An antibacterial sanitary ware, a long-acting antibacterial ceramic, and a preparation method and use thereof

Abstract

An antibacterial sanitary ware, a long-acting antibacterial ceramic and its preparation method and use. In the preparation method, the white ground glaze and the crystal silver glaze slurries are successively applied to a green body with a matching coefficient of thermal expansion, and the white ground glaze and the crystal silver glaze slurries are sprayed by means of double glazing, so as to further make the crystal grains denser and finer, with a small surface tension, which can fully exert the antibacterial effect of the formula, and has good antibacterial effect and antibacterial persistence; the long-acting antibacterial ceramic is prepared by using the above preparation method; the antibacterial sanitary ware uses the above long-acting antibacterial ceramic. This solution solves the problem that the antibacterial and easy-to-clean components are prone to component compatibility after being added to the bottom glaze, resulting in uneven and unstable distribution of the antibacterial layer and a decrease in the smoothness of the glaze surface.

Description

Technical Field

[0001] The present invention relates to the field of ceramics, and particularly to an antibacterial sanitary ware, a long-acting antibacterial ceramic, and a preparation method and use thereof. Background Art

[0002] Among the numerous sanitary ware products on the market at present, the antibacterial agents that are widely used and have good antibacterial effects are mainly inorganic silver-based antibacterial agents, and their antibacterial rate can reach about 95%. However, the introduction of silver ion antibacterial materials, on the one hand, greatly increases the production cost of the surface glaze, which does not conform to the economic benefits of the products; on the other hand, the silver ions have poor stability and are prone to color change due to oxidation problems. After being placed for half a year under ultraviolet light and high temperature conditions, its antibacterial rate is likely to drop below 85%. Especially after the glaze layer is worn after long-term use, the antibacterial rate is even lower. And for the glaze coating prepared by simply using other antibacterial metal ions, although the cost is relatively low and safer, the antibacterial effect is relatively weaker than that of silver ions.

[0003] The currently widely used technologies for the antibacterial and easy-to-clean surface treatment of ceramic sanitary wares are mainly divided into two categories: one is to achieve the surface curing of the antibacterial layer, for example, fixing metal compounds densely on the photocatalyst reduction coating, and then spraying metal ion water on the surface layer. However, this method has a high preparation cost and poor wear-resistant and durable performance of the surface antibacterial layer; the other is to prepare an antibacterial functional glaze. This method directly sprays and covers the glaze containing antibacterial components on the surface of the green body, and it is easy to appear phenomena such as glaze color change, uneven glazing, and glaze layer cracking during production.

[0004] Therefore, when preparing the antibacterial and easy-to-clean glaze, it is necessary to consider the matching degree between the glaze base composition, the antibacterial material, and the easy-to-clean material. Adding antibacterial and easy-to-clean elements to the ceramic glaze often changes its composition, structure, and density. Due to the matching of the thermal expansion coefficients of the three, it is easy to appear the problem of glaze layer cracking after sintering, seriously affecting the appearance of the product. And most of the existing ceramic glazes contain low-temperature materials such as high-sodium stone powder and potassium-sodium feldspar, and their high-temperature resistance is low, making the green body prone to deformation at high temperatures. Summary of the Invention

[0005] The object of the present invention is to provide a preparation method of a long-acting antibacterial ceramic, in which the white base glaze and the crystal silver glaze slurries are successively applied to a green body with a thermal expansion coefficient matching theirs, and the white base glaze and the crystal silver glaze slurries are sprayed by the method of secondary glazing, so as to further make the crystal grains denser and finer, with a small surface tension, and the antibacterial effect of the formula can be fully exerted, and the antibacterial effect and antibacterial persistence are good.

[0006] The present invention also provides a long-acting antibacterial ceramic prepared by the above preparation method.

[0007] The present invention also provides an antibacterial sanitary ware, which uses the above-mentioned long-acting antibacterial ceramic.

[0008] The present invention also provides a use of a ceramic in an antibacterial sanitary ware.

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

[0010] A preparation method of a long-acting antibacterial ceramic, including: a green body preparation method, a glaze slurry preparation method, and a spraying method;

[0011] The green body preparation method includes: making a green body from green body raw materials;

[0012] The chemical composition of the green body, by mass percentage, includes: 60-70% of SiO2, 15-25% of Al2O3, within 3% of Fe2O3, within 0.5% of TiO2, within 1% of CaO, within 0.5% of MgO, 1-5% of K2O, within 1% of Na2O, and the balance of IL;

[0013] The glaze slurry preparation method includes:

[0014] (B1) Preparing a crystalline silver glaze slurry, the fineness of the slurry is ≤0.1 wt% of the residue on a 325-mesh sieve, and the stacking ratio of particles with a particle size of 10 μm in the slurry accounts for 80-90 wt%;

[0015] The raw materials of the crystalline silver glaze slurry, by mass parts, include: 15-25 parts of quartz powder, 20-30 parts of wollastonite, 35-50 parts of potassium feldspar powder, 10-20 parts of submicron zinc oxide antibacterial material, and 0.01-0.05 parts of nano silver antibacterial material;

[0016] (B2) Preparing a white glaze, the expansion coefficient α of the white glaze is (4.2-6.5)×10 -6 / °C at 100-800 °C;

[0017] The spraying method includes:

[0018] (C1) Setting a plurality of sub-spray fixed points on the spraying surface of the green body; the spray gun is sequentially positioned and moved to each sub-spray fixed point and sprayed, first spraying a white base glaze; after the water luster of the glaze layer disappears, the spray gun is then sequentially positioned to each sub-spray fixed point to spray the crystalline silver glaze slurry; before and after spraying the white base glaze and the crystalline silver glaze slurry, measuring the color uniformity and the thickness of the glaze layer, the spray gun is moved to a specific sub-spray fixed point, and a region with color difference and / or thickness difference is corrected and re-sprayed; after the glaze surface of the green body is dried, it is put into a kiln at 1210-1220 °C to be fired to obtain the antibacterial ceramic.

[0019] Preferably, the spraying method also performs step (C0) before step (C1);

[0020] Step (C0): In step (C0), prepare standard antibacterial ceramics in advance according to step (C1). A color developer is added to the glaze before spraying. The thickness and color uniformity are measured before and after spraying the glaze, and these are saved as standard values.

[0021] In step (C1), a color developer is applied before spraying the white base glaze and before spraying the crystal silver glaze slurry. The white base glaze and the crystal silver glaze slurry are successively sprayed onto the semi-finished blank. After each spraying, the semi-finished product is compared with the standard antibacterial ceramics, and the color difference and thickness difference of the semi-finished product are measured. Then, the blank is additionally sprayed, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference.

[0022] More preferably, in step (C0), a plurality of sub-spray fixed points are set on the spraying surface of the finished blank, and independent spraying parameters are used for spraying.

