A stain-resistant and antibacterial soft-brushed brick and a preparation method thereof

Abstract

The present application relates to the technical field of building ceramics, and particularly relates to a stain-resistant and antibacterial soft polishing brick and a preparation method thereof, comprising the following steps: A. preparing a body; B. printing color ink according to a preset pattern to form an inkjet printing layer; C. applying a stain-resistant face glaze to form a stain-resistant face glaze layer; the raw materials of the stain-resistant face glaze include potassium feldspar, quartz, kaolin, wollastonite, dolomite, calcined talc, zinc oxide, strontium carbonate, barium carbonate and barium frit; D. drying and then entering a kiln for calcination, and polishing to obtain a polished semi-finished product; E. adding a nano stain-resistant and antibacterial composite solution to the surface of the polished semi-finished product, and polishing to form a stain-resistant and antibacterial film layer, thereby obtaining the stain-resistant and antibacterial soft polishing brick; the raw materials of the nano stain-resistant and antibacterial composite solution include a water-based organic silicon-acrylic acid hybrid solution and an antibacterial dispersion liquid. The stain-resistant and antibacterial soft polishing brick and the preparation method thereof are beneficial to endowing the soft polishing brick with excellent and durable stain-resistant and antibacterial properties on the premise of soft light.

Description

Technical Field

[0001] The present invention relates to the technical field of building ceramics, in particular to a stain-resistant and antibacterial soft-polished brick and a preparation method thereof. Background Art

[0002] Soft-polished tiles are products with a semi-polished or lightly polished surface. Their glossiness is less than 50°. They not only avoid the light pollution problem caused by the glossiness of bright tiles as high as 90°, but also help create a visually comfortable and warm space with artistic atmosphere. They are widely used in living rooms, dining rooms, bedrooms and other places.

[0003] The current method for producing soft-polished tiles typically involves applying a glaze and then polishing with abrasive blocks to achieve a soft sheen. However, because finer abrasive blocks produce higher gloss, achieving a soft gloss below 50° requires the use of relatively coarse abrasive blocks. Coarser abrasive blocks are more likely to open pores enclosed in the glaze layer than finer blocks. When contaminants come into contact with the ceramic surface, capillary action allows them to penetrate deeply into the pores, reducing the stain resistance of the soft-polished tiles.

[0004] In addition, as people's requirements for the quality of life are getting higher and higher, their awareness of environmental protection is also getting stronger and stronger, which makes the requirements for soft-polished tiles not only stain-resistant but also have certain antibacterial properties.

[0005] In order to take into account both the stain resistance and antibacterial properties of soft-polished tiles, the existing technology applies an antibacterial glaze on the surface of the blank, and adjusts the glaze formula to obtain a polished semi-finished product with antibacterial properties and fewer pores after polishing. The surface of the polished semi-finished product is then coated with an anti-fouling solution and solidified into a stain-resistant film layer to fill the exposed pores, thereby obtaining a soft-polished tile with both antibacterial and stain resistance (i.e., stain-resistant and antibacterial soft-polished tile).

[0006] However, due to differences in raw material selection and manufacturing processes, the soft-polished tiles produced in the prior art only have a limited reduction in pore size. Furthermore, the anti-fouling components in the anti-fouling solution are only physically adsorbed (i.e., molecularly bonded) to the glaze surface. During daily use, these components are easily worn away, resulting in poor stain resistance and durability. Furthermore, the prior art typically utilizes titanium dioxide and / or tourmaline as antimicrobial systems. However, tourmaline readily decomposes at high temperatures, and titanium dioxide readily loses its antimicrobial activity in the absence of ultraviolet light. These factors contribute to the inadequate antimicrobial performance and durability of the soft-polished tiles.

[0007] In summary, due to the differences in the selection of raw materials and the preparation process, the soft-polished tiles produced in the existing technology are difficult to obtain excellent and lasting stain resistance and antibacterial properties. Summary of the Invention

[0008] The purpose of the present invention is to propose a stain-resistant and antibacterial soft-polished brick and a preparation method thereof, which is conducive to giving the soft-polished brick excellent and lasting stain-resistant and antibacterial properties while having soft light properties, so as to overcome the shortcomings of the existing technology.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] A method for preparing a stain-resistant and antibacterial soft-polished brick comprises the following steps:

[0011] A. Preparation of green body;

[0012] B. Printing color ink according to a preset pattern to form an inkjet printing layer;

[0013] C. Apply anti-fouling glaze to form an anti-fouling glaze layer;

[0014] The raw materials of the antifouling glaze include potassium feldspar, quartz, kaolin, wollastonite, dolomite, burned talc, zinc oxide, strontium carbonate, barium carbonate and barium frit;

[0015] D. After drying, calcination in a kiln and polishing to obtain a polished semi-finished product;

[0016] E. adding the nano-fouling-resistant and antibacterial composite solution dropwise to the surface of the polished semi-finished product, and forming a fouling-resistant and antibacterial film layer after polishing to obtain a fouling-resistant and antibacterial soft-polished tile;

[0017] The raw materials of the nano-fouling resistant and antibacterial composite solution include aqueous organosilicon-acrylic acid hybrid solution and antibacterial dispersion;

[0018] The raw materials of the aqueous organosilicon-acrylic acid hybrid solution include nano-silicon dioxide, organosilicon-grafted acrylic acid ionomer and water, and the neutralization degree of the organosilicon-grafted acrylic acid ionomer is 50-70%;

[0019] The raw materials of the antibacterial dispersion include modified nanorod-shaped zinc oxide, a quaternized silane coupling agent and water, and the surface of the modified nanorod-shaped zinc oxide contains hydroxyl groups.

[0020] Furthermore, in step C, the chemical composition of the barium frit, calculated by mass percentage, includes BaO 35.28-51.24%, SiO2 32.13-44.37%, Al2O3 2.18-8.13%, B2O3 1.51-8.95%, ZnO 1.28-7.65%, CaO 1.25-3.87%, MgO 1.24-1.58%, Na2O 0.23-1.61%, TiO2 0.2-0.3%, K2O 1.28-1.65% and ZrO2 2.53-4.89%.

[0021] Furthermore, in step D, the calcination temperature curve of the kiln calcination includes a drying section, an oxidation section, a sintering section, a rapid cooling section and a slow cooling section in sequence;

[0022] The drying stage is heated from room temperature to 300°C, which takes 10 to 15 minutes;

[0023] The oxidation stage is heated from 300°C to 900°C, which takes 20 to 30 minutes;

[0024] The firing stage is heated from 900°C to 1220°C, which takes 20 to 25 minutes;

[0025] The rapid cooling stage is from 1220°C to 700°C, which takes 5 to 8 minutes;

[0026] The slow cooling stage is from 700°C to 400°C, which takes 15 to 20 minutes.

[0027] Furthermore, in step E, the raw materials of the antibacterial dispersion further include a dispersant, an aqueous polyurethane resin, glycerol and water;

[0028] Calculated by weight, the raw materials of the antibacterial dispersion include 12 to 20 parts of modified nanorod-shaped zinc oxide, 2 to 4 parts of dispersant, 8 to 13 parts of waterborne polyurethane resin, 0.5 to 0.8 parts of quaternized silane coupling agent, 1.2 to 2.5 parts of glycerol and 60 to 70 parts of water.

[0029] Furthermore, in step E, the raw materials of the nano-fouling resistant and antibacterial composite solution also include antifouling solution;

[0030] Calculated by weight, the raw materials of the nano-fouling resistant and antibacterial composite solution include 5 to 10 parts of antibacterial dispersion, 10 to 18 parts of aqueous silicone-acrylic acid hybrid solution and 3 to 5 parts of antifouling solution.

[0031] Furthermore, calculated by mass, the raw materials of the antifouling solution include 4 to 8 parts of dimethyldiethoxysilane, 0.6 to 1.2 parts of dimethylhydrogensilane, 0.5 to 2 parts of methyl silicone oil, 4 to 8 parts of methylpolysilazane resin and 60 to 75 parts of 120# solvent oil.

