Antiskid antibacterial ceramic tile and preparation method thereof

Abstract

The invention discloses an antiskid antibacterial ceramic tile and a preparation method thereof, and belongs to the technical field of ceramic materials. Through the unique design of the green body layer, the composite functional layer and the surface treatment layer, the anti-skid and antibacterial ceramic tile achieves good anti-skid and lasting antibacterial performance. The raw material formula of the green body layer, such as kaolin, silicon carbide micro powder and the like, is reasonably proportioned, so that the basic strength and stability of the ceramic tile are ensured. In the composite functional layer, zinc phosphate coated nano-zinc oxide and silver-loaded zeolite are key antibacterial materials, and the ceramic tile has an efficient and lasting antibacterial effect under the combined action of the zinc phosphate coated nano-zinc oxide and the silver-loaded zeolite. The surface treatment layer is formed by carrying out gradient concentration treatment on anti-skid liquid containing an organic metal framework material, the anti-skid antibacterial ceramic tile solves the problems that a traditional ceramic tile is insufficient in anti-skid performance and not lasting in antibacterial effect, can be widely applied to various public places and home decoration, and provides a safe and sanitary living and working environment for people.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic materials, and particularly relates to an anti-slip and antibacterial ceramic tile and a preparation method thereof. Background Art

[0002] Ceramic tiles, a new architectural decorative material, are available in a wide variety of patterns and designs, significantly enhancing the decorative effect of any building and gaining widespread popularity. Their use in public buildings and office spaces, where they offer a beautifying effect and ease of cleaning, has led to their widespread adoption in the renovation and construction of high-end structures such as office buildings. While ceramic tiles play a significant role in enhancing environmental beauty, their smooth surface is susceptible to stains and slipping, making them prone to falls and safety hazards. Every year, slippery surfaces cause casualties in public spaces.

[0003] The friction coefficient of ceramic tiles is affected by their friction coefficient. When choosing tiles for public places, such as plazas, shopping malls, and restaurants, it is important to pay attention to their friction coefficient. Choosing an incorrect friction coefficient can lead to safety issues and accidents. During use, ceramic tiles lose their surface finish due to friction, and the surface becomes worn, affecting their performance.

[0004] In addition, as people pay more and more attention to healthy living, the antibacterial properties of ceramic tiles are becoming more and more important. In the daily use of traditional ceramic tiles, bacteria such as Escherichia coli and Staphylococcus aureus are easily bred on the surface. These bacteria not only affect the indoor environmental hygiene, but may also pose a threat to human health, especially in places with dense crowds or high hygiene requirements such as hospitals, schools, and homes. Although some existing antibacterial ceramic tiles can inhibit bacterial growth to a certain extent, the antibacterial effect is often not long-lasting. As the use time increases, the antibacterial performance gradually decreases. Moreover, the antibacterial agents used in the preparation process of some antibacterial ceramic tiles may have potential hazards to the environment and are not in line with the development concept of green environmental protection. Therefore, it is of great practical significance to develop a ceramic tile that has good anti-slip properties, long-lasting antibacterial properties and is environmentally friendly. The present invention aims to solve the above problems and provide a new anti-slip and antibacterial ceramic tile and a preparation method thereof to meet the market demand for high-quality ceramic tiles. Summary of the Invention

[0005] The present invention addresses the problems existing in the prior art and provides a non-slip and antibacterial ceramic tile and a preparation method thereof. The non-slip and antibacterial ceramic tile achieves excellent non-slip and long-lasting antibacterial properties through a unique design of a base layer, a composite functional layer, and a surface treatment layer.

[0006] The raw material formula of the body layer, such as the rational ratio of kaolin and silicon carbide micropowder, ensures the basic strength and stability of the tile. In the composite functional layer, diatomaceous earth has excellent adsorption properties, which can help other antimicrobial ingredients to work better. Zinc phosphate-coated nano-zinc oxide and silver-loaded zeolite are key antimicrobial materials. Their synergistic effect gives the tile a highly effective and long-lasting antimicrobial effect.

[0007] The surface treatment layer is formed using an anti-slip liquid containing an organometallic skeleton material through a gradient concentration treatment. The water-based polyurethane resin provides excellent film-forming properties and wear resistance, while the modified Zn-MOF-74 antimicrobial agent further enhances the antimicrobial properties. Nano-silica anti-slip particles improve the anti-slip properties of the tile surface. This gradient concentration treatment method allows the anti-slip liquid to better penetrate and solidify on the tile surface, forming a stable anti-slip and antimicrobial layer. This anti-slip and antibacterial tile not only addresses the shortcomings of traditional tiles in terms of anti-slip performance and short-lasting antimicrobial effects, but also emphasizes environmental protection during the manufacturing process, meeting modern society's requirements for green building materials. It can be widely used in various public spaces and home decoration, providing people with a safe and hygienic living and working environment.

[0008] In order to achieve the above technical objectives, the technical solution adopted by the present invention is: An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0009] Furthermore, the waste layer comprises the following raw materials in parts by mass: 40-50 parts of kaolin, 8-12 parts of silicon carbide powder, 15-20 parts of waste porcelain particles, and 10-15 parts of bentonite.

[0010] Furthermore, the composite functional layer comprises the following raw materials in parts by mass: 15-25 parts of diatomaceous earth, 5-10 parts of zinc phosphate-coated nano-zinc oxide, 3-8 parts of silver-loaded zeolite, 10-15 parts of potassium feldspar powder, and 1-3 parts of carboxymethyl cellulose.

[0011] Furthermore, the preparation method of the zinc phosphate-coated nano zinc oxide is: (1) Preparation of precursor solution: 2.0 mol / L zinc nitrate Zn(NO3)2·6H2O solution was mixed with an equal volume of ethanol, stirred until clear, and citric acid was added as a complexing agent with a molar ratio of Zn 2+ : citric acid = 1:1.5, and use ammonia water to maintain pH = 8-9 to obtain a precursor solution; (2) Gel formation: Heat the precursor solution in a water bath at 50-60°C and continue stirring until a transparent sol is formed; dry at 75-80°C for 10-12 hours to obtain a ZnO precursor xerogel; (3) Calcination treatment: The dry gel was placed in a muffle furnace and heated to 450°C at a rate of 5°C / min, kept at this temperature for 2 hours, cooled naturally, and ground to obtain white powder nano-ZnO with a particle size of 30-50 nm; (4) Dispersion system construction: Nano-ZnO was dispersed in deionized water to prepare a suspension with a concentration of 5 wt%, and ultrasonicated for 30 min at an ultrasonic power of 300 W; (5) Phosphate precipitation: add 0.5 mol / L Na2HPO4 solution to the suspension at a molar ratio of ZnO:Zn3(PO4)2=7:3 at a flow rate of 2 mL / min. The reaction temperature was controlled at 60°C. The pH was adjusted to 8.5 with NaOH and the mixture was stirred for 4 h. (6) Post-treatment: centrifugation at 8000 rpm for 10 min, washing with ethanol three times to remove impurities, vacuum drying at 80°C for 6 hours, and ball milling to obtain zinc phosphate-coated nano-zinc oxide with a particle size of 300-500 nm.

