Antibacterial rock plate and production process thereof

Abstract

This invention discloses an antibacterial slab and its production process, belonging to the field of ceramic technology. The antibacterial slab comprises a green body, a glaze layer, a decorative pattern layer, and an outermost antibacterial dry granule layer, arranged sequentially. The antibacterial dry granule layer includes frit, quartz, potassium feldspar, colorant, and dispersed antibacterial material and ammonium chloride. The antibacterial material is a silver-containing composite powder, obtained by coating a filler with an aluminosilicate precursor solution, hydrothermal crystallization, and silver ion exchange treatment. The filler is at least one of β-SiAlON and fluorides; the fluoride is at least one of CaF2, YF3, CeF3, and AlF3. This invention also provides its preparation method. Compared with existing technologies, the antibacterial slab prepared by this invention has a higher antibacterial rate and durability, while maintaining good flexural strength, wear resistance, and resistance to household chemicals, acids, and alkalis, making it suitable for widespread use in kitchens, bathrooms, and other applications requiring long-term cleaning and antibacterial properties.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, and in particular to an antibacterial slab and its production process. Background Technology

[0002] In the industry, sintered stone is generally considered a type of large-format artificial rock slab produced using ceramic processes. Its raw materials are primarily feldspar, quartz, kaolin, and other natural minerals. It is prepared using high-solids slurry, pressed or rolled at high tonnage, and sintered at temperatures above approximately 1200℃ to obtain large-format slab-like products with high density and extremely low water absorption. Compared to traditional architectural ceramics, sintered stone is characterized by its large size, variable thickness, dense structure, scratch and wear resistance, and a form closer to slabs. Its applications extend beyond floor and wall decoration to include countertops and furniture panels. Currently, large-format sintered stone and dry-granule textured ceramic tiles are widely used for kitchen countertops, dining tabletops, bathroom spaces, and wall and floor decoration in public places. Users not only require wear resistance, stain resistance, and decorative effects, but also desire long-term stable antibacterial properties on the surface. Most existing antibacterial ceramic products achieve their antibacterial function by adding silver, zinc, or copper-based antibacterial agents to the glaze layer, either by formulating antibacterial glazes or directly incorporating antibacterial powders into transparent glazes. These solutions primarily target flat glazed ceramic tiles, with less consideration given to products with a distinct granular texture, such as dry-granulated slabs and dry-granulated glazes. This often leads to a difficulty in balancing antibacterial function with surface feel and decorative effect. CN111995438A discloses a method for preparing high-strength antibacterial ceramic slabs. The method involves wet ball milling and spray granulation of slab blanks, followed by pressing and drying to obtain the slab blanks. A base glaze and a top glaze are sprayed onto the surface of the slab blanks, which are then sintered in a kiln. After cooling to 600-700℃, an antibacterial glaze is sprayed onto the blanks to obtain the high-strength antibacterial ceramic slabs. The antibacterial glaze is prepared as follows: zinc oxide, magnesium oxide, and diatomaceous earth are mixed evenly, added to a phosphoric acid solution, and stirred for 0.5-1 hour. Then, AgNO3 solution is added and stirred in a light-protected environment for 1.5-2 hours. Finally, the mixture is wet ball-milled for 5-8 hours and spray-granulated to obtain the antibacterial glaze. The high-strength antibacterial ceramic slab prepared by the method described in this invention has high surface hardness and wear resistance. The surface glaze and antibacterial glaze layer work together to provide dual antibacterial capabilities, thus broadening the application range of ceramic slabs. CN112876227A discloses a method for preparing a high-strength, high-transmittance, antibacterial, and mildew-resistant ceramic slab. The method includes the following steps: S1: preparing the raw materials for the green body layer; S2: adding the raw materials and an appropriate amount of water to a ball mill to obtain a slurry, sieving to remove iron and remove rot; S3: spray drying to obtain powder; S4: pressing the powder into shape and drying to obtain the green body layer; S5: applying a base glaze to obtain a base glaze layer; S6: decorating with patterns and drying to obtain a decorative layer; S7: applying a polishing glaze to obtain a polished glaze layer; S8: firing; S9: polishing to obtain the slab body; wherein, during polishing in S9, an antibacterial agent is added, including a liquid antibacterial agent and a nano-polishing anti-fouling liquid. The slab prepared by the method of this invention has high strength, good light transmittance, and an antibacterial efficacy of up to 99%.In the aforementioned literature, antibacterial coatings are applied during the low-temperature antibacterial glaze and polishing stages. The integration of the antibacterial phase with the main body of the slab is limited. There is a clear contradiction between antibacterial durability and high-frequency cleaning, abrasion, and chemical effects. It is also difficult to take into account the characteristics of high-end slabs such as dry granule feel and three-dimensional texture. Summary of the Invention

[0003] In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is to provide an antibacterial slab with durable antibacterial properties, wear resistance, and chemical reagent resistance, as well as its production process.

[0004] Silver-based antibacterial agents are prone to volatilization or rearrangement during long-term melting at high temperatures, resulting in significantly larger particle sizes; they may form coarse silver phases or composite crystals, reducing their activity or even turning them into purely decorative substances.

[0005] To achieve the above objectives, the present invention provides an antibacterial slab and its production process.

[0006] A production process for antibacterial slabs includes the following steps:

[0007] Step 1: Preparation of the green body;

[0008] Step 2: Apply glaze;

[0009] Step 3: Print the pattern;

[0010] Step 4: Apply antibacterial dry granules;

[0011] Step 5: Firing.

[0012] Preferably, a production process for antibacterial slabs includes the following steps:

[0013] Step 1, Green Body Preparation: Weigh potassium feldspar, quartz, clay, and electrolyte dispersant; add water to make a slurry; ball mill using a ball mill, controlling the average particle size D50 of the slurry to 3-8µm; send the prepared green body slurry into a spray drying tower, controlling the particle size D50 to 200-350µm; evenly distribute the spray powder into a mold using a spreading machine, and press it using a roller press to obtain a slab green body; send the green body into a drying kiln to dry, obtaining a dried green body;

[0014] Step 2, Glazing: Weigh frit, quartz, potassium feldspar, clay, and coloring oxides; add water to make a slurry; ball mill; adjust the density of the glaze slurry. Pass the dried blank through the glazing line; the glaze layer forms a continuous and dense thin layer on the surface of the blank, and after glazing, it is pre-dried in the preheating section;

[0015] Step 3, Printing the Pattern: Use ceramic-specific inkjet ink; feed the pre-dried and glazed ceramic body into the inkjet printer to complete the pattern printing; adjust the inkjet volume according to the color depth; after the pattern is printed, allow the ceramic body to dry.

[0016] Step 4, Applying antibacterial dry granules: Add the antibacterial dry granules to the hopper of the granulation machine, and adjust the width of the granule curtain and the amount of material falling according to the billet speed; if necessary, install a slight vibration device under the billet.

[0017] Step 5, Firing: The body coated with glaze, decorative patterns and antibacterial dry granules is sent into a roller kiln for firing, and then naturally cooled to room temperature.

[0018] A further preferred method for producing antibacterial slabs includes the following steps:

[0019] Step 1, Green body preparation: Weigh 40-60 parts by weight of potassium feldspar, 20-40 parts by weight of quartz, 10-25 parts by weight of clay, and 0.1-0.5 parts by weight of electrolyte dispersant; add water to make a slurry with a solid content of 68-72 wt%; ball mill for 10-16 hours, controlling the residue of the slurry passing through a 45µm sieve to be ≤0.5 wt%, and the average particle size D50 of the slurry to be controlled at 3-8µm; send the green body slurry obtained above into a spray drying tower, control the inlet temperature of the spray drying to be 480-550℃, control the outlet temperature to be 105-125℃, and control the moisture content of the obtained spray powder to be 5.5-7.0 wt%, and control the particle size D50 to be 200-350µm. The above-mentioned spray powder is evenly distributed into the mold by a cloth feeder, and pressed by a roller press at a pressure of 35-45MPa; the forming size is 900×1800 rock slab blank; the green blank is sent into a drying kiln and dried at 110-150℃ for 40-90min, so that the residual moisture of the blank is ≤0.5wt%, and the dried blank is obtained.