[0023] In step (C1), a color developer is applied before spraying the white base glaze and before spraying the crystal silver glaze slurry. According to the spraying parameters of step (C0), the white base glaze and the crystal silver glaze slurry are successively sprayed onto the semi-finished blank. After each spraying, the semi-finished product is compared with the standard antibacterial ceramics, and the color difference and thickness difference of the semi-finished product are measured. Then, the spray gun is moved to the sub-spray fixed points of the blank to perform additional spraying on specific areas, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference.

[0024] Further optimally, in step (C0), after each application of the color developer, the pattern of the blank is recorded as a standard image. The standard image corresponds to a spraying standard parameter, and the spraying standard parameter is associated with the spraying parameters of a plurality of sub-spray fixed points.

[0025] In step (C1), image recognition is performed on the surface of the semi-finished blank before spraying the glaze, which is matched with the standard image. The spray gun applies the spraying standard parameter, and spraying and / or additional spraying are performed on each sub-spray fixed point of the semi-finished blank.

[0026] Preferably, a plurality of sub-spray fixed points are set on the spraying surface of the finished blank, each sub-spray fixed point is 10 cm × 10 cm, and a spray gun with a caliber of Φ1.4 mm is used for spraying the white base glaze and the crystal silver glaze slurry.

[0027] A long-acting antibacterial ceramic is prepared by the preparation method of the above-mentioned long-acting antibacterial ceramic.

[0028] An antibacterial sanitary ware uses the above-mentioned long-acting antibacterial ceramic.

[0029] The use of a ceramic in antibacterial sanitary ware, wherein the ceramic is prepared by the preparation method of the above-mentioned long-acting antibacterial ceramic.

[0030] Compared with the prior art, one of the above technical solutions has the following beneficial effects:

[0031] This solution provides a preparation method for long-acting antibacterial ceramics. The white base glaze and the crystalline silver glaze slurries are respectively applied onto a green body with a thermal expansion coefficient matching theirs, and the white base glaze and the crystalline silver glaze slurries are sprayed by means of double glazing. Further, the crystal grains are made denser and finer, with a small surface tension, which can fully exert the antibacterial effect of the formulation. The antibacterial effect and antibacterial persistence are good, solving the problem that when antibacterial and easy-to-clean components are added to the base glaze, component compatibility is likely to occur, resulting in uneven and unstable distribution of the antibacterial layer and a decrease in the smoothness of the glaze surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is the test result of the thermal expansion coefficient of the green body in Example A;

[0033] Figure 2 is the test result of the thermal expansion coefficient of the white glaze in Example A;

[0034] Figure 3 is the test result of the thermal expansion coefficient of the crystalline silver glaze in Example A;

[0035] Figure 4 is the schematic diagram of the cross-sectional microstructure of Example B and Comparative Example B4;

[0036] Figure 5 is the schematic diagram of the surface microstructure of the glaze layer of Example B and Comparative Example B4; DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] The embodiments of the present invention will be described in detail below. The examples of the embodiments are shown in the drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are only used to explain the present invention and should not be construed as a limitation to the present invention.

[0038] A preparation method for long-acting antibacterial ceramics includes: a green body preparation method, a glaze slurry preparation method, and a spraying method;

[0039] The green body preparation method includes: making a green body from green body raw materials;

[0040] The chemical composition of the green body, by mass percentage, includes: 60-70% of SiO2, 15-25% of Al2O3, Fe2O3 within 3%, TiO2 within 0.5%, CaO within 1%, MgO within 0.5%, K2O within 1-5%, Na2O within 1%, and the balance of IL;

[0041] The green body preparation method is replaced by the existing ceramic green body preparation method; this green body raw material is selected to match the crystal silver glaze slurry. The green body raw material has rapid cooling and heating properties and can balance the firing green body formula, which is matched with the crystal silver glaze slurry to avoid the problem of component compatibility and bonding that easily occurs after the antibacterial and easy-to-clean ingredients are added to the base glaze, resulting in uneven and unstable distribution of the antibacterial layer and affecting the smoothness of the glaze surface.

[0042] The glaze slurry preparation method comprises:

[0043] (B1) preparing a crystal silver glaze slurry, wherein the fineness of the slurry is 325 mesh sieve residue ≤ 0.1 wt %, and the accumulation ratio of particles with a particle size of 10 μm in the slurry accounts for 80-90 wt %;

[0044] The crystal particles formed at this particle size are more dense and fine, with low surface tension, which can effectively reduce the concave and convex effect of the surface glaze. After the combination of nano silver and zinc oxide, small particles in the surface area can gather together to form a huge surface, so the antibacterial and easy-to-clean glaze of the particles has the best glaze performance. In combination with the particle size parameter requirements and the secondary glazing process to provide a fully covered glaze layer of uniform thickness, the uniform coverage of the antibacterial and easy-to-clean glaze can be achieved, and the entire glaze surface has both antibacterial properties and the best glaze performance.

[0045] The raw materials of the crystal silver glaze slurry include, by weight: 15-25 parts of quartz powder, 20-30 parts of wollastonite, 35-50 parts of potassium feldspar powder, 10-20 parts of submicron zinc oxide antibacterial material and 0.01-0.05 parts of nano silver antibacterial material;

[0046] The raw materials of the crystal silver glaze slurry are selected to match the thermal expansion coefficient of the white glaze and the body after firing. Combined with the selection of the slurry fineness of the crystal silver glaze slurry, the crystal particles formed after the silver glaze slurry is fired can be denser and finer, and the surface tension is small;

[0047] (B2) Preparation of white glaze, the expansion coefficient of the white glaze at 100-800°C is (4.2-6.5)×10 -6 / ℃;

[0048] In this scheme, the white glaze can be replaced by the white base glaze currently available on the market. The raw materials selected can be calculated based on limited experiments. As long as the expansion coefficient α of the white glaze at 100-800°C is (4.2-6.5)×10 -6 / °C is sufficient. Here is an example that can be implemented. For example, for the formula of white glaze, by mass fraction, its raw materials include: 10 - 15 parts of limestone, 20 - 40 parts of quartz, 30 - 40 parts of feldspar, 0 - 10 parts of kaolin, 5 - 15 parts of zirconium silicate, 0 - 10 parts of dolomite, and 0 - 10 parts of zinc oxide. Based on this formula, one or more of the raw materials can be increased or decreased, and through limited experiments, the expansion coefficient α at 100 - 800 °C is calculated and measured to be (4.2 - 6.5)×10 -6 / °C.

[0049] The spraying method includes:

[0050] (C1) Set multiple sub - spraying fixed points on the spraying surface of the green body; the spray gun is sequentially positioned and moved to each sub - spraying fixed point for spraying. First, spray the white base glaze; after the water luster of the glaze layer disappears, the spray gun is then sequentially positioned to each sub - spraying fixed point to spray the crystal silver glaze slurry; before and after spraying the white base glaze and the crystal silver glaze slurry, measure the color uniformity and the thickness of the glaze layer. The spray gun moves to a specific sub - spraying fixed point and corrects and re - sprays an area with color difference and / or thickness difference; after the glaze surface of the green body is dried, it is fired in a kiln at 1210 - 1220 °C to obtain the antibacterial ceramic.

