Antibacterial ceramic closestool and manufacturing process thereof

Abstract

The invention relates to an antibacterial ceramic closestool and a manufacturing process thereof, and belongs to the technical field of ceramic closestools. The manufacturing process of the antibacterial ceramic closestool comprises the following steps: putting potassium feldspar, albite, quartz powder, calcined kaolin, talcum powder, glass powder, zinc oxide, magnesite, calcite, zirconium silicate and illite-based antibacterial particles into a material tank of a ball mill, then adding sodium carboxymethyl cellulose and deionized water, uniformly mixing, and carrying out ball milling treatment to obtain glaze slip; and glazing the glaze slip on the surface of a ceramic closestool green body in a glaze dipping manner to obtain a glaze layer, naturally airing, carrying out heat treatment, and then cooling along with a furnace to obtain the antibacterial ceramic closestool. Stable adsorption and slow release of antibacterial metal ions can be achieved through the glaze layer, the long-acting antibacterial performance capable of resisting washing of a disinfectant is provided for the antibacterial ceramic closestool, the wear resistance of the antibacterial ceramic closestool is enhanced by optimizing the glaze layer structure, finally, the antibacterial performance and the wear resistance are synergistically improved, and the long-term use effect of the closestool is guaranteed.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ceramic toilets and relates to an antibacterial ceramic toilet and a manufacturing process thereof. BACKGROUND

[0002] As a sanitary ceramic product that combines antibacterial technology in the face glaze layer, the antibacterial ceramic toilet can inhibit the reproduction of Escherichia coli and Staphylococcus aureus for a long time, and reduce stains and odors. However, the current mainstream preparation process generally directly mixes the antibacterial agent into the face glaze raw material, which is prone to agglomeration due to poor compatibility with the raw material, resulting in uneven dispersion, poor antibacterial durability, and difficulty in achieving ideal and durable antibacterial effect. Therefore, it is necessary to find a carrier material that can improve the dispersibility of the antibacterial agent.

[0003] Illite has shown significant advantages in the field of sanitary ceramics due to its unique layered aluminosilicate structure: it can impart good plasticity and dry strength to the body, reducing the risk of cracking during shaping and drying; when compounded with raw materials such as kaolin, it can also optimize the sintering performance of the body, improving the product's texture and whiteness after high-temperature sintering, and achieving excellent appearance without relying on a large amount of bleaching agent.

[0004] However, natural illite has a relatively tight accumulation between layers, which limits its adsorption performance and ion exchange capacity to some extent, making it difficult to be used directly as an efficient carrier. Therefore, modifying illite is a simple and effective method to increase its specific surface area and optimize its structural performance. Common modification methods include acidification and high-temperature calcination. However, low calcination temperatures have little effect on the fineness, specific surface area, and dispersion effect of illite, and have limited impact on the performance improvement of sanitary ceramics. On the other hand, high calcination temperatures (700-800℃) can damage the layered structure of illite octahedral, reducing its specific surface area. A large number of illite particles aggregate together, easily forming an interface difference between the "loose zone" and "dense zone" in the body, resulting in a large number of micro-pores after sintering, which leads to a decrease in the body's density. Therefore, the modification degree of illite is directly related to the forming quality, sintering stability, and long-term antibacterial performance of sanitary ceramics. SUMMARY

[0005] The purpose of the present application is to provide an antibacterial ceramic toilet and a manufacturing process thereof. The glaze layer of the present application can achieve stable adsorption and slow release of antibacterial metal ions, providing long-term antibacterial performance against disinfectant flushing for the antibacterial ceramic toilet, and enhancing its wear resistance by optimizing the glaze layer structure. Ultimately, the antibacterial performance and wear resistance are synergistically improved, ensuring the long-term use effect of the toilet.

[0006] The purpose of the present application can be achieved by the following technical solutions:

[0007] A manufacturing process for an antibacterial ceramic toilet includes the following steps:

[0008] S1, feldspar, soda feldspar, quartz powder, calcined kaolin, talc powder, glass powder, zinc oxide, magnesite, calcite, zirconium silicate, illite-based antibacterial particles into the ball mill tank, then add sodium carboxymethyl cellulose and deionized water, ball milling, get glaze;

[0009] S2, glaze with glaze glaze on the surface of the ceramic toilet body, get glaze layer, natural drying after heat treatment, then with the furnace cooling, get antibacterial ceramic toilet.