[0020] Step 2, Glazing: Weigh 60-80 parts by weight of frit, 5-15 parts by weight of quartz, 5-15 parts by weight of potassium feldspar, 3-8 parts by weight of clay, and 0.1-3 parts by weight of coloring oxide; add water to make a glaze slurry with a solid content of 60-68 wt%; ball mill for 6-10 hours, controlling the amount of residue passing through a 45µm sieve to ≤0.5 wt%; adjust the density of the glaze slurry to 1.55-1.70 g / cm³. 3 The viscosity (Ford Cup 4) is controlled at 20-40s. The dried blank is then passed through a glazing line, with the glazing pressure and flow rate adjusted to achieve a glaze application rate of 250-450 g / m². 2 The glaze layer forms a continuous and dense thin layer on the surface of the body. After glazing, it is pre-dried at 80-120℃ for 3-8 minutes in the preheating section to make the glaze surface non-sticky and easy to apply patterns later.

[0021] Step 3: Printing the pattern: Use ceramic-specific inkjet ink, with a solid content of 20-35 wt%; feed the pre-dried and glazed ceramic body into the inkjet printer, and print the pattern at an online speed of 10-25 m / min; control the pattern coverage to 20-80 g / m². 2Adjust the spray volume according to the depth of the pattern; after the pattern is printed, pre-dry the blank at 90-130℃ for 5-10 minutes to allow the water in the pattern ink to evaporate, so that the pattern layer adheres firmly and does not drip.

[0022] Step 4: Applying Antibacterial Dry Granules: Add the antibacterial dry granules to the hopper of the granulator and adjust the vibrating conveyor to ensure stable granule feeding. Control the billet running speed of the production line at 8-20 m / min. Adjust the granule curtain width and feeding amount according to the billet speed to achieve an antibacterial dry granule application rate of 200-800 g / m² per unit area. 2 By adjusting the dry granule drop height to 200-400mm, the dry granules are evenly dropped onto the surface of the patterned glaze layer. If necessary, a slight vibration device is installed under the body, with a vibration frequency of 10-30Hz and an amplitude of 0.5-2mm, to eliminate local accumulation and ensure that the dry granules are evenly distributed and have a natural texture. After applying the dry granules, the dry granule coverage rate on the body surface is controlled at 60-100% to ensure that the surface has a distinct dry granule feel and three-dimensional effect, while forming an antibacterial functional layer on the entire surface.

[0023] Step 5, Firing: The green body coated with glaze, decorative patterns, and antibacterial dry granules is sent into a roller kiln for firing. The total firing cycle is 50-90 minutes. The temperature rise rate from room temperature to 600-800℃ is 30-60℃ / min. The temperature is then raised to 1180-1250℃ and held for 5-15 minutes to ensure that the green body is fully sintered and the glaze is completely melted. The antibacterial dry granules are partially melted and firmly bonded to the glaze. Then the temperature is lowered to 600℃ at 40-80℃ / min and allowed to cool naturally to room temperature.

[0024] The method for preparing the antibacterial dry granules is as follows: Weigh 70-90 parts of frit, 5-15 parts of quartz, 3-10 parts of potassium feldspar, 0.1-5 parts of colorant, and 0.1-5 parts of antibacterial material; mix the above raw materials evenly and place them in a furnace, and melt them at 1150-1350℃ for 30-90 minutes to obtain antibacterial glass melt; pour the antibacterial glass melt into a cooling steel belt and cool it rapidly to form a glass block; after coarse crushing and fine crushing, the glass block is pulverized by ball milling or vibration milling to control the powder D50 to be 40-80µm; mix the obtained powder with 1-3wt% binder and 0.1-0.5wt% wetting agent, and add water to make a mixture with a water content of 6-10wt%; granulate by fluidized bed granulation to obtain antibacterial dry granules with a particle size of 0.2-1.5mm.

[0025] The method for preparing the antibacterial material includes the following steps:

[0026] S1. Add the filler to water and disperse it evenly. Add 0.1-1 wt% of dispersant and ultrasonically disperse to obtain a suspension.

[0027] S2. Take water glass solution (calculated as SiO2) and sodium aluminate solution, add them to water and mix evenly. Based on the actual contents of Na2O and SiO2 in the water glass solution and the actual contents of Na2O and Al2O3 in the sodium aluminate solution, convert each raw material into the amount of Na2O, Al2O3, and SiO2, and add water to make the molar ratio of Na2O, Al2O3, SiO2, and H2O in the system 2.0-3.0:1.0:1.8-2.5:120-180 to prepare the precursor system; control the temperature at 20-40℃ and treat for 0.5-1h, adjust the pH to 11-13 to obtain a milky precursor solution;

[0028] S3. Add the suspension obtained in step S1 to the emulsified precursor liquid in step S2 and mix evenly. Stir at room temperature for 1-4 hours to obtain a mixed system.

[0029] S4. The above mixture is allowed to stand and age at room temperature to 40°C for 4-24 hours; then it is transferred to a lined hydrothermal reactor and crystallized at 90-120°C for 2-8 hours; after crystallization, it is cooled to room temperature, centrifuged, washed with water until the pH of the filtrate is neutral, and dried to obtain the composite powder.

[0030] S5. Add the composite powder prepared above to a 0.01-0.1 mol / L silver nitrate aqueous solution and mix evenly, wherein the solid-liquid ratio is 5-50 g / L; stir at 20-80℃ for 1-8 h, and after the reaction is completed, filter, wash and dry to obtain the antibacterial material.

[0031] The electrolyte dispersant is at least one of sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, and sodium carbonate.

[0032] The clay mentioned therein is at least one of kaolin and porcelain clay;

[0033] The coloring oxide is at least one of cobalt oxide, iron oxide, nickel oxide, copper oxide, manganese oxide, and chromium oxide;

[0034] The colorant is a zirconium-based encapsulated or spinel-type ceramic colorant, specifically at least one of zirconium iron yellow, pigment black 30, and zirconium vanadium blue;

[0035] The adhesive is at least one of polyvinyl alcohol, hydroxypropyl methylcellulose, and sodium carboxymethyl cellulose;

[0036] The wetting agent is at least one of sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether, and sulfosuccinate salts;

[0037] The filler is at least one of β-SiAlON and fluoride; the fluoride is at least one of CaF2, YF3, CeF3, and AlF3; preferably, the filler is a mixture of β-SiAlON and CaF2 in a mass ratio of (0.5-2):(1-3).

[0038] The dispersant is ammonium polyacrylate.

[0039] The frit, by mass percentage, comprises 50-65wt% SiO2, 6-15wt% Al2O3, 6-18wt% B2O3, 8-20wt% CaO, 2-10wt% ZnO, 1-5wt% Na2O, 1-5wt% K2O, 0-6wt% MgO, and the balance being loss on ignition; the frit is fired at 1200-1350℃ for 30-90 minutes.