[0051] This solution provides a preparation method for a long - acting antibacterial ceramic, which sequentially applies the white base glaze and the crystal silver glaze slurry on a green body with a matching thermal expansion coefficient, and the white base glaze and the crystal silver glaze slurry are sprayed by the method of secondary glazing. Further, the crystal grains are made denser and finer, with a small surface tension, which can fully exert the antibacterial effect of the formula, having good antibacterial effect and antibacterial persistence, and solving the problem that the antibacterial and easy - to - clean components are prone to component compatibility after being added to the base glaze, resulting in uneven and unstable distribution of the antibacterial layer and a decrease in the smoothness of the glaze surface.

[0052] Preferably, the spraying method also performs step (C0) before step (C1);

[0053] Step (C0): Prepare a standard antibacterial ceramic in advance according to step (C1). Add a color developer to the glaze before spraying, and measure the thickness and color uniformity before and after spraying the glaze, and save them as standard values;

[0054] Preparing a standard antibacterial ceramic according to step (C1) means first preparing a standard finished product according to the standard preparation method. During the preparation of the finished product, add a color developer before spraying the white base glaze and before spraying the crystal silver glaze slurry, and measure and record the thickness and color uniformity after spraying; that is, record the standard values of the white base glaze layer and the crystal silver glaze layer. The addition of the color developer can be used to judge the color uniformity comparison between the subsequent semi - finished product and the standard finished product, thus avoiding the influence on color development due to the addition of antibacterial components.

[0055] In the step (C1), a developer is applied before spraying the white base glaze and before spraying the crystal silver glaze slurry. The white base glaze and the crystal silver glaze slurry are sequentially sprayed on the semi-finished blank. After each spraying, the semi-finished product is compared with the standard antibacterial ceramic, and the color difference and thickness difference of the semi-finished product are measured. Then, the blank is additionally sprayed, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference.

[0056] Among them, the measurement of the thickness and color uniformity can be manually determined or automatically determined by a mechanical device. For example, a vernier caliper and a high-power scale (such as 40×) magnifying glass can be used for manual or automatic measurement and recording. For example, a spectrophotometer can be used to test the color uniformity of a certain area for manual or automatic measurement and recording, and compared with the standard genuine product to obtain the color difference.

[0057] After spraying the white base glaze, the thickness and color uniformity of the semi-finished product are measured, compared with the standard finished product, and then additionally sprayed according to the color difference and thickness difference of the semi-finished product to further ensure that the parameters of the white base glaze in each semi-finished product are close to the parameters of the white base glaze layer of the standard finished product, and the white base glaze layer can completely cover all positions of the blank, serving as the basis for applying the crystal silver glaze, thereby improving the basis of the glaze surface performance. Similarly, after spraying the crystal silver glaze, the thickness and color uniformity of the semi-finished product are measured, compared with the standard finished product, and then additionally sprayed according to the color difference and thickness difference of the semi-finished product to further ensure that the parameters of the crystal silver glaze layer in each semi-finished product are close to the parameters of the crystal silver glaze layer of the standard finished product, and the crystal silver glaze can completely cover all positions of the white base glaze layer. Based on the fact that the stacking ratio of particles with a particle size of 10 μm in the slurry accounts for 80 - 90 wt%, the formed crystal grains are dense, fine, have a small surface tension, a small concave-convex structure, and the glaze spraying effect is more uniform and smooth, thus avoiding the problem of cracking during firing, and further solving the problem of the decline in antibacterial performance caused by cracking.

[0058] More preferably, in the step (C0), a plurality of sub-spray fixed points are set on the spraying surface of the finished blank, and independent spraying parameters are used for spraying;

[0059] Among them, the sub-spray fixed points can be physical points or virtual points. The physical points can be marks such as ink. The virtual points are industrial cameras set on the spray gun. The industrial camera scans the blank before spraying starts and divides it into different grids according to the product model, and the intersection points between the grids are virtual points. The sub-spray fixed points are arranged in a certain order, for example, distributed sequentially from left to right, or can also be distributed sequentially from top to bottom.

[0060] In the step (C1), a color developer is applied before spraying the white base glaze and before spraying the crystal silver glaze slurry. According to the spraying parameters in the step (C0), the white base glaze and the crystal silver glaze slurry are sequentially sprayed onto the semi-finished blank. After each spraying, the semi-finished product is compared with the standard antibacterial ceramic, and the color difference and thickness difference of the semi-finished product are measured. Then, the spray gun is moved to the fixed spraying point of the blank for supplementary spraying of a specific area, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference.

[0061] When the color difference and thickness difference of the semi-finished product appear locally on the blank, the spray gun is moved and positioned to a fixed spraying point of the blank. At this fixed spraying point, since the fixed spraying point records specific spraying parameters, and the spraying parameters record parameters such as the moving position, direction, angle, flow rate, and running time of the spray gun, the spray gun can spray the area to be supplementary sprayed on the blank, so that the color difference and thickness of this area are close to the standard values.

[0062] In the step (C0), each fixed spraying point of the standard finished blank has specific spraying parameters. When the spray head is at a certain fixed spraying point, it will adjust and record the spraying parameters of the spraying, so as to represent the thickness and color uniformity of the whole and / or part of the blank, as well as the parameters such as the moving position, direction, angle, flow rate, and running time of the spray gun at the fixed spraying point. And optimally, each fixed spraying point records the range that the spray gun can supplement spray, so that the thickness and color uniformity of the semi-finished product of the specific area of the blank can be corrected respectively for each fixed spraying point subsequently, further ensuring the thickness and color uniformity of the ceramic, preventing the wear resistance and smoothness of the antibacterial layer from decreasing due to missed coating or excessive coating of the glaze, and thus avoiding the problem of uneven and unstable distribution of the antibacterial layer.

[0063] Further optimally, in the step (C0), after each application of the color developer, the pattern of the blank is recorded as a standard image; the standard image corresponds to a spraying standard parameter, and the spraying standard parameter is associated with the spraying parameters of multiple fixed spraying points;

[0064] In the step (C1), image recognition is performed on the surface of the semi-finished blank before glaze spraying, and it is matched with the standard image. The spray gun applies the spraying standard parameter and sprays and / or supplements spray each fixed spraying point of the semi-finished blank.

[0065] For standard finished green bodies, in this solution, the color developer can be directly applied to the green body, white glaze or crystalline silver glaze, and can be colored on different layers; different color developers on different layers are combined to improve the aesthetic degree; before spraying the white bottom glaze subsequently, image recognition is first performed, which can be achieved by an industrial camera here; among them, one image corresponds to one spraying standard parameter, and each spraying standard parameter is associated with the spraying parameters of multiple sub-spraying fixed points; the nozzle can directly apply the spraying standard parameter and apply different spraying parameters at different sub-spraying fixed points. In this way, the parameters of the standard finished product during white bottom glaze spraying are directly retrieved for white bottom glaze spraying; similarly, before spraying the crystalline silver glaze subsequently, image recognition is first performed and the corresponding spraying standard parameter is obtained to obtain different spraying parameters applied at different sub-spraying fixed points during crystalline silver glaze spraying. The subsequent preparation of the antibacterial ceramic is closer to the standard finished product, and thus the antibacterial performance is closer to the standard finished product.

