Manufacturing process of an easy-to-clean antibacterial ceramic product

Abstract

The invention discloses a manufacturing process of an easy-to-clean antibacterial ceramic product, belonging to the technical field of porcelain product production. The preparation process includes the following steps: mixing potassium feldspar, quartz, calcite, wollastonite, and frit, grinding, sieving, adding deionized water I, and wet ball milling with flint pebbles to obtain a premixed glaze slurry, followed by sanding to obtain glaze slurry I. Spraying the glaze slurry I evenly on a green ceramic body, loading it into a drying kiln for drying to form a substrate glaze surface; mixing modified halloysite and deionized water II, wet ball milling with the flint pebbles, and sanding to obtain glaze slurry II. Spraying the glaze slurry II evenly on the substrate glaze surface, allowing it to stand, and then feeding it into a tunnel kiln for one-time firing to obtain the easy-to-clean antibacterial ceramic product; making the glaze surface smoother and denser, improving the easy-to-clean performance of the glaze surface, firmly attaching the antibacterial agent to the glaze surface, enhancing the antibacterial persistence, and improving the antibacterial performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of porcelain production, and particularly relates to a manufacturing process for an easy-to-clean and antibacterial ceramic product. Background Art

[0002] Glaze is a silicate compound that adheres to the surface of a green body after high-temperature heating. Coating a ceramic product with glaze can provide the ceramic product with rich and colorful colors and textures, increase its decorative effect and artistic value, and make it more attractive and aesthetic; at the same time, coating the glaze on the surface of the ceramic product can form a protective film, increase the hardness and wear resistance of the ceramic product, avoid deformation or cracking under high-temperature conditions, and effectively prevent the erosion and damage of the ceramic material by external factors, such as stain resistance, acid and alkali corrosion resistance, etc. Moreover, the glaze can make the surface of the ceramic product flat and smooth, reduce its adsorption of dirt, and thus be easier to clean and hygienic.

[0003] Although the surface of the ceramic product looks smooth, there are still tiny pores inside it, which can absorb liquids and dirt, making it difficult to completely remove the stains during cleaning; and the main component of the glaze of the ceramic product is silicate, and the high surface activity of silicate is easy to adsorb other substances, including silver-based antibacterial agents. When the silicate material contacts the solution containing the silver-based antibacterial agent, the active sites on the surface of the silicate adsorb silver ions, forming silver agglomeration, which makes the dispersibility of the antibacterial agent poor, difficult to adhere to the glaze surface of the ceramic product, and reduces the antibacterial effect. Summary of the Invention

[0004] The present invention discloses a manufacturing process for an easy-to-clean and antibacterial ceramic product, belonging to the technical field of porcelain production. The preparation process includes the following steps: mixing potassium feldspar, quartz, calcite, wollastonite, and frit, grinding, sieving, adding deionized water I, and wet ball milling with flint pebbles to obtain a premixed glaze slurry, then sanding to obtain glaze slurry I, uniformly spraying the glaze slurry I on the green ceramic body, loading it into a drying kiln for drying to form a substrate glaze surface; mixing modified halloysite and deionized water II, wet ball milling with the flint pebbles, and sanding to obtain glaze slurry II, uniformly spraying the glaze slurry II on the substrate glaze surface, standing, and feeding it into a tunnel kiln for one-time firing to obtain the easy-to-clean and antibacterial ceramic product.

[0005] The technical problems to be solved by the present invention are: to prepare an easy-to-clean and antibacterial ceramic product, improve the easy-to-clean performance and antibacterial persistence of the glaze surface, and improve the antibacterial performance.

[0006] The object of the present invention can be achieved by the following technical solutions:

[0007] A manufacturing process for an easy-to-clean and antibacterial ceramic product, the preparation process includes the following steps:

[0008] (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind them, sieve them, add deionized water I, and wet ball mill with flint pebbles to obtain a premixed glaze slurry. Then, perform sanding to obtain glaze slurry I. Spray the glaze slurry I evenly on the green ceramic body, and load it into a drying kiln to dry for 2 - 3 h to form a substrate glaze surface;

[0009] (2) Mix modified halloysite powder and deionized water II, and wet ball mill with the flint pebbles to obtain a mixed slurry. Then, perform sanding to obtain glaze slurry II. Spray the glaze slurry II evenly on the substrate glaze surface, let it stand for 3 - 5 h, and send it into a tunnel kiln for a first firing at 1025 - 1065 °C to obtain the easy - to - clean antibacterial ceramic product.

[0010] As a preferred technical solution of the present invention, the mass ratio of potassium feldspar, quartz, calcite, modified halloysite powder, wollastonite, frit, deionized water I, flint pebbles, and deionized water II is 10 - 15:5 - 8:2 - 6:10 - 15:4 - 10:50 - 70:26.45 - 70.6:113.4 - 272.8:10.2 - 10.8.