[0032] Furthermore, in step E, the particle size of the nano-silicon dioxide is 5 to 500 nm;

[0033] The modified nanorod-shaped zinc oxide has a length of 100 to 500 nm and a diameter of 20 to 50 nm;

[0034] The thickness of the antifouling and antibacterial film layer is 2 to 5 μm.

[0035] Further, in step C, the raw materials of the anti-fouling glaze include potassium feldspar 50-65 parts, quartz 24-30 parts, kaolin 9-14 parts, wollastonite 22-28 parts, dolomite 12-16 parts, calcined talc 3-8 parts, zinc oxide 8-15 parts, strontium carbonate 2-6 parts, barium carbonate 2-5 parts and barium frit 5-10 parts, calculated by mass fraction.

[0036] Further, in step E, the raw materials of the aqueous silicone-acrylic hybrid solution include nano-silicon dioxide 10-18 parts, silicone grafted acrylic ionomer 45-65 parts and water 40-50 parts, calculated by mass fraction.

[0037] An anti-fouling and antibacterial soft polishing brick is prepared by using the above-mentioned method for preparing an anti-fouling and antibacterial soft polishing brick, the glossiness of the anti-fouling and antibacterial soft polishing brick is ≤ 35°, the anti-fouling performance is ≥ 5 levels, the antibacterial rate on Escherichia coli is ≥ 99.5%, the antibacterial rate on Staphylococcus aureus is ≥ 99.2%, the antibacterial durability on Escherichia coli is ≥ 88.7%, and the antibacterial durability on Staphylococcus aureus is ≥ 88.3%.

[0038] The technical solution provided by the present application can include the following beneficial effects:

[0039] 1. The present technical solution realizes the synergistic optimization of the ordered release of carbon dioxide gas and the self-healing of the glaze surface through the dynamic evolution (depolymerization-recombination) of the silicon-oxygen network in each temperature section and the formation kinetics of the glass phase, forms an anti-fouling glaze layer with few pores itself, greatly reduces the pores of the polished semi-finished glaze surface, reduces the pollutants adhering to the polished semi-finished glaze surface, and further improves the anti-fouling performance of the soft polishing brick.

[0040] 2. The frictional heat generated by polishing promotes the volatilization of the solvent (such as water) in the nano anti-fouling and antibacterial composite solution, so that the effective components (including the antibacterial dispersion, nano silicon dioxide and silicone grafted acrylic ionomer) form an anti-fouling and antibacterial film layer at high temperature and adhere to the anti-fouling glaze layer, and firmly fill the pores in the anti-fouling glaze layer. In addition, the quaternary ammonium silane coupling agent can be hydrolyzed to obtain hydrolysis product quaternary ammonium silanol under the action of water. Quaternary ammonium silanol contains silanol groups and quaternary ammonium cations. Quaternary ammonium silanol forms Si-O-Zn covalent bond through the condensation of silanol groups (Si-OH) and the hydroxyl groups on the surface of modified nano rod-shaped zinc oxide, realizes the quaternization of the surface of nano rod-shaped zinc oxide, and the positively charged quaternary ammonium on the surface of the nano rod-shaped zinc oxide can be arranged vertically through the electrostatic action of the negatively charged carboxylate in the silicone grafted acrylic ionomer (the silicone grafted acrylic ionomer has carboxyl and carboxylate with a neutralization degree of 50-70%), deeply into the pore depth and realize the dense plugging, so that the glaze surface of the soft polishing brick is dense and pore-free, thereby effectively improving the anti-fouling performance of the soft polishing brick.

[0041] 3. In the surface quaternized nanorod-shaped zinc oxide, the positively charged quaternary ammonium ions can be adsorbed to the surface of the negatively charged bacterial cell wall, penetrate the cell wall by diffusion, bind to the cell membrane, destroy its phospholipid structure, and cause the intracellular K + , DNA, RNA and other substances leak out, thereby killing bacteria. In addition, the unique morphology of nanorod-shaped zinc oxide itself can enhance physical penetration ability, and the Zn in nanorod-shaped zinc oxide 2+ The release of will not only destroy the internal environment of the bacteria and cause damage to the cell wall of the bacteria, but also combine with the active protease in the bacteria to make it lose its activity, thereby blocking the life activities of the bacteria, further synergistically enhancing the antibacterial effect and giving the soft-polished tiles excellent antibacterial properties.

[0042] 4. The modified nanorod-shaped zinc oxide makes the glaze surface have soft light properties through the following effects: (1) The rod-shaped structure of the modified nanorod-shaped zinc oxide makes it randomly oriented in the anti-fouling and antibacterial film layer, forming micron-level bumps and grooves, causing diffuse reflection and significantly reducing the mirror reflectivity; (2) After the tip (end) of the modified nanorod-shaped zinc oxide enters the pore, its curvature radius is extremely small, making its end a strong scattering center, reducing direct reflection; (3) The rod-shaped arrangement of the modified nanorod-shaped zinc oxide extends the light propagation path, enhances the multiple scattering of light inside the anti-fouling and antibacterial film layer, and realizes uniform diffusion of light; (4) The refractive index of the modified nanorod-shaped zinc oxide (about 2.0) is different from the refractive index of the silicone grafted acrylic ionomer (about 1.5), which reduces Fresnel reflection through the gradient refraction effect in the anti-fouling and antibacterial film layer formed with the silicone grafted acrylic ionomer as the matrix. DETAILED DESCRIPTION

[0043] This technical solution provides a method for preparing stain-resistant and antibacterial soft-polished tiles, comprising the following steps:

[0044] A. Preparation of green body;

[0045] B. Printing color ink according to a preset pattern to form an inkjet printing layer;

[0046] C. Apply anti-fouling glaze to form an anti-fouling glaze layer;

[0047] The raw materials of the antifouling glaze include potassium feldspar, quartz, kaolin, wollastonite, dolomite, burned talc, zinc oxide, strontium carbonate, barium carbonate and barium frit;

[0048] D. After drying, calcination in a kiln and polishing to obtain a polished semi-finished product;

[0049] E. adding the nano-fouling-resistant and antibacterial composite solution dropwise to the surface of the polished semi-finished product, and forming a fouling-resistant and antibacterial film layer after polishing to obtain a fouling-resistant and antibacterial soft-polished tile;

[0050] The raw materials of the nano-fouling resistant and antibacterial composite solution include aqueous organosilicon-acrylic acid hybrid solution and antibacterial dispersion;

[0051] The raw materials of the aqueous organosilicon-acrylic acid hybrid solution include nano-silicon dioxide, organosilicon-grafted acrylic acid ionomer and water, and the neutralization degree of the organosilicon-grafted acrylic acid ionomer is 50-70%;

[0052] The raw materials of the antibacterial dispersion include modified nanorod-shaped zinc oxide, a quaternized silane coupling agent and water, and the surface of the modified nanorod-shaped zinc oxide contains hydroxyl groups.

[0053] To address the technical problem of soft-polished tiles in the prior art, which is the difficulty in achieving excellent and lasting stain resistance and antibacterial properties, this technical solution proposes a method for preparing stain-resistant and antibacterial soft-polished tiles, comprising five steps: A (making the tiles), B (printing color inks), C (applying an anti-fouling glaze), D (firing and polishing in a kiln), and E (forming a stain-resistant and antibacterial film layer). By optimizing the anti-fouling glaze formulation and the nano-fouling-resistant and antibacterial composite solution formulation, the soft-polished tiles not only possess soft light properties but also excellent and lasting stain resistance and antibacterial properties. It should be noted that the tiles in this solution are formed by pressing and drying conventional ceramic tiles; the inkjet printing layer is printed using conventional color inks in the ceramic field; and the polishing process is a commonly used polishing process for soft-polished tiles. Further description of the ceramic tiles, color inks, and polishing process is not provided herein.

[0054] Specifically, this technical solution proposes an antifouling glaze whose raw materials include potassium feldspar, quartz, kaolin, wollastonite, dolomite, calcined talc, zinc oxide, strontium carbonate, barium carbonate, and barium frit. During the low-temperature stage (800-1000°C) of the calcination process, the dolomite (primarily composed of calcium magnesium carbonate, CaMg(CO3)2) and some strontium carbonate (SrCO3) decompose, producing carbon dioxide gas. The flaky structure of the calcined talc and the suspended network of the kaolin synergistically create an open pore structure, providing an early escape path for the carbon dioxide gas generated by the decomposition of the dolomite and strontium carbonate. At this stage, the amorphous metakaolin (Al2O3·2SiO2) and quartz (SiO2) produced by dehydroxylation of the kaolin have not yet fully melted, but the surface begins to activate, initially forming a localized silicon-oxygen network, laying the foundation for the subsequent formation of a glassy phase.