[0066] Preferably, in the step (C1), a plurality of sub-spraying fixed points are arranged on the spraying surface of the finished green body, each sub-spraying fixed point is 10 cm × 10 cm, and a spray gun with a caliber of Φ1.4 mm is used to spray the white bottom glaze and the crystalline silver glaze slurries.

[0067] In this solution, the size of the sub-spraying fixed points and the caliber of the spray gun can be selected according to needs; the sub-spraying fixed points can be 20 cm × 20 cm, 10 cm × 20 cm, 10 cm × 30 cm, etc.; the spray gun can be selected as Φ1.0 mm, Φ1.1 mm, Φ1.2 mm, Φ1.3 mm, Φ1.4 mm, Φ1.5 mm, Φ2.0 mm, etc.; and optimally, each sub-spraying fixed point is selected as 10 cm × 10 cm, and a spray gun with a caliber selected as Φ1.4 mm is used to spray the white bottom glaze and the crystalline silver glaze slurries, and the uniformity is the best.

[0068] A long-acting antibacterial ceramic is prepared by the preparation method of the above-mentioned long-acting antibacterial ceramic.

[0069] The ceramic can be any ceramic utensil such as a ceramic tile, sanitary ware, reactor, etc.

[0070] An antibacterial sanitary ware uses the above-mentioned long-acting antibacterial ceramic.

[0071] The antibacterial sanitary ware includes common sanitary wares in life such as toilets, washbasins, bathtubs, etc.

[0072] A use of a ceramic in an antibacterial sanitary ware, wherein the ceramic is prepared by the preparation method of the above-mentioned long-acting antibacterial ceramic.

[0073] Examples and comparative examples of this solution are all based on ceramic tiles as products, specifically as follows:

[0074] Example A:

[0075] A method for preparing long-lasting antibacterial ceramics, comprising: a body preparation method, a glaze slurry preparation method and a spraying method;

[0076] The green body preparation method comprises: preparing a green body from green body raw materials;

[0077] (A1) weighing a green body raw material;

[0078] (A2) Raw material mixing: The above green body raw materials are mixed evenly to form green body slurry.

[0079] (A3) Molding: The mixed green body slurry is placed in a green body machine and formed into a green body through extrusion and compaction.

[0080] (A4) Drying: Dry the blank in air.

[0081] (A5) Putting into kiln: putting the green body into kiln and firing it at 1220° C. The chemical composition of the green body, by mass percentage, includes: 65% SiO2, 25% Al2O3, 3% Fe2O3, 0.5% TiO2, 1% CaO, 0.5% MgO, 1% K2O, 1% Na2O and 3% IL;

[0082] (A6) Drying: Drying of the blank;

[0083] The glaze slurry preparation method comprises:

[0084] (B1) preparing a crystal silver glaze slurry, wherein the fineness of the slurry is 325 mesh sieve residue ≤ 0.1 wt %, and the accumulation ratio of particles with a particle size of 10 μm in the slurry accounts for 85 wt %;

[0085] The raw materials of the crystal silver glaze slurry include, by mass, 15 parts of quartz powder, 30 parts of wollastonite, 35 parts of potassium feldspar powder, 10 parts of submicron zinc oxide antibacterial material and 0.01 parts of nano silver antibacterial material;

[0086] (B2) Preparation of white glaze, the expansion coefficient of the white glaze at 100-800°C is (4.2-6.5)×10 -6 / ℃; the formula of white glaze, by mass, includes: 12 parts of limestone, 30 parts of quartz, 35 parts of bell feldspar, 6 parts of kaolin, 10 parts of zirconium silicate, 3 parts of dolomite and 3 parts of zinc oxide;

[0087] The spraying method comprises:

[0088] (C1) The spraying surface of the green body is set with multiple sub-spraying fixed points; each sub-spraying fixed point is 10 cm × 10 cm, and a spray gun with a caliber of Φ1.4 mm is used to spray the white base glaze and the crystal silver glaze slurries; before spraying, a color developer accounting for 1% of the total mass of the glaze is added to the glaze; the spray gun is successively positioned and moved to each sub-spraying fixed point for spraying, and the white base glaze is sprayed first; after the water luster of the glaze layer disappears, the spray gun is successively positioned to each sub-spraying fixed point to spray the crystal silver glaze slurry; before and after spraying the white base glaze and the crystal silver glaze slurry, the color uniformity and the thickness of the glaze layer are measured, the spray gun is moved to a specific sub-spraying fixed point, and a region with color difference and / or thickness difference is corrected and re-sprayed; after the glaze surface of the green body is dried, it is put into a kiln at 1210 °C for firing to obtain antibacterial ceramics.

[0089] The construction parameters of the white base glaze control a 10-μm stacking particle size of 66%, a specific gravity of 1.75 - 1.76 g / mL, a fluidity of 145 - 165°, a thixotropy of ≤60°, and a blotting time of 27 min;

[0090] The construction parameters of the crystal silver glaze slurry are a 10-μm stacking particle size of 80%, a specific gravity of 1.55 - 1.60 g / mL, a fluidity of 230 - 270°, a thixotropy of ≤60°, and a blotting time of 40 min.

[0091] First, the thermal expansion coefficients of the green body slurry, the white base glaze, and the crystal silver glaze slurry are measured according to "GB / T 16920-2015 Determination of the Mean Linear Thermal Expansion Coefficient of Glass", and the results are as Figure 3 shown.

[0092] Note:

[0093] As Figures 1-3 , in the vertical coordinate, CTE is the thermal expansion coefficient, △L is the expansion value, and dL / L o is the expansion percentage; as Figure 1 , the expansion coefficient α of the green body at 100 - 800 °C is (4.3 - 6.5)×10 -6 / °C; as Figure 2 , the expansion coefficient α of the white glaze at 100 - 800 °C is (4.2 - 6.5)×10 -6 / °C; as Figure 3 , the expansion coefficient α of the crystal silver glaze at 100 - 800 °C is (4.6 - 7.4)×10 -6 / °C.

[0094] When the experimental temperature of the green body slurry is between 84-168℃ and 589-674℃, the expansion value curve shows a slight downward trend respectively; when the experimental temperature of the white base glaze is between 752-836℃, the expansion value curve shows an obvious downward trend, but the crystal silver glaze slurry hardly shows a downward expansion value curve with temperature changes, which has a better balanced burning process, and thus the material expansion cracking stability is good. In this way, the green body slurry, white base glaze and crystal silver glaze slurry have matching expansion coefficients. The green body slurry and crystal silver glaze slurry have an expansion coefficient of (4.2-6.5)×10 -6 The white base glaze of / ℃ combined with the secondary glazing spraying method can avoid firing cracks, and the glaze surface of Example A has no cracks.