[0011] As a preferred technical solution of the present invention, in step (1), the grinding time is 5 - 8 h; the sieve mesh for sieving is 120 - 200 meshes; the median particle size of the premixed glaze slurry obtained after wet ball milling is less than or equal to 50 microns; the median particle size of glaze slurry I obtained after sanding is less than or equal to 0.1 micron; the drying temperature is 95 °C.

[0012] As a preferred technical solution of the present invention, in step (2), the time for the first firing is 3 - 6 h; the median particle size of the mixed slurry obtained after wet ball milling is less than or equal to 50 microns; the median particle size of glaze slurry II obtained after sanding is less than or equal to 0.1 micron.

[0013] As a preferred technical solution of the present invention, the preparation of the modified halloysite powder includes the following steps:

[0014] (11) Centrifuge and purify halloysite, grind it to obtain halloysite powder, take the halloysite powder and ultrasonically disperse it in toluene to obtain dispersion liquid A;

[0015] (12) Ultrasonically disperse polyethylene glycol in toluene to obtain dispersion liquid B;

[0016] (13) Take the dispersion liquid A and dispersion liquid B, add them to a reactor, add p - toluenesulfonic acid, stir, control the temperature for reaction. After the reaction is completed, centrifuge the reaction solution, take the precipitate, wash it, centrifuge it again, perform extraction, and dry it to obtain the carrier;

[0017] (14) Mix the nano-titanium dioxide silver antibacterial agent powder and absolute ethanol, stir, and ultrasonically vibrate to obtain an antibacterial agent dispersion liquid;

[0018] (15) Take the carrier and the antibacterial agent dispersion liquid and add them to absolute ethanol. Heat in a water bath at 40 °C, dropwise add a silane coupling agent while stirring. After the dropping is completed, add ammonia water, stir, dry, and grind to obtain the modified halloysite powder.

[0019] As a preferred technical solution of the present invention, in step (11), the mass ratio of the halloysite powder to toluene is 0.2 - 0.4:40; the time of ultrasonic dispersion is 1 - 2 h.

[0020] As a preferred technical solution of the present invention, in step (12), the mass ratio of polyethylene glycol to toluene is 1 - 1.2:40; the time of ultrasonic dispersion is 30 - 40 min.

[0021] As a preferred technical solution of the present invention, in step (13), the mass ratio of dispersion liquid A, dispersion liquid B, and p-toluenesulfonic acid is 2 - 3:2 - 3:1 - 2; the stirring time is 0.5 - 1 h; the temperature-controlled reaction refers to reacting at 150 - 155 °C for 3 h.

[0022] As a preferred technical solution of the present invention, in step (14), the mass ratio of the nano-titanium dioxide silver antibacterial agent powder to absolute ethanol is 2 - 3:60 - 70; the stirring time is 30 min; the time of ultrasonic vibration is 30 min.

[0023] As a preferred technical solution of the present invention, in step (15), the mass ratio of the carrier, absolute ethanol, antibacterial agent dispersion liquid, silane coupling agent, and ammonia water is 1 - 2:55 - 65:0.5 - 0.8:0.02 - 0.06:40; the concentration of the ammonia water is 13.38 mol / L; the silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0024] The beneficial effects of the present invention:

[0025] (1) The manufacturing process of an easy-to-clean antibacterial ceramic product disclosed by the present invention can fill the micropores and voids in the ceramic glaze by adding halloysite, making the glaze particles more closely arranged, forming a dense structure, effectively preventing the infiltration of external substances such as stains and bacteria, avoiding the infiltration of stains and bacteria into the interior of the ceramic, improving the anti-infiltration performance of the glaze and the ceramic product. At the same time, the dense structure can also enhance the smoothness and improve the surface texture and touch of the ceramic product.

[0026] (2) The manufacturing process of an easy-to-clean and antibacterial ceramic product disclosed by the present invention modifies halloysite. By introducing hydrophilic groups on the Al side of halloysite, its hydrophilicity is improved, and the Si side is hydrophobic. As a result, the modified halloysite powder has a lower tendency to coalesce and aggregate, is easily and uniformly dispersed in the solvent, improves the fluidity of the glaze slip, makes the glaze surface more uniform and flat. At the same time, it can make the antibacterial agent better dispersed evenly in the glaze slip. The effective dispersion of the antibacterial agent can avoid the growth of microorganisms and improve the antibacterial performance of the ceramic product.