[0055] During the medium temperature stage (1000-1150℃) of the calcination heating process, barium carbonate (BaCO3) and the remaining strontium carbonate decompose and produce carbon dioxide gas; the barium frit melts first due to its low eutectic characteristics, and during the melting process, the Ba introduced into the barium frit 2+As a network modifier, it is embedded in the initially formed local silicon-oxygen network structure and cuts off the Si-O-Si bond in the local silicon-oxygen network structure, thereby depolymerizing the local silicon-oxygen network structure into low-polymerization SiO3 2- Chain or ring structure; at the same time, Ba 2+ The high ionic radius (1.35Å) and low field strength characteristics enable it to reduce SiO3 2- The bonding energy of the silicon-oxygen units in the chain or ring structure, combined with the low surface tension of barium oxide, promotes the reaction between the melted barium frit and the initially formed local silicon-oxygen network to form a low-viscosity, low-surface-tension barium oxide-based glass phase. Furthermore, zinc oxide acts as a flux, incorporating it into the barium oxide-based glass phase and reducing the degree of polymerization of the silicon-oxygen network within it, promoting its expansion. The low-surface-tension barium oxide-based glass phase (i.e., melt) rapidly spreads and penetrates the intergranular spaces between unmelted components (such as quartz and kaolin), forming a three-dimensional network of melt channels. This allows the carbon dioxide generated by the decomposition of the formulation to be released in a targeted manner under pressure. Furthermore, zinc oxide reduces the viscosity of the melt, enhancing the upward buoyancy of the carbon dioxide gas and synergistically promoting its targeted release. It should be noted that the zinc oxide in the anti-fouling glaze can be either micron-sized (i.e., conventional zinc oxide) or nano-sized, with no specific limitation being imposed.

[0056] During the high-temperature stage (1150-1220°C) of the calcination process, the remaining quartz and kaolin further melt, causing the silica network in the melt to continuously depolymerize and reorganize at high temperatures. The addition of wollastonite significantly reduces the high-temperature viscosity of the melt, making it highly fluid and thus accelerating the removal of residual carbon dioxide gas. Simultaneously, strontium carbonate introduces strontium oxide during the calcination process, and barium carbonate and barium frit introduce barium oxide during the calcination process. Barium oxide and strontium oxide act as network modifiers, embedding themselves into the gaps in the silica network structure of the melt, inhibiting bubble merging and promoting the rapid escape of microbubbles. Furthermore, the highly fluid melt quickly levels during cooling, and the silica network in the melt repolymerizes and solidifies, sealing any remaining microscopic pores and forming an anti-fouling glaze layer with minimal pores.

[0057] In summary, this technical solution achieves the synergistic optimization of the phased and orderly release of carbon dioxide gas and the self-healing of the glaze through the dynamic evolution (depolymerization-recombination) of the silicon-oxygen network in each temperature range and the formation dynamics of the glass phase, forming an anti-fouling glaze layer with extremely few pores. This greatly reduces the pores of the polished semi-finished glaze surface, reduces the pollutants adhering to the polished semi-finished glaze surface, and thus improves the stain resistance of the soft-polished tiles.

[0058] It should be noted that the principle of wollastonite reducing the high-temperature viscosity of the melt is as follows: (1) Wollastonite is a single-chain silicate mineral. Its crystal structure is composed of [SiO4] tetrahedra connected by corner-sharing vertices to form a one-dimensional infinitely extended chain structure, with only Ca2+ between the chains. 2+ Ion maintenance. The above structure is more prone to chain breakage at high temperatures, destroying the continuity of the silicon-oxygen network of the melt, thereby weakening the three-dimensional polymerization degree of the melt; (2) Wollastonite will form a low eutectic with components such as potassium feldspar and quartz in the anti-fouling glaze formula at high temperatures (about 1100℃), generating a liquid phase in advance and promoting the kinetics of the melting process; (3) The Ca introduced by wollastonite 2+ As a network-modifying cation, it can cut the Si-O-Si bond in the silicon-oxygen network of the melt, depolymerize the high-polymerization [SiO4] network into low-polymerization [SiO4] units (such as Q² or Q³ structure), resulting in a loose structure of the melt and a significant reduction in viscosity.

[0059] It should be further explained that the specific mechanism by which barium oxide and strontium oxide reduce the tendency of bubbles to merge and promote the rapid escape of tiny bubbles is as follows: (1) Ba in barium oxide 2+ and Sr in strontium oxide 2+ As a cation with large radius and low charge density, when Ba 2+ and Sr 2+ After entering the melt, the two will destroy the connection between the silicon-oxygen tetrahedrons in the melt, resulting in a decrease in the degree of polymerization of the melt, making the structure of the melt looser and the surface tension reduced, thereby inhibiting the merging of bubbles; (2) Ba 2+ and Sr 2+ It is easy to accumulate at the bubble interface and form a positive charge layer. When two bubbles with positive charge layers approach each other, the mutual repulsion between the same-sign charges prevents the bubbles from getting closer and merging, thus weakening the tendency of the bubbles to merge; (3) Ba 2+ and Sr 2+ The addition of makes the melt form a low viscosity state, which is conducive to accelerating the floating of bubbles, reducing the chances of bubbles contacting and merging with each other, further inhibiting the merging of bubbles, and allowing tiny bubbles to escape quickly.

[0060] Secondly, while reducing the porosity of the antifouling glaze layer itself can improve the stain resistance of soft-polished tiles, the pores still exist in the antifouling glaze layer, resulting in limited stain resistance, making it difficult to meet the requirements of applications requiring extremely high stain resistance. Therefore, to improve stain resistance, this technical solution specifically adds a nano-antifouling and antibacterial composite solution to the surface of the polished semi-finished product. During the polishing process, nano-silica, with its high hardness and permeability, acts as a grinding aid, opening the pores of the polished semi-finished product. Simultaneously, the frictional heat generated by polishing causes the solvent (e.g., water) in the nano-antifouling and antibacterial composite solution to evaporate, allowing its active ingredients (including the antimicrobial dispersion, nano-silica, and the silicone-grafted acrylic ionomer) to form a stain-resistant and antibacterial film at high temperatures, adhering to the antifouling glaze layer and firmly filling the pores within the antifouling glaze layer. Furthermore, the quaternized silane coupling agent hydrolyzes in water to produce a hydrolysis product, a quaternized silanol, which contains silanol groups and quaternary ammonium cations. Quaternized silanols condense the silanol groups (Si-OH) with the hydroxyl groups on the surface of modified nanorod-shaped zinc oxide to form Si-O-Zn covalent bonds, quaternizing the nanorod-shaped zinc oxide surface. The positively charged quaternary ammonium groups in the surface-quaternized nanorod-shaped zinc oxide interact with the negatively charged carboxyl groups in the organosilicon-grafted acrylic ionomer (organosilicon-grafted acrylic ionomers with a neutralization degree of 50-70% contain both carboxyl groups and carboxyl groups) through electrostatic interaction, causing the nanorod-shaped zinc oxide to align vertically. These interactions penetrate deep into the pores and achieve a tight seal, resulting in a dense, pore-free glaze surface for the soft-polished tiles, effectively improving their stain resistance. It should be noted that the organosilicon-grafted acrylic ionomer also serves as a dispersant to stabilize the components of the nanorod-shaped antimicrobial composite solution and prevent aggregation. Furthermore, the introduction of the quaternary ammonium group imparts a positive surface charge to the nanorod-shaped zinc oxide. The electrostatic repulsion between like-charged groups effectively prevents nanoparticle aggregation, significantly improving the stability of the antimicrobial dispersion. The degree of neutralization refers to the proportion of carboxyl groups in the silicone grafted acrylic ionomer that are neutralized by alkali.

