Antifouling and anti-skid bright brick and preparation method thereof

Abstract

The present application relates to the technical field of building ceramics, and particularly relates to a slip-resistant bright tile with antifouling performance and a preparation method thereof, comprising the following steps: A. applying a base glaze to the surface of a body layer to form a base glaze layer; B. spraying engraved dry particles to the surface of the base glaze layer to obtain an engraved dry particle layer; C. applying a protective glaze to the surface of the engraved dry particle layer to obtain a protective glaze layer; D. drying and then entering a kiln for calcination, and then polishing to obtain a polished semi-finished product; wherein the polished semi-finished product has holes formed by the falling of the engraved dry particles; E. applying a nano antifouling solution to the surface of the polished semi-finished product, and then using a super-clean bright machine to polish to generate an antifouling film layer in situ on the surface of the polished semi-finished product and the inner surface of the holes, thereby obtaining the slip-resistant bright tile with antifouling performance. The slip-resistant bright tile with antifouling performance and the preparation method thereof have the advantages of good slip resistance and antifouling performance while ensuring the bright effect.

Description

Technical Field

[0001] This invention relates to the field of building ceramics technology, and in particular to a non-slip glossy tile with anti-fouling properties and its preparation method. Background Technology

[0002] Glossy tiles, as an important decorative material for everyday homes, are favored by consumers for their mirror-like gloss, luxurious and grand visual appeal, high-temperature resistance, and rich glaze colors. They are widely used in home decoration, commercial spaces, and cultural tourism scenic areas. With the development of technology and the improvement of people's living standards, people have increasingly higher requirements for the quality of life, which means that in addition to stain resistance, glossy tiles are also expected to have a certain degree of slip resistance.

[0003] To achieve both slip resistance and stain resistance in glossy tiles, a typical approach in existing technologies involves applying a protective glaze to the surface of the tile, followed by the addition of a high-temperature dry granule anti-slip and stain-resistant glaze (wherein the ball-milled high-temperature dry granules have a smooth surface). Specifically, this method involves mixing high-temperature dry granules with a protective glaze and ball-milling with water to obtain the anti-slip and stain-resistant glaze. After firing, the dry granules protrude from the glaze surface, utilizing their slight undulations to achieve slip resistance through mechanical interlocking with the sole of a shoe. Simultaneously, the formation principle of the high-temperature dry granules with a smooth surface is similar to the mechanism by which pebbles in flowing water form a smooth surface, making it difficult for stains to accumulate on the surface of the high-temperature dry granules, thus obtaining a glossy tile that simultaneously possesses anti-slip and stain-resistant properties.

[0004] However, the above process has the following drawbacks: During the overall ball milling of the anti-slip and anti-fouling glaze, the high-temperature dry particles are prone to breakage. These broken particles (high-melting-point components) mix into the protective glaze (low-melting-point matrix). Furthermore, as a high-melting-point heterogeneous component, the broken high-temperature dry particles easily increase the initial melting and firing temperatures of the overall anti-slip and anti-fouling glaze. This prevents the glaze from fully melting and vitrifying at the original firing temperature, resulting in incomplete firing (i.e., under-firing). Consequently, the glaze surface fails to form a dense, non-porous glassy structure, resulting in numerous micropores and defects. Ultimately, stains (such as ink, soy sauce, and tea stains) can easily penetrate into the glaze layer through these pores and cannot be removed by conventional cleaning, creating permanent stains and reducing its anti-fouling performance. In addition, the large microscopic undulations on the surface formed by the anti-slip dry particles also cause diffuse light reflection, leading to a decrease in the glaze's gloss and making it difficult to achieve the desired high-gloss effect. It should be noted that the protective glaze (low-melting-point matrix) constitutes the majority of the volume of the glaze layer obtained from firing the anti-slip and anti-fouling glaze, and is the main component forming the continuous glassy phase. High-temperature dry granules, on the other hand, are a functional additive designed to maintain their granular shape or not fully melt at the firing temperature of the protective glaze to provide the micro-protrusion structure required for anti-slip properties. Therefore, the original firing temperature mainly refers to the firing temperature of the "protective glaze (low-melting-point matrix)" in the anti-slip and anti-fouling glaze.

[0005] In summary, existing technologies cannot produce glossy bricks that also possess good anti-slip and anti-fouling properties while ensuring a glossy finish. Summary of the Invention

[0006] The purpose of this invention is to propose a non-slip glossy tile with anti-fouling properties and its preparation method, which is beneficial to have good anti-slip and anti-fouling properties while ensuring the gloss effect, so as to overcome the shortcomings of the prior art.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] A method for preparing a non-slip glossy tile with anti-fouling properties includes the following steps:

[0009] A. Apply the base glaze to the surface of the body layer to form the base glaze layer;

[0010] B. Spray the engraved dry granules onto the surface of the base glaze layer to obtain the engraved dry granule layer;

[0011] The method for preparing the engraved dry granules is as follows:

[0012] B1. The core glaze is dried and granulated sequentially to obtain core particles; wherein, according to the mass parts, the raw materials of the core glaze include 30-40 parts of periclase, 10-20 parts of magnesite, 5-12 parts of forsterite, 10-20 parts of spodumene, 15-25 parts of barium carbonate, 10-20 parts of quartz, 10-15 parts of dolomite, 5-8 parts of kaolin and 35-50 parts of water;

[0013] B2. The bridging material is atomized and pulse-sprayed onto the surface of the core particles in a fluidized state, so that a discontinuous bridging layer is formed on the surface of the core particles to obtain the first intermediate particles; wherein, the raw materials of the bridging material include glass frit powder, anhydrous ethanol and binder.

[0014] B3. The coating glaze is continuously sprayed onto the surface of the first intermediate particle, and after drying, a coating layer is formed on the surface of the bridging layer and the core particle to obtain the second intermediate particle; wherein, according to the mass parts, the raw materials of the coating glaze include 40-50 parts of α-alumina, 20-30 parts of zircon sand, 20-30 parts of corundum, 5-10 parts of aluminum magnesium spinel, 5-10 parts of kaolin and 5-10 parts of talc;

[0015] B4. After the second intermediate particles are calcined and vibrating sieve in sequence, the engraved dry particles are obtained;

[0016] C. Apply a protective glaze to the surface of the carved dry granule layer to obtain a protective glaze layer; wherein, calculated by mass parts, the raw materials of the protective glaze include 30-40 parts of potassium feldspar, 10-15 parts of quartz, 8-12 parts of washed kaolin, 5-10 parts of calcite, 3-8 parts of dolomite, 4-8 parts of nepheline powder, 6-10 parts of wollastonite, 5-15 parts of aluminum oxide and 3-7 parts of zinc oxide;

[0017] D. After drying, the product is calcined in a kiln and then polished to obtain a polished semi-finished product; wherein, the polished semi-finished product has holes, which are formed by the detachment of the carved dry particles;

[0018] E. Apply the nano anti-fouling solution to the surface of the polished semi-finished product, and after polishing with an ultra-clean polishing machine, generate an anti-fouling film layer in situ on the surface of the polished semi-finished product and the inner surface of the holes, thereby obtaining a non-slip glossy tile with anti-fouling properties; wherein, the raw materials of the nano anti-fouling solution include silica sol, heptadecafluorodecyltrimethoxysilane, hydrophobic silica, dispersant, propylene glycol methyl ether and water.

[0019] Further, in step B2, the raw materials of the glass frit powder, calculated by mass parts, include 40-50 parts of borax, 20-25 parts of quartz powder, 10-15 parts of zinc oxide, 8-12 parts of sodium carbonate, 3-5 parts of calcite, 2-4 parts of aluminum hydroxide, and 0-2 parts of zirconium oxide.