[0027] (3) The manufacturing process of an easy-to-clean and antibacterial ceramic product disclosed by the present invention modifies halloysite. First, hydrophilic functional groups are bonded to the Al-based side of halloysite to avoid binding with the antibacterial agent. At the same time, the hydrophobic Si-based side of halloysite faces outward and fully attaches the antibacterial agent through a silane coupling agent, firmly fixing the antibacterial agent on the surface, so that the antibacterial performance of the glaze surface of the prepared ceramic product is improved, and the compactness and smoothness of the product surface are enhanced;

[0028] Furthermore, during the high-temperature calcination process, the silane coupling agent undergoes a strong chemical bond with the Si-based side on the surface of halloysite, filling and sealing the pores and microcracks inside the ceramic, making the antibacterial agent more firmly attached to the glaze surface, having better durability, being able to effectively inhibit the growth of bacteria for a long time, and improving the antibacterial persistence. Specific Embodiments

[0029] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following, in combination with embodiments, details the specific embodiments, structures, features and their effects according to the present invention as follows.

[0030] Example 1

[0031] Preparation of modified halloysite powder:

[0032] (11) Centrifuge and purify halloysite, grind it to obtain halloysite powder, and ultrasonically disperse the obtained halloysite powder in toluene to obtain dispersion liquid A; the mass ratio of the halloysite powder to toluene is 0.2:40; the time of ultrasonic dispersion is 1 h;

[0033] (12) Ultrasonically disperse polyethylene glycol in toluene to obtain dispersion liquid B; the mass ratio of polyethylene glycol to toluene is 1:40; the time of ultrasonic dispersion is 30 min;

[0034] (13) Take the dispersion liquid A and dispersion liquid B, add them to a reactor, add p-toluenesulfonic acid, stir, control the temperature for reaction. After the reaction is completed, centrifuge the reaction solution, take the precipitate for washing, centrifuge again, extract, and dry to obtain the carrier; the mass ratio of the dispersion liquid A, dispersion liquid B, and p-toluenesulfonic acid is 2:2:1; the stirring time is 0.5 h; the temperature-controlled reaction means reacting at 150 °C for 3 h;

[0035] (14) Mix the nano-titanium dioxide silver antibacterial agent powder and absolute ethanol, stir, and perform ultrasonic oscillation to obtain an antibacterial agent dispersion liquid; the mass ratio of the nano-titanium dioxide silver antibacterial agent powder to absolute ethanol is 2:60; the stirring time is 30 min; the ultrasonic oscillation time is 30 min;

[0036] (15) Take the carrier and the antibacterial agent dispersion liquid, add them to absolute ethanol, heat in a water bath at 40 °C, while stirring, dropwise add a silane coupling agent. After the dropping is completed, add ammonia water, stir, dry, and grind to obtain the modified halloysite powder; the mass ratio of the carrier, absolute ethanol, antibacterial agent dispersion liquid, silane coupling agent, and ammonia water is 1:55:0.5:0.02:40; the concentration of the ammonia water is 13.38 mol / L; the silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

[0037] Preparation of the easy-to-clean antibacterial ceramic product:

[0038] (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind, sieve, add deionized water I, and perform wet ball milling with flint pebbles to obtain a premixed glaze slurry. After sanding, obtain glaze slurry I. Spray the glaze slurry I evenly on the green ceramic body, load it into a drying kiln and dry for 2 h to form a substrate glaze surface; the grinding time is 5 h; the sieve mesh for sieving is 120 mesh; the median particle size of the premixed glaze slurry obtained after wet ball milling is 50 microns; the median particle size of the glaze slurry I obtained after sanding is 0.1 micron; the drying temperature is 95 °C;

[0039] (2) Mix the modified halloysite powder and deionized water II, perform wet ball milling with the flint pebbles to obtain a mixed slurry. After sanding, obtain glaze slurry II. Spray the glaze slurry II evenly on the substrate glaze surface, let it stand for 3 h, and send it to a tunnel kiln for a first firing at 1025 °C to obtain the easy-to-clean antibacterial ceramic product; the time for the first firing is 3 h; the median particle size of the mixed slurry obtained after wet ball milling is 50 microns; the median particle size of the glaze slurry II obtained after sanding is 0.1 micron;

[0040] The mass ratio of the potassium feldspar, quartz, calcite, modified halloysite powder, wollastonite, frit, deionized water I, flint pebbles, and deionized water II is 10:5:2:10:4:50:26.45:113.4:10.2; the chemical composition of the frit is in a mass ratio of: 1 part by mass of R2O: 9 parts by mass of CaO: 1 part by mass of BaO: 8 parts by mass of ZnO: 2 parts by mass of PbO: 7 parts by mass of Al2O3: 0.5 part by mass of B2O3: 56 parts by mass of SiO2: 2.4 parts by mass of ZrO.