[0012] Furthermore, the preparation method of the silver-loaded zeolite is as follows: the natural zeolite is crushed and passed through a 400-mesh sieve, soaked in 3 mol / L HCl for 2 hours at a solid-liquid ratio of 1:10 to remove impurity ions, washed with deionized water until neutral, and dried at 120°C to obtain a pretreated zeolite for standby use; the pretreated zeolite is mixed with a 0.1 mol / LAgNO3 solution at a solid-liquid ratio of 1:15, stirred in a water bath at 60°C and 200 rpm for 6 hours, and operated in the dark; 0.12% NaBH4 by mass of the system is added, stirred for 30 minutes, and washed with deionized water until there is no NO3 - Detection: After centrifugal separation, the solid is crushed by jet mill to control the particle size D 50 =5μm, calcined at 300℃ for 1 hour to obtain silver-loaded zeolite.

[0013] Furthermore, the surface treatment layer is formed by gradient concentration treatment of an anti-slip liquid containing an organic metal skeleton material. Anti-slip liquids of different concentrations are prepared by the following method: 40 parts of aqueous polyurethane resin, 10 parts of modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain anti-slip liquids with premix mass concentrations of 50%, 70% and 90%, respectively.

[0014] The nano-silicon dioxide anti-skid particles can be commercially available nano-scale silicon dioxide.

[0015] Furthermore, the preparation method of the modified Zn-MOF-74 antibacterial agent is: (1) Dissolve 6.5 g of 2-methylimidazole and 3.0 g of Zn(NO3)2·6H2O in 80 mL of methanol, react at 80°C for 12 h, and centrifuge and wash to obtain a solid; (2) 10 g of solid was immersed in 0.05 MAgNO3 solution, H2 was introduced to 0.5 MPa, the reaction was carried out at 80 °C for 4 h, and then centrifuged and dried to obtain Ag@MOF; (3) 5 g of Ag@MOF was dispersed in 20 mL of 2 wt% acetic acid solution, 1.5 g of chitosan (deacetylation degree ≥ 90%) was added, stirred at 60 °C for 4 h, and centrifuged to obtain CS&Ag@MOF; (4) Immerse the CS&Ag@MOF in a mineralization solution composed of 3 g / L Na2SiO3, 2 g / L KH2PO4, and 1 g / L CaCl2, stir at 60 °C for 48 h, and dry to obtain the finished product.

[0016] A method for preparing anti-slip and antibacterial tiles comprises the following steps: (1) Green body forming: Weigh the raw materials of the green body layer according to their mass, ball-mill them to a particle size of ≤45 μm, add water according to 6%-7% of the total mass of the raw materials, mix them evenly, and press them into a green body using a semi-dry pressing process. The green body forming pressure is 20-30 MPa, the holding time is 10-15 s, and the temperature is raised to 1180-1220 ° C at 5 ° C / min, kept at this temperature for 30 min, and cooled to room temperature with the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Functional layer coating: Weigh the raw materials of the composite functional layer according to their mass, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1000-1500 mPa·s and the coating thickness is 0.5-1 mm; (4) Drying treatment: Dry the green body coated with the composite functional layer at 100-120°C for 2-3 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Anti-slip liquids of different concentrations are sequentially applied to the surface of the ceramic tiles in a gradient concentration manner. First, an anti-slip liquid with a mass concentration of 50% is sprayed at a spraying amount of 30 g / m² and cured at 80°C for 5 minutes. Then, an anti-slip liquid with a mass concentration of 70% is sprayed at a spraying amount of 25 g / m² and cured at 90°C for 8 minutes. Finally, an anti-slip liquid with a mass concentration of 90% is sprayed at a spraying amount of 20 g / m² and cured at 100°C for 10 minutes. After natural cooling, fine grinding and polishing are performed to obtain anti-slip and antibacterial ceramic tiles.

[0017] Beneficial effects: First, the present invention divides traditional ceramic materials into three layers, including a body layer, a composite functional layer, and a surface treatment layer. Silicon carbide micropowder, waste porcelain particles, and other raw materials are added to the body layer. Silicon carbide micropowder has high hardness and can form micro-protrusions on the body surface, thereby increasing the bonding strength of the composite functional layer. The acid-soluble CaO / MgO in the waste porcelain particles can generate calcium feldspar during sintering, filling gaps and reducing water absorption. At the same time, it can reduce the production cost of the body and achieve effective resource utilization. The rational proportion of the two with raw materials such as kaolin and bentonite ensures the basic strength and stability of the tiles, making them less likely to break or deform during use.

[0018] In the composite functional layer, the porous structure of diatomaceous earth gives it excellent adsorption properties, capable of absorbing harmful gases and odors in the air, while also assisting other antibacterial ingredients in better functioning. Zinc phosphate-coated nano-zinc oxide and silver-loaded zeolite are key antibacterial materials, and their combined effect gives the tiles a highly efficient and long-lasting antibacterial effect. Zinc phosphate-coated nano-zinc oxide can continuously release zinc ions, which has inhibitory and killing effects on a variety of bacteria; the silver ions in the silver-loaded zeolite have broad-spectrum antibacterial properties and can effectively inhibit the growth and reproduction of common bacteria such as Escherichia coli and Staphylococcus aureus. The addition of potassium feldspar powder and carboxymethyl cellulose helps to adjust the properties of the slurry, allowing the composite functional layer to be better coated on the surface of the body.