[0020] Further, in step B2, the mass of the bridging material is calculated as a percentage of the mass of the core glaze material, which is 50-80% of the mass of the core glaze material.

[0021] Further, step B3 includes:

[0022] B31. The coating glaze is continuously sprayed onto the surface of the first intermediate particle, and after drying, a coating base layer is formed on the surface of the bridging layer and the core particle.

[0023] B32. Repeat step B31 4 to 10 times to form an encapsulation layer.

[0024] Further, in step B, the particle size of the core particles is 80-150 μm, and the particle size of the etched dry particles is 100-200 μm.

[0025] Furthermore, in step B4, the calcination temperature is 900–950°C, and the calcination time is 10–15 min;

[0026] In step D, the calcination temperature is 1200–1230°C, and the calcination time is 20–25 min.

[0027] Further, step B involves spraying the engraved dry granules onto the surface of the base glaze layer using digital inkjet printing or screen printing to obtain an engraved dry granule layer, wherein the spraying amount of the engraved dry granules is 20–150 granules / cm². 2 .

[0028] Furthermore, in step C, the thickness of the protective glaze layer is 1.2 to 1.5 times the particle size of the engraved dry particles.

[0029] Further, in step E, the raw materials of the nano antifouling solution, calculated by mass parts, include 30-60 parts of silica sol, 1-5 parts of heptadecafluorodecyltrimethoxysilane, 0.5-3 parts of hydrophobic silica, 0.1-1 parts of dispersant, 5-15 parts of propylene glycol methyl ether, and 25-35 parts of water.

[0030] A non-slip glossy tile with anti-fouling properties is prepared using the above-mentioned preparation method for non-slip glossy tiles with anti-fouling properties. The non-slip glossy tile with anti-fouling properties has a gloss level >90°, a stain resistance level of 5, a dry static friction coefficient >0.70, and a wet static friction coefficient ≥0.60.

[0031] The technical solution provided by this invention may include the following beneficial effects:

[0032] 1. After pre-firing and glazing, the resulting carved dry particles, from the inside out, actually consist of a core particle and an outer layer. The bridging layer is distributed inside the outer layer, and the inner end of the bridging layer abuts against the outer end of the core particle. The coefficient of thermal expansion of the core particle is >10×10⁻⁶. -6 / ℃, the coefficient of thermal expansion of the coating layer is less than 5.5×10. -6 / ℃, the expansion coefficients of the two are vastly different.

[0033] 2. The core particles develop internal microcracks, causing them to break and pulverize, thus forming cavities within the carved dry particles. In the subsequent polishing process, the protective glaze layer is partially polished, exposing the carved dry particles. The vibration force can be effectively transmitted to the internal cavity structure of the carved dry particles through the intact and brittle coating layer. At the same time, thanks to the preferential fracture of the weak bonding interface between the coating layer and the glaze surface, the entire carved dry particle is loosened and detached, and almost all of the carved dry particles are detached, ultimately forming a microporous structure on the glaze surface.

[0034] 3. Inside the holes, the anti-fouling membrane layer covers the hole walls and bottom (i.e., the inner surface of the hole) in a thin layer, not completely filling the hole, thus retaining a slightly smaller microporous structure inside. Furthermore, the anti-fouling membrane layer can also cover the entire surface of the tile. Ultimately, the microporous structure retained within the holes increases the friction between the shoe sole and the tile surface, thus achieving an anti-slip effect; while the anti-fouling membrane layer covering the inner surface of the holes and the entire surface of the tile utilizes its own stain-resistant properties to ensure the tile's stain resistance. Detailed Implementation

[0035] This technical solution provides a method for preparing anti-slip glossy tiles with anti-fouling properties, including the following steps:

[0036] A. Apply the base glaze to the surface of the body layer to form the base glaze layer;

[0037] B. Spray the engraved dry granules onto the surface of the base glaze layer to obtain the engraved dry granule layer;

[0038] The method for preparing the engraved dry granules is as follows:

[0039] B1. The core glaze is dried and granulated sequentially to obtain core particles; wherein, according to the mass parts, the raw materials of the core glaze include 30-40 parts of periclase, 10-20 parts of magnesite, 5-12 parts of forsterite, 10-20 parts of spodumene, 15-25 parts of barium carbonate, 10-20 parts of quartz, 10-15 parts of dolomite, 5-8 parts of kaolin and 35-50 parts of water;

[0040] B2. The bridging material is atomized and pulse-sprayed onto the surface of the core particles in a fluidized state, so that a discontinuous bridging layer is formed on the surface of the core particles to obtain the first intermediate particles; wherein, the raw materials of the bridging material include glass frit powder, anhydrous ethanol and binder.

[0041] B3. The coating glaze is continuously sprayed onto the surface of the first intermediate particle, and after drying, a coating layer is formed on the surface of the bridging layer and the core particle to obtain the second intermediate particle; wherein, according to the mass parts, the raw materials of the coating glaze include 40-50 parts of α-alumina, 20-30 parts of zircon sand, 20-30 parts of corundum, 5-10 parts of aluminum magnesium spinel, 5-10 parts of kaolin and 5-10 parts of talc;

[0042] B4. After the second intermediate particles are calcined and vibrating sieve in sequence, the engraved dry particles are obtained;

[0043] C. Apply a protective glaze to the surface of the carved dry granule layer to obtain a protective glaze layer; wherein, calculated by mass parts, the raw materials of the protective glaze include 30-40 parts of potassium feldspar, 10-15 parts of quartz, 8-12 parts of washed kaolin, 5-10 parts of calcite, 3-8 parts of dolomite, 4-8 parts of nepheline powder, 6-10 parts of wollastonite, 5-15 parts of aluminum oxide and 3-7 parts of zinc oxide;

[0044] D. After drying, the product is calcined in a kiln and then polished to obtain a polished semi-finished product; wherein, the polished semi-finished product has holes, which are formed by the detachment of the carved dry particles;

[0045] E. Apply the nano anti-fouling solution to the surface of the polished semi-finished product, and after polishing with an ultra-clean polishing machine, generate an anti-fouling film layer in situ on the surface of the polished semi-finished product and the inner surface of the holes, thereby obtaining a non-slip glossy tile with anti-fouling properties; wherein, the raw materials of the nano anti-fouling solution include silica sol, heptadecafluorodecyltrimethoxysilane, hydrophobic silica, dispersant, propylene glycol methyl ether and water.

[0046] To address the technical challenge of existing glossy tiles simultaneously achieving a glossy finish, slip resistance, and stain resistance, this technical solution proposes a method for preparing slip-resistant glossy tiles with stain resistance. The method comprises five steps: A (applying a base glaze), B (spraying carved dry granules), C (applying a protective glaze), D (firing and polishing), and E (forming a stain-resistant film). Through innovative preparation methods, raw material formulations for the carved dry granules, and protective glaze formulations, this method achieves both excellent slip resistance and stain resistance while ensuring a glossy finish. It should be noted that the body layer in this technical solution is formed by pressing and drying conventional ceramic blanks, and the base glaze layer is formed by applying conventional base glazes. Further description of the ceramic blanks and base glazes is omitted here.