[0061] Furthermore, the positively charged quaternary ammonium ions in the surface quaternized nanorod-shaped zinc oxide can be adsorbed to the negatively charged bacterial cell wall surface, and penetrate the cell wall of the bacteria by diffusion and bind to the cell membrane, destroying the phospholipid structure of the bacteria, resulting in the intracellular K + , DNA, RNA and other substances leak out, thereby killing bacteria. In addition, the unique morphology of nanorod-shaped zinc oxide itself can enhance physical penetration ability, and the Zn in nanorod-shaped zinc oxide 2+ The release of will not only destroy the internal environment of the bacteria and cause damage to the cell wall of the bacteria, but also combine with the active protease in the bacteria to make it lose its activity, thereby blocking the life activities of the bacteria, further synergistically enhancing the antibacterial effect and giving the soft-polished tiles excellent antibacterial properties.

[0062] Secondly, the depolymerization and recombination of the silicon-oxygen network in the anti-fouling glaze produces non-bridging oxygen. These non-bridging oxygen dipoles can react with moisture (such as ambient moisture adsorbed on the surface of the raw materials, water of crystallization bound between glaze components, or equilibrium moisture introduced during the processing) to form hydroxyl groups, resulting in a hydroxyl-containing surface in the anti-fouling glaze. The quaternized silanols, the hydrolysis products of the quaternized silane coupling agent, can form chemical bonds through the silanol groups (Si-OH) not only with the hydroxyl groups on the surface of the anti-fouling glaze, but also with the carboxyl groups (derived from the silicone-grafted acrylic ionomer) in the anti-fouling and anti-bacterial film. This allows the quaternized silane coupling agent to act as a bonding bridge at the interface between the anti-fouling glaze and the anti-fouling film, firmly adhering the anti-fouling and anti-bacterial film to the surface of the anti-fouling glaze (i.e., the semi-finished polished product) through chemical bonds. This prevents the anti-fouling and anti-bacterial film from detaching even during daily use, thus endowing the soft-polished tiles with long-lasting stain resistance and antibacterial properties.

[0063] In addition, the carboxyl groups (-COOH) on the molecular chains of the silicone-grafted acrylic ionomer (flexible phase) can undergo a condensation reaction with the silanol groups (Si-OH) on the surface of the nano-silica (rigid phase), forming Si-O-COO- groups to bond and achieve organic-inorganic hybridization. The silanol groups on the surface of the quaternized silanol can react with the nano-silica to form Si-O-Si covalent bonds, achieving interfacial bonding reinforcement. In other words, through organic-inorganic hybridization and interfacial bonding reinforcement, this technical solution ensures that the resulting stain-resistant and antibacterial film layer after polishing has both hardness and toughness. This not only ensures surface hardness to withstand daily wear and tear, but also maintains sufficient fracture toughness to inhibit crack propagation, which is beneficial to improving the overall service reliability of the stain-resistant and antibacterial film layer, thereby further improving the durability of the stain resistance and antibacterial properties of the soft-polished tiles.

[0064] Finally, the modified nanorod-shaped zinc oxide gives the glaze a soft light property through the following effects: (1) The rod-shaped structure of the modified nanorod-shaped zinc oxide makes it randomly oriented in the anti-fouling and antibacterial film layer, forming micron-level bumps and grooves, which induce diffuse reflection and significantly reduce the mirror reflectivity; (2) After the tip (end) of the modified nanorod-shaped zinc oxide enters the pore, its curvature radius is extremely small, making its end a strong scattering center, reducing direct reflection; (3) The rod-shaped arrangement of the modified nanorod-shaped zinc oxide extends the light propagation path, enhances the multiple scattering of light inside the anti-fouling and antibacterial film layer, and achieves uniform light diffusion; (4) The refractive index of the modified nanorod-shaped zinc oxide (about 2.0) is different from the refractive index of the silicone grafted acrylic ionomer (about 1.5), which reduces Fresnel reflection in the anti-fouling and antibacterial film layer formed with the silicone grafted acrylic ionomer as the matrix through the gradient refraction effect. It should be noted that Fresnel reflection refers to the phenomenon that when light is incident on the interface between two media with different refractive indices, part of the light will be reflected.

[0065] It should be further explained that the quaternized silane coupling agent can be dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride and dimethyloctadecyl[3-(triethoxysilyl)propyl]ammonium chloride, and the specific type is not limited here.

[0066] Preferably, in step E, the preparation method of the modified nanorod-shaped zinc oxide is as follows: dissolving 8 to 10 parts of zinc nitrate or zinc acetate in 15 to 20 parts of water, calculated by weight, to obtain a first mixed solution; adding ammonia water to the first mixed solution and adjusting the pH to 10 to 12, and then adding 0.5 to 1 part of dodecyltrimethylammonium chloride to obtain a second mixed solution; subjecting the second mixed solution to a hydrothermal reaction at a temperature of 100 to 180° C. for 6 to 24 hours, cooling, washing, and drying to obtain the modified nanorod-shaped zinc oxide.

[0067] The preparation method of the organosilicon grafted acrylic ionomer comprises the following steps: uniformly mixing 20-35 parts of ethylene glycol butyl ether, 35-45 parts of methyl eleostearate anhydride and 20-25 parts of dihydroxy silicone oil, calculated by weight, and reacting the mixture at a temperature of 120-130° C. for 2-5 hours to obtain a fifth mixed solution; uniformly mixing 6-8 parts of butyl acrylate, 20-28 parts of butyl methacrylate, 8-12 parts of acrylic acid, 1-2 parts of glycidyl methacrylate, 0.5-1 part of dodecyl mercaptan and 1-3 parts of benzoyl peroxide to obtain a sixth mixed solution; and dropwise adding the sixth mixed solution to the fifth mixed solution heated to 135-140° C., reacting the mixture for 3-8 hours, then cooling the mixture to 80° C., adding 3-10 parts of triethylamine, reacting the mixture for 0.5-1 hour, and then cooling the mixture to room temperature to obtain the organosilicon grafted acrylic ionomer.

[0068] This technical solution also proposes a preparation method of modified nanorod-shaped zinc oxide and organosilicon-grafted acrylic acid ionomer, which is beneficial to ensuring the relevant properties of the modified nanorod-shaped zinc oxide and organosilicon-grafted acrylic acid ionomer during the preparation process.

[0069] It should be noted that the manufacturer of the dihydroxy silicone oil in this technical solution is Ark (Fogang) Chemical Materials Co., Ltd., and the model is AC-001.

[0070] Further description, in step C, calculated by mass percentage, the chemical composition of the barium frit includes BaO35.28~51.24%, SiO232.13~44.37%, Al2O32.18~8.13%, B2O31.51~8.95%, ZnO 1.28~7.65%, CaO 1.25~3.87%, MgO 1.24~1.58%, Na2O 0.23~1.61%, TiO20.2~0.3%, K2O 1.28~1.65% and ZrO22.53~4.89%.

[0071] This technical solution preferably adds barium frit with a BaO content of 35.28-51.24% by mass to the anti-fouling glaze, helping to increase the BaO content in the formulation and thereby reduce glaze porosity. Furthermore, the SiO2 content in the barium frit is as high as 32% or more, which helps to increase the silicon content in the formulation, improving the mechanical properties of the soft-polished tile while ensuring the barium frit's ability to reduce glaze porosity.

[0072] Further, in step D, the calcination temperature curve of the kiln calcination includes a drying section, an oxidation section, a sintering section, a rapid cooling section and a slow cooling section in sequence;

[0073] The drying stage is heated from room temperature to 300°C, which takes 10 to 15 minutes;

[0074] The oxidation stage is heated from 300°C to 900°C, which takes 20 to 30 minutes;

[0075] The firing stage is heated from 900°C to 1220°C, which takes 20 to 25 minutes;

[0076] The rapid cooling stage is from 1220°C to 700°C, which takes 5 to 8 minutes;

[0077] The slow cooling stage is from 700°C to 400°C, which takes 15 to 20 minutes.

[0078] This technical solution is beneficial to ensuring the performance of soft polished bricks by optimizing the temperature curve of calcination in the kiln.