[0010] As a preferred technical solution of the application, the ball milling treatment of step S1 is to use zirconia balls as grinding medium, 4:1 ball-to-material ratio, 750-850 rpm ball mill speed ball milling for 7-8h.

[0011] As a preferred technical solution of the application, the glaze of step S1 includes the following components by weight fraction: feldspar 25-35 parts, soda feldspar 10-15 parts, quartz powder 25-40 parts, calcined kaolin 20-30 parts, talc powder 15-20 parts, glass powder 3-4 parts, zinc oxide 5-10 parts, magnesite 3-6 parts, calcite 8-12 parts, zirconium silicate 6-10 parts, illite-based antibacterial particles 4-5 parts, sodium carboxymethyl cellulose 3-7 parts and deionized water 65-85 parts.

[0012] As a preferred technical solution of the application, the thickness of the glaze layer of step S2 is 0.8mm, and the heat treatment is 600-800℃ for 4-6h in nitrogen atmosphere, sintering at 1250-1350℃ for 4-8h, and cooling to 500-700℃ for 4-8h.

[0013] As a preferred technical solution of the application, the preparation method of the illite-based antibacterial particles comprises the following steps:

[0014] S11, illite is crushed, ground and placed in a container, deionized water is added and high-temperature stirring treatment is carried out, the suspension is obtained after standing, ammonia water is added and mixed, heated, cooled to room temperature, centrifuged, washed, tetra-n-propyl zirconate solution is added and stirred, filtered, washed with pure ethanol, placed in a ventilated drying oven for low-temperature drying treatment, preheated and placed in a tube furnace for high-temperature calcination treatment, to get composite illite powder;

[0015] S12, the composite illite powder and anhydrous ethanol are ultrasonically dispersed to obtain a suspension, which is then placed in a reaction container, 2-amino-6-hydroxybenzothiazole and 3-carboxybenzaldehyde are added and magnetically stirred, glacial acetic acid is added and heated to reflux, centrifugal separation is performed, the lower solid is collected and washed, and the obtained solid is placed in a stirred tank, deionized water and nitrate are added and stirred and adsorbed, then urea and ethylene glycol are added and subjected to hydrothermal reaction, the product after washing and drying is placed in a calcining furnace for calcination, and an illite-based antibacterial particle is obtained.

[0016] As a preferred technical solution of the present application, the grinding in step S11 is grinding to a grinding powder with a particle size of 20-40 μm, the high-temperature stirring treatment is stirring at 40-45 °C for 1-2 h, the standing time is 30-40 min, and the heating treatment temperature is 300-320 °C and the treatment time is 1.5-2.0 h.

[0017] As a preferred technical solution of the present application, the use amount ratio of illite, deionized water, ammonia water and tetra-n-propyl zirconate solution in step S11 is 10-12 g: 35-40 mL: 200-220 mL: 40-50 mL, the mass concentration of the ammonia water is 30%, and the mass concentration of the tetra-n-propyl zirconate solution is 10-12% and the solvent is anhydrous ethanol.

[0018] As a preferred technical solution of the present application, the stirring reaction temperature in step S11 is 35-45 °C and the reaction time is 4-5 h, the washing frequency is 3-4 times, the low-temperature drying treatment temperature is 70-80 °C and the time is 30-45 min.

[0019] As a preferred technical solution of the present application, the preheating temperature in step S11 is 130-150 °C and the time is 45-60 min, and the high-temperature calcination treatment conditions are calcination at 480-560 °C for 2-3 h in a nitrogen atmosphere.

[0020] As a preferred technical solution of the present application, the ultrasonic dispersion power in step S12 is 300-400 W and the time is 30-40 min, the magnetic stirring speed is 400-600 rpm and the time is 25-30 min, the heating reflux reaction temperature is 70-80 °C, the stirring speed is 300-400 rpm, the reaction time is 5-6 h, the lower solid is washed with anhydrous ethanol for 3 times, and the vacuum drying temperature is 70-80 °C and the time is 9-10 h.