[0047] Specifically, the raw materials for the core glaze include periclase, magnesite, forsterite, spodumene, barium carbonate, quartz, dolomite, kaolin, and water. Among these, forsterite (Mg₂SiO₄) has a high coefficient of thermal expansion (approximately 13.5 × 10⁻⁶). -6Pernicopterus (at / ℃) undergoes solid-phase reaction and liquid-phase sintering at high temperature during step B4 (i.e., pre-firing) to form a multiphase ceramic structure with periclase as the main crystalline phase and forsterite as the stable auxiliary phase. This multiphase ceramic structure not only provides a high intrinsic physical expansion basis, but the presence of forsterite effectively suppresses abnormal grain growth and hydration tendency of the periclase phase, ensuring the continuity and thermal stability of the expansion framework at high temperatures, and providing a reliable carrier for subsequent expansion enhancement. Simultaneously, spodumene (LiAlSi2O5) decomposes during the pre-firing stage and provides active Li2O, kaolinite decomposes to introduce SiO2 and A2O3, and quartz introduces SiO2. That is, during the pre-firing stage, the components in the core glaze exist in a porous pre-sintered matrix as highly dispersed, highly reactive oxides, amorphous substances, or intermediates. Subsequently, during the later high-temperature stage (1150℃ and above) of the calcination (i.e., glaze firing) in step D, the aforementioned active components such as Li₂O, SiO₂, and A₂O₃ further react, promoting the formation of β-lithium nepheline (LiAlSiO₄) or related high-lithium silicate phases. When these lithium-containing crystalline phases pass through their specific phase transition temperature range during the cooling process after glaze firing, they undergo intense lattice contraction or structural transformation. This contraction process, macroscopically, manifests as a strong, reverse expansion stress source relative to the continuously thermally contracting matrix—namely, chemical expansion—which significantly increases the apparent average thermal expansion coefficient of the multiphase ceramic structure, resulting in an expansion coefficient of the core particles >10 × 10⁻⁶. -6 / ℃.

[0048] Furthermore, the raw materials for the coating glaze include α-alumina, zircon sand, corundum, aluminum-magnesium spinel, kaolin, and talc. Zircon sand decomposes at high temperatures to generate active SiO2 and ZrO2, which react with components in the system such as MgO (introduced by talc) and Al2O3 (introduced by kaolin) to form a continuous magnesium-aluminum silicate glass phase between the α-alumina grains. This glass phase itself has an extremely low coefficient of thermal expansion (as low as 4–5 × 10⁻⁶). -6 / ℃), and through encapsulation and bonding, it provides strong mechanical constraint on the highly expandable crystalline phase. Simultaneously, the main phases α-alumina and corundum provide skeletal strength and wear resistance, but their intrinsic high expansion (approximately 8.0 × 10⁻⁶ °C) results in significant mechanical constraint on the highly expandable crystalline phase. -6 The aluminum-magnesium spinel (α-alumina) is physically restrained by the surrounding continuous low-expansion glass phase when heated, preventing it from expanding freely and thus significantly reducing its effective contribution to the macroscopic expansion coefficient. Furthermore, the aluminum-magnesium spinel introduced into the formulation has a lower expansion coefficient than α-alumina. It can partially replace the higher-expansion α-alumina as the crystal phase framework, thereby reducing the overall average thermal expansion coefficient of the rigid crystal phase network. Based on this, combined with the strong constraint of the low-expansion glass phase, the two work synergistically to ultimately achieve an expansion coefficient of less than 5.5 × 10⁻⁶. -6 / ℃.

[0049] Meanwhile, the raw materials for the bridging material include glass frit powder, anhydrous ethanol, and a binder. The fluidized core particles refer to core particles placed in a fluidized bed reactor, through which an inert gas such as nitrogen is introduced, causing the core particles to be in a "boiling" fluidized state under the action of the gas flow. This ensures that each core particle has an equal opportunity to be exposed to the atomized bridging material formed after atomization. The atomized bridging material is then pulsedly sprayed onto the surface of the fluidized core particles, causing the solvent (anhydrous ethanol) in the atomized bridging material to evaporate rapidly after spraying onto the core particles, preventing the atomized bridging material from spreading or merging. Simultaneously, the binder firmly bonds the glass frit powder to the surface of the core particles, forming randomly distributed but unconnected micro-powder protrusions composed of glass frit powder and binder on the surface of the core particles.

[0050] Furthermore, the core function of the binder in this technical solution is to act as a temporary bonding medium, ensuring that the glass frit powder adheres to the surface of the core particles during the low-temperature stage. During the pre-firing and glazing processes, as the temperature rises, the glass frit powder melts first to form a liquid phase. At this point, although the binder begins to decompose, its bonding function is taken over by the molten glaze. Ultimately, the binder completely decomposes, carbonizes, and volatilizes during the pre-firing process, leaving no residue and detaching from the system. This ensures that the bridging layer formed by the glass frit powder fully melts, densifies, and forms a permanent glass phase structure at high temperatures. This glass phase structure adheres to the surface of the core particles in a dotted pattern. In other words, the bridging layer ultimately obtained in this application is essentially a glass phase formed by calcining the glass frit powder. Due to the limited chemical compatibility between this glass phase and the coating layer, and between the glass phase and the core particles, complete mutual dissolution and diffusion are impossible, resulting in weak interfacial bonding strength between the bridging layer and the coating layer, and between the bridging layer and the core particles.

[0051] In summary, after pre-firing and glazing, the sculpted dry particles obtained by this technical solution actually consist of a core particle and an encapsulation layer from the inside out. The bridging layer is distributed inside the encapsulation layer, and the inner end of the bridging layer abuts against the outer end of the core particle. The expansion coefficient of the core particle is >10×10⁻⁶. -6 / ℃, the coefficient of thermal expansion of the coating layer is less than 5.5×10. -6 / ℃, the expansion coefficients of the two are vastly different.

[0052] Secondly, during the high-temperature calcination stage in step B4, the magnesite (MgCO3) and barium carbonate (BaCO3) in the core glaze formulation can be thermally decomposed to release CO2 gas and form multi-scale pores inside the core particles. However, during the cooling process after calcination in step D, the significant thermal expansion mismatch between the core particles and the coating layer generates extremely high tensile stress within the core particles. The pre-existing pores act as stress concentration points, inducing and propagating numerous dispersed microcracks. The irreversible opening of these microcracks during cooling is recorded as an additional, nonlinear structural expansion increment in macroscopic thermal expansion measurements, thereby causing the core particles to crack and generate microcracks.

[0053] Furthermore, as described above, after calcination, the bridging layer material melts and forms a discontinuously distributed glassy interface region with relatively low bonding strength. This interface region forms weak mechanically weak zones with both the core particles and the encapsulation layer. During the cooling process after calcination in step D, the core particles exhibit a strong tendency to contract due to the large thermal expansion difference, but are tightly constrained by the rigid encapsulation layer, thus generating circumferential compressive stress within the encapsulation layer and extremely high radial and circumferential tensile stresses within the core particles. At this point, under the action of internal and external stresses, the weakest bridging layer glassy interface region among the carved dry particles reaches its shear strength limit first, resulting in nanoscale interfacial slip (i.e., relative slip between interfacial atoms) or microcrack initiation, locally releasing shear stress. Because the macroscopic structure of the encapsulation layer is intact and rigid, this local stress release does not lead to overall failure, but rather causes the stress to redistribute along the weak interfacial zones and further concentrate. Ultimately, these shear stresses, which cannot be completely dissipated through interface slip, change their transmission path and instead are directed and concentrated in the interior of the region with the least mechanical resistance (i.e., the core particles with existing pores and initial microcracks), thereby drastically aggravating the crack propagation and fragmentation inside the core.