[0019] The surface treatment layer is formed using an anti-slip liquid containing an organic metal skeleton material through a gradient concentration treatment. The water-based polyurethane resin provides excellent film-forming properties and abrasion resistance, imparting a certain gloss and scratch resistance to the tile surface. The modified Zn-MOF-74 antimicrobial agent further enhances the antimicrobial properties. The porous organic skeleton structure enables a long-lasting and efficient sustained-release antimicrobial effect, enhancing the antibacterial effect. The addition of nano-silica anti-slip particles significantly improves the anti-slip properties of the tile surface.

[0020] Crucially, the present invention uses anti-skid liquids of varying mass concentrations: 50% anti-skid liquid treatment deeply penetrates the micropores of the base, 70% spraying fills the interspaces in the middle layer, and forms an interpenetrating network with the base layer; 90% spraying enriches the surface with nano-SiO2 particles, forming a micron-scale rough structure. When a person's foot or a vehicle's tire contacts the tile surface, the particles on the surface generate a mechanical bite force with the contact surface, and the pore structure on the tile surface forms a suction force with the contact surface. The combined effect of these two forces increases the friction between the tile surface and the contact surface. Silane coupling agent KH-560 enhances the bonding strength between nano-SiO2 and the Zn-MOF-74 skeleton, making the system more stable.

[0021] This gradient concentration treatment allows the anti-slip liquid to better penetrate and solidify on the tile surface, forming a stable anti-slip and antibacterial layer. It also facilitates the stable release of the antimicrobial agent, enhancing its antimicrobial effect. This treatment not only improves the tile's anti-slip performance but also enhances the durability of its antimicrobial effect.

[0022] In summary, the anti-slip and antibacterial tiles of the present invention, through their unique three-layer structure and rational raw material ratio, not only address the issues of conventional tiles with insufficient anti-slip performance and short-lasting antibacterial effects, but also prioritize environmental protection during their production, meeting modern society's demand for green building materials. These tiles can be widely used in various public spaces and home decoration, providing a safe and hygienic living and working environment. DETAILED DESCRIPTION

[0023] The technical solution of the present invention will be further described below with reference to specific embodiments, but is not limited thereto.

[0024] Example 1 An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0025] The bad layer comprises the following raw materials in parts by mass: 40 parts of kaolin, 12 parts of silicon carbide powder, 15 parts of waste porcelain particles, and 10 parts of bentonite.

[0026] The composite functional layer comprises the following raw materials in parts by mass: 15 parts of diatomaceous earth, 10 parts of zinc phosphate-coated nano-zinc oxide, 8 parts of silver-loaded zeolite, 10 parts of potassium feldspar powder, and 1 part of carboxymethyl cellulose.

[0027] The preparation method of the zinc phosphate-coated nano zinc oxide is as follows: (1) Preparation of precursor solution: 2.0 mol / L zinc nitrate Zn(NO3)2·6H2O solution was mixed with an equal volume of ethanol, stirred until clear, and citric acid was added as a complexing agent with a molar ratio of Zn 2+ : citric acid = 1:1.5, and use ammonia water to maintain pH = 8-9 to obtain a precursor solution; (2) Gel formation: Heat the precursor solution in a water bath at 50-60°C and continue stirring until a transparent sol is formed; dry at 75-80°C for 10-12 hours to obtain a ZnO precursor xerogel; (3) Calcination treatment: The dry gel was placed in a muffle furnace and heated to 450°C at a rate of 5°C / min, kept at this temperature for 2 hours, cooled naturally, and ground to obtain white powder nano-ZnO with a particle size of 30-50 nm; (4) Dispersion system construction: Nano-ZnO was dispersed in deionized water to prepare a suspension with a concentration of 5 wt%, and ultrasonicated for 30 min at an ultrasonic power of 300 W; (5) Phosphate precipitation: add 0.5 mol / L Na2HPO4 solution to the suspension at a molar ratio of ZnO:Zn3(PO4)2=7:3 at a flow rate of 2 mL / min. The reaction temperature was controlled at 60°C. The pH was adjusted to 8.5 with NaOH and the mixture was stirred for 4 h. (6) Post-treatment: centrifugation at 8000 rpm for 10 min, washing with ethanol three times to remove impurities, vacuum drying at 80°C for 6 hours, and ball milling to obtain zinc phosphate-coated nano-zinc oxide with a particle size of 300-500 nm.

[0028] The preparation method of the silver-loaded zeolite is as follows: natural zeolite is crushed and then passed through a 400-mesh sieve, soaked in 3 mol / L HCl for 2 hours at a solid-liquid ratio of 1:10 to remove impurity ions, washed with deionized water until neutral, and dried at 120° C. to obtain pretreated zeolite for use; the pretreated zeolite is mixed with a 0.1 mol / L AgNO3 solution at a solid-liquid ratio of 1:15, stirred in a water bath at 60° C. and 200 rpm for 6 hours in the dark; 0.12% of NaBH4 by mass of the system is added, stirred for 30 minutes, and washed with deionized water until no NO3 is present. - Detection: After centrifugal separation, the solid is crushed by jet mill to control the particle size D 50 =5μm, calcined at 300℃ for 1 hour to obtain silver-loaded zeolite.

[0029] The surface treatment layer is formed by an anti-slip liquid containing an organic metal skeleton material through gradient concentration treatment. The anti-slip liquids of different concentrations are prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain anti-slip liquids with premix mass concentrations of 50%, 70%, and 90%, respectively.

[0030] The preparation method of the modified Zn-MOF-74 antibacterial agent is: (1) Dissolve 6.5 g of 2-methylimidazole and 3.0 g of Zn(NO3)2·6H2O in 80 mL of methanol, react at 80°C for 12 h, and centrifuge and wash to obtain a solid; (2) 10 g of solid was immersed in 0.05 MAgNO3 solution, H2 was introduced to 0.5 MPa, the reaction was carried out at 80 °C for 4 h, and then centrifuged and dried to obtain Ag@MOF; (3) 5 g of Ag@MOF was dispersed in 20 mL of 2 wt% acetic acid solution, 1.5 g of chitosan (deacetylation degree ≥ 90%) was added, stirred at 60 °C for 4 h, and centrifuged to obtain CS&Ag@MOF; (4) Immerse the CS&Ag@MOF in a mineralization solution composed of 3 g / L Na2SiO3, 2 g / L KH2PO4, and 1 g / L CaCl2, stir at 60 °C for 48 h, and dry to obtain the finished product.