[0041] Example 2

[0042] Preparation of modified halloysite powder:

[0043] (11) Centrifuge and purify halloysite, grind it to obtain halloysite powder, take the halloysite powder and ultrasonically disperse it in toluene to obtain dispersion A; the mass ratio of the halloysite powder to toluene is 0.3:40; the time of ultrasonic dispersion is 1.5 h;

[0044] (12) Ultrasonically disperse polyethylene glycol in toluene to obtain dispersion B; the mass ratio of polyethylene glycol to toluene is 1.1:40; the time of ultrasonic dispersion is 35 min;

[0045] (13) Take dispersion A and dispersion B, add them to a reactor, add p-toluenesulfonic acid, stir, control the temperature for reaction, after the reaction is completed, centrifuge the reaction solution, take the precipitate, wash it, centrifuge it again, extract, concentrate, and dry it to obtain a carrier; the mass ratio of dispersion A, dispersion B, and p-toluenesulfonic acid is 2.5:2.5:1.5; the stirring time is 0.7 h; the temperature-controlled reaction means reacting at 153 °C for 3 h;

[0046] (14) Mix nano-titanium dioxide silver antibacterial agent powder and absolute ethanol, stir, and ultrasonically oscillate to obtain an antibacterial agent dispersion; the mass ratio of the nano-titanium dioxide silver antibacterial agent powder to absolute ethanol is 2.5:65; the stirring time is 30 min; the ultrasonic oscillation time is 30 min;

[0047] (15) Take the carrier and the antibacterial agent dispersion, add them to absolute ethanol, heat in a water bath at 40 °C, while stirring, dropwise add a silane coupling agent, after the addition is completed, add ammonia water, stir, dry, and grind to obtain the modified halloysite powder; the mass ratio of the carrier, absolute ethanol, antibacterial agent dispersion, silane coupling agent, and ammonia water is 1.5:60:0.65:0.04:40; the concentration of the ammonia water is 13.38 mol / L; the silane coupling agent is 3-(2,3-epoxypropoxy)propyltrihydroxysilane.

[0048] Preparation of easy-to-clean antibacterial ceramic products:

[0049] (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind, sieve, add deionized water I, and wet ball mill with flint pebbles to obtain a premixed glaze slurry. Then, sand mill to obtain glaze slurry I. Uniformly spray the glaze slurry I onto the green ceramic body and load it into a drying kiln to dry for 2.5 h to form a substrate glaze surface. The grinding time is 6 h. The sieve mesh for sieving is 180 mesh. The median particle size of the premixed glaze slurry obtained after wet ball milling is 40 microns. The median particle size of the glaze slurry I obtained after sand milling is 0.08 microns. The drying temperature is 95 °C.

[0050] (2) Mix modified halloysite powder and deionized water II, and wet ball mill with the flint pebbles to obtain a mixed slurry. Then, sand mill to obtain glaze slurry II. Uniformly spray the glaze slurry II onto the substrate glaze surface, let it stand for 4 h, and send it into a tunnel kiln for a first firing at 1045 °C to obtain the easy-to-clean and antibacterial ceramic product. The time for the first firing is 5 h. The median particle size of the mixed slurry obtained after wet ball milling is 40 microns. The median particle size of the glaze slurry II obtained after sand milling is 0.08 microns.

[0051] The mass ratio of potassium feldspar, quartz, calcite, modified halloysite powder, wollastonite, frit, deionized water I, flint pebbles, and deionized water II is 12:6:4:12:6:60:50:200:10.6. The chemical composition of the frit is by mass ratio: 1 part R2O: 9 parts CaO: 1 part BaO: 8 parts ZnO: 2 parts PbO: 7 parts Al2O3: 0.5 part B2O3: 56 parts SiO2: 2.4 parts ZrO.

[0052] Example 3

[0053] Preparation of modified halloysite powder:

[0054] (11) Centrifuge and purify halloysite, grind to obtain halloysite powder, and ultrasonically disperse the halloysite powder in toluene to obtain dispersion liquid A. The mass ratio of the halloysite powder to toluene is 0.4:40. The ultrasonic dispersion time is 2 h.

[0055] (12) Ultrasonically disperse polyethylene glycol in toluene to obtain dispersion liquid B. The mass ratio of polyethylene glycol to toluene is 1.2:40. The ultrasonic dispersion time is 40 min.

[0056] (13) Take the dispersion A and dispersion B and add them to a reactor. Add p-toluenesulfonic acid, stir, control the temperature for reaction. After the reaction is completed, centrifuge the reaction solution, take the precipitate, wash it, centrifuge it again, extract, and dry to obtain the carrier. The mass ratio of the dispersion A, dispersion B, and p-toluenesulfonic acid is 3:3:2. The stirring time is 1 h. The temperature-controlled reaction means reacting at 155 °C for 3 h.