[0054] Furthermore, the coating layer and the protective glaze layer cooperate through chemical inert interface and the introduction of weak stress by the coefficient of expansion to achieve a bonding interface with low bonding strength, which is mainly mechanical interlocking. This makes the bonding strength between the coating layer and the protective glaze layer weaker than that between the bridging layer and the coating layer. The specific principle of the bonding interface with low bonding strength between the coating layer and the protective glaze layer is as follows: (1) The protective glaze adopts a formula system with relatively high flux content and low alumina content, which makes the chemical potential matching degree between the glaze melt formed by calcination and the surface of the coating glaze poor. At the glaze firing temperature, the chemical compatibility between the protective glaze melt and the surface of the coating layer is poor, which makes the reaction kinetics slow and effectively inhibits the formation of strong chemical bonds between the two. This makes the bonding between the protective glaze layer and the coating layer mainly rely on the mechanical anchoring (physical interlocking) formed after the glaze melt penetrates into the surface micropores of the coating layer, rather than a strong chemically miscible layer. Meanwhile, although the glaze melt can quickly erode the surface of the main phase α-alumina in the glaze, the rapidly formed saturated and viscous aluminosilicate glass layer will hinder the subsequent deep reaction between the glaze melt and the coating layer, thereby suppressing the interfacial reaction to a very low level and further weakening the chemical bonding strength; (2) The protective glaze generates a low-expansion aluminosilicate glass network through the reaction of quartz, alumina and nepheline in its formula, and directly contributes with wollastonite as a low-expansion crystalline phase, supplemented by the CaO stabilizing crystalline phase provided by calcite, thereby adjusting the thermal expansion coefficient of the protective glaze layer obtained by calcination to the target range (approximately 4.5~5.2×10). -6 The coefficient of thermal expansion (°C) is slightly lower than that of the coating layer. During cooling, the difference in the coefficients of thermal expansion between the coating layer and the protective glaze layer causes a shrinkage difference between them. This shrinkage difference generates a weak tensile stress at the interface, which offsets part of the physical bonding force, keeping the overall interface strength at a low level.

[0055] Furthermore, the main crystalline phase α-alumina and the zircon oxide generated from the decomposition of zircon sand in the coating glaze are both brittle materials with high hardness and low toughness; the bonding phase is composed of magnesium aluminosilicate glass formed by talc and other materials, which also exhibits brittleness. Therefore, the coating layer as a whole is a composite of brittle crystalline and brittle glass phases, which is prone to elastic deformation and brittle fracture when subjected to impact. This makes the coating layer a complete force conductor, effectively transmitting the vibration force generated by the polishing head during the external polishing process to the interior.

[0056] In summary, the internal microcracks in the core particles cause them to break down and pulverize, thus forming cavities within the carved dry particles. During the subsequent polishing process, the protective glaze layer is partially polished, exposing the carved dry particles. The vibration force can be effectively transmitted to the internal cavity structure of the carved dry particles through the intact yet brittle coating. Simultaneously, thanks to the preferential fracture at the weak interface between the coating layer and the glaze surface, the entire carved dry particle is loosened and detached, with almost all of the particles falling off, ultimately forming a microporous structure on the glaze surface.

[0057] It should be noted that the coating layer in this technical solution can protect the core particles and achieve time-series control. The specific principle is as follows: In the early stage of glaze firing (<1150℃), the coating layer mainly acts as an isolation shield. Due to the inherent high refractoriness and chemical inertness of its main raw materials (α-alumina, zircon sand), and the initial dense structure formed by the small amount of liquid phase bonding generated by kaolin, talc, etc. during the dry particle preparation stage, the coating layer can effectively block the penetration of the external glaze melt and its alkaline ions, preventing the highly reactive components in the core particles (such as Li2O produced by the decomposition of spodumene) from reacting prematurely with the glaze melt, thereby ensuring that the reaction process of the core layer is not disturbed, creating conditions for the concentrated triggering of subsequent functions. Entering the high-temperature stage of the later stage of glaze firing (1150℃ and above), the role of the coating layer evolves into a pressure vessel and thermodynamic confinement. At this time, the coating layer further densifies at high temperatures, and its low chemical compatibility and poor wettability with the glaze melt still exist, continuously providing chemical isolation. Simultaneously, the outer shell layer serves as a channel to uniformly introduce external heat into the interior of the carved dry particles. During the high-temperature stage of the later glaze firing, the energy accumulated inside the carved dry particles is sufficient to cause the active components Li2O, SiO2, and A2O3 in the core glaze to react and generate β-lithium nepheline (LiAlSiO4) or related high-lithium silicate phases. Meanwhile, the barium carbonate in the core glaze continues to decompose and release CO2 gas (i.e., gas generation reaction), increasing the internal pressure. The generated BaO enters the glass phase or forms a barium-containing crystalline phase, and its high coefficient of thermal expansion also contributes to secondary expansion. During the cooling process after glaze firing, a significant internal stress field is established between the fully densified, robust outer shell layer and the core particles due to the huge difference in the coefficient of thermal expansion. The above-mentioned constraint protects the expansion and gas generation reaction of the core layer within the confined space formed by the outer shell layer, allowing the accumulated energy to be concentrated and released violently during the preset high-temperature period, thereby driving the generation of internal microcracks and ensuring that the reactions of each raw material occur precisely according to the designed sequence.

[0058] Finally, the nano-antifouling solution is applied to the surface of the polished semi-finished product. During application, the nano-antifouling solution can not only rapidly penetrate and spread along the pore walls of the holes through capillary action, but also evenly wet and spread along the surface of the polished semi-finished product. Subsequently, during the ultra-bright polishing process, the frictional heat generated causes the water and propylene glycol methyl ether in the antifouling solution to evaporate, allowing its effective components (including silica sol, heptadecafluorodecyltrimethoxysilane, hydrophobic silica, and dispersant) to undergo a cross-linking and curing reaction at high temperature to form an antifouling film layer.

[0059] Inside the holes, a thin layer of anti-fouling membrane covers the hole walls and bottom (i.e., the inner surface of the hole), not completely filling it, thus preserving a slightly smaller microporous structure inside. Alternatively, the anti-fouling membrane can cover the entire surface of the tile. Ultimately, the microporous structure preserved within the holes increases the friction between the shoe sole and the tile surface, thus achieving an anti-slip effect; while the anti-fouling membrane covering the inner surface of the holes and the entire surface of the tile utilizes its own stain-resistant properties to ensure the tile's stain resistance.

[0060] Furthermore, if the carved dry granules are directly added to the protective glaze for integral ball milling, the granules will be further broken down during the process. These broken granules, as a high-melting-point heterogeneous component, increase the overall initial melting temperature and firing temperature of the protective glaze, increasing the risk of underfiring. Underfiring of the protective glaze easily leads to the absorption of large amounts of liquid components (such as water) from the antifouling solution, resulting in a loose and discontinuous antifouling film due to insufficient material, significantly reducing its antifouling performance. Therefore, this solution employs a separate spraying technique for the carved dry granules and the protective glaze, fundamentally eliminating the interference of the carved dry granules on the sintering temperature of the protective glaze and ensuring stable and reliable antifouling performance.