[0021] As a preferred technical scheme of the present application, the stirring adsorption in step S12 is stirring for 4-5 hours at room temperature, the temperature of the hydrothermal reaction is 110-125 DEG C, the reaction time is 15-18 hours, and the washing is washing twice with deionized water and anhydrous ethanol in sequence.

[0022] As a preferred technical scheme of the present application, the drying temperature in step S12 is 110 DEG C, the drying time is 6-8 hours, the calcining temperature is 480-550 DEG C in a nitrogen atmosphere, and the calcining time is 2-3 hours.

[0023] As a preferred technical scheme of the present application, the use amount ratio of the composite illite powder, anhydrous ethanol, 2-amino-6-hydroxybenzothiazole, 3-carboxybenzaldehyde and glacial acetic acid in step S12 is 55-60 g:380-450 mL:6.0-6.5 g:7.0-8.2 g:0.8-1.2 g.

[0024] As a preferred technical scheme of the present application, the reaction formula of 2-amino-6-hydroxybenzothiazole and 3-carboxybenzaldehyde with glacial acetic acid as a catalyst is as follows:

[0025]

[0026] As a preferred technical scheme of the present application, the use amount ratio of the solid, deionized water, nitrate, urea and ethylene glycol in step S12 is 5.0-5.6 g:20-25 mL:1.0-1.2 g:1.2-1.5 g:15-18 mL, and the nitrate is one or a combination of two of silver nitrate and zinc nitrate.

[0027] The present application also discloses an antibacterial ceramic closestool prepared by the preparation method.

[0028] The present application has the following beneficial effects:

[0029] The glaze layer can realize stable adsorption and slow release of antibacterial metal ions, provides long-acting antibacterial performance against disinfectant flushing for the antibacterial ceramic closestool, enhances the wear resistance of the glaze layer through optimization, and finally realizes synergistic improvement of the antibacterial property and the wear resistance, and guarantees long-term use effect of the closestool. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 SEM image of the pretreated illite after drying treatment for Example 3;

[0031] Figure 2 SEM image of the composite illite powder for Example 3;

[0032] Figure 3 SEM image of the illite-based antibacterial particles for Example 3;

[0033] Figure 4 SEM image of the illite after drying treatment for Comparative Example 1;

[0034] Figure 5 SEM image of the illite-based antibacterial granule for Comparative Example 5. DETAILED DESCRIPTION

[0035] To further illustrate the technical means and effects adopted by the present application to achieve the predetermined object, the specific embodiments, structures, features and effects according to the present application are described in detail below in combination with the examples.

[0036] The particle size of the sodium feldspar powder, the potassium feldspar powder and the quartz powder is 325 mesh;

[0037] The average particle size of the calcined kaolin is 1250 mesh;

[0038] The talc powder has a silicon dioxide content of 60%, a magnesium oxide content of 30% and an average particle size of 1250 mesh;

[0039] The glass powder is a low-temperature glass powder with a melting temperature lower than 500℃, and has an average particle size of 400 mesh;

[0040] The zinc oxide has a model of DK-ZnO-30;

[0041] The magnesite has an average particle size of 100-130 mesh;

[0042] The calcite has an average particle size of 120-140 mesh;

[0043] The zirconium silicate has an average particle size of 150-180 mesh;

[0044] The carboxymethyl cellulose sodium has a carboxyl substitution degree of 0.8-1.0 DS and a purity of ≥90%.

[0045] Example 1

[0046] A manufacturing process of the antibacterial ceramic toilet includes the following steps:

[0047] S1, the potassium feldspar, the sodium feldspar, the quartz powder, the calcined kaolin, the talc powder, the glass powder, the zinc oxide, the magnesite, the calcite, the zirconium silicate, the illite-based antibacterial granule are put into the ball mill tank, then the carboxymethyl cellulose sodium and the deionized water are mixed uniformly, the zirconium oxide ball is used as the grinding medium, the ball-to-material ratio is 4:1, the ball mill speed is 750 rpm, and the ball milling time is 7h, so as to obtain the glaze slurry;