[0095] Embodiment B:

[0096] The basic steps of Example B are substantially the same as those of Example A, except that Example B uses the following spraying method:

[0097] (C1) Standard antibacterial ceramics were prepared in advance, and a color developer accounting for 1% of the total mass of the glaze was added to the glaze before spraying. Multiple spraying points were set on the spraying surface of the finished body, each of which was 10 cm×10 cm. A spray gun with a diameter of Φ1.4 mm was used to spray the white base glaze and crystal silver glaze slurry. Independent spraying parameters were used for spraying, and the thickness and color uniformity were measured for each spraying point;

[0098] (C2) before spraying the white base glaze, a color developer accounting for 1% of the total mass of the glaze is applied, the spray gun is positioned and moved to each sub-spraying fixed point in turn, and the white base glaze is sprayed on the semi-finished body according to the spraying parameters of the corresponding sub-spraying fixed point in step (C1), the semi-finished product after spraying is compared with the standard antibacterial ceramic, and the color difference and thickness difference of the semi-finished product are measured; then the spray gun is positioned at a certain sub-spraying fixed point to perform supplementary spraying on the color difference position and / or thickness difference position of the body, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference; the construction parameters of the white base glaze are controlled to be 10μm stacking particle size 60%, specific gravity 1.75-1.76g / mL, fluidity 145-165°, thixotropy ≤60°, and drying time 30min;

[0099] (C3) After the water luster disappears in the glaze layer of the white base glaze, a color developer accounting for 1% of the total mass of the glaze material is applied before spraying the crystalline silver glaze slurry. The spray gun is repositioned and moved successively to each sub-spray fixed point, and the crystalline silver glaze slurry is sprayed onto the surface of the white base glaze according to the spraying parameters corresponding to each sub-spray fixed point in step (C1). After spraying, the semi-finished product is compared with the standard antibacterial ceramic, and the color difference and thickness difference of the semi-finished product are measured. Then, the spray gun is positioned at a certain sub-spray fixed point to perform supplementary spraying on the color difference position and / or thickness difference position of the green body, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference. The construction parameters of the crystalline silver glaze slurry are as follows: the stacking particle size of 90% is 10 μm, the specific gravity is 1.55 - 1.60 g / mL, the fluidity is 230 - 270°, the thixotropy is ≤60°, and the blotting time is 50 min. After the glaze surface of the green body is dried, it is fired in a kiln at 1220 °C to obtain the antibacterial ceramic.

[0100] Comparative Example B0:

[0101] Comparative Example B0 is a blank control sample, which applies sub-micron zinc oxide antibacterial material and nano-silver antibacterial material to the surface of the green body, and the mass ratio of the sub-micron zinc oxide antibacterial material to the nano-silver antibacterial material is 1000:1.

[0102] The performance tests of Example B and Comparative Example B0 were carried out according to "JC / T 897-2014 Antibacterial Performance of Antibacterial Ceramic Products" and "GB / T 9266-2009 Determination of Washability Resistance of Architectural Coating Coatings", and the results are shown in Table 1.

[0103] Table 1 - Performance Test of Example B

[0104]

[0105] Note:

[0106] Refer to "JC / T 897-2014 Antibacterial Performance of Antibacterial Ceramic Products" to detect the antibacterial performance of each blank control sample's test sample against Escherichia coli and Staphylococcus aureus. After the blank control sample stands for 24 hours, more mildew is generated. The antibacterial ceramic of Example B hardly generates mildew. After detection, it can effectively inhibit 99.99% of Escherichia coli and Staphylococcus aureus.

[0107] Comparative Example B1

[0108] The basic steps of Comparative Example B1 are basically the same as those of Example B, except that in Comparative Example B1, the white base glaze is directly sprayed onto the surface of the green body without setting sub-spray fixed points, and then the crystalline silver glaze slurry is sprayed onto the surface of the green body without setting sub-spray fixed points.

[0109] Comparative Example B2

[0110] The basic steps of Comparative Example B2 are basically the same as those of Example B. The difference is that in step (C2) of Comparative Example B2, the white ground glaze is sprayed on the surface of the green body without setting fixed points for separate spraying.

[0111] Comparative Example B3

[0112] The basic steps of Comparative Example B3 are basically the same as those of Example B. The difference is that in step (C3) of Comparative Example B3, the crystalline silver glaze slurry is sprayed on the surface of the green body without setting fixed points for separate spraying.

[0113] Perform performance tests on Example B and Comparative Examples B1 - B3 according to "JC / T 897 - 2014 Antibacterial Properties of Antibacterial Ceramic Products". The results are shown in Table 2.

[0114] Based on the method of "GB / T 9266 - 2009 Determination of Scrub Resistance of Architectural Coating Films", increase the scrubbing times of Example B by 5000, 10000, and 15000 times respectively on the basis of the standard requirement of 500 scrubbing times, and then conduct the antibacterial durability limit on the antibacterial porcelain tile samples. The results are shown in Table 2.

[0115] Table 2 - Performance Comparison between Example B and Comparative Examples B1 - B3

[0116]

[0117] Note:

[0118] 1. From the comparison between Example B and Comparative Example B1, it can be seen that although Comparative Example B1 used the same white base glaze and crystalline silver glaze slurries, it did not separately set the sub-spray fixed points and then spray the white base glaze and crystalline silver glaze slurries in each sub-spray fixed point in sequence. When spraying at the sub-spray fixed points, the crystalline grains formed by piling up 80 - 90% of the particles below 10μm can be made denser and finer, with a small surface tension, which can effectively reduce the unevenness of the surface glaze, thereby improving the antibacterial performance and antibacterial persistence. The antibacterial rate of the antibacterial brick in Comparative Example B1 was 95%. When the surface of the antibacterial brick was scrubbed 500 times, it was equivalent to the surface of the simulated brick being rubbed by the sole for a long time. Obviously, the antibacterial rate of the antibacterial brick decreased from 95% to 86% (Escherichia coli) and 87% (Staphylococcus aureus). The spraying method of using fixed-point secondary glazing on its surface can further improve the long-term antibacterial effect of the crystalline silver glaze slurry. In Example B1, the white base glaze and crystalline silver glaze slurries were sprayed in each sub-spray fixed point respectively. It has high antibacterial persistence, realizes the uniform dispersion and controllable thickness effect of the antibacterial components on the glaze surface, and can also ensure the smoothness of the product glaze surface itself. Especially after being washed 5000, 10000, and 15000 times, the antibacterial rate can still be maintained as low as 99.98%, indicating that the crystalline grains of the crystalline silver glaze slurry by fixed-point secondary glazing are denser and finer, with a small surface tension, which can fully exert the antibacterial effect of the formula, and the antibacterial effect and antibacterial persistence are good.