[0031] A method for preparing anti-slip and antibacterial tiles comprises the following steps: (1) Green body forming: The raw materials of the green body layer were weighed by weight, ball-milled to a particle size of ≤45 μm, and water was added according to 6% of the total weight of the raw materials. After mixing evenly, the green body was pressed into a green body by a semi-dry pressing process. The green body forming pressure was 20 MPa, the holding time was 10 s, and the temperature was raised to 1180-1220 °C at 5 °C / min, kept at this temperature for 30 min, and cooled to room temperature in the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Functional layer coating: Weigh the raw materials of the composite functional layer according to their mass, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1000 mPa·s and the coating thickness is 0.5 mm. (4) Drying treatment: Dry the green body coated with the composite functional layer at 100°C for 2 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Anti-slip liquids of different concentrations are sequentially applied to the surface of the ceramic tiles in a gradient concentration manner. First, an anti-slip liquid with a mass concentration of 50% is sprayed at a spraying amount of 30 g / m² and cured at 80°C for 5 minutes. Then, an anti-slip liquid with a mass concentration of 70% is sprayed at a spraying amount of 25 g / m² and cured at 90°C for 8 minutes. Finally, an anti-slip liquid with a mass concentration of 90% is sprayed at a spraying amount of 20 g / m² and cured at 100°C for 10 minutes. After natural cooling, fine grinding and polishing are performed to obtain anti-slip and antibacterial ceramic tiles.

[0032] Example 2 An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0033] The bad layer comprises the following raw materials in parts by mass: 45 parts of kaolin, 10 parts of silicon carbide powder, 18 parts of waste porcelain particles, and 12 parts of bentonite.

[0034] The composite functional layer comprises the following raw materials in parts by mass: 20 parts of diatomaceous earth, 7 parts of zinc phosphate-coated nano-zinc oxide, 5 parts of silver-loaded zeolite, 13 parts of potassium feldspar powder, and 2 parts of carboxymethyl cellulose.

[0035] The preparation method of the zinc phosphate-coated nano zinc oxide is as follows: (1) Preparation of precursor solution: 2.0 mol / L zinc nitrate Zn(NO3)2·6H2O solution was mixed with an equal volume of ethanol, stirred until clear, and citric acid was added as a complexing agent with a molar ratio of Zn 2+ : citric acid = 1:1.5, and use ammonia water to maintain pH = 8-9 to obtain a precursor solution; (2) Gel formation: Heat the precursor solution in a water bath at 50-60°C and continue stirring until a transparent sol is formed; dry at 75-80°C for 10-12 hours to obtain a ZnO precursor xerogel; (3) Calcination treatment: The dry gel was placed in a muffle furnace and heated to 450°C at a rate of 5°C / min, kept at this temperature for 2 hours, cooled naturally, and ground to obtain white powder nano-ZnO with a particle size of 30-50 nm; (4) Dispersion system construction: Nano-ZnO was dispersed in deionized water to prepare a suspension with a concentration of 5 wt%, and ultrasonicated for 30 min at an ultrasonic power of 300 W; (5) Phosphate precipitation: add 0.5 mol / L Na2HPO4 solution to the suspension at a molar ratio of ZnO:Zn3(PO4)2=7:3 at a flow rate of 2 mL / min. The reaction temperature was controlled at 60°C. The pH was adjusted to 8.5 with NaOH and the mixture was stirred for 4 h. (6) Post-treatment: centrifugation at 8000 rpm for 10 min, washing with ethanol three times to remove impurities, vacuum drying at 80°C for 6 hours, and ball milling to obtain zinc phosphate-coated nano-zinc oxide with a particle size of 300-500 nm.

[0036] The preparation method of the silver-loaded zeolite is as follows: natural zeolite is crushed and then passed through a 400-mesh sieve, soaked in 3 mol / L HCl for 2 hours at a solid-liquid ratio of 1:10 to remove impurity ions, washed with deionized water until neutral, and dried at 120° C. to obtain pretreated zeolite for use; the pretreated zeolite is mixed with a 0.1 mol / L AgNO3 solution at a solid-liquid ratio of 1:15, stirred in a water bath at 60° C. and 200 rpm for 6 hours in the dark; 0.12% of NaBH4 by mass of the system is added, stirred for 30 minutes, and washed with deionized water until no NO3 is present. - Detection: After centrifugal separation, the solid is crushed by jet mill to control the particle size D 50 =5μm, calcined at 300℃ for 1 hour to obtain silver-loaded zeolite.

[0037] The surface treatment layer is formed by an anti-slip liquid containing an organic metal skeleton material through gradient concentration treatment. The anti-slip liquids of different concentrations are prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain anti-slip liquids with premix mass concentrations of 50%, 70%, and 90%, respectively.

[0038] The preparation method of the modified Zn-MOF-74 antibacterial agent is: (1) Dissolve 6.5 g of 2-methylimidazole and 3.0 g of Zn(NO3)2·6H2O in 80 mL of methanol, react at 80°C for 12 h, and centrifuge and wash to obtain a solid; (2) 10 g of solid was immersed in 0.05 MAgNO3 solution, H2 was introduced to 0.5 MPa, the reaction was carried out at 80 °C for 4 h, and then centrifuged and dried to obtain Ag@MOF; (3) 5 g of Ag@MOF was dispersed in 20 mL of 2 wt% acetic acid solution, 1.5 g of chitosan (deacetylation degree ≥ 90%) was added, stirred at 60 °C for 4 h, and centrifuged to obtain CS&Ag@MOF; (4) Immerse the CS&Ag@MOF in a mineralization solution composed of 3 g / L Na2SiO3, 2 g / L KH2PO4, and 1 g / L CaCl2, stir at 60 °C for 48 h, and dry to obtain the finished product.