[0048] The glaze slurry comprises the following components in parts by weight: 25 parts of potassium feldspar, 10 parts of sodium feldspar, 25 parts of quartz powder, 20 parts of calcined kaolin, 15 parts of talc powder, 3 parts of glass powder, 5 parts of zinc oxide, 3 parts of magnesite, 8 parts of calcite, 6 parts of zirconium silicate, 4 parts of illite-based antibacterial particles, 3 parts of sodium carboxymethyl cellulose, and 65 parts of deionized water;

[0049] S2, glaze the glaze slurry on the surface of the ceramic toilet bowl body in a glazing manner to obtain a glaze layer of 0.8 mm, and then naturally air dry, sinter at 600 DEG C for 4 h in a nitrogen atmosphere, heat to 1250 DEG C for 4 h, cool to 500 DEG C for 4 h, and then cool down with the furnace to obtain the antibacterial ceramic toilet bowl.

[0050] The preparation method of the illite-based antibacterial particles comprises the following steps:

[0051] S11, crush the illite, grind to a grinding powder with a particle size of 20 mu m, and then place in a container, add deionized water and stir at 40 DEG C for 1 h, stand for 30 min to obtain a suspension, add 30% mass concentration of ammonia water, mix, heat treat at 300 DEG C for 1.5 h in a sealed high-pressure container, cool to room temperature, centrifugal separation, wash with distilled water for 3 times, add tetra-n-propyl zirconate solution, stir at 35 DEG C for 4 h, filter, wash with pure ethanol for 3 times, place in a ventilated drying box, low-temperature drying treatment at 70 DEG C for 30 min, preheat at 130 DEG C for 45 min, then place in a tube furnace, calcine at 480 DEG C for 2 h in a nitrogen atmosphere to obtain composite illite powder;

[0052] The amount ratio of the illite, deionized water, ammonia water and tetra-n-propyl zirconate solution is 10 g:35 mL:200 mL:40 mL, the mass concentration of the tetra-n-propyl zirconate solution is 10%, and the solvent is anhydrous ethanol;

[0053] S12, ultrasonic dispersion of the composite illite powder and anhydrous ethanol at 300 W power for 30 min to obtain a suspension, then place in a reaction container, add 2-amino-6-hydroxybenzothiazole and 3-carboxybenzaldehyde, magnetic stirring at 400 rpm for 25 min, add glacial acetic acid, heat reflux reaction at 70 DEG C under a nitrogen atmosphere, 300 rpm stirring speed for 5 h, centrifugal separation, collect the lower solid, wash with anhydrous ethanol for 3 times, vacuum drying at 70 DEG C for 9 h to obtain a solid, place in a stirred tank, add deionized water and nitrate at room temperature for 4 h, then add urea and ethylene glycol, hydrothermal reaction at 110 DEG C for 15 h, filter, wash with deionized water and anhydrous ethanol for 2 times respectively, dry at 110 DEG C for 6 h to obtain a product, place in a calcination furnace, calcine at 480 DEG C for 2 h in a nitrogen atmosphere to obtain illite-based antibacterial particles;

[0054] The use amount ratio of the composite illite powder, anhydrous ethanol, 2-amino-6-hydroxybenzothiazole, 3-carboxybenzaldehyde and glacial acetic acid is 55g:380mL:6.0g:7.0g:0.8g, and the use amount ratio of the solid, deionized water, nitrate, urea and ethylene glycol is 5.0g:20mL:1.0g:1.2g:15mL, and the nitrate is composed of silver nitrate and zinc nitrate with a mass ratio of 2:1.