[0057] (14) Mix the nano-titanium dioxide silver antibacterial agent powder and absolute ethanol, stir, and ultrasonically vibrate to obtain the antibacterial agent dispersion. The mass ratio of the nano-titanium dioxide silver antibacterial agent powder and absolute ethanol is 3:70. The stirring time is 30 min. The ultrasonically vibrating time is 30 min.

[0058] (15) Take the carrier and the antibacterial agent dispersion and add them to absolute ethanol. Heat in a water bath at 40 °C, add the silane coupling agent dropwise while stirring. After the addition is completed, add ammonia water, stir, dry, and grind to obtain the modified halloysite powder. The mass ratio of the carrier, absolute ethanol, antibacterial agent dispersion, silane coupling agent, and ammonia water is 2:65:0.8:0.06:40. The concentration of the ammonia water is 13.38 mol / L. The silane coupling agent is 3-(2,3-epoxypropoxy)propyltrihydroxysilane.

[0059] Preparation of the easy-to-clean antibacterial ceramic product:

[0060] (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind, sieve, add deionized water I, and wet ball mill with flint pebbles to obtain a premixed glaze slurry. Then, sand mill to obtain glaze slurry I. Spray the glaze slurry I evenly on the green ceramic body, load it into a drying kiln and dry for 3 h to form a substrate glaze surface. The grinding time is 8 h. The sieve mesh for sieving is 200 mesh. The median particle size of the premixed glaze slurry obtained after wet ball milling is 30 microns. The median particle size of the glaze slurry I obtained after sand milling is 0.06 microns. The drying temperature is 95 °C.

[0061] (2) Mix the modified halloysite powder and deionized water II, wet ball mill with the flint pebbles, and sand mill to obtain glaze slurry II. Spray the glaze slurry II evenly on the substrate glaze surface, let it stand for 5 h, and then send it to a tunnel kiln for a first firing at 1065 °C to obtain the easy-to-clean antibacterial ceramic product. The time for the first firing is 6 h. The median particle size of the mixed slurry obtained after wet ball milling is 30 microns. The median particle size of the glaze slurry II obtained after sand milling is 0.06 microns.

[0062] The mass ratio of the potassium feldspar, quartz, calcite, modified halloysite powder, wollastonite, frit, deionized water I, flint pebbles, and deionized water II is 15:8:6:15:10:70:70.6:272.8:10.8; the chemical composition of the frit is in a mass ratio of: 1 part by mass of R2O: 9 parts by mass of CaO: 1 part by mass of BaO: 8 parts by mass of ZnO: 2 parts by mass of PbO: 7 parts by mass of Al2O3: 0.5 part by mass of B2O3: 56 parts by mass of SiO2: 2.4 parts by mass of ZrO.

[0063] Comparative Example 1

[0064] Preparation of the modified halloysite powder:

[0065] (11) Centrifuge and purify the halloysite, grind it to obtain halloysite powder, take the halloysite powder and ultrasonically disperse it in toluene to obtain dispersion A; the mass ratio of the halloysite powder to toluene is 0.2:40; the time of ultrasonic dispersion is 1 h;

[0066] (12) Ultrasonically disperse polyethylene glycol in toluene to obtain dispersion B; the mass ratio of polyethylene glycol to toluene is 1:40; the time of ultrasonic dispersion is 30 min;

[0067] (13) Take dispersion A and dispersion B, add them to a reactor, add p-toluenesulfonic acid, stir, control the temperature for reaction, after the reaction is completed, centrifuge the reaction solution, take the precipitate, wash it, centrifuge it again, extract it, and dry it to obtain the carrier; the mass ratio of dispersion A, dispersion B, and p-toluenesulfonic acid is 2:2:1; the stirring time is 0.5 h; the temperature-controlled reaction refers to reacting at 150 °C for 3 h;

[0068] (14) Mix the nano-titanium dioxide silver antibacterial agent powder and absolute ethanol, stir, and ultrasonically vibrate to obtain an antibacterial agent dispersion; the mass ratio of the nano-titanium dioxide silver antibacterial agent powder to absolute ethanol is 2:60; the stirring time is 30 min; the ultrasonic vibration time is 30 min;

[0069] (15) Take the carrier and the antibacterial agent dispersion, add them to absolute ethanol, add ammonia water, stir, dry, and grind to obtain the modified halloysite powder; the mass ratio of the carrier, absolute ethanol, antibacterial agent dispersion, and ammonia water is 1:55:0.5:40; the concentration of the ammonia water is 13.38 mol / L.