[0079] Further, in step E, the raw materials of the antibacterial dispersion also include a dispersant, an aqueous polyurethane resin, glycerol and water;

[0080] Calculated by weight, the raw materials of the antibacterial dispersion include 12 to 20 parts of modified nanorod-shaped zinc oxide, 2 to 4 parts of dispersant, 8 to 13 parts of waterborne polyurethane resin, 0.5 to 0.8 parts of quaternized silane coupling agent, 1.2 to 2.5 parts of glycerol and 60 to 70 parts of water.

[0081] This technical solution, by adding a waterborne polyurethane resin to the antimicrobial dispersion, leverages the waterborne polyurethane's combined soft and hard segments, further enhancing the hardness and flexibility of the stain-resistant and antimicrobial film, thereby improving the durability of both stain resistance and antimicrobial properties of the soft-polished tiles. Furthermore, the -NHCOO- groups of the waterborne polyurethane resin react with the -OH groups on the surface of the modified nanorod-shaped zinc oxide to form allophanate bonds, further strengthening the bonding between the components and enhancing the wear resistance of the stain-resistant and antimicrobial film. This also further improves the durability of both stain resistance and antimicrobial properties of the soft-polished tiles.

[0082] It should be noted that the manufacturer of the waterborne polyurethane resin in the technical solution is Wanhua Chemical Group Co., Ltd., and the model is WANNATE 6120 of Wanhua.

[0083] Preferably, the dispersant is sodium polyacrylate, and the manufacturer of the sodium polyacrylate is Zhengzhou Baiying Chemical Product Co., Ltd., and the model is 22565.

[0084] Further, in step E, the raw materials of the nano-pollution-resistant and antibacterial composite solution further include a stain-resistant solution.

[0085] According to mass fraction, the raw materials of the nano-pollution-resistant and antibacterial composite solution include 5-10 parts of the antibacterial dispersion, 10-18 parts of the waterborne silicone-acrylic hybrid solution, and 3-5 parts of the stain-resistant solution.

[0086] The technical solution adds the stain-resistant solution to the nano-pollution-resistant and antibacterial composite solution, which is conducive to utilizing the stain-resistant performance of the stain-resistant solution, thereby further improving the stain-resistant performance of the soft polishing brick.

[0087] Further, by limiting the addition amount of each raw material in the nano-pollution-resistant and antibacterial composite solution, the stain-resistant performance and antibacterial performance of the nano-pollution-resistant and antibacterial composite solution can be ensured.

[0088] Further, according to mass fraction, the raw materials of the stain-resistant solution include 4-8 parts of dimethyldiethoxysilane, 0.6-1.2 parts of dimethylsilane, 0.5-2 parts of methyl silicone oil, 4-8 parts of methyl polysilazane resin, and 60-75 parts of 120# solvent oil.

[0089] In the technical solution, the raw materials of the stain-resistant solution include dimethyldiethoxysilane, dimethylsilane, methyl silicone oil, oligomers, methyl polysilazane resin, and 120# solvent. Among them, dimethyldiethoxysilane is a monomer for reaction, which forms siloxane oligomers through hydrolysis and condensation reaction in the process of frictional heat generated by polishing, thereby enhancing the film-forming performance of the nano-pollution-resistant and antibacterial composite solution; dimethylsilane is a crosslinking agent and an active modifier, which enhances the crosslinking density of the siloxane oligomers; the long-chain siloxane structure of the methyl silicone oil is inserted into the siloxane oligomers, which not only enhances the hydrophobicity of the stain-resistant and antibacterial film layer by utilizing the low surface energy characteristics of the methyl silicone oil, thereby improving the stain-resistant performance of the soft polishing brick, but also enhances the flexibility and leveling property by utilizing the certain flexibility of the methyl silicone oil. The methyl polysilazane resin has low surface energy and super-hydrophobic characteristics after curing, which also enhances the hydrophobicity of the stain-resistant and antibacterial film layer, thereby improving the stain-resistant performance of the soft polishing brick.

[0090] It should be noted that 120# solvent oil, also known as industrial heptane or rubber solvent oil, is a low-boiling-point petroleum distillate. Methyl silicone oil can be dimethylsiloxane (DMSO) or trimethylsiloxane (TMSO). Furthermore, the manufacturer of methyl polysilazane is Anhui Mingyi Silicon Industry Co., Ltd., model number MY9N1501.

[0091] Further, in step E, the particle size of the nano-silica is 5 to 500 nm;

[0092] The modified nanorod-shaped zinc oxide has a length of 100 to 500 nm and a diameter of 20 to 50 nm;

[0093] The thickness of the antifouling and antibacterial film layer is 2 to 5 μm.

[0094] When the nano-silica particle size is less than 5nm, its strength is too low, which is not conducive to improving the strength of the anti-fouling and antibacterial film layer. On the other hand, when the nano-silica particle size is greater than 500nm, its particle size is too large, which is not conducive to achieving its filling effect. Therefore, this technical solution limits the nano-silica particle size to 5-500nm, which is conducive to ensuring its filling and strength-enhancing properties.

[0095] At the same time, by limiting the length of the modified nanorod-shaped zinc oxide to 100-500 nm and the diameter to 20-50 nm, the modified nanorod-shaped zinc oxide has a high aspect ratio (5-25), and is arranged vertically (diameter 20-50 nm to ensure high specific surface area, length 100-500 nm to achieve deep pore penetration), forming a pinning effect at the interface, which not only closes the pores but also retains the Zn 2+ The sustained-release channel optimizes the antibacterial performance and stain resistance simultaneously.

[0096] Furthermore, when the thickness of the anti-fouling and antibacterial film is less than 2 μm, the effective anti-fouling and antibacterial ingredients are insufficient, resulting in poor anti-fouling and antibacterial performance. When the thickness of the anti-fouling and antibacterial film is greater than 5 μm, the film is too thick, which can easily lead to production cost issues for anti-fouling and antibacterial soft-polished tiles. Therefore, this technical solution limits the nano-anti-fouling and antibacterial composite solution to 2-5 μm, which helps ensure the performance of the anti-fouling and antibacterial film while reducing costs.

[0097] Further explanation, in step C, calculated by mass, the raw materials of the anti-fouling glaze include 50-65 parts of potassium feldspar, 24-30 parts of quartz, 9-14 parts of kaolin, 22-28 parts of wollastonite, 12-16 parts of dolomite, 3-8 parts of calcined talc, 8-15 parts of zinc oxide, 2-6 parts of strontium carbonate, 2-5 parts of barium carbonate and 5-10 parts of barium frit.

[0098] This technical solution further optimizes the anti-fouling glaze formula, which is conducive to giving full play to the performance of each raw material and achieving the best performance of soft-polished tiles.

[0099] Further, in step E, the raw materials of the aqueous organosilicon-acrylic hybrid solution include 10-18 parts of nano-silicon dioxide, 45-65 parts of organosilicon-grafted acrylic ionomer and 40-50 parts of water, calculated by weight.

[0100] This technical solution further optimizes the formula of the water-based organosilicon-acrylic acid hybrid solution, which is conducive to giving full play to the performance of each raw material, so that the performance of the water-based organosilicon-acrylic acid hybrid solution is optimal, thereby ensuring the performance of soft-polished tiles.

[0101] A stain-resistant and antibacterial soft-polished tile is prepared using the above-mentioned method for preparing a stain-resistant and antibacterial soft-polished tile. The stain-resistant and antibacterial soft-polished tile has a glossiness of ≤35°, a stain resistance of ≥level 5, an antibacterial rate against Escherichia coli ≥99.5%, an antibacterial rate against Staphylococcus aureus ≥99.2%, an antibacterial durability against Escherichia coli ≥88.7%, and an antibacterial durability against Staphylococcus aureus ≥88.3%.

[0102] This technical solution also proposes a stain-resistant and antibacterial soft-polished tile, whose glossiness is ≤35°, stain resistance ≥level 5, antibacterial rate against Escherichia coli ≥99.5%, antibacterial rate against Staphylococcus aureus ≥99.2%, antibacterial durability against Escherichia coli ≥88.7%, and antibacterial durability against Staphylococcus aureus ≥88.3%, which is beneficial to give the soft-polished tile excellent and long-lasting stain resistance and antibacterial properties while making it soft.