[0055] Example 2

[0056] A manufacturing process of the antibacterial ceramic toilet comprises the following steps:

[0057] S1, put the potassium feldspar, sodium feldspar, quartz powder, calcined kaolin, talc powder, glass powder, zinc oxide, magnesite, calcite, zirconium silicate, illite-based antibacterial particles into the ball mill tank, then add sodium carboxymethyl cellulose and deionized water and mix uniformly, use zirconium oxide balls as the grinding medium, the ball-to-material ratio is 4:1, the ball mill speed is 800rpm, and ball mill for 7.5h to obtain the glaze slurry;

[0058] The glaze slurry comprises the following components in parts by weight: 30 parts of potassium feldspar, 12 parts of sodium feldspar, 32 parts of quartz powder, 25 parts of calcined kaolin, 18 parts of talc powder, 3.5 parts of glass powder, 8 parts of zinc oxide, 4 parts of magnesite, 10 parts of calcite, 8 parts of zirconium silicate, 4.5 parts of illite-based antibacterial particles, 5 parts of sodium carboxymethyl cellulose and 75 parts of deionized water;

[0059] S2, apply the glaze slurry to the surface of the ceramic toilet body in a dipping glazing manner to obtain a glaze layer with a thickness of 0.8mm, then naturally air dry, sinter at 700℃ for 5h under a nitrogen atmosphere, then heat to 1300℃ and sinter for 6h, then cool to 600℃ and keep for 6h, and then cool down with the furnace to obtain the antibacterial ceramic toilet.

[0060] The preparation method of the illite-based antibacterial particles comprises the following steps:

[0061] S11, crush the illite, grind to a grinding powder with a particle size of 30μm, then put into a container, add deionized water and stir at 42℃ for 1.5h, then stand for 35min to obtain a suspension, then add 30% ammonia water with a mass concentration, mix, heat treat in a sealed high-pressure container at 310℃ for 1.8h, cool to room temperature, centrifugal separate, wash with distilled water for 3 times, add tetra-n-propyl zirconate solution, stir at 40℃ for 4.5h, filter, wash with pure ethanol for 4 times, put into a ventilated drying box, low-temperature dry at 75℃ for 38min, preheat at 140℃ for 52min, then put into a tube furnace, calcine at 520℃ for 2.5h under a nitrogen atmosphere to obtain the composite illite powder;

[0062] The amount ratio of the illite, deionized water, ammonia water and tetra-n-propyl zirconium acid ester solution is 11g:38mL:210mL:45mL, the mass concentration of the tetra-n-propyl zirconium acid ester solution is 11%, and the solvent is anhydrous ethanol;

[0063] S12, the composite illite powder and anhydrous ethanol are dispersed at 350W power ultrasonic for 35min to obtain a suspension, then the suspension is placed in a reaction container, 2-amino-6-hydroxybenzothiazole and 3-carboxybenzaldehyde are added and magnetically stirred at a rotating speed of 500rpm for 28min, glacial acetic acid is added, and the reaction is heated to reflux at a temperature of 75℃, a rotating speed of 350rpm and under a nitrogen atmosphere for 5.5h, then centrifugal separation is performed, the lower solid is collected and washed with anhydrous ethanol for 3 times, and the solid obtained after vacuum drying at a temperature of 75℃ for 9.5h is placed in a stirred tank, deionized water and nitrate are added and stirred at room temperature for 4.5h, then urea and ethylene glycol are added, and hydrothermal reaction is performed at 118℃ for 16h, then the product obtained after filtration and washing with deionized water and anhydrous ethanol for 2 times respectively is dried at 110℃ for 7h, and then the product is placed in a calcination furnace and calcined at 515℃ under a nitrogen atmosphere for 2.5h to obtain the illite-based antibacterial particles;

[0064] The amount ratio of the composite illite powder, anhydrous ethanol, 2-amino-6-hydroxybenzothiazole, 3-carboxybenzaldehyde and glacial acetic acid is 58g:415mL:6.2g:7.6g:1g, the amount ratio of the solid, deionized water, nitrate, urea and ethylene glycol is 5.3g:22mL:1.1g:1.4g:16mL, and the nitrate is composed of silver nitrate and zinc nitrate at a mass ratio of 2:1.