[0070] Preparation of the easy-to-clean antibacterial ceramic product:

[0071] (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind, sieve, add deionized water I, and wet ball mill with flint pebbles to obtain a premixed glaze slurry. Then, perform sanding to obtain glaze slurry I. Uniformly spray the glaze slurry I onto a green ceramic body and load it into a drying kiln to dry for 2 h to form a substrate glaze surface. The grinding time is 5 h, the sieve mesh for sieving is 120 mesh, the median particle size of the premixed glaze slurry obtained after wet ball milling is 50 microns, the median particle size of the glaze slurry I obtained after sanding is 0.1 micron, and the drying temperature is 95 °C.

[0072] (2) Mix modified halloysite powder and deionized water II, and wet ball mill with the flint pebbles to obtain a mixed slurry. Then, perform sanding to obtain glaze slurry II. Uniformly spray the glaze slurry II onto the substrate glaze surface, let it stand for 3 h, and send it into a tunnel kiln for a first firing at 1025 °C to obtain the easy-to-clean and antibacterial ceramic product. The time for the first firing is 3 h, the median particle size of the mixed slurry obtained after wet ball milling is 50 microns, and the median particle size of the glaze slurry II obtained after sanding is 0.1 micron.

[0073] The mass ratio of potassium feldspar, quartz, calcite, modified halloysite powder, wollastonite, frit, deionized water I, flint pebbles, and deionized water II is 10:5:2:10:4:50:26.45:113.4:10.2. The chemical composition of the frit is in a mass ratio of: 1 part by mass of R2O: 9 parts by mass of CaO: 1 part by mass of BaO: 8 parts by mass of ZnO: 2 parts by mass of PbO: 7 parts by mass of Al2O3: 0.5 part by mass of B2O3: 56 parts by mass of SiO2: 2.4 parts by mass of ZrO.

[0074] Comparative Example 2

[0075] Preparation of modified halloysite powder:

[0076] (11) Centrifuge and purify halloysite, grind to obtain halloysite powder, and ultrasonically disperse the halloysite powder in toluene to obtain dispersion liquid A. The mass ratio of the halloysite powder to toluene is 0.2:40, and the ultrasonic dispersion time is 1 h.

[0077] (12) Mix nano-titanium dioxide silver antibacterial agent powder and absolute ethanol, stir, and ultrasonically vibrate to obtain an antibacterial agent dispersion liquid. The mass ratio of the nano-titanium dioxide silver antibacterial agent powder to absolute ethanol is 2:60, the stirring time is 30 min, and the ultrasonic vibration time is 30 min.

[0078] (13) Take the dispersion A and the antibacterial agent dispersion, add them to absolute ethanol, heat in a water bath at 40 °C, dropwise add a silane coupling agent while stirring, after the addition is complete, add ammonia water, stir, dry, and grind to obtain the modified halloysite powder; the mass ratio of the dispersion A, absolute ethanol, antibacterial agent dispersion, silane coupling agent, and ammonia water is 1:55:0.5:0.02:40; the concentration of the ammonia water is 13.38 mol / L; the silane coupling agent is 3-(2,3-epoxypropoxy)propyltrihydroxysilane.

[0079] Preparation of the easy-to-clean antibacterial ceramic product:

[0080] (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind, sieve, add deionized water I, and wet ball mill with flint pebbles to obtain a premixed glaze slurry, then sand mill to obtain glaze slurry I. Spray the glaze slurry I evenly on the green ceramic body, load it into a drying kiln and dry for 2 h to form a substrate glaze surface; the grinding time is 5 h; the sieve mesh for sieving is 120 mesh; the median particle size of the premixed glaze slurry obtained after wet ball milling is 50 μm; the median particle size of the glaze slurry I obtained after sand milling is 0.1 μm; the drying temperature is 95 °C;

[0081] (2) Mix the modified halloysite powder and deionized water II, wet ball mill with the flint pebbles to obtain a mixed slurry, then sand mill to obtain glaze slurry II. Spray the glaze slurry II evenly on the substrate glaze surface, let it stand for 3 h, and send it into a tunnel kiln for a first firing at 1025 °C to obtain the easy-to-clean antibacterial ceramic product; the first firing time is 3 h; the median particle size of the mixed slurry obtained after wet ball milling is 50 μm; the median particle size of the glaze slurry II obtained after sand milling is 0.1 μm;

[0082] The mass ratio of the potassium feldspar, quartz, calcite, modified halloysite powder, wollastonite, frit, deionized water I, flint pebbles, and deionized water II is 10:5:2:10:4:50:26.45:113.4:10.2; the chemical composition of the frit is in a mass ratio of: 1 part by mass of R2O: 9 parts by mass of CaO: 1 part by mass of BaO: 8 parts by mass of ZnO: 2 parts by mass of PbO: 7 parts by mass of Al2O3: 0.5 part by mass of B2O3: 56 parts by mass of SiO2: 2.4 parts by mass of ZrO.