[0103] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0104] Gloss effect: Observe the glaze gloss effect of soft-polished tiles with the naked eye.

[0105] Glossiness: The glossiness of the soft-polished tiles was tested using an LS191 ceramic gloss meter. The test was repeated five times in parallel, and the average value of the five tests was taken.

[0106] Stain resistance: Using 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 product glaze is tested with green dye in light oil as the stain agent. Stain resistance level 5 is qualified.

[0107] Stain resistance durability: Use a Φ0.2mm steel wool to wipe the glaze surface of the soft-polished tile back and forth 10,000 times, and then use the test method of GB / T3810.14-2016 "Test methods for ceramic tiles - Part 14 - Determination of stain resistance - Building materials standard" to test the stain resistance of the soft-polished tile, and measure it in parallel 5 times, and take the average value of the 5 measurements.

[0108] Antibacterial rate determination: the soft brick was sterilized at a temperature of 120℃ and a pressure of 0.11MPa for 20min, 10 4 The test bacteria liquid of 10 cfu was inoculated on the surface of the sterilized soft brick, sterilized plastic wrap was pasted, and the sample was placed in a constant temperature incubator at 37℃. After 24h of culture, the bacteria liquid of the sample and the plastic wrap was washed to a plate with normal saline, 10-fold dilution was performed, and then the sample was inoculated into a culture dish and placed in a constant temperature incubator at 37℃. After 24h of culture, the antibacterial rate was calculated.

[0109] Antibacterial durability determination: the surface of the soft brick was washed with hypochlorous acid disinfectant for 500 times, and then washed with sterilized distilled water to obtain the washed soft brick; the washed soft brick was sterilized at a temperature of 120℃ and a pressure of 0.11MPa for 20min to obtain the sterilized soft brick; 10 4 The test bacteria liquid of 10 cfu was inoculated on the surface of the sterilized soft brick, sterilized plastic wrap was pasted, and the sample was placed in a constant temperature incubator at 37℃. After 24h of culture, the bacteria liquid of the sample and the plastic wrap was washed to a plate with normal saline, 10-fold dilution was performed, and then the sample was inoculated into a culture dish and placed in a constant temperature incubator at 37℃. After 24h of culture, the antibacterial rate was calculated. The hypochlorous acid disinfectant was a hypochlorous acid solution with a content of 5% of hypochlorous acid according to mass percentage.

[0110] In all the following examples and comparative examples, the chemical composition of the barium frit included BaO 42.82%, SiO2 35.79%, Al2O3 4.32%, B2O3 2.99%, ZnO 3.96%, CaO 2.44%, MgO 1.36%, Na2O 1.07%, TiO2 0.2%, K2O 1.52%, and ZrO2 3.53% according to mass percentage;

[0111] The preparation method of the modified nanorod-shaped zinc oxide was as follows: 8 parts of zinc nitrate was dissolved in 20 parts of water to obtain a first mixed solution; after ammonia water was added to the first mixed solution and the pH was adjusted to 12, 1 part of dodecyltrimethylammonium chloride was added to obtain a second mixed solution; the second mixed solution was subjected to hydrothermal reaction at a temperature of 120℃ for 10h, and then washed, dried to obtain the modified nanorod-shaped zinc oxide.

[0112] The preparation method of the organosilicon grafted acrylic ionomer is as follows: 20 parts of ethylene glycol butyl ether, 35 parts of methyl eleostearate anhydride, and 20 parts of dihydroxy silicone oil are mixed uniformly according to parts by mass, and the mixture is reacted at a temperature of 130° C. for 4 hours to obtain a fifth mixed solution; 6 parts of butyl acrylate, 26 parts of butyl methacrylate, 10 parts of acrylic acid, 2 parts of glycidyl methacrylate, 0.5 parts of dodecyl mercaptan, and 1 part of benzoyl peroxide are mixed uniformly to obtain a sixth mixed solution; the sixth mixed solution is added dropwise to the fifth mixed solution heated to 135° C., reacted for 5 hours, and then cooled to 80° C., 4 parts of triethylamine are added, the mixture is reacted for 1 hour, and then cooled to room temperature to obtain an organosilicon grafted acrylic ionomer with a neutralization degree of 60%;

[0113] The manufacturer of dihydroxy silicone oil is Ark (Fogang) Chemical Materials Co., Ltd., model number is AC-001;

[0114] The manufacturer of methyl polysilazane is Anhui Mingyi Silicon Industry Co., Ltd., model MY9N1501; the manufacturer of sodium polyacrylate is Zhengzhou Baiying Chemical Products Co., Ltd., model 22565; the manufacturer of water-based polyurethane resin is Wanhua Chemical Group Co., Ltd., model Wanhua Chemical (Wanhua)® WANNATE 6120.

[0115] Example 1

[0116] A. Preparation of green body;

[0117] B. Printing color ink according to a preset pattern to form an inkjet printing layer;

[0118] C. Apply anti-fouling glaze to form an anti-fouling glaze layer;

[0119] Calculated by weight, the raw materials of the antifouling glaze include 60 parts of potassium feldspar, 30 parts of quartz, 12 parts of kaolin, 25 parts of wollastonite, 14 parts of dolomite, 5 parts of calcined talc, 10 parts of zinc oxide, 4 parts of strontium carbonate, 3 parts of barium carbonate and 8 parts of barium frit;

[0120] D. After drying, calcining in a kiln and polishing to obtain a polished semi-finished product; wherein the calcining temperature curve of calcining in the kiln includes a drying section, an oxidation section, a firing section, a rapid cooling section and a slow cooling section;

[0121] The drying stage is heated from room temperature to 300°C, which takes 10 minutes;

[0122] The oxidation stage is heated from 300°C to 900°C, which takes 25 minutes;

[0123] The firing stage was heated from 900°C to 1220°C, which took 22 minutes;

[0124] The rapid cooling stage is from 1220℃ to 700℃, which takes 6 minutes;

[0125] The slow cooling stage is from 700℃ to 400℃, which takes 20min;

[0126] E. Add the nano-fouling-resistant and antibacterial composite solution dropwise onto the surface of the polished semi-finished product, and after polishing, form a 3 μm thick antibacterial film layer to obtain a fouling-resistant and antibacterial soft-polished tile; wherein, calculated by weight, the nano-fouling-resistant and antibacterial composite solution includes 12 parts of an aqueous organosilicon-acrylic hybrid solution, 6 parts of an antibacterial dispersion, and 4 parts of an antifouling solution; calculated by weight, the raw materials of the aqueous organosilicon-acrylic hybrid solution include 12 parts of nano-silica (particle size of 300 nm), 50 parts of an organosilicon-grafted acrylic ionomer with a neutralization degree of 60%, and 40 parts of water; calculated by weight, the raw materials of the antibacterial dispersion include modified nanorod-shaped zinc oxide (length of 300 nm, diameter of 30 nm), 20 parts of oligomeric sodium acrylate, 3 parts of water-based polyurethane resin, 8 parts of dimethyloctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride 0.5 parts, 2 parts of glycerol and 60 parts of water; calculated by mass, the raw materials of the antifouling solution include 5 parts of dimethyldiethoxysilane, 1.2 parts of dimethylhydrogensilane, 1 part of dimethylsiloxane, 6 parts of methylpolysilazane resin and 60 parts of 120# solvent oil.