[0061] It should be noted that the antifouling principle of the antifouling membrane is as follows: The raw materials of the nano-antifouling solution in this technical solution include silica sol, heptadecafluorodecyltrimethoxysilane, hydrophobic silica, dispersant, propylene glycol methyl ether, and water. Among them, the nano-silica particles in the silica sol and the hydrophobic silica particles are uniformly dispersed in the system under the action of the dispersant, forming a high-surface-area nanoparticle dispersion phase. Heptadecafluorodecyltrimethoxysilane hydrolyzes in an aqueous environment to generate silanol. Its silanol groups undergo a condensation reaction with the silanol groups on the surface of the silica sol and hydrophobic silica, forming a three-dimensional inorganic network framework mainly composed of silicon-oxygen bonds (Si-O-Si). Long-chain fluorocarbon groups are then grafted onto the inorganic network framework through chemical bonds. During the film formation process, the perfluoroalkyl segments grafted onto the inorganic network framework, due to their extremely low surface energy, spontaneously migrate and accumulate towards the film-air interface, forming a dense, low-surface-energy outer layer. Hydrophobic silica particles are fixed within the network framework through both physical intercalation and chemical bonding, further constructing a micro-nano composite rough structure on the surface. Propylene glycol methyl ether, as a film-forming aid, works with water to regulate the evaporation gradient, promoting uniform and dense film formation. The final antifouling film is an organic-inorganic hybrid coating with a chemically bonded inorganic silica network as its framework, a surface enriched with perfluoroalkyl segments, and a micro-nano rough structure. This structure combines a low surface energy effect with a lotus leaf-inspired roughness effect, synergistically endowing the glaze with excellent hydrophobic, oleophobic, and antifouling properties.

[0062] This technical solution achieves high gloss through the following principle: Based on the protective glaze formulation design, the formula possesses low viscosity and high fluidity. During firing, the protective glaze forms an extremely smooth macroscopic glassy substrate due to surface tension, thereby minimizing diffuse light reflection caused by surface undulations and laying the foundation for high gloss. Simultaneously, during the polishing process of the nano-antifouling solution, the thermo-mechanical coupling effect of mechanical polishing allows the nano-antifouling solution to fully flow and fill residual microscopic scratches and pores on the protective glaze surface. Subsequently, the nano-silica particles (typically 5-100 nm in diameter) in the silica sol (derived from the nano-antifouling solution) can tightly aggregate and undergo a condensation reaction after solvent evaporation, resulting in a dense, smooth, and transparent network structure forming in situ at glaze surface defects. This network structure fills the microscopic pores and scratches on the glaze surface, reducing the microscopic roughness to the nanoscale, making its surface highly smooth on an optical scale. When light shines on it, the aforementioned high flatness produces specular reflection rather than diffuse reflection, thus significantly enhancing the surface gloss and creating a bright effect.

[0063] It should be noted that vibrating screening refers to placing the calcined dry granules obtained after calcining the second intermediate particles on a 200-300 mesh screen and applying vibration at a frequency of 100-200Hz, so that the agglomerated calcined dry granules roll and collide on the screen, naturally deagglomerate and pass through the screen to obtain carved dry granules.

[0064] Preferably, in step B1, the core glaze material, calculated by mass percentage, passes through a 325-mesh sieve, with a residue of 0.5% to 1.0%.

[0065] Preferably, in step B2, the raw materials of the bridging material, calculated by mass parts, include 7-10 parts of glass frit powder, 3-5 parts of binder, and 85-90 parts of anhydrous ethanol.

[0066] This technical solution, by limiting the anhydrous ethanol content in the bridging material to 85-90 parts, facilitates rapid and controllable drying and the formation of a discontinuous "dot-like" encapsulation structure. The extremely low boiling point and surface tension of anhydrous ethanol allow the atomized bridging material to evaporate instantly upon contact with the fluidized core particles, quickly "freezing" the glass frit powder and binder at the initial collision point, effectively preventing them from spreading and forming a continuous liquid film. This rapid shaping capability, combined with the moderate solid content provided by 7-10 parts glass frit powder and 3-5 parts binder, ensures the formation of uniformly distributed, isolated, and firmly bonded isolated "bridging points" on the surface of the core particles. This lays a crucial foundation for the subsequent pre-firing to form a discontinuous, weak interface structure, while simultaneously avoiding process defects that may result from solvent residue.

[0067] Preferably, in step B2, the adhesive is either a polyvinyl butyral aqueous solution or a polyvinyl alcohol aqueous solution, and the polyvinyl butyral content in the polyvinyl butyral aqueous solution is 10-20% by mass percentage, and the polyvinyl alcohol content in the polyvinyl alcohol aqueous solution is 10-20%.

[0068] Preferably, in step B2, the single spraying time in the pulse spraying is 0.5 to 1 second, and the time interval between two adjacent sprays is 0.5 to 1 second.

[0069] To further explain, in step B2, the raw materials of the glass frit powder, calculated by mass parts, include 40-50 parts of borax, 20-25 parts of quartz powder, 10-15 parts of zinc oxide, 8-12 parts of sodium carbonate, 3-5 parts of calcite, 2-4 parts of aluminum hydroxide, and 0-2 parts of zirconium oxide.

[0070] This technical solution optimizes the formulation of the glass frit powder, employing a low-temperature glass frit formulation primarily composed of borax (introducing B2O3) and sodium carbonate (introducing Na2O). B2O3 forms the framework for the low-temperature glass network, while Na2O acts as a strong network modifier. Together, they lower the softening point of the glass frit powder to approximately 800°C, ensuring preferential melting at the calcination temperature in step B4. The addition of zinc oxide (ZnO) further reduces the high-temperature viscosity and improves the wettability of the melt on the core particle surface, allowing the melt to adhere to the core particles. Simultaneously, the introduction of aluminum hydroxide (Al2O3) and calcite (CaO) enhances the structural stability and chemical durability of the glass network, preventing deliquescence or excessive reaction during storage and the calcination stage in step B4. Furthermore, during pre-firing, the powder bumps melt, forming isolated glassy "bridging points" under the wetting effect promoted by ZnO. In addition, during the final glaze firing, this bridging layer completely melts and forms a glassy phase. However, because Al2O3 in the glass frit powder formulation enhances the chemical stability of the glass network, it limits the chemical compatibility between the glass phase and the coating layer, as well as between the glass frit powder and the core particles. This prevents complete miscibility and diffusion, resulting in weak interfacial bonding between the bridging layer and the coating layer, and between the bridging layer and the core particles. This weak interface cannot compensate for the significant thermal expansion mismatch between the core particles and the coating layer. Stress generated during cooling concentrates here, causing stress to propagate into the core particles and induce microcracks. This method, which achieves specific melting characteristics and interfacial properties through raw material composition design and combines this with a discontinuous structure to create a weak interface, precisely controls the stress release path. This helps ensure that the carved dry particles detach completely during subsequent polishing, preventing the formation of pores.

[0071] To further explain, in step B2, the mass of the bridging material is calculated as a percentage of the mass of the core glaze material, which is 50-80% of the mass of the core glaze material.

[0072] If the mass of the bridging material is less than 50% of the mass of the core glaze, the amount of bridging material used is too low. During pulse spraying, the trace amount of bridging material will not easily form a sufficient number of dimensionally stable powder protrusions on the surface of the core particles. This results in too few adhesion points between the core particles and the coating layer, which not only reduces the strength of the bridging layer but also makes the adhesion points too low and easy to melt flat, affecting the performance of the bridging layer. If the mass of the bridging material is more than 80% of the mass of the core glaze, the amount of bridging material used is too high. The bridging material will easily accumulate and fuse on the surface of the core particles and tend to spread during pre-firing, evolving from "discrete points" to "quasi-continuous films," affecting the performance of engraved dry particles.

[0073] To further explain, step B3 includes:

[0074] B31. The coating glaze is continuously sprayed onto the surface of the first intermediate particle, and after drying, a coating base layer is formed on the surface of the bridging layer and the core particle.

[0075] B32. Repeat step B31 4 to 10 times to form an encapsulation layer.