[0040] The body uses a conventional porcelain formula of feldspar, quartz, and kaolin, combined with a high-solids-content finely ground slurry and appropriate spray particle size. Under high forming pressure and a reasonable drying regime, a dense and dimensionally stable slab matrix is ​​formed, providing reliable support for the upper glaze layer and dry granule layer. The surface glaze uses a high proportion of frit combined with quartz, feldspar, and a small amount of kaolin to form a continuous and dense glassy phase glaze layer while controlling the fineness and rheological properties of the glaze slurry. During firing, this glaze layer partially fuses with the antibacterial dry granules, forming a transition interface that firmly bonds the dry granule functional layer to the body, ensuring overall flexural strength and wear resistance.

[0041] The antibacterial dry granules are primarily composed of a frit, quartz, and feldspar glass matrix, with an antibacterial composite filler consisting of β-SiAlON and CaF2. β-SiAlON is a high-temperature structural ceramic, compatible with silicate systems and maintaining its framework morphology at high temperatures. CaF2, upon partial melting, forms a fluorine-oxynitride glass with the surrounding glass phase, facilitating the formation of a continuous, non-overflowing glass layer on the framework surface. This is achieved through hydrothermal crystallization using a water glass and sodium aluminate system, followed by Ag... + In ion exchange, silver ions are mainly immobilized in aluminosilicate or fluorine-containing glass microphases coated on the β-SiAlON and CaF2 framework. During sintering, the framework maintains structural stability, and the silver-containing microphase slightly accumulates on the surface of dry particles as the glass phase softens. At the same time, it is confined by the framework and glass network, making it difficult for it to coarsely aggregate or deeply embed itself in the matrix at high temperatures.

[0042] The synergistic effect of β-SiAlON ceramic framework and fluorides forms a composite powder with high-temperature load-bearing capacity, good thermal expansion matching, and rich, highly dispersed antibacterial phase on the surface of dry particles after firing. This significantly improves antibacterial performance and durability while maintaining the tactile feel and mechanical strength of the slab. The introduction of fluorides around the nitride framework creates a fluorinated oxynitride glass phase with a low softening temperature at the framework interface, thereby improving the wetting bond between the framework and the silicate matrix and promoting the enrichment of the antibacterial functional phase on the framework surface.

[0043] The beneficial effects of this invention are:

[0044] 1. Compared with existing technologies, this invention introduces an antibacterial material obtained by the interaction of β-SiAlON and CaF2 through hydrothermal crystallization and silver ion exchange into the antibacterial dry granules. This confines the silver-based antibacterial agent within the aluminosilicate or fluorinated glass microphase surrounding the framework, preferentially enriching it on the surface of the dry granules after sintering. This avoids the volatilization, coarse crystallization, and deep burial failure of silver during high-temperature melting, while simultaneously achieving the surface-controlled release of silver ions.

[0045] 2. Compared with the prior art, the slab of the present invention achieves a distinct dry granular feel and three-dimensional decorative effect, while its bending strength, wear resistance and other indicators are basically the same as or improved with ordinary dry granular slabs. It avoids the problem of easy surface wear and peeling caused by antibacterial modification, and achieves a comprehensive balance between antibacterial function and mechanical and wear resistance properties. Detailed Implementation

[0046] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0047] The β-SiAlON in this embodiment was prepared according to the preparation method of Example 4 in patent CN113173800B. The preparation method of β-SiAlON is as follows: 40g of Si powder with a median diameter of 4.5µm, 38.6g of Si3N4 powder with a median diameter of 20µm and a β-phase content of 50wt%, 6.1g of AlN powder with a median diameter of 1.0µm, 15.3g of Al2O3 powder with a median diameter of 1.0µm, and 2g of Yb2O3 powder were weighed, where z=1; the powders were ball-milled and mixed using anhydrous ethanol as a solvent; the mixed powder was then cold isostatically pressed at 50MPa to form a mold; the molded blank was embedded with the embedded powder, and then 5MPa nitrogen gas was introduced and the embedded powder was ignited to initiate the reaction, resulting in the β-SiAlON.

[0048] The frit in the example, by mass percentage, has the following chemical composition: 60wt% SiO2, 10wt% Al2O3, 12wt% B2O3, 10wt% CaO, 4wt% ZnO, 2wt% Na2O, 1wt% K2O, 0.5wt% MgO, with the balance being loss on ignition; it is prepared by firing at 1250℃ for 60 minutes.

[0049] The ceramic-specific inkjet ink used in this embodiment is the HCR series ceramic inkjet ink manufactured by Esmalglass-ItacaGrupo.

[0050] In this embodiment, the water glass is industrial liquid sodium silicate with a Baume degree of 40. ° It has a modulus of 3.2 (based on the molar ratio of SiO2 / Na2O) and is a colorless to pale yellow viscous liquid. It conforms to the standard GB / T4209-2022 "Industrial Sodium Silicate".

[0051] Other raw materials not mentioned are all common raw materials. The above content is only for the purpose of illustrating the present invention and should not be construed as a strict limitation of the present invention. Those skilled in the art can directly purchase the same / similar raw materials from the market or prepare them themselves.

[0052] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0053] Example 1

[0054] A production process for antibacterial slabs includes the following steps:

[0055] Step 1, Green Body Preparation: Weigh 50 parts by weight of potassium feldspar, 30 parts by weight of quartz, 19.5 parts by weight of kaolin, and 0.5 parts by weight of sodium hexametaphosphate; add water to make a slurry with a solid content of 70 wt%; ball mill for 12 hours, controlling the residue amount of the slurry passing through a 45µm sieve to be ≤0.5 wt%, and the average particle size D50 of the slurry to be controlled at 5µm; send the green body slurry obtained above into a spray drying tower, controlling the inlet temperature of the spray drying to be 520℃ and the outlet temperature to be 115℃, controlling the moisture content of the obtained spray powder to be 6.2 wt%, and the particle size D50 to be controlled at 280µm; evenly distribute the above spray powder into the mold through a spreading machine, and press it with a roller press at a pressure of 40MPa; the forming size is 900×1800 rock slab green body; send the green body into a drying kiln and dry it at 130℃ for 60 minutes, so that the residual moisture content of the green body is ≤0.5 wt%, to obtain the dried green body;

[0056] Step 2, Glazing: Weigh 70 parts by weight of frit, 10 parts by weight of quartz, 10 parts by weight of potassium feldspar, 6 parts by weight of kaolin, and 1 part by weight of nickel oxide; add water to make a glaze slurry with a solid content of 65 wt%; ball mill for 8 hours, controlling the amount of residue passing through a 45 µm sieve to ≤0.5 wt%; adjust the density of the glaze slurry to 1.62 g / cm³. 3 The viscosity (Ford Cup 4) is controlled at 30s; the dried blank is passed through the glazing line, and the glazing pressure and flow rate are adjusted to achieve a glaze application rate of 350g / m² per unit area. 2 The glaze layer forms a continuous and dense thin layer on the surface of the body. After glazing, it is pre-dried at 100°C for 5 minutes in the preheating section to make the glaze surface non-sticky and easy to apply patterns later.

[0057] Step 3, Printing the Pattern: Use ceramic-specific inkjet ink, with a solid content typically of 30wt%; feed the pre-dried and glazed ceramic body into the inkjet printer, and print the pattern at a line speed of 15m / min; control the pattern coverage to 50g / m². 2 Adjust the spray volume according to the depth of the pattern; after the pattern is printed, pre-dry the blank at 100℃ for 8 minutes to allow the water in the pattern ink to evaporate, so that the pattern layer adheres firmly and does not drip.