[0119] 2. From the comparison between Example B1 and Comparative Examples B1 - B3, it can be seen that in Comparative Example B2, only the crystalline silver glaze slurry was sprayed at fixed points in step (C3). Its antibacterial rate can reach 97% (Escherichia coli) and 96% (Staphylococcus aureus), and its antibacterial performance is better than that of Comparative Example B1, indicating that spraying the crystalline silver glaze slurry in a fixed-point manner can further improve the antibacterial performance. At the same time, the antibacterial long-term effect of Comparative Example B2 is better than that of Comparative Example B1. Even after being scrubbed 500 times, it can still maintain 94%, and the antibacterial rate only decreases by 3% (Escherichia coli) and 2% (Staphylococcus aureus), indicating that spraying the crystalline silver glaze slurry in a fixed-point manner can further improve the antibacterial long-term performance. However, since the white base glaze was not sprayed at fixed points in Comparative Example B2, the fineness of the base glaze on the green body decreased, the dispersion degree of the crystalline silver glaze slurry on the white base glaze was low, and the wear resistance when carrying and attaching the crystalline silver glaze slurry was insufficient, resulting in a deterioration of the antibacterial performance after long-term use. In Example B, the white base glaze and crystalline silver glaze slurries were sprayed respectively using the partitioned spraying method. Its antibacterial rate can reach 99.98%, and the antibacterial persistence is good, indicating that the spraying method of combining the white base glaze and crystalline silver glaze slurries with fixed-point secondary glazing can further improve the antibacterial long-term performance.

[0120] In Comparative Example B3, spot spraying of the white base glaze was only carried out in step (C2), while the crystal silver glaze slurry was directly sprayed on the surface of the green body; thus, the density of the crystal grains of the crystal silver glaze slurry was not fine enough. Although it had an antibacterial rate of 95%, when washed 500 times, it could only maintain an antibacterial rate of 90%. The crystal silver glaze slurry did not fully cover all positions, so the antibacterial components were not evenly covered; while in Example B, the white base glaze and the crystal silver glaze slurry were respectively sprayed using the spot double glazing spraying method, and its antibacterial rate could reach 99.98%, and the antibacterial persistence was good; further indicating that spraying the crystal silver glaze slurry in the spot double glazing spraying method can further improve the antibacterial persistence performance.

[0121] Comparative Example B4:

[0122] The steps of Comparative Example B4 were basically the same as those of Example B. In Comparative Example B4, the crystal silver glaze slurry was not sprayed in step (C3). The following experimental comparisons were made between Example B and Comparative Example B4:

[0123] (1) The cross-sectional microstructures of Example B and Comparative Example B4 were observed under an electron microscope, and the results were as Figure 4 .

[0124] (2) The surface microstructures of the glaze layers of Example B and Comparative Example B4 were observed under an electron microscope, and the results were as Figure 5 .

[0125] (3) Roughness tests were carried out on Example B and Comparative Example B4: On the surface of the glaze layer of ordinary white base glaze and crystal silver glaze samples, 3 points were respectively tested using a roughness tester, and 3 roughness test results were obtained, and then the average value was calculated. The results are shown in Table 3.

[0126] (4) Stain resistance tests were carried out on Example B and Comparative Example B4: The sanitary ware of the test specimen was thoroughly cleaned with hot soapy water, and then dried with a clean dry cotton cloth. A red ink solution was dropped on the glaze surface of the test specimen, and the glaze surface of the test specimen was rinsed with deionized water and dried with a clean dry cotton cloth. Then, the situation of the glaze surface of the test specimen was observed with the naked eye. The results are shown in Table 3.

[0127] (5) Pencil scratch wiping tests were carried out on Example B and Comparative Example B4, and tested according to "GB / T3810.14-2016 Test Methods for Ceramic Tiles - Part 14". The results are shown in Table 3.

[0128] Table 3 - Performance Comparison between Example B and Comparative Example B4

[0129]

[0130] Note:

[0131] (1) Cross-sectional microstructure: The cross-sectional diagrams of the glaze layers of Comparative Example B4 and Example B under an electron microscope are as shown in Figure 4 ; It can be seen from the cross-section that Comparative Example B4 only has a white-bottom glaze layer, and there are bubbles, crystals, microcracks, etc. in the glaze layer. The silver-crystalline glaze antibacterial layer of Example B can be well stabilized on the surface layer of the green body and form a dense antibacterial protective layer with a thickness of about 109 μm, indicating that the silver-crystalline glaze antibacterial layer can improve the surface structure of the white-bottom glaze layer, thereby avoiding the decline of antibacterial performance caused by the structure of the white-bottom glaze layer.

[0132] (2) Microstructure of the glaze surface: Analysis of the surfaces of Comparative Example B4 and Example B using an EDS energy spectrometer found that there are a large number of obvious bubbles on the surface of the white-bottom glaze of Comparative Example B4, while it can be clearly seen from the image of the silver-crystalline glaze of Example B that there are only extremely tiny bubbles in the middle layer of the glaze, and a dense antibacterial glaze layer has been formed on its surface. Through microscopic structure analysis, a smoother silver-crystalline glaze surface can be visually observed under magnification. Compared with the unevenness caused by the surface bubbles of the ordinary white-bottom glaze of Comparative Example B4, which is prone to dirt accumulation, the silver-crystalline glaze layer of Example B achieves a more obvious anti-staining and easy-to-clean effect.

[0133] (3) Roughness test: According to the comparative analysis of the data of Comparative Example B4 and Example B, the smaller the Ra value, the smaller the roughness, the fewer the pores, and the smoother the surface. The silver-crystalline glaze layer of Example B has a higher glass phase content than that of Comparative Example B4, so the surface is smoother and the easy-to-clean effect is better.

[0134] (4) Anti-staining test: According to the comparative analysis of the data of Comparative Example B4 and Example B, the higher the level, the better the anti-staining level; thus, Example B is more stain-resistant than Comparative Example B4.

[0135] (5) Pencil scratch wiping test: The glaze layers of the products of Comparative Example B4 and Example B are wiped respectively. The glaze surface of Example B is smooth, and there is no residue after the HB pencil test, and it is easier to clean.

[0136] In summary, in this solution, the white-bottom glaze and the silver-crystalline glaze are sprayed onto the green body by the spraying method of fixed-point secondary glazing, which can further make the crystal grains denser and finer, with a small surface tension, effectively reduce the uneven effect of the surface glaze, improve the antibacterial performance and antibacterial persistence, not only keep the green body with high antibacterial property, but also solve the problem of the decline of antibacterial effect caused by bubbles, crystals, and microcracks on the surface of the green body, and can also maintain the anti-staining ability and easy-to-clean ability of the green body.

[0137] Example C:

[0138] A preparation method of a long-acting antibacterial ceramic, including: a green body preparation method, a glaze slurry preparation method, and a spraying method;

[0139] The green body preparation method includes: making a green body from green body raw materials;

[0140] (A1) Weigh the green body raw materials;

[0141] (A2) Mix the raw materials: Mix the above green body raw materials evenly into a green body slurry.

