: (1) Mix kaolin, intercalating agent and deionized water in a mass ratio of 1:(1-1.5):(8-15) to obtain suspension A; heat suspension A to 60-70℃ and stir for 4-6h. After the reaction is completed, filter, wash and dry to obtain precursor; calcine the precursor at 250-350℃ for 0.5-1.5h to obtain expanded kaolin. (2) Expanded kaolin, deionized water and silane coupling agent in a mass ratio of 1:(15-25):(0.03-0.07) are ultrasonically dispersed to obtain a suspension; under stirring, a mixture of 0.08-0.15 mol / L zinc acetate solution and 0.01-0.05 mol / L rare earth salt solution is added dropwise to the suspension, reacted for 1 h, the pH is adjusted to 7.5-8.0, and the reaction continues for 2 h; the mixture is filtered, washed and dried to obtain a composite precursor, which is then calcined at 450-550℃ for 1.5-2.5 h, cooled and ground to obtain expanded kaolin-supported nano zinc oxide-rare earth oxide; the mass-volume ratio of expanded kaolin to zinc acetate solution is 1:(10-15) g / mL; the mass-volume ratio of expanded kaolin to rare earth salt solution is 1:(2-4) g / mL; The fluorosilane functional material is a nanofiller-coated fluorosilane, and the preparation method of the nanofiller-coated fluorosilane includes the following steps: Step 1: Add 25-35 parts by weight of perfluorooctyltrimethoxysilane, 0.15-0.25 parts by weight of acetic acid and 4-6 parts by weight of nonionic fluorinated surfactant to 100 parts by weight of deionized water and stir to form an emulsion; Step 2: Under stirring, mix 35-45 parts by weight of tetraethyl orthosilicate with 100 parts by weight of deionized water to obtain a mixture. Add the mixture dropwise to the emulsion. After the addition is complete, maintain stirring for 0.5-1.5 hours, adjust the pH of the system to 9-10, raise the temperature to 45-55°C, and react for 3-5 hours. After the reaction is complete, cool the system to room temperature, centrifuge, wash, and dry to obtain nano-silica coated with fluorosilane.

2. The high stain-resistant ceramic glaze according to claim 1, characterized in that, The intercalating agent is a mixture of urea and glycerol in a mass ratio of (2-4):

1.

3. The high stain-resistant ceramic glaze according to claim 1, characterized in that, The rare earth salt solution is a mixed solution of lanthanum nitrate and cerium nitrate in a mass ratio of (1-3):

1.

4. The high stain-resistant ceramic glaze according to claim 1, characterized in that, Step 2: Under stirring, mix 35-45 parts by weight of tetraethyl orthosilicate with 100 parts by weight of deionized water to obtain a mixture. Add the mixture dropwise to the emulsion. After the addition is complete, maintain stirring for 0.5-1.5 hours and adjust the pH of the system to 9-10. Raise the temperature to 45-55℃ and react for 3-5 hours to obtain a reaction solution. Add 2-4 parts by weight of nano-zirconia dispersion to the reaction solution and react at 50℃ for 1 hour. After the reaction is complete, cool the system to room temperature, centrifuge, wash and dry to obtain nano-zirconia-nano-silica coated fluorosilane.

5. The high stain-resistant ceramic glaze according to claim 1, characterized in that, The raw materials also include 0.1-0.3 parts by weight of aminosilane-grafted amphoteric carboxymethyl cellulose sodium; the amphoteric carboxymethyl cellulose sodium is prepared by a two-step method of carboxymethylation-cationization, and an amino-containing silane coupling agent is introduced in the cationization process.

6. The method for preparing the highly stain-resistant ceramic glaze according to any one of claims 1-5, characterized in that, Potassium feldspar, quartz, talc, calcium carbonate, and kaolin were added to a portion of deionized water and ball-milled according to the specified ratio. Then, a stain-resistant agent and sodium hexametaphosphate were added and ball-milled again. Finally, fluorosilyl functional materials were added and ball-milled again to obtain a glaze slurry. The glaze slurry was then sieved to obtain the highly stain-resistant ceramic glaze.

7. A highly stain-resistant ceramic, comprising a green body and a highly stain-resistant ceramic glaze layer disposed on the upper surface of the green body, wherein the highly stain-resistant ceramic glaze layer is fired using the highly stain-resistant ceramic glaze material as described in any one of claims 1-5.

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