[0076] This technical solution uses 4 to 10 sprays to construct the coating layer, which helps to avoid the problems of glaze dripping, uneven thickness, or drying cracking caused by a single thick coating. It ensures that the uniformity, density, and thickness of the coating layer are precisely controllable, providing reliable thermodynamic protection and stable low expansion performance for subsequent firing.

[0077] To further explain, in step B, the particle size of the core particles is 80–150 μm, and the particle size of the etched dry particles is 100–200 μm.

[0078] If the core particles are too small, they are easily carried away by the airflow, which is not conducive to the spraying of bridging material; if the core particles are too large, the fluidization state is unstable, which is also not conducive to the spraying of bridging material.

[0079] Furthermore, if the particle size of the carving granules is too large, the holes formed after the granules fall off will be too large and too obvious, affecting the decorative effect; if the particle size of the carving granules is too small, the holes formed after the granules fall off will be too small, resulting in limited effect on increasing the friction between the shoe sole and the brick surface, which may affect the anti-slip function.

[0080] To further explain, in step B4, the calcination temperature is 900–950°C, and the calcination time is 10–15 min;

[0081] In step D, the calcination temperature is 1200–1230°C, and the calcination time is 20–25 min.

[0082] This technical solution, by limiting the calcination temperature and calcination time in steps B4 and D, helps to ensure the gloss effect, anti-slip performance, and stain resistance of the final calcined ceramic tile.

[0083] Further explanation: Step B involves spraying engraved dry granules onto the surface of the base glaze layer using digital inkjet printing or screen printing to obtain an engraved dry granule layer, wherein the spraying amount of the engraved dry granules is 20–150 granules / cm². 2 .

[0084] Using digital inkjet printing or screen printing instead of traditional mixed spraying or random spraying can achieve patterning of engraved dry granules, thereby improving the decorative effect.

[0085] Furthermore, if the spraying amount of sculpted dry granules is too low, there will be too few effective friction points per unit area, making it difficult to form a continuous and reliable water film disruption zone on the tile surface (especially in a wet state). This results in a small actual contact area between the shoe sole and the tile surface, leading to insufficient mechanical interlocking and low friction, significantly increasing the risk of slipping. If the spraying amount of sculpted dry granules is too high, the high-density pores will give the tile surface a sandy or frosted feel, deviating from the smooth, mirror-like texture that high-end tiles should have, thus affecting the product's grade.

[0086] To further explain, in step C, the thickness of the protective glaze layer is 1.2 to 1.5 times the particle size of the engraved dry particles.

[0087] By limiting the thickness of the protective oil layer, it is beneficial to ensure that the carved dry particles are completely immersed in the protective glaze layer while reducing the amount of protective glaze applied and saving costs. This allows for a uniform temperature field and stable atmosphere during glaze firing, and provides sufficient medium for the formation of a weak interface between the coating layer of the carved dry particles and the protective glaze layer.

[0088] To further explain, in step E, the raw materials of the nano antifouling solution, calculated by mass parts, include 30-60 parts of silica sol, 1-5 parts of heptadecafluorodecyltrimethoxysilane, 0.5-3 parts of hydrophobic silica, 0.1-1 parts of dispersant, 5-15 parts of propylene glycol methyl ether, and 25-35 parts of water.

[0089] This technical solution optimizes the formulation of the nano-antifouling solution, which helps ensure its performance. It should be noted that the dispersant can be sodium polyacrylate or ammonium polyacrylate; the specific type is not limited here. The hydrophobic silica can be hydrophobic HB-132 or hydrophobic HB-139 from Hubei Huifu Nanomaterials Co., Ltd., etc.; the specific manufacturer and type are not limited here.

[0090] A non-slip glossy tile with anti-fouling properties is prepared using the above-mentioned preparation method for non-slip glossy tiles with anti-fouling properties. The non-slip glossy tile with anti-fouling properties has a gloss level >90°, a stain resistance level of 5, a dry static friction coefficient >0.70, and a wet static friction coefficient ≥0.60.

[0091] This technical solution also proposes a non-slip glossy tile with anti-fouling properties prepared by the above-mentioned method for preparing non-slip glossy tiles with anti-fouling properties. The tile has a gloss level > 90°, a stain resistance level of 5, a dry static friction coefficient > 0.70, and a wet static friction coefficient ≥ 0.60. This is beneficial to ensure both gloss and good anti-slip and anti-fouling properties.

[0092] The technical solution of the present invention will be further illustrated below through specific embodiments.

[0093] Performance testing:

[0094] Gloss: The gloss of the ceramic tile was tested using an LS191 ceramic gloss meter, and the test was performed in parallel 5 times. The average value of the 5 tests was taken.

[0095] Stain resistance: According to the test method of GB / T3810.14-2016 "Test Methods for Ceramic Tiles Part 14: Determination of Stain Resistance - Building Materials Standard", the stain resistance of the glaze of the product is tested using a green dye in light oil as the staining agent. A stain resistance level of 5 is considered qualified.

[0096] Coefficient of friction: The coefficient of friction of ceramic tiles is tested according to GB / T 4100-2015 "Ceramic Tiles" (Appendix M).

[0097] Example 1

[0098] A. Apply the base glaze to the surface of the body layer to form the base glaze layer;

[0099] B. Using digital inkjet printing, engraved dry granules are sprayed onto the surface of the base glaze layer to obtain an engraved dry granule layer, with a spraying density of 50 granules / cm². 2 ;

[0100] The method for preparing the engraved dry granules is as follows:

[0101] B1. The core glaze is dried and granulated sequentially to obtain core particles with a particle size of 120μm; wherein, according to the mass parts, the raw materials of the core glaze include 35 parts of periclase, 15 parts of magnesite, 8 parts of forsterite, 15 parts of spodumene, 20 parts of barium carbonate, 15 parts of quartz, 12 parts of dolomite, 6 parts of kaolin and 40 parts of water.

[0102] B2. The bridging material is atomized and pulse-sprayed (single spray time is 0.5s, and the time interval between two adjacent sprays is 0.5s) onto the surface of the fluidized core particles, so that a discontinuous bridging layer is formed on the surface of the core particles, resulting in the first intermediate particles; wherein, calculated by mass percentage, the mass of the bridging material is 60% of the mass of the core glaze; calculated by mass percentage, the bridging material includes 8 parts of glass frit powder, 4 parts of binder, and 88 parts of anhydrous ethanol; calculated by mass percentage, the raw materials of the glass frit powder include 45 parts of borax, 23 parts of quartz powder, 12 parts of zinc oxide, 10 parts of sodium carbonate, 4 parts of calcite, 3 parts of aluminum hydroxide, and 1 part of zirconium oxide; the binder is a polyvinyl butyral aqueous solution, and calculated by mass percentage, the polyvinyl butyral content in the polyvinyl butyral aqueous solution is 15%;

[0103] B3. The coating glaze is continuously sprayed onto the surface of the first intermediate particle. After drying, a coating base layer is formed on the surface of the bridging layer and the core particle. The step of forming the coating base layer is repeated 5 times to form a coating layer, resulting in the second intermediate particle. The raw materials of the coating glaze, calculated by mass, include 45 parts of α-alumina, 25 parts of zircon sand, 25 parts of corundum, 8 parts of aluminum magnesium spinel, 8 parts of kaolin, and 7 parts of talc.

[0104] B4. The second intermediate particles were calcined and vibrated and sieved in sequence to obtain engraved dry particles with a particle size of 150 μm; the calcination temperature was 950℃ and the calcination time was 12 min.