[0083] Comparative Example 3

[0084] Preparation of the antibacterial agent dispersion:

[0085] Mix the nano-titanium dioxide silver antibacterial agent powder and absolute ethanol, stir, and ultrasonically vibrate to obtain an antibacterial agent dispersion; the mass ratio of the nano-titanium dioxide silver antibacterial agent powder to absolute ethanol is 2:60; the stirring time is 30 min; the ultrasonically vibrating time is 30 min;

[0086] Preparation of the easy-to-clean antibacterial ceramic product:

[0087] (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind, sieve, add deionized water I, and wet ball mill with flint pebbles to obtain a premixed glaze slurry. Then sand mill to obtain glaze slurry I. Spray the glaze slurry I evenly on the green ceramic body, load it into a drying kiln and dry for 2 h to form a substrate glaze surface; the grinding time is 5 h; the sieve mesh for sieving is 120 mesh; the median particle size of the premixed glaze slurry obtained after wet ball milling is 50 μm; the median particle size of the glaze slurry I obtained after sand milling is 0.1 μm; the drying temperature is 95 °C;

[0088] (2) Mix halloysite powder and deionized water II, wet ball mill with the flint pebbles to obtain a mixed slurry, sand mill to obtain glaze slurry II. Spray the glaze slurry II evenly on the substrate glaze surface, and continue to evenly spray the antibacterial agent dispersion on the substrate glaze surface after spraying the glaze slurry II. Let it stand for 3 h, and then send it into a tunnel kiln for a one-time firing at 1025 °C to obtain the easy-to-clean antibacterial ceramic product; the one-time firing time is 3 h; the median particle size of the mixed slurry obtained after wet ball milling is 50 μm; the median particle size of the glaze slurry II obtained after sand milling is 0.1 μm;

[0089] The mass ratio of potassium feldspar, quartz, calcite, halloysite powder, wollastonite, frit, deionized water I, flint pebbles, deionized water II to the antibacterial agent dispersion is 10:5:2:10:4:50:26.45:113.4:10.2:0.5; the chemical composition of the frit is in a mass ratio of: 1 part by mass of R2O: 9 parts by mass of CaO: 1 part by mass of BaO: 8 parts by mass of ZnO: 2 parts by mass of PbO: 7 parts by mass of Al2O3: 0.5 part by mass of B2O3: 56 parts by mass of SiO2: 2.4 parts by mass of ZrO.

[0090] Performance test

[0091] Conduct the easy-to-clean performance test according to the standard GB / T 31859-2015;

[0092] Conduct the antibacterial performance test according to the standard JC / T 897-2014.

[0093] The glaze materials of the ceramic products prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests according to the above standards, and the test results are shown in Table 1 below:

[0094] Table 1

[0095]

[0096]

[0097] As can be seen from the test results in Table 1, the glazes of the ceramic products prepared in Examples 1-3 have good easy-cleaning performance and antibacterial performance; for Comparative Example 1, the glaze of the ceramic product prepared on the basis of Example 1 has a decreased easy-cleaning performance, and the antibacterial performance is significantly reduced. The reason may be that no silane coupling agent was added during the preparation process, resulting in a poor adhesion rate of the antibacterial agent under high-temperature calcination, and the densification rate of the surface of the ceramic blank is lower than that of Example 1, resulting in a decrease in the easy-cleaning performance; for Comparative Example 2, the glaze of the ceramic product prepared on the basis of Example 1 has a significantly decreased easy-cleaning performance, and the antibacterial performance is lower than that of Comparative Example 1. The reason may be that the dispersion performance of halloysite powder is poor, resulting in poor dispersion of the antibacterial agent, and the densification rate of the surface of the ceramic blank is even lower, resulting in a decrease in the easy-cleaning performance and antibacterial performance; for Comparative Example 3, the dispersion performance of halloysite powder in the ceramic product prepared on the basis of Example 1 is worse than that of Comparative Example 2, and the adhesion rate of the antibacterial agent is even lower, resulting in worse easy-cleaning performance and antibacterial performance than those of Comparative Example 2.

[0098] Note: The nano-titanium dioxide silver antibacterial agent powder (model ZM-T30A) involved in this application is all sourced from Hangzhou Zheming New Materials Co., Ltd.