[0065] Example 3

[0066] A manufacturing process of the antibacterial ceramic toilet comprises the following steps:

[0067] S1, potash feldspar, soda feldspar, quartz powder, calcined kaolin, talc powder, glass powder, zinc oxide, magnesite, calcite, zirconium silicate and illite-based antibacterial particles are put into a ball mill tank, then carboxymethyl cellulose sodium and deionized water are added and uniformly mixed, zirconium oxide balls are used as grinding medium, the ball-to-material ratio is 4:1, the ball mill rotates at a speed of 850rpm for 8h to obtain a glaze slurry;

[0068] The glaze slurry comprises the following components in parts by weight: 35 parts of potash feldspar, 15 parts of soda feldspar, 40 parts of quartz powder, 30 parts of calcined kaolin, 20 parts of talc powder, 4 parts of glass powder, 10 parts of zinc oxide, 6 parts of magnesite, 12 parts of calcite, 10 parts of zirconium silicate, 5 parts of illite-based antibacterial particles, 7 parts of carboxymethyl cellulose sodium and 85 parts of deionized water;

[0069] S2, glaze the ceramic toilet bowl blank surface with glaze in a dipping glazing manner to obtain a glaze layer of 0.8 mm, and then naturally air dry, sinter at 800 DEG C for 6 h in a nitrogen atmosphere, heat to 1350 DEG C and sinter for 8 h, cool to 700 DEG C and sinter for 8 h, and then cool down with the furnace to obtain the antibacterial ceramic toilet bowl.

[0070] The preparation method of the illite-based antibacterial particles comprises the following steps:

[0071] S11, crush illite, grind to a grinding powder with a particle size of 40 mu m, and then place in a container, add deionized water, stir at 45 DEG C for 2 h, stand for 40 min to obtain a suspension, add 30% mass concentration of ammonia water, mix, heat treat at 320 DEG C for 2.0 h in a sealed high-pressure container, cool to room temperature, centrifugal separation, wash with distilled water 3 times to obtain pretreated illite, add tetra-n-propyl zirconate solution, stir at 45 DEG C for 5 h, filter, wash 4 times with pure ethanol, place in a ventilated drying box, low-temperature drying treatment at 80 DEG C for 45 min, preheat at 150 DEG C for 60 min, and then place in a tube furnace, calcine at 560 DEG C for 3 h in a nitrogen atmosphere to obtain composite illite powder;

[0072] The amount ratio of the illite, deionized water, ammonia water and tetra-n-propyl zirconate solution is 12 g:40 mL:220 mL:50 mL, the mass concentration of the tetra-n-propyl zirconate solution is 12%, and the solvent is anhydrous ethanol;

[0073] S12, ultrasonic dispersion of the composite illite powder and anhydrous ethanol at 400 W power for 40 min to obtain a suspension, then place in a reaction container, add 2-amino-6-hydroxybenzothiazole and 3-carboxybenzaldehyde, and magnetically stir at a rotation speed of 600 rpm for 30 min, add glacial acetic acid, heat reflux at a temperature of 80 DEG C and a rotation speed of 400 rpm for 6 h in a nitrogen atmosphere, centrifugal separation, collect the lower solid, wash with anhydrous ethanol 3 times, and then vacuum dry at a temperature of 80 DEG C for 10 h to obtain a solid, place the solid in a stirred tank, add deionized water and nitrate at room temperature and stir for 5 h, then add urea and ethylene glycol, and hydrothermal reaction at 125 DEG C for 18 h, filter, and then wash with deionized water and anhydrous ethanol each 2 times, and then dry at 110 DEG C for 8 h to obtain a product, place the product in a calcination furnace, and calcine at 550 DEG C for 3 h in a nitrogen atmosphere to obtain illite-based antibacterial particles;

[0074] The amount ratio of the composite illite powder, anhydrous ethanol, 2-amino-6-hydroxybenzothiazole, 3-carboxybenzaldehyde and glacial acetic acid is 60g:450mL:6.5g:8.2g:1.2g, the amount ratio of the solid, deionized water, nitrate, urea and ethylene glycol is 5.6g:25mL:1.2g:1.5g:18mL, and the nitrate is composed of silver nitrate and zinc nitrate with a mass ratio of 2:1.

[0075] Comparative Example 1

[0076] Comparative Example 1 is different from Example 3 in that deionized water is used instead of ammonia water in Comparative Example 1, and the rest is consistent.

[0077] Comparative Example 2

[0078] Comparative Example 2 is different from Example 3 in that anhydrous ethanol is used instead of tetra-n-propyl zirconate in Comparative Example 2, and the rest is consistent.