[0039] A method for preparing anti-slip and antibacterial tiles comprises the following steps: (1) Green body forming: The raw materials of the green body layer were weighed by weight, ball-milled to a particle size of ≤45 μm, and water was added according to 7% of the total weight of the raw materials. After mixing evenly, the green body was pressed into a green body by a semi-dry pressing process. The green body forming pressure was 30 MPa, the holding time was 15 s, and the temperature was raised to 1180-1220 °C at 5 °C / min, kept at this temperature for 30 min, and cooled to room temperature in the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Functional layer coating: Weigh the raw materials of the composite functional layer according to their mass, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1500 mPa·s and the coating thickness is 1 mm. (4) Drying treatment: Dry the green body coated with the composite functional layer at 120°C for 3 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Anti-slip liquids of different concentrations are sequentially applied to the surface of the ceramic tiles in a gradient concentration manner. First, an anti-slip liquid with a mass concentration of 50% is sprayed at a spraying amount of 30 g / m² and cured at 80°C for 5 minutes. Then, an anti-slip liquid with a mass concentration of 70% is sprayed at a spraying amount of 25 g / m² and cured at 90°C for 8 minutes. Finally, an anti-slip liquid with a mass concentration of 90% is sprayed at a spraying amount of 20 g / m² and cured at 100°C for 10 minutes. After natural cooling, fine grinding and polishing are performed to obtain anti-slip and antibacterial ceramic tiles.

[0040] Example 3 An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0041] The bad layer comprises the following raw materials in parts by mass: 50 parts of kaolin, 8 parts of silicon carbide powder, 20 parts of waste porcelain particles, and 15 parts of bentonite.

[0042] The composite functional layer comprises the following raw materials in parts by mass: 25 parts of diatomaceous earth, 5 parts of zinc phosphate-coated nano-zinc oxide, 3 parts of silver-loaded zeolite, 15 parts of potassium feldspar powder, and 3 parts of carboxymethyl cellulose.

[0043] The preparation method of the zinc phosphate-coated nano zinc oxide is as follows: (1) Preparation of precursor solution: 2.0 mol / L zinc nitrate Zn(NO3)2·6H2O solution was mixed with an equal volume of ethanol, stirred until clear, and citric acid was added as a complexing agent with a molar ratio of Zn 2+ : citric acid = 1:1.5, and use ammonia water to maintain pH = 8-9 to obtain a precursor solution; (2) Gel formation: Heat the precursor solution in a water bath at 50-60°C and continue stirring until a transparent sol is formed; dry at 75-80°C for 10-12 hours to obtain a ZnO precursor xerogel; (3) Calcination treatment: The dry gel was placed in a muffle furnace and heated to 450°C at a rate of 5°C / min, kept at this temperature for 2 hours, cooled naturally, and ground to obtain white powder nano-ZnO with a particle size of 30-50 nm; (4) Dispersion system construction: Nano-ZnO was dispersed in deionized water to prepare a suspension with a concentration of 5 wt%, and ultrasonicated for 30 min at an ultrasonic power of 300 W; (5) Phosphate precipitation: add 0.5 mol / L Na2HPO4 solution to the suspension at a molar ratio of ZnO:Zn3(PO4)2=7:3 at a flow rate of 2 mL / min. The reaction temperature was controlled at 60°C. The pH was adjusted to 8.5 with NaOH and the mixture was stirred for 4 h. (6) Post-treatment: centrifugation at 8000 rpm for 10 min, washing with ethanol three times to remove impurities, vacuum drying at 80°C for 6 hours, and ball milling to obtain zinc phosphate-coated nano-zinc oxide with a particle size of 300-500 nm.

[0044] The preparation method of the silver-loaded zeolite is as follows: natural zeolite is crushed and then passed through a 400-mesh sieve, soaked in 3 mol / L HCl for 2 hours at a solid-liquid ratio of 1:10 to remove impurity ions, washed with deionized water until neutral, and dried at 120° C. to obtain pretreated zeolite for use; the pretreated zeolite is mixed with a 0.1 mol / L AgNO3 solution at a solid-liquid ratio of 1:15, stirred in a water bath at 60° C. and 200 rpm for 6 hours in the dark; 0.12% of NaBH4 by mass of the system is added, stirred for 30 minutes, and washed with deionized water until no NO3 is present. - Detection: After centrifugal separation, the solid is crushed by jet mill to control the particle size D 50 =5μm, calcined at 300℃ for 1 hour to obtain silver-loaded zeolite.

[0045] The surface treatment layer is formed by an anti-slip liquid containing an organic metal skeleton material through gradient concentration treatment. The anti-slip liquids of different concentrations are prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain anti-slip liquids with premix mass concentrations of 50%, 70%, and 90%, respectively.

[0046] The preparation method of the modified Zn-MOF-74 antibacterial agent is: (1) Dissolve 6.5 g of 2-methylimidazole and 3.0 g of Zn(NO3)2·6H2O in 80 mL of methanol, react at 80°C for 12 h, and centrifuge and wash to obtain a solid; (2) 10 g of solid was immersed in 0.05 MAgNO3 solution, H2 was introduced to 0.5 MPa, the reaction was carried out at 80 °C for 4 h, and then centrifuged and dried to obtain Ag@MOF; (3) 5 g of Ag@MOF was dispersed in 20 mL of 2 wt% acetic acid solution, 1.5 g of chitosan (deacetylation degree ≥ 90%) was added, stirred at 60 °C for 4 h, and centrifuged to obtain CS&Ag@MOF; (4) Immerse the CS&Ag@MOF in a mineralization solution composed of 3 g / L Na2SiO3, 2 g / L KH2PO4, and 1 g / L CaCl2, stir at 60 °C for 48 h, and dry to obtain the finished product.

[0047] A method for preparing anti-slip and antibacterial tiles comprises the following steps: (1) Green body forming: The raw materials of the green body layer were weighed by weight, ball-milled to a particle size of ≤45 μm, and water was added according to 7% of the total weight of the raw materials. After mixing evenly, the green body was pressed into a green body by a semi-dry pressing process. The green body forming pressure was 30 MPa, the holding time was 15 s, and the temperature was raised to 1180-1220 °C at 5 °C / min, kept at this temperature for 30 min, and cooled to room temperature in the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Functional layer coating: Weigh the raw materials of the composite functional layer according to their mass, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1500 mPa·s and the coating thickness is 1 mm. (4) Drying treatment: Dry the green body coated with the composite functional layer at 120°C for 3 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Anti-slip liquids of different concentrations are sequentially applied to the surface of the ceramic tiles in a gradient concentration manner. First, an anti-slip liquid with a mass concentration of 50% is sprayed at a spraying amount of 30 g / m² and cured at 80°C for 5 minutes. Then, an anti-slip liquid with a mass concentration of 70% is sprayed at a spraying amount of 25 g / m² and cured at 90°C for 8 minutes. Finally, an anti-slip liquid with a mass concentration of 90% is sprayed at a spraying amount of 20 g / m² and cured at 100°C for 10 minutes. After natural cooling, fine grinding and polishing are performed to obtain anti-slip and antibacterial ceramic tiles.