[0099] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the above-disclosed technical content within the scope of the technical solution of the present invention to obtain equivalent embodiments with equivalent changes. However, as long as the content of the technical solution of the present invention is not departed from, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A manufacturing process for an easy-to-clean and antibacterial ceramic product, characterized in that, The manufacturing process includes the following steps: (1) Mix potassium feldspar, quartz, calcite, wollastonite, and frit, grind, sieve, add deionized water I, and wet ball mill with flint pebbles to obtain a premixed glaze slurry. Then, perform sanding to obtain glaze slurry I. Uniformly spray the glaze slurry I onto the green ceramic body and load it into a drying kiln for drying for 2 - 3 h to form a substrate glaze surface; (2) Mix modified halloysite powder and deionized water II, wet ball mill with the flint pebbles to obtain a mixed slurry, perform sanding to obtain glaze slurry II. Uniformly spray the glaze slurry II onto the substrate glaze surface, let it stand for 3 - 5 h, and then send it into a tunnel kiln for a first firing at 1025 - 1065 °C to obtain the easy - to - clean antibacterial ceramic product; The preparation of the modified halloysite powder includes the following steps: (11) Centrifuge and purify halloysite, grind to obtain halloysite powder. Take the halloysite powder and ultrasonically disperse it in toluene to obtain dispersion liquid A; (12) Ultrasonically disperse polyethylene glycol in toluene to obtain dispersion liquid B; (13) Take the dispersion liquid A and dispersion liquid B and add them to a reactor, add p - toluenesulfonic acid, stir, control the temperature for reaction. After the reaction is completed, centrifuge the reaction liquid, take the precipitate, wash it, centrifuge again, extract, and dry to obtain a carrier; (14) Mix nano - titanium dioxide - silver antibacterial agent powder and absolute ethanol, stir, and ultrasonically vibrate to obtain an antibacterial agent dispersion liquid; (15) Take the carrier and the antibacterial agent dispersion liquid and add them to absolute ethanol, heat in a water bath at 40 °C, while stirring, dropwise add a silane coupling agent. After dropping, add ammonia water, stir, dry, and grind to obtain the modified halloysite powder.

2. The manufacturing process of an easy-to-clean antibacterial ceramic product according to claim 1, characterized in that, The mass ratio of potassium feldspar, quartz, calcite, modified halloysite powder, wollastonite, frit, deionized water I, flint pebbles, deionized water II is 10 - 15:5 - 8:2 - 6:10 - 15:4 - 10:50 - 70:26.45 - 70.6:113.4 - 272.8:10.2 - 10.

8.

3. The manufacturing process of an easy-to-clean and antibacterial ceramic product according to claim 1, characterized in that, In step (1), the grinding time is 5 - 8 h; the sieve mesh for sieving is 120 - 200 meshes; the median particle size of the premixed glaze slurry obtained after wet ball milling is less than or equal to 50 microns; the median particle size of the glaze slurry I obtained after sanding is less than or equal to 0.1 micron; the drying temperature is 95 °C.

4. The manufacturing process of an easy-to-clean antibacterial ceramic product according to claim 1, characterized in that, In step (2), the first firing time is 3 - 6 h; the median particle size of the mixed slurry obtained after wet ball milling is less than or equal to 50 microns; the median particle size of the glaze slurry II obtained after sanding is less than or equal to 0.1 micron.

5. The manufacturing process of an easy-to-clean antibacterial ceramic product according to claim 4, characterized in that, In step (11), the mass ratio of halloysite powder to toluene is 0.2 - 0.4:40; the ultrasonic dispersion time is 1 - 2 h.

6. The manufacturing process of an easy-to-clean antibacterial ceramic product according to claim 4, characterized in that, In step (12), the mass ratio of polyethylene glycol to toluene is 1 - 1.2:40; the ultrasonic dispersion time is 30 - 40 min.

7. The manufacturing process of an easy-to-clean antibacterial ceramic product according to claim 4, characterized in that, In step (13), the mass ratio of dispersion liquid A, dispersion liquid B, and p - toluenesulfonic acid is 2 - 3:2 - 3:1 - 2; the stirring time is 0.5 - 1 h; the temperature - controlled reaction refers to reacting at 150 - 155 °C for 3 h.

8. The manufacturing process of an easy-to-clean antibacterial ceramic product according to claim 1, characterized in that, In step (14), the mass ratio of the nano-titanium dioxide silver antibacterial agent powder to absolute ethanol is 2 - 3:60 - 70; the stirring time is 30 min; the ultrasonic oscillation time is 30 min.

9. The manufacturing process of an easy-to-clean antibacterial ceramic product according to claim 1, characterized in that, In step (15), the mass ratio of the carrier, absolute ethanol, antibacterial agent dispersion, silane coupling agent, and ammonia water is 1 - 2:55 - 65:0.5 - 0.8:0.02 - 0.06:40; the concentration of the ammonia water is 13.38 mol / L; the silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane.

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