[0142] (A3) Molding: Put the mixed green body slurry into a green body machine and form a green body through extrusion and compaction.

[0143] (A4) Air dry: Air dry the green body.

[0144] (A5) Put into the kiln: Put the green body into the kiln and fire it at a temperature of 1210 °C; The chemical composition of the green body, by mass percentage, includes: 60% SiO2, 25% Al2O3, 1% Fe2O3, 0.1% TiO2, 0.5% CaO, 0.1% MgO, 5% K2O, 0.3% Na2O, and 8% IL;

[0145] (A6) Drying: Conduct drying treatment on the green body;

[0146] The glaze slurry preparation method includes:

[0147] (B1) Prepare the crystalline silver glaze slurry, the fineness of the slurry is that the residue on a 325-mesh sieve is ≤ 0.1 wt%, and the stacking ratio of particles with a particle size of 10 μm in the slurry accounts for 90 wt%;

[0148] The raw materials of the crystalline silver glaze slurry, by mass parts, include: 25 parts of quartz powder, 20 parts of wollastonite, 50 parts of potassium feldspar powder, 20 parts of sub-micron zinc oxide antibacterial material, and 0.05 part of nano-silver antibacterial material;

[0149] (B2) Prepare the white glaze, the expansion coefficient α of the white glaze at 100 - 800 °C is (4.2 - 6.5) × 10 -6 / °C; The formula of the white glaze, by mass parts, its raw materials include: 10 parts of limestone, 25 parts of quartz, 40 parts of bell feldspar, 8 parts of kaolin, 7 parts of zirconium silicate;

[0150] The spraying method includes:

[0151] (C1) Prepare a standard antibacterial ceramic in advance, add a color developer accounting for 1% of the total mass of the glaze before spraying, set multiple sub-spraying fixed points on the spraying surface of the finished green body, each sub-spraying fixed point is 10 cm × 10 cm, use a spray gun with a caliber of Φ1.4 mm to spray the white glaze and the crystalline silver glaze slurry, spray using independent spraying parameters, measure the thickness and color uniformity for each sub-spraying fixed point, and record the pattern of the green body as a standard image; The standard image is correspondingly associated with the spraying standard parameters of multiple sub-spraying fixed points;

[0152] (C2) Perform image recognition on the surface of the semi-finished body and match it with the standard image to obtain the standard spraying parameters; before spraying the white base glaze, apply a color developer accounting for 1% of the total mass of the glaze, apply the standard spraying parameters to the spray gun, load the spraying parameters correspondingly at each sub-spraying fixed point, and spray the white base glaze on the semi-finished body. Compare the semi-finished product after spraying with the standard antibacterial ceramic, and measure the color difference and thickness difference of the semi-finished product; move the nozzle to a specific sub-spraying fixed point according to the spraying parameters, and then spray the body again, and correct the thickness and color uniformity of the semi-finished product according to the color difference and thickness difference;

[0153] The construction parameters of the white base glaze are controlled as follows: 10μm stacking particle size 63%, specific gravity 1.75-1.76g / mL, fluidity 145-165°, thixotropy ≤ 60°, and drying time 33min;

[0154] (C3) After the water sheen disappears in the glaze layer of the white base glaze, the surface of the semi-finished body is image-recognized and matched with the standard image to obtain the standard spraying parameters; before spraying the crystal silver glaze slurry, a color developer accounting for 1% of the total mass of the glaze is applied, and the spray gun uses the spraying standard parameters, and the crystal silver glaze slurry is sprayed on the surface of the white base glaze according to the corresponding spraying parameters loaded at each sub-spraying fixed point, and the semi-finished product after spraying is compared with the standard antibacterial ceramic, and the color difference and thickness difference of the semi-finished product are measured; the nozzle moves to a specific sub-spraying fixed point according to the spraying parameters, and then the sub-spraying fixed point of the body is re-sprayed, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference; after the glaze surface of the body is dried, it is placed in a kiln at 1220°C for firing to obtain the antibacterial ceramic.

[0155] The construction parameters of crystal silver glaze slurry are 10μm stacking particle size 85%, specific gravity 1.55-1.60g / mL, fluidity 230-270°, thixotropy ≤60°, and drying time 60min.

[0156] Embodiment D:

[0157] A method for preparing long-lasting antibacterial ceramics, comprising: a body preparation method, a glaze slurry preparation method and a spraying method;

[0158] The green body preparation method comprises: preparing a green body from green body raw materials;

[0159] (A1) weighing a green body raw material;

[0160] (A2) Raw material mixing: The above green body raw materials are mixed evenly to form green body slurry.

[0161] (A3) Molding: The mixed green body slurry is placed in a green body machine and formed into a green body through extrusion and compaction.

[0162] (A4) Drying: Dry the blank in air.

[0163] (A5) Putting into kiln: putting the green body into kiln and firing it at 1225°C; the chemical composition of the green body, by mass percentage, includes: 70% SiO2, 15% Al2O3, 0.1% Fe2O3, 1% TiO2, 1% CaO, 0.3% MgO, 5% K2O, 0.6% Na2O and 7% IL;

[0164] (A6) Drying: Drying of the blank;

[0165] The glaze slurry preparation method comprises:

[0166] (B1) preparing a crystal silver glaze slurry, wherein the fineness of the slurry is 325 mesh sieve residue ≤ 0.1 wt %, and the accumulation ratio of particles with a particle size of 10 μm in the slurry accounts for 90 wt %;

[0167] The raw materials of the crystal silver glaze slurry include, by mass, 15 parts of quartz powder, 30 parts of wollastonite, 35 parts of potassium feldspar powder, 10 parts of submicron zinc oxide antibacterial material and 0.05 parts of nano silver antibacterial material;

[0168] (B2) Preparation of white glaze, the expansion coefficient of the white glaze at 100-800°C is (4.2-6.5)×10 -6 / ℃; the formula of white glaze, by mass, includes: 10 parts of limestone, 20 parts of quartz, 35 parts of bell feldspar, 10 parts of zirconium silicate, 2 parts of albite and 3 parts of potassium feldspar;

[0169] The spraying method comprises:

[0170] (C1) Standard antibacterial ceramics are prepared in advance, and a color developer accounting for 2% of the total mass of the glaze is added to the glaze before spraying. A plurality of spraying points are set on the spraying surface of the finished body, each of which is 10 cm×10 cm. A spray gun with a diameter of Φ1.5 mm is used to spray the white base glaze and the crystal silver glaze slurry. Independent spraying parameters are used for spraying. The thickness and color uniformity of each spraying point are measured, and the pattern of the body is recorded as a standard image; the standard image corresponds to the spraying standard parameters of the plurality of spraying points;