[0048] Comparative Example 1 In this comparative example, except that only ordinary Zn-MOF-74 antibacterial agent was used in the surface treatment layer, the rest of the raw materials and process steps were the same as those in Example 1. An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0049] The surface treatment layer is formed by gradient concentration treatment of an anti-slip liquid containing an organic metal skeleton material. Anti-slip liquids of different concentrations are prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are thoroughly mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain anti-slip liquids with premix mass concentrations of 50%, 70%, and 90%, respectively.

[0050] The preparation method of the Zn-MOF-74 antibacterial agent is as follows: (1) Dissolve 6.5 g of 2-methylimidazole and 3.0 g of Zn(NO3)2·6H2O in 80 mL of methanol, react at 80°C for 12 h, and centrifuge and wash to obtain a solid; (2) Take 10g of the solid and immerse it in 0.05MAgNO3 solution, pass H2 to 0.5MPa, react at 80℃ for 4h, and centrifuge and dry to obtain the finished product.

[0051] Comparative Example 2 In this comparative example, except that only 50% of the anti-slip liquid was used for the surface treatment layer, the remaining raw materials and process steps were the same as those of Example 1.

[0052] An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0053] The surface treatment layer is formed by treating an anti-slip liquid containing an organic metal skeleton material. The anti-slip liquid is prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain an anti-slip liquid with a premix mass concentration of 50%.

[0054] A method for preparing anti-slip and antibacterial tiles comprises the following steps: (1) Green body forming: The raw materials of the green body layer were weighed by weight, ball-milled to a particle size of ≤45 μm, and water was added according to 6% of the total weight of the raw materials. After mixing evenly, the green body was pressed into a green body by a semi-dry pressing process. The green body forming pressure was 20 MPa, the holding time was 10 s, and the temperature was raised to 1180-1220 °C at 5 °C / min, kept at this temperature for 30 min, and cooled to room temperature in the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Functional layer coating: Weigh the raw materials of the composite functional layer according to their mass, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1000 mPa·s and the coating thickness is 0.5 mm. (4) Drying treatment: Dry the green body coated with the composite functional layer at 100°C for 2 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Treat the surface of the ceramic tile with anti-slip liquid, spray with a mass concentration of 50%, spray amount of 30g / m², and cure at 80℃ for 5min; then spray with a mass concentration of 50%, spray amount of 25g / m², and cure at 90℃ for 8min; finally spray with a mass concentration of 50%, spray amount of 20g / m², and cure at 100℃ for 10min. After natural cooling, fine grinding and polishing are carried out to obtain anti-slip and antibacterial ceramic tiles.

[0055] Comparative Example 3 In this comparative example, except that only 70% of the anti-slip liquid was used for the surface treatment layer, the remaining raw materials and process steps were the same as those of Example 1.

[0056] An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0057] The surface treatment layer is formed by treating an anti-slip liquid containing an organic metal skeleton material. The anti-slip liquid is prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain an anti-slip liquid with a premix mass concentration of 70%.

[0058] A method for preparing anti-slip and antibacterial tiles comprises the following steps: (1) Green body forming: The raw materials of the green body layer were weighed by weight, ball-milled to a particle size of ≤45 μm, and water was added according to 6% of the total weight of the raw materials. After mixing evenly, the green body was pressed into a green body by a semi-dry pressing process. The green body forming pressure was 20 MPa, the holding time was 10 s, and the temperature was raised to 1180-1220 °C at 5 °C / min, kept at this temperature for 30 min, and cooled to room temperature in the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Functional layer coating: Weigh the raw materials of the composite functional layer according to their mass, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1000 mPa·s and the coating thickness is 0.5 mm. (4) Drying treatment: Dry the green body coated with the composite functional layer at 100°C for 2 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Treat the surface of the ceramic tile with anti-slip liquid. Spray the anti-slip liquid with a mass concentration of 70% at a spraying amount of 30g / m² and cure it at 80℃ for 5min. Then spray the anti-slip liquid with a mass concentration of 70% at a spraying amount of 25g / m² and cure it at 90℃ for 8min. Finally, spray the anti-slip liquid with a mass concentration of 70% at a spraying amount of 20g / m² and cure it at 100℃ for 10min. After cooling naturally, fine grinding and polishing are carried out to obtain anti-slip and antibacterial ceramic tiles.

[0059] Comparative Example 4 In this comparative example, except that only 90% of the anti-slip liquid was used for the surface treatment layer, the rest of the raw materials and process steps were the same as those in Example 1.

[0060] An anti-slip and antibacterial ceramic tile comprises a body layer, a composite functional layer and a surface treatment layer.

[0061] The surface treatment layer is formed by treating an anti-slip liquid containing an organic metal skeleton material. The anti-slip liquid is prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain an anti-slip liquid with a premix mass concentration of 90%.

[0062] A method for preparing anti-slip and antibacterial tiles comprises the following steps: (1) Green body forming: The raw materials of the green body layer were weighed by weight, ball-milled to a particle size of ≤45 μm, and water was added according to 6% of the total weight of the raw materials. After mixing evenly, the green body was pressed into a green body by a semi-dry pressing process. The green body forming pressure was 20 MPa, the holding time was 10 s, and the temperature was raised to 1180-1220 °C at 5 °C / min, kept at this temperature for 30 min, and cooled to room temperature in the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Functional layer coating: Weigh the raw materials of the composite functional layer according to their mass, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1000 mPa·s and the coating thickness is 0.5 mm. (4) Drying treatment: Dry the green body coated with the composite functional layer at 100°C for 2 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Treat the surface of the ceramic tile with anti-slip liquid. Spray the anti-slip liquid with a mass concentration of 90% at a spraying amount of 30g / m² and cure it at 80℃ for 5min. Then spray the anti-slip liquid with a mass concentration of 90% at a spraying amount of 25g / m² and cure it at 90℃ for 8min. Finally, spray the anti-slip liquid with a mass concentration of 90% at a spraying amount of 20g / m² and cure it at 100℃ for 10min. After cooling naturally, fine grinding and polishing are carried out to obtain anti-slip and antibacterial ceramic tiles.