[0058] Step 4: Applying Antibacterial Dry Granules: Add the antibacterial dry granules to the hopper of the granulator and adjust the vibrating conveyor to ensure stable granule feeding. Control the billet running speed at 12 m / min. Adjust the granule curtain width and feeding amount according to the billet speed to achieve an antibacterial dry granule application rate of 400 g / m² per unit area. 2 By adjusting the dry granule drop height to 300mm, the dry granules are evenly dropped onto the surface of the patterned glaze layer. If necessary, a slight vibration device is set under the body with a vibration frequency of 20Hz and an amplitude of 1mm to eliminate local accumulation and make the dry granules evenly distributed with a natural texture. After applying the dry granules, the dry granule coverage rate on the body surface is controlled at 80% to ensure that the surface has a clear dry granule feel and three-dimensional effect, while forming an antibacterial functional layer on the entire surface.

[0059] Step 5, Firing: The green body coated with glaze, decorative patterns and antibacterial dry granules is sent into the roller kiln for firing. The total firing cycle of the kiln is 70 minutes. The heating rate from room temperature to 700℃ is 40℃ / min. The temperature is then raised to 1220℃ and held for 10 minutes to ensure that the green body is fully sintered and the glaze is completely melted. The antibacterial dry granules are partially melted and firmly bonded to the glaze. Then the temperature is lowered to 600℃ at 60℃ / min and then allowed to cool naturally to room temperature.

[0060] The method for preparing the antibacterial dry granules is as follows: Weigh 80 parts of frit, 8 parts of quartz, 7 parts of potassium feldspar, 3 parts of pigment black 30, and 2 parts of antibacterial material; mix the above raw materials evenly and put them into a furnace, melt them at 1250℃ for 60 minutes to obtain antibacterial glass melt; pour the antibacterial glass melt into a cooling steel belt and cool it rapidly to form a glass block; after coarse crushing and fine crushing, the glass block is pulverized by ball milling or vibration milling to control the powder D50 to 60µm; mix the powder obtained above with 2wt% hydroxypropyl methylcellulose and 0.3wt% sodium dodecyl sulfate, and add water to make a mixture with a water content of 8wt%; granulate by fluidized bed granulation to obtain antibacterial dry granules with a particle size of 0.3-1.2mm.

[0061] The method for preparing the antibacterial material includes the following steps:

[0062] S1. Add 10 parts of filler to 190 parts of water and disperse evenly. Add 0.5 wt% of ammonium polyacrylate and disperse ultrasonically to obtain a suspension.

[0063] S2. Take water glass solution (calculated as SiO2) and sodium aluminate solution, add them to water and mix evenly. Based on the actual contents of Na2O and SiO2 in the water glass solution and the actual contents of Na2O and Al2O3 in the sodium aluminate solution, convert each raw material into the amount of Na2O, Al2O3, and SiO2, and add water to make the molar ratio of Na2O, Al2O3, SiO2, and H2O in the system 2.5:1.0:2.1:150 to prepare the precursor system; control the temperature at 30℃ for 0.5h, adjust the pH to 12, and obtain a milky precursor solution.

[0064] S3. Add the suspension obtained in step S1 to the emulsified precursor liquid in step S2 and mix evenly. Stir at room temperature for 2 hours to obtain a mixed system.

[0065] S4. The above mixture was allowed to stand and age at 40°C for 24 hours; then it was transferred to a lined hydrothermal reactor and crystallized at 100°C for 4 hours; after crystallization, it was cooled to room temperature, centrifuged, washed with water until the pH of the filtrate was neutral, and dried to obtain the composite powder.

[0066] S5. The composite powder prepared above is added to a 0.05 mol / L silver nitrate aqueous solution and mixed evenly, wherein the solid-liquid ratio is 50 g / L; the mixture is stirred at 60°C for 4 h; after the reaction is completed, the mixture is filtered, washed, and dried to obtain the antibacterial material.

[0067] The filler is composed of β-SiAlON and CaF2 mixed in a mass ratio of 1:1.

[0068] Example 2

[0069] It is basically the same as Example 1, except that the filler is β-SiAlON.

[0070] Example 3

[0071] It is basically the same as Example 1, except that the filler is CaF2.

[0072] Comparative Example 1

[0073] A production process for antibacterial slabs includes the following steps:

[0074] Step 1, Green Body Preparation: Weigh 50 parts by weight of potassium feldspar, 30 parts by weight of quartz, 19.5 parts by weight of kaolin, and 0.5 parts by weight of sodium hexametaphosphate; add water to make a slurry with a solid content of 70 wt%; ball mill for 12 hours, controlling the residue amount of the slurry passing through a 45µm sieve to be ≤0.5 wt%, and the average particle size D50 of the slurry to be controlled at 5µm; send the green body slurry obtained above into a spray drying tower, controlling the inlet temperature of the spray drying to be 520℃ and the outlet temperature to be 115℃, controlling the moisture content of the obtained spray powder to be 6.2 wt%, and the particle size D50 to be controlled at 280µm; evenly distribute the above spray powder into the mold through a spreading machine, and press it with a roller press at a pressure of 40MPa; the forming size is 900×1800 rock slab green body; send the green body into a drying kiln and dry it at 130℃ for 60 minutes, so that the residual moisture content of the green body is ≤0.5 wt%, to obtain the dried green body;

[0075] Step 2, Glazing: Weigh 70 parts by weight of frit, 10 parts by weight of quartz, 10 parts by weight of potassium feldspar, 6 parts by weight of kaolin, and 1 part by weight of nickel oxide; add water to make a glaze slurry with a solid content of 65 wt%; ball mill for 8 hours, controlling the amount of residue passing through a 45 µm sieve to ≤0.5 wt%; adjust the density of the glaze slurry to 1.62 g / cm³. 3 The viscosity (Ford Cup 4) is controlled at 30s; the dried blank is passed through the glazing line, and the glazing pressure and flow rate are adjusted to achieve a glaze application rate of 350g / m² per unit area. 2 The glaze layer forms a continuous and dense thin layer on the surface of the body. After glazing, it is pre-dried at 100°C for 5 minutes in the preheating section to make the glaze surface non-sticky and easy to apply patterns later.

[0076] Step 3, Printing the Pattern: Use ceramic-specific inkjet ink, with a solid content typically of 30wt%; feed the pre-dried and glazed ceramic body into the inkjet printer, and print the pattern at a line speed of 15m / min; control the pattern coverage to 50g / m². 2 Adjust the spray volume according to the depth of the pattern; after the pattern is printed, pre-dry the blank at 100℃ for 8 minutes to allow the water in the pattern ink to evaporate, so that the pattern layer adheres firmly and does not drip.

[0077] Step 4: Applying Antibacterial Dry Granules: Add the antibacterial dry granules to the hopper of the granulator and adjust the vibrating conveyor to ensure stable granule feeding. Control the billet running speed at 12 m / min. Adjust the granule curtain width and feeding amount according to the billet speed to achieve an antibacterial dry granule application rate of 400 g / m² per unit area. 2 By adjusting the dry granule drop height to 300mm, the dry granules are evenly dropped onto the surface of the patterned glaze layer. If necessary, a slight vibration device is set under the body with a vibration frequency of 20Hz and an amplitude of 1mm to eliminate local accumulation and make the dry granules evenly distributed with a natural texture. After applying the dry granules, the dry granule coverage rate on the body surface is controlled at 80% to ensure that the surface has a clear dry granule feel and three-dimensional effect, while forming an antibacterial functional layer on the entire surface.

[0078] Step 5, Firing: The green body coated with glaze, decorative patterns and antibacterial dry granules is sent into the roller kiln for firing. The total firing cycle of the kiln is 70 minutes. The heating rate from room temperature to 700℃ is 40℃ / min. The temperature is then raised to 1220℃ and held for 10 minutes to ensure that the green body is fully sintered and the glaze is completely melted. The antibacterial dry granules are partially melted and firmly bonded to the glaze. Then the temperature is lowered to 600℃ at 60℃ / min and then allowed to cool naturally to room temperature.