[0127] Example 2

[0128] A. Preparation of green body;

[0129] B. Printing color ink according to a preset pattern to form an inkjet printing layer;

[0130] C. Apply anti-fouling glaze to form an anti-fouling glaze layer;

[0131] Calculated by weight, the raw materials of the antifouling glaze include 65 parts of potassium feldspar, 30 parts of quartz, 12 parts of kaolin, 23 parts of wollastonite, 14 parts of dolomite, 8 parts of calcined talc, 8 parts of zinc oxide, 2 parts of strontium carbonate, 3 parts of barium carbonate and 8 parts of barium frit;

[0132] D. After drying, calcining in a kiln and polishing to obtain a polished semi-finished product; wherein the calcining temperature curve of calcining in the kiln includes a drying section, an oxidation section, a firing section, a rapid cooling section and a slow cooling section;

[0133] The drying stage is heated from room temperature to 300°C, which takes 12 minutes;

[0134] The oxidation stage is heated from 300°C to 900°C, which takes 20 minutes;

[0135] The firing stage was heated from 900°C to 1220°C, which took 23 minutes;

[0136] The rapid cooling stage is from 1220℃ to 700℃, which takes 6 minutes;

[0137] The slow cooling stage is from 700℃ to 400℃, which takes 20min;

[0138] E. Add the nano-fouling-resistant and antibacterial composite solution dropwise to the surface of the polished semi-finished product, and after polishing, form a fouling-resistant and antibacterial film layer with a thickness of 4 μm to obtain a fouling-resistant and antibacterial soft-polished tile; wherein, calculated by weight, the raw materials of the nano-fouling-resistant and antibacterial composite solution include 18 parts of an aqueous organosilicon-acrylic hybrid solution, 8 parts of an antibacterial dispersion, and 5 parts of an antifouling solution; calculated by weight, the raw materials of the aqueous organosilicon-acrylic hybrid solution include 12 parts of nano-silica (particle size of 50 nm), 60 parts of an organosilicon-grafted acrylic ionomer with a neutralization degree of 60%, and 40 parts of water; calculated by weight, the raw materials of the antibacterial dispersion include modified nano-rod-shaped zinc oxide (length of 200 nm, diameter 20nm), 12 parts of sodium polyacrylate, 13 parts of water-based polyurethane resin, 0.8 parts of dimethyloctadecyl[3-(triethoxysilyl)propyl]ammonium chloride, 2.5 parts of glycerol and 60 parts of water; calculated by mass, the raw materials of the antifouling solution include 8 parts of dimethyldiethoxysilane, 1.2 parts of dimethylhydrogensilane, 2 parts of trimethylsiloxane, 5 parts of methylpolysilazane resin and 55 parts of 120# solvent oil.

[0139] Example 3

[0140] A. Preparation of green body;

[0141] B. Printing color ink according to a preset pattern to form an inkjet printing layer;

[0142] C. Apply anti-fouling glaze to form an anti-fouling glaze layer;

[0143] Calculated by weight, the raw materials of the antifouling glaze include 60 parts of potassium feldspar, 28 parts of quartz, 12 parts of kaolin, 28 parts of wollastonite, 16 parts of dolomite, 8 parts of calcined talc, 10 parts of zinc oxide, 4 parts of strontium carbonate, 4 parts of barium carbonate and 5 parts of barium frit;

[0144] D. After drying, calcining in a kiln and polishing to obtain a polished semi-finished product; wherein the calcining temperature curve of calcining in the kiln includes a drying section, an oxidation section, a firing section, a rapid cooling section and a slow cooling section;

[0145] The drying stage is heated from room temperature to 300°C, which takes 15 minutes;

[0146] The oxidation stage is heated from 300°C to 900°C, which takes 20 minutes;

[0147] The firing stage is from 900℃ to 1220℃, which takes 20min;

[0148] The rapid cooling stage is from 1220℃ to 700℃, which takes 6 minutes;

[0149] The slow cooling stage is from 700℃ to 400℃, which takes 18 minutes;

[0150] E. Add the nano-fouling-resistant and antibacterial composite solution dropwise onto the surface of the polished semi-finished product, and after polishing, form a 5 μm thick antibacterial film layer to obtain a fouling-resistant and antibacterial soft-polished tile; wherein, calculated by weight, the nano-fouling-resistant and antibacterial composite solution includes 16 parts of an aqueous organosilicon-acrylic hybrid solution, 7 parts of an antibacterial dispersion, and 3 parts of an antifouling solution; calculated by weight, the raw materials of the aqueous organosilicon-acrylic hybrid solution include 18 parts of nano-silica (particle size of 400 nm), 65 parts of an organosilicon-grafted acrylic ionomer with a neutralization degree of 60%, and 45 parts of water; calculated by weight, the raw materials of the antibacterial dispersion include modified nanorod-shaped zinc oxide (length of 500 nm, diameter of 40 nm), 15 parts of sodium polyacrylate, 4 parts of water-based polyurethane resin, 10 parts of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, 0.8 parts of glycerol, 2 parts of water, and 70 parts of water; calculated by mass, the raw materials of the antifouling solution include 4 parts of dimethyldiethoxysilane, 0.8 parts of dimethylhydrogensilane, 1 part of trimethylsiloxane, 4 parts of methylpolysilazane resin, and 75 parts of 120# solvent oil.

[0151] Comparative Example 1

[0152] The preparation method and raw materials of Comparative Example 1 are the same as those of Example 1, except that the existing technology is used to prepare the stain-resistant and antibacterial soft-polished tiles in Comparative Example 1. The specific preparation method is as follows:

[0153] A. Preparation of green body;

[0154] B. Printing color ink according to a preset pattern to form an inkjet printing layer;

[0155] C. Apply antifouling and antibacterial glaze to form an antifouling and antibacterial glaze layer;

[0156] Calculated by weight, the raw materials of the antifouling and antibacterial glaze include 29 parts of albite, 23 parts of quartz sand, 30 parts of calcined kaolin, 7 parts of antibacterial compound (made by mixing titanium dioxide and tourmaline in a mass ratio of 3:2), 3 parts of strontium titanate, 2 parts of copper oxide microspheres, 2 parts of organosilicon-modified sodium phosphate, 1 part of tetraethyl orthosilicate, 1 part of polyvinyl alcohol, 1 part of polymethylsiloxane, and 5 parts of anti-wear agent (made by mixing wollastonite and zirconium oxide in a mass ratio of 3:2).

[0157] D. After drying, calcination in a kiln and polishing to obtain a polished semi-finished product;

[0158] The calcination temperature curve of the kiln calcination includes the drying section, oxidation section, sintering section, rapid cooling section and slow cooling section in sequence;

[0159] The drying stage is heated from room temperature to 300°C, which takes 10 minutes;

[0160] The oxidation stage is heated from 300°C to 900°C, which takes 25 minutes;

[0161] The firing stage was heated from 900°C to 1220°C, which took 22 minutes;

[0162] The rapid cooling stage is from 1220℃ to 700℃, which takes 6 minutes;

[0163] The slow cooling stage is from 700℃ to 400℃, which takes 20min;

[0164] E. Add the antifouling solution dropwise onto the surface of the polished semi-finished product, and form an antifouling glaze layer after polishing to obtain a stain-resistant and antibacterial soft-polished tile; wherein, calculated by weight, the raw materials of the antifouling solution include 10 parts of nano wax, 2 parts of hydroxypropyl cellulose, 3 parts of nano indium oxide, 2 parts of nano titanium dioxide, 1 part of polyacrylate leveling agent and 5 parts of γ-aminopropyl triethoxysilane.

[0165] Comparative Example 2

[0166] The preparation method and raw materials of Comparative Example 2 are the same as those of Example 1, except that step E is missing in Comparative Example 2, that is, no anti-fouling glaze layer is provided in Comparative Example 2.

[0167] Comparative Example 3

[0168] The preparation method and raw materials of Comparative Example 3 are the same as those of Example 1, except that wollastonite is not added to the antifouling glaze in Comparative Example 3.

[0169] Comparative Example 4

[0170] The preparation method and raw materials of Comparative Example 4 are the same as those of Example 1, except that zinc oxide is not added to the antifouling glaze in Comparative Example 4.

[0171] Comparative Example 5

[0172] The preparation method and raw materials of Comparative Example 5 are the same as those of Example 1, except that no barium frit is added to the antifouling glaze in Comparative Example 5.

[0173] Comparative Example 6

[0174] The preparation method and raw materials of Comparative Example 6 are the same as those of Example 1, except that the modified nanorod-shaped zinc oxide is not added to the antibacterial dispersion of Comparative Example 6.