[0063] Performance Testing The water absorption rate of ceramic tiles was determined according to GB-T4100-2015. The stain resistance of ceramic tiles was determined according to GB / T3810.14-2016. The antibacterial rate test method was determined according to the building materials industry standard JC / T897-2014.

[0064] Static friction coefficient: The static friction coefficient of the product is measured according to the standards in GB / T4100-2015 Ceramic Tiles (Appendix M) Ceramic Tiles Appendix M Determination of Friction Coefficient.

[0065] Table 1 Physical properties test of examples and comparative examples Antibacterial performance test: The antibacterial rate of ceramic tiles was determined in accordance with the building materials industry standard JC / T897-2014. The operation steps are divided into four steps: sterilization and disinfection of ceramic tiles, dilution of bacterial solution, inoculation of bacterial solution, and elution and coating. The specific steps are as follows: 1. Disinfection of sample pieces: Soak the sample tiles in water for 24 hours, take them out and wipe off the water droplets on the surface, place them on a clean operating table, and perform UV sterilization; 2. Dilute the bacterial solution: dilute the original bacterial solution to a concentration of 10 4 CFU / mL, the specific operation is to add 2mL of broth to a 5ml centrifuge tube, and number the centrifuge tubes with broth as 1, 2, 3, etc., take 20μL of the refrigerated bacterial solution and add it to the No. 1 centrifuge tube. After vortexing, take out 20μL of the mixed bacterial solution from the No. 1 centrifuge tube and add it to the No. 2 centrifuge tube. After vortexing, take out 20μL of the mixed bacterial solution from the No. 1 centrifuge tube and add it to the No. 2 centrifuge tube. After vortexing, take out 20μL of the mixed bacterial solution from the No. 2 centrifuge tube and add it to the No. 3 centrifuge tube. Repeat the same operation, diluting the concentration 10 times each time until the bacterial solution is diluted to 10 4 CFU / mL, spare; 3. Inoculation: Take 300 μL of the diluted bacterial solution obtained in step 2 and drop it on the surface of the tile to evenly cover the upper surface. Then apply a cover film and incubate at a temperature of 37°C and a humidity of 56% for 24 hours. 4. Elution and coating: For each tile sample, take 10mL of physiological saline solution, rinse the bacterial solution under the covering film 5 times, and pour it into a test tube. Dilute the solution in each test tube 10 times, and then take 20μL of the diluted bacterial solution at different concentrations, spread it on the agar culture dish, culture it for 24 hours after coating, count the colonies in the culture dish, and calculate the antibacterial rate.

[0066] = Wherein: R is the antibacterial rate; B is the average colony count value of the ordinary non-antibacterial ceramic tile sample after culturing for 24 hours, and the unit is colony count (CFU); C is the average colony count value of the antibacterial ceramic sample of the embodiment or comparative example after culturing for 24 hours, and the unit is colony count (CFU).

[0067] Table 2 Antibacterial performance test of examples and comparative examples Antimicrobial durability test: Taking Example 1 as an example, according to GB / T9266, the cleaning method during product use was simulated, and the surface of the sample was washed 500-1000 times with sodium hypochlorite disinfectant. After the washing test, the sample was removed, rinsed thoroughly with tap water, and then rinsed with sterile distilled water. The sample was then removed and the excess water on the surface of the sample was gently wiped off with sterilized dry gauze. The sample was placed in a sterilized culture dish for testing, and the antibacterial test was performed according to the aforementioned antibacterial process.

[0068] Table 3 Antibacterial durability performance test of embodiments and comparative examples (washed 500 times) Table 3 Antibacterial durability performance test of embodiments and comparative examples (washed 1000 times) From the data in Tables 1-3, we can see that Examples 1-3 exhibit good overall performance. In terms of the static friction coefficient, the value can reach 0.92-0.95 under dry conditions and can be maintained at 0.75-0.82 under wet conditions, demonstrating excellent anti-slip performance. The water absorption rate is controlled within a relatively low range of 0.2-0.3%, and the antifouling performance reaches level 6. In terms of antibacterial performance, the inhibition rates against Escherichia coli and Staphylococcus aureus can reach 99.6-99.8% and 99.5-100%, respectively, and the antibacterial durability is good. Even after washing with sodium hypochlorite disinfectant 500-1000 times, the inhibition rate against both bacteria can still remain at a high level.

[0069] Comparative Example 1, in which the antibacterial agent in the surface layer is changed, has little effect on the physical properties of the ceramic tile, and its antibacterial persistence is far inferior to that of Example 1. However, the various properties of Comparative Examples 2-4, in which the surface layer preparation method is changed, are reduced to varying degrees. This is superior to the surface treatment with a single concentration. The functional components of the anti-slip liquid, such as the modified Zn-MOF-74 antibacterial agent and nano-silica particles, cannot be effectively and evenly deposited, and the quality of the surface layer is reduced, thus leading to a decline in comprehensive performance. It can be inferred that according to the anti-slip liquid used in the embodiment of the present invention and the surface treatment process with the relevant gradient concentration, ceramic tiles with excellent and long-lasting anti-slip and antibacterial properties can be prepared, which can meet the use requirements of places with high requirements for anti-slip and antibacterial properties, such as kitchens and bathrooms.

[0070] It should be noted that the above embodiments are only some of the preferred embodiments of the present invention, and not all of them. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present invention.

Claims

1. A non-slip and antibacterial tile, characterized in that: It includes a body layer, a composite functional layer and a surface treatment layer.

2. The anti-slip and antibacterial ceramic tile according to claim 1, characterized in that: The bad layer comprises the following raw materials in parts by mass: 40-50 parts of kaolin, 8-12 parts of silicon carbide powder, 15-20 parts of waste porcelain particles, and 10-15 parts of bentonite.

3. The anti-slip and antibacterial ceramic tile according to claim 1, characterized in that: The composite functional layer comprises the following raw materials in parts by mass: 15-25 parts of diatomaceous earth, 5-10 parts of zinc phosphate-coated nano zinc oxide, 3-8 parts of silver-loaded zeolite, 10-15 parts of potassium feldspar powder, and 1-3 parts of carboxymethyl cellulose.