[0079] The method for preparing the antibacterial dry granules is as follows: 80 parts of frit, 8 parts of quartz, 7 parts of potassium feldspar, 3 parts of pigment black 30, and 2 parts of antibacterial material are weighed; the above raw materials are mixed evenly and placed in a furnace, and melted at 1250℃ for 60 minutes to obtain antibacterial glass melt; the antibacterial glass melt is poured into a cooling steel belt and rapidly cooled to form glass blocks; the glass blocks are coarsely crushed and finely crushed, and then pulverized by ball milling or vibration milling to control the powder D50 to 60µm; the powder obtained above is mixed with 2wt% hydroxypropyl methylcellulose and 0.3wt% sodium dodecyl sulfate, and water is added to prepare a mixture with a water content of 8wt%; the mixture is granulated by fluidized bed granulation to obtain antibacterial dry granules with a particle size of 0.3-1.2mm; the antibacterial material is silver nitrate.

[0080] Comparative Example 2

[0081] A production process for antibacterial slabs includes the following steps:

[0082] Step 1, Green Body Preparation: Weigh 50 parts by weight of potassium feldspar, 30 parts by weight of quartz, 19.5 parts by weight of kaolin, and 0.5 parts by weight of sodium hexametaphosphate; add water to make a slurry with a solid content of 70 wt%; ball mill for 12 hours, controlling the residue amount of the slurry passing through a 45µm sieve to be ≤0.5 wt%, and the average particle size D50 of the slurry to be controlled at 5µm; send the green body slurry obtained above into a spray drying tower, controlling the inlet temperature of the spray drying to be 520℃ and the outlet temperature to be 115℃, controlling the moisture content of the obtained spray powder to be 6.2 wt%, and the particle size D50 to be controlled at 280µm; evenly distribute the above spray powder into the mold through a spreading machine, and press it with a roller press at a pressure of 40MPa; the forming size is 900×1800 rock slab green body; send the green body into a drying kiln and dry it at 130℃ for 60 minutes, so that the residual moisture content of the green body is ≤0.5 wt%, to obtain the dried green body;

[0083] Step 2, Glazing: Weigh 70 parts by weight of frit, 10 parts by weight of quartz, 10 parts by weight of potassium feldspar, 6 parts by weight of kaolin, and 1 part by weight of nickel oxide; add water to make a glaze slurry with a solid content of 65 wt%; ball mill for 8 hours, controlling the amount of residue passing through a 45 µm sieve to ≤0.5 wt%; adjust the density of the glaze slurry to 1.62 g / cm³. 3 The viscosity (Ford Cup 4) is controlled at 30s; the dried blank is passed through the glazing line, and the glazing pressure and flow rate are adjusted to achieve a glaze application rate of 350g / m² per unit area. 2 The glaze layer forms a continuous and dense thin layer on the surface of the body. After glazing, it is pre-dried at 100°C for 5 minutes in the preheating section to make the glaze surface non-sticky and easy to apply patterns later.

[0084] Step 3, Printing the Pattern: Use ceramic-specific inkjet ink, with a solid content typically of 30wt%; feed the pre-dried and glazed ceramic body into the inkjet printer, and print the pattern at a line speed of 15m / min; control the pattern coverage to 50g / m². 2 Adjust the spray volume according to the depth of the pattern; after the pattern is printed, pre-dry the blank at 100℃ for 8 minutes to allow the water in the pattern ink to evaporate, so that the pattern layer adheres firmly and does not drip.

[0085] Step 4: Applying Antibacterial Dry Granules: Add the antibacterial dry granules to the hopper of the granulator and adjust the vibrating conveyor to ensure stable granule feeding. Control the billet running speed at 12 m / min. Adjust the granule curtain width and feeding amount according to the billet speed to achieve an antibacterial dry granule application rate of 400 g / m² per unit area. 2By adjusting the dry granule drop height to 300mm, the dry granules are evenly dropped onto the surface of the patterned glaze layer. If necessary, a slight vibration device is set under the body with a vibration frequency of 20Hz and an amplitude of 1mm to eliminate local accumulation and make the dry granules evenly distributed with a natural texture. After applying the dry granules, the dry granule coverage rate on the body surface is controlled at 80% to ensure that the surface has a clear dry granule feel and three-dimensional effect, while forming an antibacterial functional layer on the entire surface.

[0086] Step 5, Firing: The green body coated with glaze, decorative patterns and antibacterial dry granules is sent into the roller kiln for firing. The total firing cycle of the kiln is 70 minutes. The heating rate from room temperature to 700℃ is 40℃ / min. The temperature is then raised to 1220℃ and held for 10 minutes to ensure that the green body is fully sintered and the glaze is completely melted. The antibacterial dry granules are partially melted and firmly bonded to the glaze. Then the temperature is lowered to 600℃ at 60℃ / min and then allowed to cool naturally to room temperature.

[0087] The method for preparing the antibacterial dry granules is as follows: Weigh 80 parts of frit, 8 parts of quartz, 7 parts of potassium feldspar, 3 parts of pigment black 30, and 2 parts of antibacterial material; mix the above raw materials evenly and put them into a furnace, melt them at 1250℃ for 60 minutes to obtain antibacterial glass melt; pour the antibacterial glass melt into a cooling steel belt and cool it rapidly to form a glass block; after coarse crushing and fine crushing, the glass block is pulverized by ball milling or vibration milling to control the powder D50 to 60µm; mix the powder obtained above with 2wt% hydroxypropyl methylcellulose and 0.3wt% sodium dodecyl sulfate, and add water to make a mixture with a water content of 8wt%; granulate by fluidized bed granulation to obtain antibacterial dry granules with a particle size of 0.3-1.2mm.

[0088] The method for preparing the antibacterial material includes the following steps:

[0089] S1. Take water glass solution (calculated as SiO2) and sodium aluminate solution, add them to water and mix evenly. Based on the actual contents of Na2O and SiO2 in the water glass solution and the actual contents of Na2O and Al2O3 in the sodium aluminate solution, convert each raw material into the amount of Na2O, Al2O3, and SiO2, and add water to make the molar ratio of Na2O, Al2O3, SiO2, and H2O in the system 2.5:1.0:2.1:150 to prepare the precursor system; control the temperature at 30℃ for 0.5h, adjust the pH to 12, and obtain a milky precursor solution.

[0090] S2. The above emulsified precursor solution was allowed to stand and age at 40°C for 24 hours; then it was transferred to a lined hydrothermal reactor and crystallized at 100°C for 4 hours; after crystallization, it was cooled to room temperature, centrifuged, washed with water until the pH of the filtrate was neutral, and dried to obtain the composite powder.

[0091] S3. The composite powder prepared above is added to a 0.05 mol / L silver nitrate aqueous solution and mixed evenly, wherein the solid-liquid ratio is 50 g / L; the mixture is stirred at 60°C for 4 h, and after the reaction is completed, it is filtered, washed and dried to obtain the antibacterial material.