[0171] (C2) performing image recognition on the surface of the semi-finished body and matching it with the standard image to obtain the standard spraying parameters; applying a color developer accounting for 2% of the total mass of the glaze before spraying the white base glaze, positioning the spray gun to each sub-spraying fixed point in turn, and spraying the white base glaze on the semi-finished body according to the spraying parameters of the corresponding sub-spraying fixed point in step (C1), comparing the semi-finished product after spraying with the standard antibacterial ceramic, and measuring the color difference and thickness difference of the semi-finished product; then positioning the spray gun to a certain sub-spraying fixed point to perform supplementary spraying on the color difference position and / or thickness difference position of the body, and correcting the thickness and color uniformity of the semi-finished product according to the color difference and thickness difference;

[0172] Construction parameter control of white base glaze: 63% of the 10μm stacking particle size, specific gravity of 1.75 - 1.76 g / mL, fluidity of 145 - 165°, thixotropy ≤ 60°, drying time of 33 min;

[0173] (C3) After the water gloss disappears in the glaze layer of the white base glaze, perform image recognition on the surface of the semi-finished green body and match it with the standard image to obtain the spraying standard parameters; Apply a color developer accounting for 2% of the total mass of the glaze before spraying the crystalline silver glaze slurry. The spray gun is repositioned and moved to each sub-spray fixed point in turn, and the crystalline silver glaze slurry is sprayed on the surface of the white base glaze according to the spraying parameters of the corresponding sub-spray fixed point in step (C1). Compare the semi-finished product after spraying with the standard antibacterial ceramic, and measure the color difference and thickness difference of the semi-finished product; Then position the spray gun at a certain sub-spray fixed point to perform supplementary spraying on the color difference position and / or thickness difference position of the green body, and correct the thickness and color uniformity of the semi-finished product according to the color difference and thickness difference. After the glaze surface of the green body is dried, it is fired in a kiln at 1220°C to obtain the antibacterial ceramic.

[0174] Among them, the construction parameters of the crystalline silver glaze slurry are 85% of the 10μm stacking particle size, specific gravity of 1.55 - 1.60 g / mL, fluidity of 230 - 270°, thixotropy ≤ 60°, drying time of 60 min.

[0175] Example E:

[0176] The basic steps of Example E are basically the same as those of Example D, except that in step (C1) of Example E, each sub-spray fixed point is 20 cm × 20 cm, and a spray gun with a diameter of Φ1.6 mm is used to spray the white base glaze and the crystalline silver glaze slurry.

[0177] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the claims and their equivalents.

Claims

1. A preparation method of a long-acting antibacterial ceramic, characterized in that, include: Green body preparation method, glaze slurry preparation method and spraying method; The green body preparation method comprises: preparing a green body from green body raw materials; The chemical composition of the green body, by mass percentage, includes: 60-70% SiO2, 15-25% Al2O3, less than 3% Fe2O3, less than 0.5% TiO2, less than 1% CaO, less than 0.5% MgO, 1-5% K2O, less than 1% Na2O and the balance IL; The glaze slurry preparation method comprises: (B1) preparing a crystal silver glaze slurry, wherein the fineness of the slurry is 325 mesh sieve residue ≤ 0.1wt%, and the accumulation ratio of particles with a particle size of 10μm in the slurry accounts for 80-90wt%; The raw materials of the crystal silver glaze slurry include, by weight: 15-25 parts of quartz powder, 20-30 parts of wollastonite, 35-50 parts of potassium feldspar powder, 10-20 parts of submicron zinc oxide antibacterial material and 0.01-0.05 parts of nano silver antibacterial material; (B2) Prepare a white glaze, the coefficient of thermal expansion α of the white glaze is (4.2 - 6.5)×10 -6 / °C at 100 - 800 °C; The spraying method comprises: (C0): Prepare standard antibacterial ceramics in advance according to step (C1), add a color developer to the glaze before spraying, measure the thickness and color uniformity of the glaze before and after spraying, and save them as standard values; (C1) A plurality of spraying fixed points are set on the spraying surface of the blank; the spray gun is positioned and moved to each spraying fixed point in turn and spraying is performed, and the white base glaze is sprayed first; after the water gloss of the glaze layer disappears, the spray gun is positioned to each spraying fixed point in turn and sprays the crystal silver glaze slurry; before and after spraying the white base glaze and the crystal silver glaze slurry, the color uniformity and thickness of the glaze layer are measured, the spray gun is moved to a specific spraying fixed point, and a certain area with color difference and / or thickness difference is corrected and sprayed again; after the glaze surface of the blank is dried, it is placed in a kiln at 1210-1220° C. for firing to obtain an antibacterial ceramic; In the step (C1), a color developer is applied before spraying the white base glaze and before spraying the crystal silver glaze slurry, and the white base glaze and the crystal silver glaze slurry are sprayed on the semi-finished body in sequence. The semi-finished product after each spraying is compared with the standard antibacterial ceramic to measure the color difference and thickness difference of the semi-finished product; the body is then re-sprayed, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference.

2. The preparation method of a long-acting antibacterial ceramic according to claim 1, wherein, In the step (C0), a plurality of spraying fixed points are set on the spraying surface of the finished blank, and independent spraying parameters are used for spraying; In the step (C1), a color developer is applied before spraying the white base glaze and before spraying the crystal silver glaze slurry, and the white base glaze and the crystal silver glaze slurry are sprayed on the semi-finished body in sequence according to the spraying parameters of the step (C0). The semi-finished product after each spraying is compared with the standard antibacterial ceramic, and the color difference and thickness difference of the semi-finished product are measured; then the spray gun is moved to the fixed spraying point of the body to perform supplementary spraying on a specific area, and the thickness and color uniformity of the semi-finished product are corrected according to the color difference and thickness difference.

3. The preparation method of a long-acting antibacterial ceramic according to claim 2, characterized in that, In the step (C0), after each application of the developer, the pattern of the blank is recorded as a standard image; the standard image corresponds to a spraying standard parameter, and the spraying standard parameter is associated with the spraying parameters of multiple sub-spraying fixed points; In the step (C1), before the glaze is sprayed, image recognition is performed on the surface of the semi-finished blank, which is matched with the standard image. The spray gun applies the standard spraying parameters, and spraying and / or supplementary spraying are carried out at each separate spraying fixed point of the semi-finished blank.

4. The preparation method of a long-acting antibacterial ceramic according to claim 1, characterized in that, A plurality of separate spraying fixed points are set on the spraying surface of the finished blank. Each separate spraying fixed point is 10 cm × 10 cm. A spray gun with a caliber of Φ1.4 mm is used to spray the white base glaze and the crystal silver glaze slurries.

5. A long-acting antibacterial ceramic, characterized in that, It is prepared by the preparation method of a long-acting antibacterial ceramic according to any one of claims 1-4.

6. An antibacterial sanitary ware, characterized in that, Use a long-acting antibacterial ceramic according to claim 5.

7. Use of a ceramic in an antibacterial sanitary ware, characterized in that, The ceramic is prepared by the preparation method of a long-acting antibacterial ceramic according to any one of claims 1-4.

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