[0105] C. Apply a protective glaze to the surface of the carved dry granule layer to obtain a protective glaze layer with a thickness of 1.2 times the particle size of the carved dry granules; wherein, according to the mass parts, the raw materials of the protective glaze include 35 parts potassium feldspar, 12 parts quartz, 10 parts washed kaolin, 8 parts calcite, 5 parts dolomite, 6 parts nepheline powder, 8 parts wollastonite, 10 parts aluminum oxide and 5 parts zinc oxide.

[0106] D. After drying, the product is calcined in a kiln and then polished to obtain a polished semi-finished product; wherein, the polished semi-finished product has holes, which are formed by the detachment of the carved dry particles; the calcination temperature is 1230℃ and the calcination time is 20min;

[0107] E. Apply the nano anti-fouling solution to the surface of the polished semi-finished product, and then use an ultra-clean polishing machine to grind it, forming an anti-fouling film layer in situ on the surface of the polished semi-finished product and the inner surface of the holes, thus obtaining a non-slip glossy tile with anti-fouling properties; wherein, calculated by mass parts, the raw materials of the nano anti-fouling solution include 45 parts of silica sol, 3 parts of heptadecafluorodecyltrimethoxysilane, 2 parts of hydrophobic silica, 0.5 parts of sodium polyacrylate, 10 parts of propylene glycol methyl ether, and 30 parts of water; the hydrophobic silica is hydrophobic HB-139 from Hubei Huifu Nanomaterials Co., Ltd.

[0108] Example 2

[0109] A. Apply the base glaze to the surface of the body layer to form the base glaze layer;

[0110] B. Using screen printing, sculpted dry granules are sprayed onto the surface of the base glaze layer to obtain a sculpted dry granule layer, with a spraying density of 80 granules / cm². 2 ;

[0111] The method for preparing the engraved dry granules is as follows:

[0112] B1. The core glaze is dried and granulated sequentially to obtain core particles with a particle size of 80μm; wherein, according to the mass parts, the raw materials of the core glaze include 30 parts of periclase, 20 parts of magnesite, 12 parts of forsterite, 10 parts of spodumene, 25 parts of barium carbonate, 18 parts of quartz, 10 parts of dolomite, 8 parts of kaolin and 35 parts of water.

[0113] B2. The bridging material is atomized and pulse-sprayed (single spray time is 1s, and the time interval between two adjacent sprays is 1s) onto the surface of the fluidized core particles, so that a discontinuous bridging layer is formed on the surface of the core particles, resulting in the first intermediate particles; wherein, calculated by mass percentage, the mass of the bridging material is 70% of the mass of the core glaze; calculated by mass percentage, the bridging material includes 7 parts of glass frit powder, 5 parts of binder, and 88 parts of anhydrous ethanol; calculated by mass percentage, the raw materials of the glass frit powder include 50 parts of borax, 20 parts of quartz powder, 10 parts of zinc oxide, 12 parts of sodium carbonate, 3 parts of calcite, 2 parts of aluminum hydroxide, and 2 parts of zirconium oxide; the binder is any one of the polyvinyl alcohol aqueous solution, and calculated by mass percentage, the polyvinyl alcohol content in the polyvinyl alcohol aqueous solution is 10%;

[0114] B3. The coating glaze is continuously sprayed onto the surface of the first intermediate particle. After drying, a coating base layer is formed on the surface of the bridging layer and the core particle. The step of forming the coating base layer is repeated 4 times to form a coating layer, resulting in the second intermediate particle. The raw materials of the coating glaze, calculated by mass, include 40 parts of α-alumina, 30 parts of zircon sand, 30 parts of corundum, 10 parts of aluminum magnesium spinel, 5 parts of kaolin, and 6 parts of talc.

[0115] B4. The second intermediate particles were calcined and vibrating sieved sequentially to obtain engraved dry particles with a particle size of 100 μm; the calcination temperature was 900℃ and the calcination time was 15 min.

[0116] C. Apply a protective glaze to the surface of the carved dry granule layer to obtain a protective glaze layer with a thickness of 1.3 times the particle size of the carved dry granules; wherein, according to the mass parts, the raw materials of the protective glaze include 30 parts potassium feldspar, 15 parts quartz, 12 parts washed kaolin, 10 parts calcite, 8 parts dolomite, 4 parts nepheline powder, 10 parts wollastonite, 5 parts aluminum oxide and 7 parts zinc oxide.

[0117] D. After drying, the product is calcined in a kiln and then polished to obtain a polished semi-finished product; wherein, the polished semi-finished product has holes, which are formed by the detachment of the carved dry particles; the calcination temperature is 1220℃ and the calcination time is 20min;

[0118] E. Apply the nano anti-fouling solution to the surface of the polished semi-finished product, and then use an ultra-clean polishing machine to grind it, forming an anti-fouling film layer in situ on the surface of the polished semi-finished product and the inner surface of the holes, thus obtaining a non-slip glossy tile with anti-fouling properties; wherein, calculated by mass parts, the raw materials of the nano anti-fouling solution include 40 parts of silica sol, 5 parts of heptadecafluorodecyltrimethoxysilane, 3 parts of hydrophobic silica, 1 part of ammonium polyacrylate, 15 parts of propylene glycol methyl ether and 25 parts of water; the hydrophobic silica is hydrophobic HB-132 from Hubei Huifu Nanomaterials Co., Ltd.

[0119] Example 3

[0120] A. Apply the base glaze to the surface of the body layer to form the base glaze layer;

[0121] B. Using digital inkjet printing, engraved dry granules are sprayed onto the surface of the base glaze layer to obtain an engraved dry granule layer, with a spraying density of 100 granules / cm². 2 ;

[0122] The method for preparing the engraved dry granules is as follows:

[0123] B1. The core glaze is dried and granulated sequentially to obtain core particles with a particle size of 150μm; wherein, according to the mass parts, the raw materials of the core glaze include 40 parts of periclase, 10 parts of magnesite, 5 parts of forsterite, 20 parts of spodumene, 15 parts of barium carbonate, 10 parts of quartz, 15 parts of dolomite, 5 parts of kaolin and 50 parts of water.

[0124] B2. The bridging material is atomized and pulse-sprayed (single spray time is 0.8s, and the time interval between two adjacent sprays is 0.8s) onto the surface of the fluidized core particles, so that a discontinuous bridging layer is formed on the surface of the core particles, resulting in the first intermediate particles; wherein, calculated by mass percentage, the mass of the bridging material is 60% of the mass of the core glaze; calculated by mass percentage, the bridging material includes 10 parts of glass frit powder, 3 parts of binder, and 87 parts of anhydrous ethanol; calculated by mass percentage, the raw materials of the glass frit powder include 40 parts of borax, 25 parts of quartz powder, 15 parts of zinc oxide, 8 parts of sodium carbonate, 5 parts of calcite, 4 parts of aluminum hydroxide, and 2 parts of zirconium oxide; the binder is a polyvinyl butyral aqueous solution, and calculated by mass percentage, the polyvinyl butyral content in the polyvinyl butyral aqueous solution is 20%;

[0125] B3. The coating glaze is continuously sprayed onto the surface of the first intermediate particle. After drying, a coating base layer is formed on the surface of the bridging layer and the core particle. The step of forming the coating base layer is repeated 8 times to form a coating layer, resulting in the second intermediate particle. The raw materials of the coating glaze, calculated by mass, include 50 parts of α-alumina, 20 parts of zircon sand, 20 parts of corundum, 5 parts of aluminum magnesium spinel, 10 parts of kaolin, and 9 parts of talc.