[0092] Example 4

[0093] A production process for antibacterial slabs includes the following steps:

[0094] Step 1, Green Body Preparation: Weigh 50 parts by weight of potassium feldspar, 30 parts by weight of quartz, 19.5 parts by weight of kaolin, and 0.5 parts by weight of sodium hexametaphosphate; add water to make a slurry with a solid content of 70 wt%; ball mill for 12 hours, controlling the residue amount of the slurry passing through a 45µm sieve to be ≤0.5 wt%, and the average particle size D50 of the slurry to be controlled at 5µm; send the green body slurry obtained above into a spray drying tower, controlling the inlet temperature of the spray drying to be 520℃ and the outlet temperature to be 115℃, controlling the moisture content of the obtained spray powder to be 6.2 wt%, and the particle size D50 to be controlled at 280µm; evenly distribute the above spray powder into the mold through a spreading machine, and press it with a roller press at a pressure of 40MPa; the forming size is 900×1800 rock slab green body; send the green body into a drying kiln and dry it at 130℃ for 60 minutes, so that the residual moisture content of the green body is ≤0.5 wt%, to obtain the dried green body;

[0095] Step 2, Glazing: Weigh 70 parts by weight of frit, 10 parts by weight of quartz, 10 parts by weight of potassium feldspar, 6 parts by weight of kaolin, and 1 part by weight of nickel oxide; add water to make a glaze slurry with a solid content of 65 wt%; ball mill for 8 hours, controlling the amount of residue passing through a 45 µm sieve to ≤0.5 wt%; adjust the density of the glaze slurry to 1.62 g / cm³. 3 The viscosity (Ford Cup 4) is controlled at 30s; the dried blank is passed through the glazing line, and the glazing pressure and flow rate are adjusted to achieve a glaze application rate of 350g / m² per unit area. 2 The glaze layer forms a continuous and dense thin layer on the surface of the body. After glazing, it is pre-dried at 100°C for 5 minutes in the preheating section to make the glaze surface non-sticky and easy to apply patterns later.

[0096] Step 3, Printing the Pattern: Use ceramic-specific inkjet ink, with a solid content typically of 30wt%; feed the pre-dried and glazed ceramic body into the inkjet printer, and print the pattern at a line speed of 15m / min; control the pattern coverage to 50g / m². 2 Adjust the spray volume according to the depth of the pattern; after the pattern is printed, pre-dry the blank at 100℃ for 8 minutes to allow the water in the pattern ink to evaporate, so that the pattern layer adheres firmly and does not drip.

[0097] Step 4: Applying Antibacterial Dry Granules: Add the antibacterial dry granules to the hopper of the granulator and adjust the vibrating conveyor to ensure stable granule feeding. Control the billet running speed at 12 m / min. Adjust the granule curtain width and feeding amount according to the billet speed to achieve an antibacterial dry granule application rate of 400 g / m² per unit area. 2 By adjusting the dry granule drop height to 300mm, the dry granules are evenly dropped onto the surface of the patterned glaze layer. If necessary, a slight vibration device is set under the body with a vibration frequency of 20Hz and an amplitude of 1mm to eliminate local accumulation and make the dry granules evenly distributed with a natural texture. After applying the dry granules, the dry granule coverage rate on the body surface is controlled at 80% to ensure that the surface has a clear dry granule feel and three-dimensional effect, while forming an antibacterial functional layer on the entire surface.

[0098] Step 5, Firing: The green body coated with glaze, decorative patterns and antibacterial dry granules is sent into the roller kiln for firing. The total firing cycle of the kiln is 70 minutes. The heating rate from room temperature to 700℃ is 40℃ / min. The temperature is then raised to 1220℃ and held for 10 minutes to ensure that the green body is fully sintered and the glaze is completely melted. The antibacterial dry granules are partially melted and firmly bonded to the glaze. Then the temperature is lowered to 600℃ at 60℃ / min and then allowed to cool naturally to room temperature.

[0099] The method for preparing the antibacterial dry granules is as follows: Weigh 80 parts of frit, 8 parts of quartz, 7 parts of potassium feldspar, 3 parts of pigment black 30, and 2 parts of antibacterial material; mix the above raw materials evenly and put them into a furnace, melt them at 1250℃ for 60 minutes to obtain antibacterial glass melt; pour the antibacterial glass melt into a cooling steel belt and cool it rapidly to form a glass block; after coarse crushing and fine crushing, the glass block is pulverized by ball milling or vibration milling to control the powder D50 to 60µm; mix the powder obtained above with 2wt% hydroxypropyl methylcellulose and 0.3wt% sodium dodecyl sulfate, and add water to make a mixture with a water content of 8wt%; granulate by fluidized bed granulation to obtain antibacterial dry granules with a particle size of 0.3-1.2mm.

[0100] The method for preparing the antibacterial material includes the following steps:

[0101] S1. Add 10 parts of filler to 190 parts of water and disperse evenly. Add 0.5 wt% of ammonium polyacrylate and disperse ultrasonically to obtain a suspension.

[0102] S2. The above suspension was allowed to stand and age at 40°C for 24 hours; then it was transferred to a lined hydrothermal reactor and crystallized at 100°C for 4 hours; after crystallization, it was cooled to room temperature, centrifuged, washed with water until the pH of the filtrate was neutral, and dried to obtain the composite powder.

[0103] S3. The composite powder prepared above is added to a 0.05 mol / L silver nitrate aqueous solution and mixed evenly, wherein the solid-liquid ratio is 50 g / L; the mixture is stirred at 60°C for 4 h, and after the reaction is completed, it is filtered, washed and dried to obtain the antibacterial material; the filler is composed of β-SiAlON and CaF2 mixed in a mass ratio of 1:1.

[0104] Example 5

[0105] It is basically the same as Example 1, except that the filler is composed of β-SiAlON and CaF2 mixed in a mass ratio of 2:1.

[0106] Example 6

[0107] It is basically the same as Example 1, except that the filler is composed of β-SiAlON and CaF2 mixed in a mass ratio of 1:3.

[0108] Example 7

[0109] A production process for antibacterial slabs includes the following steps:

[0110] Step 1, Green Body Preparation: Weigh 50 parts by weight of potassium feldspar, 30 parts by weight of quartz, 19.5 parts by weight of kaolin, and 0.5 parts by weight of sodium hexametaphosphate; add water to make a slurry with a solid content of 70 wt%; ball mill for 12 hours, controlling the residue amount of the slurry passing through a 45µm sieve to be ≤0.5 wt%, and the average particle size D50 of the slurry to be controlled at 5µm; send the green body slurry obtained above into a spray drying tower, controlling the inlet temperature of the spray drying to be 520℃ and the outlet temperature to be 115℃, controlling the moisture content of the obtained spray powder to be 6.2 wt%, and the particle size D50 to be controlled at 280µm; evenly distribute the above spray powder into the mold through a spreading machine, and press it with a roller press at a pressure of 40MPa; the forming size is 900×1800 rock slab green body; send the green body into a drying kiln and dry it at 130℃ for 60 minutes, so that the residual moisture content of the green body is ≤0.5 wt%, to obtain the dried green body;

[0111] Step 2, Glazing: Weigh 70 parts by weight of frit, 10 parts by weight of quartz, 10 parts by weight of potassium feldspar, 6 parts by weight of kaolin, and 1 part by weight of nickel oxide; add water to make a glaze slurry with a solid content of 65 wt%; ball mill for 8 hours, controlling the amount of residue passing through a 45 µm sieve to ≤0.5 wt%; adjust the density of the glaze slurry to 1.62 g / cm³. 3 The viscosity (Ford Cup 4) is controlled at 30s; the dried blank is passed through the glazing line, and the glazing pressure and flow rate are adjusted to achieve a glaze application rate of 350g / m² per unit area. 2 The glaze layer forms a continuous and dense thin layer on the surface of the body. After glazing, it is pre-dried at 100°C for 5 minutes in the preheating section to make the glaze surface non-sticky and easy to apply patterns later.

[0112] Step 3, Printing the Pattern: Use ceramic-specific inkjet ink, with a solid content typically of 30wt%; feed the pre-dried and glazed ceramic body into the inkjet printer, and print the pattern at a line speed of 15m / min; control the pattern coverage to 50g / m². 2 Adjust the spray volume according to the depth of the pattern; after the pattern is printed, pre-dry the blank at 100℃ for 8 minutes to allow the water in the pattern ink to evaporate, so that the pattern layer adheres firmly and does not drip.