[0079] Comparative Example 3

[0080] Comparative Example 3 is different from Example 3 in that m-aminophenol is used instead of 2-amino-6-hydroxybenzothiazole in Comparative Example 3, and the rest is consistent.

[0081] Comparative Example 4

[0082] Comparative Example 4 is different from Example 3 in that benzaldehyde is used instead of 3-carboxybenzaldehyde in Comparative Example 4, and the rest is consistent.

[0083] Comparative Example 5

[0084] Comparative Example 5 is different from Example 3 in that 2-amino-6-hydroxybenzothiazole is not used in Comparative Example 5, and the rest is consistent.

[0085] Comparative Example 6

[0086] Comparative Example 6 is different from Example 3 in that 3-carboxybenzaldehyde is not used in Comparative Example 6, and the rest is consistent.

[0087] Antibacterial durability test: after the sample is washed 1000 times with 5% concentration of sodium hypochlorite disinfectant, the antibacterial test is carried out according to JC / T897-2014;

[0088] The test results are shown in Table 1.

[0089] Table 1: Antibacterial test results

[0090]

[0091] As can be seen from the test results in Table 1, the antibacterial ceramic toilet produced by the application has excellent durable antibacterial performance compared with Comparative Examples 1-6.

[0092] Hardness test: The Vickers hardness of the glaze surface was measured by a micro Vickers hardness tester, and the test results are shown in Table 2.

[0093] Table 2 Hardness test results

[0094]

[0095] As can be seen from the test results in Table 2, the antibacterial ceramic toilet produced by the application has high Vickers hardness, excellent hardness and wear resistance compared with Comparative Examples 1-6.

[0096] The invention promotes the breaking of the weak interlayer bond of illite by high-temperature and high-pressure treatment with ammonia water, and the crystal layer is stripped to form a porous and loose structure, improving the binding property with glaze. Not only the specific surface area is significantly improved, but also a large number of active hydroxyl groups are generated on the surface. These groups provide initial binding sites for antibacterial metal ions (silver ions, zinc ions) through coordination anchoring, improving the adsorption stability of metal ions. Subsequently, the modified illite reacts with tetra-n-propyl zirconate, and the zirconium element is uniformly grafted on the surface of the illite through covalent bond. After calcination, it is converted into a nanoscale zirconia coating layer. This coating layer not only reduces the agglomeration of illite, but also enhances the wear-resistant substrate of the glaze layer by virtue of its high rigidity, and enhances the rigidity of the glaze layer. By introducing zirconia, a zirconia / illite composite carrier is formed, which significantly improves the specific surface area of the composite illite powder and greatly improves the binding capacity of silver / zinc metal ions, further preventing the migration and loss of antibacterial metal ions, and building a more stable rigid barrier for antibacterial metal ions.

[0097] In addition, the composite illite powder forms an organic coating layer by reacting 2-amino-6-hydroxybenzothiazole with 3-carboxybenzaldehyde through an imine bond. The thiazole ring heteroatom contained in the organic coating layer forms a stable chelate coordination bond with silver ions and zinc ions, which can lock more antibacterial metal ions, making them more stable during the calcination process. The antibacterial metal ions can be uniformly dispersed in the glaze layer, reducing defects such as pores and microcracks, ensuring slow release of metal ions to achieve long-term antibacterial effect, and significantly improving the hardness and wear resistance of the glaze layer.

[0098] The above merely describes the preferred embodiments of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed with the preferred embodiments as above, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content to obtain equivalent embodiments with equivalent changes, as long as the changes or modifications do not deviate from the technical solution of the present application. Any indirect modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present application still belong to the scope of the technical solution of the present application.