[0175] The performance tests of the stain-resistant and antibacterial soft-polished tiles prepared in the examples and comparative examples were carried out, and the results are shown in Table 1 below:

[0176] Table 1 Performance test results of the stain-resistant and antibacterial soft polished tiles in the examples and comparative examples

[0177]

[0178] The test data in Table 1 demonstrates that the stain-resistant, antibacterial soft-polished tiles produced using the preparation method of this technical solution have a glossiness of ≤35°, stain resistance ≥Level 5, an antibacterial rate against Escherichia coli ≥99.5%, an antibacterial rate against Staphylococcus aureus ≥99.2%, an antibacterial durability against Escherichia coli ≥88.7%, and an antibacterial durability against Staphylococcus aureus ≥88.3%. Furthermore, comparative experiments revealed that the stain-resistant, antibacterial soft-polished tiles produced using this technical solution outperformed the stain-resistant, antibacterial soft-polished tiles of Comparative Example 1 (i.e., the prior art) in all performance test indicators. Therefore, the stain-resistant, antibacterial soft-polished tiles produced using the preparation method of this technical solution possess not only soft gloss properties but also excellent and long-lasting stain resistance and antibacterial properties, meeting practical application requirements.

[0179] Since no anti-fouling glaze layer was added or set in Comparative Example 2, the anti-fouling glaze layer itself could not be used to reduce the pores, resulting in more pores on the surface of the soft-polished tiles obtained in Comparative Example 2, and the stain resistance of the soft-polished tiles decreased. The decrease in the stain resistance of the soft-polished tiles themselves will also lead to a decrease in the durability of the stain resistance.

[0180] Since wollastonite was not added to the anti-fouling glaze in Comparative Example 3, zinc oxide was not added to the anti-fouling glaze in Comparative Example 4, and barium frit was not added to the anti-fouling glaze in Comparative Example 5, the polished semi-finished products obtained in Comparative Examples 3, 4 and 5 had more pores on their surfaces. Even if the pores were filled with a nano-fouling-resistant and antibacterial composite solution, the obtained soft-polished tiles still had pores, thereby affecting their anti-fouling performance and durability.

[0181] Since the antibacterial dispersion of Comparative Example 6 did not contain modified nanorod-shaped zinc oxide, not only was the pore-filling effect of the nano-fouling-resistant antibacterial composite solution limited, affecting the antibacterial performance and durability of the antibacterial properties, but the antibacterial properties of the modified nanorod-shaped zinc oxide could not be utilized, resulting in a significant decrease in the antibacterial performance of the resulting soft-polished tiles. This decrease in the antibacterial properties of the soft-polished tiles themselves also led to a decrease in their antibacterial durability. Furthermore, the absence of modified nanorod-shaped zinc oxide in the antibacterial dispersion of Comparative Example 6 also prevented the utilization of the modified nanorod-shaped zinc oxide's light-softening effect, resulting in the resulting soft-light tiles having a high gloss and a glaring luster.

[0182] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are intended solely to illustrate the principles of the present invention and are not to be construed in any way as limiting the scope of protection of the present invention. Based on the explanations herein, those skilled in the art will readily conceive of other specific embodiments of the present invention without inventive effort, and such embodiments will fall within the scope of protection of the present invention.

Claims

1. A method for preparing a stain-resistant and antibacterial soft-polished brick, characterized in that: The following steps are involved: A. Preparation of green body; B. Printing color ink according to a preset pattern to form an inkjet printing layer; C. Apply anti-fouling glaze to form an anti-fouling glaze layer; Calculated by weight, the raw materials of the antifouling glaze include 50-65 parts of potassium feldspar, 24-30 parts of quartz, 9-14 parts of kaolin, 22-28 parts of wollastonite, 12-16 parts of dolomite, 3-8 parts of calcined talc, 8-15 parts of zinc oxide, 2-6 parts of strontium carbonate, 2-5 parts of barium carbonate and 5-10 parts of barium frit; Calculated by mass percentage, the chemical composition of the barium frit includes BaO 35.28-51.24%, SiO2 32.13-44.37%, Al2O3 2.18-8.13%, B2O3 1.51-8.95%, ZnO 1.28-7.65%, CaO 1.25-3.87%, MgO1.24-1.58%, Na2O 0.23-1.61%, TiO2 0.2-0.3%, K2O 1.28-1.65% and ZrO2 2.53-4.89%; D. After drying, calcination in a kiln and polishing to obtain a polished semi-finished product; The calcination temperature curve of the kiln calcination includes a drying section, an oxidation section, a sintering section, a rapid cooling section and a slow cooling section in sequence; The drying stage is heated from room temperature to 300°C, which takes 10 to 15 minutes; The oxidation stage is heated from 300°C to 900°C, which takes 20 to 30 minutes; The firing stage is heated from 900°C to 1220°C, which takes 20 to 25 minutes; The rapid cooling stage is from 1220°C to 700°C, which takes 5 to 8 minutes; The slow cooling stage is from 700°C to 400°C, which takes 15 to 20 minutes; E. adding the nano-fouling-resistant and antibacterial composite solution dropwise onto the surface of the polished semi-finished product, and forming a fouling-resistant and antibacterial film layer after polishing to obtain a fouling-resistant and antibacterial soft-polished tile; The raw materials of the nano-fouling resistant and antibacterial composite solution include aqueous organosilicon-acrylic acid hybrid solution and antibacterial dispersion; The raw materials of the aqueous organosilicon-acrylic acid hybrid solution include nano-silicon dioxide, organosilicon-grafted acrylic acid ionomer and water, and the neutralization degree of the organosilicon-grafted acrylic acid ionomer is 50-70%; The raw materials of the antibacterial dispersion include modified nanorod-shaped zinc oxide, a quaternized silane coupling agent and water, and the surface of the modified nanorod-shaped zinc oxide contains hydroxyl groups.

2. The method for preparing a stain-resistant and antibacterial soft polished brick according to claim 1, characterized in that: In step E, the raw materials of the antibacterial dispersion further include a dispersant, an aqueous polyurethane resin, glycerol and water; Calculated by weight, the raw materials of the antibacterial dispersion include 12 to 20 parts of modified nanorod-shaped zinc oxide, 2 to 4 parts of dispersant, 8 to 13 parts of waterborne polyurethane resin, 0.5 to 0.8 parts of quaternized silane coupling agent, 1.2 to 2.5 parts of glycerol and 60 to 70 parts of water.

3. The method for preparing a stain-resistant and antibacterial soft polished brick according to claim 1, characterized in that: In step E, the raw materials of the nano-fouling resistant and antibacterial composite solution also include antifouling solution; Calculated by weight, the raw materials of the nano-fouling resistant and antibacterial composite solution include 5 to 10 parts of antibacterial dispersion, 10 to 18 parts of aqueous silicone-acrylic acid hybrid solution and 3 to 5 parts of antifouling solution.

4. The method for preparing a stain-resistant and antibacterial soft polished brick according to claim 3, characterized in that: Calculated by mass, the raw materials of the antifouling solution include 4 to 8 parts of dimethyldiethoxysilane, 0.6 to 1.2 parts of dimethylhydrogensilane, 0.5 to 2 parts of methyl silicone oil, 4 to 8 parts of methylpolysilazane resin and 60 to 75 parts of 120# solvent oil.

5. The method for preparing a stain-resistant and antibacterial soft polished brick according to claim 1, characterized in that: In step E, the particle size of the nano-silicon dioxide is 5 to 500 nm; The modified nanorod-shaped zinc oxide has a length of 100 to 500 nm and a diameter of 20 to 50 nm; The thickness of the antifouling and antibacterial film layer is 2 to 5 μm.

6. The method for preparing a stain-resistant and antibacterial soft polished brick according to claim 1, characterized in that: In step E, the raw materials of the aqueous organosilicon-acrylic acid hybrid solution include 10 to 18 parts by mass of nano-silicon dioxide, 45 to 65 parts of organosilicon-grafted acrylic acid ionomer, and 40 to 50 parts of water.

7. A stain-resistant and antibacterial soft-polished brick, characterized in that: The stain-resistant and antibacterial soft-polished brick is prepared by the preparation method of any one of claims 1 to 6, wherein the glossiness of the stain-resistant and antibacterial soft-polished brick is ≤35°, the stain resistance is ≥level 5, the antibacterial rate against Escherichia coli is ≥99.5%, the antibacterial rate against Staphylococcus aureus is ≥99.2%, the antibacterial durability against Escherichia coli is ≥88.7%, and the antibacterial durability against Staphylococcus aureus is ≥88.3%.

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