[0113] Step 4: Applying Antibacterial Dry Granules: Add the antibacterial dry granules to the hopper of the granulator and adjust the vibrating conveyor to ensure stable granule feeding. Control the billet running speed at 12 m / min. Adjust the granule curtain width and feeding amount according to the billet speed to achieve an antibacterial dry granule application rate of 400 g / m² per unit area. 2 By adjusting the dry granule drop height to 300mm, the dry granules are evenly dropped onto the surface of the patterned glaze layer. If necessary, a slight vibration device is set under the body with a vibration frequency of 20Hz and an amplitude of 1mm to eliminate local accumulation and make the dry granules evenly distributed with a natural texture. After applying the dry granules, the dry granule coverage rate on the body surface is controlled at 80% to ensure that the surface has a clear dry granule feel and three-dimensional effect, while forming an antibacterial functional layer on the entire surface.

[0114] Step 5, Firing: The green body coated with glaze, decorative patterns and antibacterial dry granules is sent into the roller kiln for firing. The total firing cycle of the kiln is 70 minutes. The heating rate from room temperature to 700℃ is 40℃ / min. The temperature is then raised to 1220℃ and held for 10 minutes to ensure that the green body is fully sintered and the glaze is completely melted. The antibacterial dry granules are partially melted and firmly bonded to the glaze. Then the temperature is lowered to 600℃ at 60℃ / min and then allowed to cool naturally to room temperature.

[0115] The method for preparing the antibacterial dry granules is as follows: Weigh 80 parts of frit, 8 parts of quartz, 7 parts of potassium feldspar, 3 parts of pigment black 30, 2 parts of antibacterial material, and 3 parts of ammonium chloride; mix the above raw materials evenly and put them into a furnace, melt them at 1250℃ for 60 minutes to obtain antibacterial glass melt; pour the antibacterial glass melt into a cooling steel belt and cool it rapidly to form a glass block; after coarse crushing and fine crushing, the glass block is pulverized by ball milling or vibration milling to control the powder D50 to 60µm; mix the powder obtained above with 2wt% hydroxypropyl methylcellulose and 0.3wt% sodium dodecyl sulfate, and add water to make a mixture with a water content of 8wt%; granulate by fluidized bed granulation to obtain antibacterial dry granules with a particle size of 0.3-1.2mm.

[0116] The method for preparing the antibacterial material includes the following steps:

[0117] S1. Add 10 parts of filler to 190 parts of water and disperse evenly. Add 0.5 wt% of ammonium polyacrylate and disperse ultrasonically to obtain a suspension.

[0118] S2. Take water glass solution (calculated as SiO2) and sodium aluminate solution, add them to water and mix evenly. Based on the actual contents of Na2O and SiO2 in the water glass solution and the actual contents of Na2O and Al2O3 in the sodium aluminate solution, convert each raw material into the amount of Na2O, Al2O3, and SiO2, and add water to make the molar ratio of Na2O, Al2O3, SiO2, and H2O in the system 2.5:1.0:2.1:150 to prepare the precursor system; control the temperature at 30℃ for 0.5h, adjust the pH to 12, and obtain a milky precursor solution.

[0119] S3. Add the suspension obtained in step S1 to the emulsified precursor liquid in step S2 and mix evenly. Stir at room temperature for 2 hours to obtain a mixed system.

[0120] S4. The above mixture was allowed to stand and age at 40°C for 24 hours; then it was transferred to a lined hydrothermal reactor and crystallized at 100°C for 4 hours; after crystallization, it was cooled to room temperature, centrifuged, washed with water until the pH of the filtrate was neutral, and dried to obtain the composite powder.

[0121] S5. The composite powder prepared above is added to a 0.05 mol / L silver nitrate aqueous solution and mixed evenly, wherein the solid-liquid ratio is 50 g / L; the mixture is stirred at 60°C for 4 h; after the reaction is completed, the mixture is filtered, washed, and dried to obtain the antibacterial material.

[0122] The filler is composed of β-SiAlON and CaF2 mixed in a mass ratio of 1:1.

[0123] Test Example 1

[0124] The antibacterial properties and antibacterial durability of antibacterial slabs were tested according to the method for antibacterial properties of antibacterial ceramic products in JC / T897-2014; the bacteria tested included Staphylococcus aureus and Escherichia coli.

[0125] Table 1. Results of antibacterial performance test

[0126]

[0127] The antibacterial rate of the sample was determined once according to JC / T897-2014. The obtained antibacterial rate was recorded as the antibacterial rate of the 0th cycle and used as the initial value. The cycle was performed according to the steps of contamination-cleaning-recontamination. Each cycle step was as follows: (1) Contamination (inoculation): The bacterial suspension of the specified concentration was inoculated onto the sample surface according to the antibacterial performance test method. The inoculation amount and action time were kept the same as the initial antibacterial test, so that the bacteria could act on the sample surface; (2) Cleaning (wiping): After the action was completed, the standard abrasion-resistant cloth was wetted with a neutral detergent aqueous solution and the sample surface was wiped back and forth under a load of 2 kg. The number of back and forth was 200 times (one back and forth was counted as 1 time); after wiping, the sample surface was rinsed with water to remove residual detergent and dirt; (3) Drying and recontamination preparation: The sample was dried at room temperature or dried at about (40±5)℃ until there was no visible moisture on the surface. After cooling to room temperature, it was used as the sample for the next round of inoculation test; the above three steps (1)-(3) were regarded as 1 cycle; the same sample was continuously cycled 50 times according to the above steps. After the 50th cycle, the antibacterial properties of the samples were tested using the same method as the initial test, and the antibacterial rate at this time was calculated and recorded as the antibacterial rate of the 50th cycle.

[0128] Table 2 Results of Antibacterial Durability Test

[0129]

[0130] Test Example 2

[0131] Abrasion resistance tests were conducted on antibacterial slabs in accordance with GB / T3810.7-2016.

[0132] Table 3. Test results of wear resistance performance

[0133]

[0134] Test Example 3

[0135] The acid and alkali resistance of antibacterial slabs was tested in accordance with GB / T3810.13-2016.

[0136] Table 4 Results of acid and alkali resistance tests

[0137]

[0138] Table 1 shows that Example 1, using the interaction of β-SiAlON and CaF2, achieved antibacterial rates of nearly 99% against Staphylococcus aureus and Escherichia coli, the highest among all samples. Examples 5-6 were only slightly lower than Example 1, while Example 2 (containing only β-SiAlON), Example 3 (containing only CaF2), and Comparative Example 2 (without the framework) all showed varying degrees of initial antibacterial rate decrease. Comparative Example 1, which directly used silver nitrate, had the lowest rate. This may be because in Examples 1 and 5-6, β-SiAlON provided a high-temperature stable framework, and CaF2 participated in the formation of a fluorine-oxynitride glass phase in the molten glass, combined with the aluminosilicate microcrystals formed by hydrothermal crystallization and subsequent Ag... + Exchange allows silver ions to be uniformly embedded in the microcrystalline or glass composite layer surrounding the framework. After high-temperature sintering, a continuous and well-dispersed silver-rich zone is formed on the surface of the dry particles. This ensures the effective exposure area of ​​silver on the surface while avoiding localized coarse deposition or deep burial of silver, thus achieving the highest initial antibacterial efficiency. In contrast, when only β-SiAlON or only CaF2 is present, the continuity and spatial confinement effect of the silver-containing phase on the surface are weakened, making it easy for insufficient silver concentration or uneven distribution in local areas to occur, resulting in a decrease in the initial antibacterial rate. When silver salts are introduced directly into ordinary glass or water glass systems without a framework, silver is more likely to volatilize, coarsen, or become inactive at high temperatures, leading to a significantly lower antibacterial rate in Comparative Examples 1-2.