Claims

1. A manufacturing process for an antibacterial ceramic toilet, characterized in that, The manufacturing process includes the following steps: S1. Potassium feldspar, sodium feldspar, quartz powder, calcined kaolin, talc powder, glass powder, zinc oxide, magnesite, calcite, zirconium silicate, illite-based antibacterial particles are put into the ball mill feed tank, and then sodium carboxymethyl cellulose and deionized water are added and mixed evenly. The mixture is then ball-milled to obtain a glaze slurry. S2. Apply the glaze slurry to the surface of the ceramic toilet body by immersion to obtain a glaze layer. After natural drying, perform heat treatment and then cool in the kiln to obtain an antibacterial ceramic toilet. The preparation method of the illite-based antibacterial particles includes the following steps: S11. Crush illite, grind it and place it in a container. Add deionized water and stir at high temperature. After standing, a suspension is obtained. Add ammonia water and mix. Heat the mixture and cool it to room temperature. Centrifuge and wash the mixture. Add tetra-n-propylzirconate solution and stir to react. Filter the mixture and wash it with pure ethanol. Place it in a ventilated drying oven for low-temperature drying. After preheating, place it in a tube furnace for high-temperature calcination to obtain composite illite powder. S12. The composite illite powder and anhydrous ethanol were ultrasonically dispersed to obtain a suspension, which was then placed in a reaction vessel. 2-Amino-6-hydroxybenzothiazole and 3-carboxybenzaldehyde were added and magnetically stirred. Glacial acetic acid was added and the mixture was heated under reflux. After centrifugation, the lower solid layer was collected, washed, and vacuum dried. The resulting solid was placed in a stirred tank, where deionized water and nitrate were added and stirred for adsorption. Urea and ethylene glycol were then added for hydrothermal reaction. After filtration, washing, and drying, the product was placed in a calcination furnace for calcination to obtain illite-based antibacterial particles.

2. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that: The high-temperature stirring treatment in step S11 is stirring at 40-45℃ for 1-2 hours, and the heating treatment temperature is 300-320℃ and the treatment time is 1.5-2.0 hours.

3. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that: In step S11, the ratio of illite, deionized water, ammonia, and tetra-n-propylzirconate solution is 10-12g: 35-40mL: 200-220mL: 40-50mL, the mass concentration of ammonia is 30%, the mass concentration of tetra-n-propylzirconate solution is 10-12%, and the solvent is anhydrous ethanol.

4. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that: The stirring reaction in step S11 is carried out at a temperature of 35-45℃ for 4-5 hours, the preheating temperature is 130-150℃ for 45-60 minutes, and the high-temperature calcination treatment is carried out in a nitrogen atmosphere at 480-560℃ for 2-3 hours.

5. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that: The heating reflux reaction in step S12 is carried out at a temperature of 70-80℃, a stirring speed of 300-400rpm, and a reaction time of 5-6h. The hydrothermal reaction is carried out at a temperature of 110-125℃ and a reaction time of 15-18h. The calcination is carried out at a temperature of 480-550℃ in a nitrogen atmosphere and a calcination time of 2-3h.

6. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that: The ratio of the composite illite powder, anhydrous ethanol, 2-amino-6-hydroxybenzothiazole, 3-carboxybenzaldehyde and glacial acetic acid used in step S12 is 55-60g: 380-450mL: 6.0-6.5g: 7.0-8.2g: 0.8-1.2g.

7. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that: In step S12, the ratio of the solid, deionized water, nitrate, urea and ethylene glycol is 5.0-5.6g: 20-25mL: 1.0-1.2g: 1.2-1.5g: 15-18mL, and the nitrate is one or a combination of silver nitrate and zinc nitrate.

8. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that, The glaze slurry described in step S1 comprises the following components by weight: 25-35 parts potassium feldspar, 10-15 parts sodium feldspar, 25-40 parts quartz powder, 20-30 parts calcined kaolin, 15-20 parts talc powder, 3-4 parts glass powder, 5-10 parts zinc oxide, 3-6 parts magnesite, 8-12 parts calcite, 6-10 parts zirconium silicate, 4-5 parts illite-based antibacterial particles, 3-7 parts sodium carboxymethyl cellulose, and 65-85 parts deionized water.

9. The manufacturing process of an antibacterial ceramic toilet according to claim 1, characterized in that: The heat treatment in step S2 is as follows: in a nitrogen atmosphere, hold at 600-800℃ for 4-6 hours, raise the temperature to 1250-1350℃ for 4-8 hours, and lower the temperature to 500-700℃ for 4-8 hours.

10. An antibacterial ceramic toilet prepared by the preparation method according to any one of claims 1-9.

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