[0126] B4. The second intermediate particles were calcined and vibrating sieved sequentially to obtain engraved dry particles with a particle size of 180 μm; the calcination temperature was 950℃ and the calcination time was 10 min.

[0127] C. Apply a protective glaze to the surface of the carved dry granule layer to obtain a protective glaze layer with a thickness of 1.2 to 1.5 times the particle size of the carved dry granules; wherein, according to the mass parts, the raw materials of the protective glaze include 40 parts potassium feldspar, 10 parts quartz, 8 parts washed kaolin, 5 parts calcite, 3 parts dolomite, 8 parts nepheline powder, 6 parts wollastonite, 15 parts aluminum oxide and 3 parts zinc oxide.

[0128] D. After drying, the product is calcined in a kiln and then polished to obtain a polished semi-finished product; wherein, the polished semi-finished product has holes, which are formed by the detachment of the carved dry particles; the calcination temperature is 1220℃ and the calcination time is 23min;

[0129] E. Apply the nano anti-fouling solution to the surface of the polished semi-finished product, and then use an ultra-clean polishing machine to grind it, forming an anti-fouling film layer in situ on the surface of the polished semi-finished product and the inner surface of the holes, thus obtaining a non-slip glossy tile with anti-fouling properties; wherein, according to the mass parts, the raw materials of the nano anti-fouling solution include 55 parts of silica sol, 2 parts of heptadecafluorodecyltrimethoxysilane, 1 part of hydrophobic silica, 1 part of sodium polyacrylate, 12 parts of propylene glycol methyl ether and 25 parts of water; the hydrophobic silica is hydrophobic HB-132 from Hubei Huifu Nanomaterials Co., Ltd.

[0130] Comparative Example 1

[0131] The preparation method and raw materials of this comparative example are the same as those of Example 3, except that step E is missing in this comparative example.

[0132] The anti-slip glossy tiles prepared in the examples and comparative examples were subjected to conventional tests in the field of architectural ceramics for anti-slip, anti-fouling performance, and gloss. The results are shown in Table 1 below:

[0133] Table 1. Performance test results of anti-slip glossy bricks in the examples and comparative examples.

[0134]

[0135] As can be seen from the test data in Table 1, the tiles obtained by this technical solution have a gloss level >90°, a stain resistance level of 5, a dry static friction coefficient >0.70, and a wet static friction coefficient ≥0.60. This is beneficial to ensure good anti-slip and anti-stain properties while maintaining a glossy effect, so as to meet the actual use needs.

[0136] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are merely for explaining the principles of the invention and should not be construed as limiting the scope of protection of the invention in any way. Based on this explanation, those skilled in the art can readily conceive of other specific embodiments of the invention without inventive effort, and these embodiments will all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a non-slip glossy tile with anti-fouling properties, characterized in that, Includes the following steps: A. Apply the base glaze to the surface of the body layer to form the base glaze layer; B. Spray the engraved dry granules onto the surface of the base glaze layer to obtain the engraved dry granule layer; The method for preparing the engraved dry granules is as follows: B1. The core glaze is dried and granulated sequentially to obtain core particles; wherein, according to the mass parts, the raw materials of the core glaze include 30-40 parts of periclase, 10-20 parts of magnesite, 5-12 parts of forsterite, 10-20 parts of spodumene, 15-25 parts of barium carbonate, 10-20 parts of quartz, 10-15 parts of dolomite, 5-8 parts of kaolin and 35-50 parts of water; B2. The bridging material is atomized and pulse-sprayed onto the surface of the core particles in a fluidized state, so that a discontinuous bridging layer is formed on the surface of the core particles to obtain the first intermediate particles; wherein, the raw materials of the bridging material include glass frit powder, anhydrous ethanol and binder. B3. The coating glaze is continuously sprayed onto the surface of the first intermediate particle, and after drying, a coating layer is formed on the surface of the bridging layer and the core particle to obtain the second intermediate particle; wherein, according to the mass parts, the raw materials of the coating glaze include 40-50 parts of α-alumina, 20-30 parts of zircon sand, 20-30 parts of corundum, 5-10 parts of aluminum magnesium spinel, 5-10 parts of kaolin and 5-10 parts of talc; B4. After the second intermediate particles are calcined and vibrating sieve in sequence, the engraved dry particles are obtained; C. Apply a protective glaze to the surface of the carved dry granule layer to obtain a protective glaze layer; wherein, calculated by mass parts, the raw materials of the protective glaze include 30-40 parts of potassium feldspar, 10-15 parts of quartz, 8-12 parts of washed kaolin, 5-10 parts of calcite, 3-8 parts of dolomite, 4-8 parts of nepheline powder, 6-10 parts of wollastonite, 5-15 parts of aluminum oxide and 3-7 parts of zinc oxide; D. After drying, the product is calcined in a kiln and then polished to obtain a polished semi-finished product; wherein, the polished semi-finished product has holes, which are formed by the detachment of the carved dry particles; E. Apply the nano anti-fouling solution to the surface of the polished semi-finished product, and after polishing with an ultra-clean polishing machine, generate an anti-fouling film layer in situ on the surface of the polished semi-finished product and the inner surface of the holes, thereby obtaining a non-slip glossy tile with anti-fouling properties; wherein, the raw materials of the nano anti-fouling solution include silica sol, heptadecafluorodecyltrimethoxysilane, hydrophobic silica, dispersant, propylene glycol methyl ether and water.

2. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, In step B2, the raw materials of the glass frit powder, calculated by mass parts, include 40-50 parts of borax, 20-25 parts of quartz powder, 10-15 parts of zinc oxide, 8-12 parts of sodium carbonate, 3-5 parts of calcite, 2-4 parts of aluminum hydroxide, and 0-2 parts of zirconium oxide.

3. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, In step B2, the mass of the bridging material is calculated as a percentage of the mass of the core glaze, which is 50-80% of the mass of the core glaze.

4. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, Step B3 includes: B31. The coating glaze is continuously sprayed onto the surface of the first intermediate particle, and after drying, a coating base layer is formed on the surface of the bridging layer and the core particle. B32. Repeat step B31 4 to 10 times to form an encapsulation layer.

5. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, In step B, the particle size of the core particles is 80–150 μm, and the particle size of the etched dry particles is 100–200 μm.

6. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, In step B4, the calcination temperature is 900–950°C, and the calcination time is 10–15 min; In step D, the calcination temperature is 1200–1230°C, and the calcination time is 20–25 min.

7. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, Step B involves spraying etched dry granules onto the surface of the base glaze layer using digital inkjet printing or screen printing to obtain an etched dry granule layer, wherein the spraying amount of the etched dry granules is 20–150 granules / cm². 2 .

8. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, In step C, the thickness of the protective glaze layer is 1.2 to 1.5 times the particle size of the engraved dry particles.

9. The method for preparing a non-slip glossy tile with anti-fouling properties according to claim 1, characterized in that, In step E, the raw materials of the nano antifouling solution, calculated by mass parts, include 30-60 parts of silica sol, 1-5 parts of heptadecafluorodecyltrimethoxysilane, 0.5-3 parts of hydrophobic silica, 0.1-1 parts of dispersant, 5-15 parts of propylene glycol methyl ether, and 25-35 parts of water.

10. A non-slip glossy tile with anti-fouling properties, characterized in that: The anti-slip glossy tile with anti-fouling properties is prepared using the preparation method of any one of claims 1 to 9. The anti-slip glossy tile with anti-fouling properties has a gloss level > 90°, a stain resistance level of 5, a dry static friction coefficient > 0.70, and a wet static friction coefficient ≥ 0.60.

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