[0139] As shown in Table 2, the antibacterial rate of Example 1 against both bacteria remained above 95%, far exceeding the approximately 80% of Comparative Examples 1-2, and significantly better than Examples 2-3. This indicates that Example 1 not only has a high initial antibacterial rate, but also exhibits a significant slow-release characteristic in silver ion release. In Example 1, silver mainly exists in the form of ions or nanoscale dispersed phases in the aluminosilicate or fluorinated glass microregions surrounding the β-SiAlON and CaF2 framework. The outer glass network forms a multi-layer barrier for silver ion migration. During each wiping and recontamination process, only a portion of the silver participates in dissolution and sterilization, while sufficient silver remains internally, gradually replenishing the surface layer through diffusion, thus maintaining a high antibacterial rate even after multiple cycles. In Examples 2-3, the framework has only one phase, and the composition is relatively simple. The silver distribution is more concentrated in a few interface areas. Some interfaces are worn or depleted in the first few cleaning cycles, resulting in insufficient silver release in the later stages and a faster decline in antibacterial rate. In Comparative Examples 1-2, there is no high-temperature stable framework and synergistic confinement of fluorinated glass. Silver is prone to agglomeration and deposition into an inert phase during firing and use, and is also quickly carried away during the scrubbing process, resulting in a significant deterioration in antibacterial rate after 50 cycles.

[0140] Example 1: A silicate microcrystalline coating layer formed by hydrothermal crystallization of β-SiAlON and CaF2, and Ag. +Ion exchange constructs a structurally stable, uniformly distributed, and slow-release antibacterial functional zone on the surface of dry granules. This structure significantly improves the initial antibacterial rate and the residual antibacterial rate after multiple cycles, while maintaining the conventional mechanical properties, wear resistance, and chemical resistance of the body and glaze. Different adjustments to the skeleton composition, ratio, and antibacterial material preparation process in Examples 2-3 and 4-6 show consistent gradient differences in antibacterial efficiency, antibacterial durability, wear resistance, and chemical resistance. β-SiAlON, as a high-temperature stable skeleton material, works with CaF2 to form a fluorinated oxynitride glass phase, which helps stabilize silver ions and control their release. The addition of ammonium chloride forms pores during sintering, further increasing the exposure area of ​​silver ions and enhancing the antibacterial effect. The combination of these two factors ensures the uniform distribution and sustained release of silver ions while maintaining the strength and durability of the material, thereby improving antibacterial performance.

[0141] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. An antibacterial rock plate, characterized in that, The body includes a body, a surface glaze layer, a decorative pattern layer, and an antibacterial dry particle layer located at the outermost layer arranged in sequence; The antibacterial dry particle layer is formed by applying the antibacterial dry particle to the surface of the decorative pattern layer and calcining; the antibacterial dry particle layer includes frit, quartz, potassium feldspar, coloring material, and antibacterial material dispersed therein, the antibacterial material is a silver-containing composite powder, and the silver-containing composite powder is prepared by coating a filler with a silico-aluminate precursor solution, hydrothermal crystallization, and silver ion exchange treatment; The preparation method of the antibacterial dry particle includes weighing frit, quartz, potassium feldspar, coloring material, and antibacterial material; mixing the raw materials uniformly and then placing them in a melting furnace to melt at 1150-1350°C for 30-90 min to obtain an antibacterial glass melt; cooling the antibacterial glass melt to form a glass block; after coarse crushing and fine crushing, the glass block is subjected to ball milling to control the D50 of the powder to be 40-80 µm; mixing the powder with a binder and a wetting agent, and adding water to prepare a mixture with a water content of 6-10 wt%; and granulating by fluidized granulation to obtain antibacterial dry particles with a particle size of 0.2-1.5 mm. The filler is prepared by mixing β-SiAlON and CaF2 in a mass ratio of (0.5-2):(1-3).

2. The antibacterial rock plate of claim 1, wherein, The body includes the following raw materials: potassium feldspar 40-60 parts, quartz 20-40 parts, clay 10-25 parts, and 0.1-0.5 parts of an electrolyte dispersant. The surface glaze layer includes the following raw materials: frit 60-80 parts, quartz 5-15 parts, potassium feldspar 5-15 parts, clay 3-8 parts, and 0.1-3 parts of coloring oxide.

3. The antibacterial rock plate of claim 1, wherein, The antibacterial dry particle includes the following raw materials: frit 70-90 parts, quartz 5-15 parts, potassium feldspar 3-10 parts, coloring material 0.1-5 parts, and antibacterial material 0.1-5 parts.

4. The antibacterial stone slab of claim 2, wherein, The clay is at least one of kaolin and porcelain clay.

5. The antibacterial stone slab of claim 2, wherein, The coloring oxide is at least one of cobalt oxide, iron oxide, nickel oxide, copper oxide, manganese oxide, and chromium oxide.

6. The antibacterial stone slab of claim 1, wherein, The preparation method of the antibacterial material includes the following steps: S1. Disperse the filler in water, add a dispersant, and ultrasonically disperse to obtain a suspension; S2. Mix water glass solution and sodium metaaluminate solution in water to prepare a precursor system; control the temperature and adjust the pH to obtain a milky precursor solution; S3. Mix the suspension obtained in step S1 with the milky precursor solution in step S2 to obtain a mixed system; S4. Age the mixed system, then transfer it to a lined hydrothermal reaction kettle for hydrothermal treatment; after the end of the treatment, cool to room temperature, centrifuge, wash with water until the filtrate pH is neutral, dry, and obtain a composite powder; S5. Mix the prepared composite powder with an aqueous silver nitrate solution, heat and stir, filter, wash, and dry after the reaction to obtain an antibacterial material.

7. A process for producing an antibacterial stone slab as claimed in any one of claims 1-6, characterized in that, The method includes the following steps: Step 1, preparation of a green body: potash feldspar, quartz, clay and electrolyte dispersant are ball milled to prepare a slurry, the solid content of the slurry is 68-72wt%, the residue amount on a 45μm sieve is ≤0.5wt%, the spray-dried powder with a moisture content of 5.5-7.0wt% and a D50 of 200-350μm is obtained, and the green body is obtained by pressing and drying; Step 2, glazing: frit, quartz, potash feldspar, clay and coloring oxides are prepared into a glaze slurry, the solid content of the glaze slurry is 60-68wt%, the residue amount on a 45μm sieve is ≤0.5wt%, the glazing amount is 250-450g / m², and the surface glaze layer is obtained by drying; Step 3, printing a pattern: a decorative pattern layer is formed on the surface of the surface glaze layer by inkjet printing, and pre-drying is performed; Step 4, applying antibacterial dry particles: antibacterial dry particles are applied on the surface of the decorative pattern layer, the application amount is 200-800g / m², and the antibacterial dry particles form an antibacterial dry particle coating with a coverage of 60-100% on the surface; Step 5, firing: the green body obtained in step 4 is sent into a roller kiln, and is fired according to a curve with a total firing period of 50-90min and a temperature of 1180-1250℃ for 5-15min, to obtain the antibacterial rock plate.

8. The production process of antibacterial rock plate according to claim 7, characterized in that, The binder is at least one of polyvinyl alcohol, hydroxypropyl methyl cellulose and sodium carboxymethyl cellulose; the wetting agent is at least one of sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether and sulfosuccinate salt.

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