4. The anti-slip and antibacterial ceramic tile according to claim 3, characterized in that: The preparation method of the zinc phosphate-coated nano zinc oxide is as follows: (1) Preparation of precursor solution: 2.0 mol / L zinc nitrate Zn(NO3)2·6H2O solution was mixed with an equal volume of ethanol, stirred until clear, and citric acid was added as a complexing agent with a molar ratio of Zn 2+ : citric acid = 1:1.5, and use ammonia water to maintain pH = 8-9 to obtain a precursor solution; (2) Gel formation: Heat the precursor solution in a water bath at 50-60°C and continue stirring until a transparent sol is formed; dry at 75-80°C for 10-12 hours to obtain a ZnO precursor xerogel; (3) Calcination treatment: The dry gel was placed in a muffle furnace and heated to 450°C at a rate of 5°C / min, kept at this temperature for 2 hours, cooled naturally, and ground to obtain white powder nano-ZnO with a particle size of 30-50 nm; (4) Dispersion system construction: Nano-ZnO was dispersed in deionized water to prepare a suspension with a concentration of 5 wt%, and ultrasonicated for 30 min at an ultrasonic power of 300 W; (5) Phosphate precipitation: add 0.5 mol / L Na2HPO4 solution to the suspension at a molar ratio of ZnO:Zn3(PO4)2=7:3 at a flow rate of 2 mL / min. The reaction temperature was controlled at 60°C. The pH was adjusted to 8.5 with NaOH and the mixture was stirred for 4 h. (6) Post-treatment: centrifugation at 8000 rpm for 10 min, washing with ethanol three times to remove impurities, vacuum drying at 80°C for 6 hours, and ball milling to obtain zinc phosphate-coated nano-zinc oxide with a particle size of 300-500 nm.

5. The anti-slip and antibacterial ceramic tile according to claim 3, characterized in that: The preparation method of the silver-loaded zeolite is as follows: natural zeolite is crushed and then passed through a 400-mesh sieve, soaked in 3 mol / L HCl for 2 hours at a solid-liquid ratio of 1:10 to remove impurity ions, washed with deionized water until neutral, and dried at 120° C. to obtain pretreated zeolite for use; the pretreated zeolite is mixed with a 0.1 mol / L AgNO3 solution at a solid-liquid ratio of 1:15, stirred in a water bath at 60° C. and 200 rpm for 6 hours in the dark; 0.12% of NaBH4 by mass of the system is added, stirred for 30 minutes, and washed with deionized water until no NO3 is present. - Detection: After centrifugal separation, the solid is crushed by jet mill to control the particle size D 50 =5μm, calcined at 300℃ for 1 hour to obtain silver-loaded zeolite.

6. The anti-slip and antibacterial ceramic tile according to claim 1, characterized in that: The surface treatment layer is formed by an anti-slip liquid containing an organic metal skeleton material through gradient concentration treatment. The anti-slip liquids of different concentrations are prepared by the following method: 40 parts of an aqueous polyurethane resin, 10 parts of a modified Zn-MOF-74 antibacterial agent, 10 parts of nano-silica anti-slip particles, and 3 parts of a silane coupling agent KH-560 are fully mixed to obtain a premix, and the premix is ​​added to an appropriate amount of ethanol to obtain anti-slip liquids with premix mass concentrations of 50%, 70%, and 90%, respectively.

7. The anti-slip and antibacterial ceramic tile according to claim 6, characterized in that: The preparation method of the modified Zn-MOF-74 antibacterial agent is: (1) Dissolve 6.5 g of 2-methylimidazole and 3.0 g of Zn(NO3)2·6H2O in 80 mL of methanol, react at 80°C for 12 h, and centrifuge and wash to obtain a solid; (2) 10 g of solid was immersed in 0.05 MAgNO3 solution, H2 was introduced to 0.5 MPa, the reaction was carried out at 80 °C for 4 h, and then centrifuged and dried to obtain Ag@MOF; (3) 5 g of Ag@MOF was dispersed in 20 mL of 2 wt% acetic acid solution, 1.5 g of chitosan was added, stirred at 60 °C for 4 h, and centrifuged to obtain CS&Ag@MOF; (4) Immerse the CS&Ag@MOF in a mineralization solution composed of 3 g / L Na2SiO3, 2 g / L KH2PO4, and 1 g / L CaCl2, stir at 60 °C for 48 h, and dry to obtain the finished product.

8. A method for preparing the anti-slip and antibacterial ceramic tile according to any one of claims 1 to 7, characterized in that: The method comprises the following preparation steps: (1) Green body forming: Weigh the raw materials of the green body layer according to their mass, ball-mill them to a particle size of ≤45 μm, add water according to 6%-7% of the total mass of the raw materials, mix them evenly, and press them into a green body using a semi-dry pressing process. The green body forming pressure is 20-30 MPa, the holding time is 10-15 s, and the temperature is raised to 1180-1220 ° C at 5 ° C / min, kept at this temperature for 30 min, and cooled to room temperature with the furnace to obtain a green body; (2) Pretreatment of the blank: sandblast the surface of the blank obtained in step (1), spray it with a 5% silane coupling agent KH-550 ethanol solution after cleaning, dry it at 80°C for 10 minutes, and then proceed to the next step; (3) Composite functional layer coating: Weigh the raw materials of the composite functional layer by weight, add water to make a slurry, and evenly coat it on the surface of the blank by spraying or curtain coating. The slurry viscosity is 1000-1500 mPa·s and the coating thickness is 0.5-1 mm; (4) Drying treatment: Dry the green body coated with the composite functional layer at 100-120°C for 2-3 hours to reduce the moisture content to less than 1%; (5) High temperature sintering: The dried green body is placed in a kiln for high temperature sintering at a temperature of 1100-1200°C for 2-3 hours; (6) Surface treatment: Anti-slip liquids of different concentrations are sequentially applied to the surface of the ceramic tiles in a gradient concentration manner. First, an anti-slip liquid with a mass concentration of 50% is sprayed at a spraying amount of 30 g / m² and cured at 80°C for 5 minutes. Then, an anti-slip liquid with a mass concentration of 70% is sprayed at a spraying amount of 25 g / m² and cured at 90°C for 8 minutes. Finally, an anti-slip liquid with a mass concentration of 90% is sprayed at a spraying amount of 20 g / m² and cured at 100°C for 10 minutes. After natural cooling, fine grinding and polishing are performed to obtain anti-slip and antibacterial ceramic tiles.

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