Positioning ceramic tile with double superimposed effect of ice crystals and floc and preparation method thereof

Abstract

This invention discloses a positioning ceramic tile with a dual superimposed effect of ice crystals and flocculent inclusions, and its preparation method, belonging to the field of building materials technology. This invention uses a positioning application process to create rich layers of crystalline dry particles and flocculent white dry particles of different particle sizes and chemical compositions, resulting in a dual superimposed effect of ice crystals and flocculent inclusions, with excellent three-dimensionality and artistic appeal. Furthermore, a composite antibacterial agent is added to the protective glaze. Silver-loaded silica microspheres are surface-modified with a silane coupling agent and then reacted with 2-methacryloyloxyethyltrimethylammonium chloride, significantly improving antibacterial properties. Combined with a cationic surfactant, the composite antibacterial agent can interact with the anionic surfactant in the protective glaze, helping to improve the uniform dispersion of the composite antibacterial agent and reduce its migration. Overall, it possesses excellent artistic decoration while also exhibiting excellent antibacterial effects, achieving a balance between function and art, and meeting market demands.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, and more specifically, to a positioning ceramic tile with a dual superposition effect of ice crystals and flocculent inclusions, and its preparation method. Background Technology

[0002] As an important building decoration material, the surface decoration effect of ceramic tiles directly affects the aesthetic value of a space. With the improvement of consumers' aesthetic standards, higher demands are being placed on the decorative properties of ceramic tiles, evolving from single colors and flat textures to tiles pursuing more complex artistic effects with glazes. To achieve unique glaze decorative effects, existing technologies apply colorants or special glazes to the surface of the tile body to form decorations with fixed patterns and positions, such as positioning borders and decorative tiles. This technology can achieve precise pattern presentation, but the patterns are usually flat or have simple layers, making it difficult to achieve complex visual effects, such as the artistic conception of combining the clear and crystalline appearance of ice crystals with the soft, cloud-like texture of natural stone. Existing technologies also involve mixing different dry granules and applying them to the surface of the tile, creating a certain tile surface effect after firing. However, when different dry granules are mixed, during the high-temperature firing process, the different granules melt and penetrate, resulting in poor clarity and transparency of the ice crystals, making it difficult to achieve the double superposition effect of ice crystals and cloud-like textures. Moreover, this application method lacks three-dimensionality and layering, making it difficult to achieve the ideal artistic effect. At the same time, in order to highlight the double superposition effect of ice crystals and flocculent material, a transparent protective glaze is used. If bacteria grow, the antibacterial properties will be poor, which will also affect the glaze effect.

[0003] Therefore, there is an urgent need in this field to provide a technical solution that can spatially distribute multiple functional dry particles, so that different dry particles can form a composite glaze structure with clear boundaries and synergistic effects in a preset area after firing, thereby enhancing the decorative texture and artistic feel of the ceramic tile, while also exhibiting significant antibacterial properties. This is of great significance. Summary of the Invention

[0004] Based on this, in order to solve one of the above-mentioned technical problems, the present invention provides a positioning ceramic tile with the dual superposition effect of ice crystals and flocculent clusters, and a method for preparing the same. The specific technical solution is as follows:

[0005] A positioning ceramic tile with a double superposition effect of ice crystals and flocculent particles includes a body, a surface glaze layer, a pattern layer, a dry granule layer and a protective glaze layer arranged in sequence, wherein the dry granule layer includes crystalline dry granules and flocculent white dry granules.

[0006] The crystalline dry granules comprise the following chemical composition by mass percentage: ZrO2: 65~68%, SiO2: 32~35%;

[0007] The flocculated white dry granules comprise the following chemical composition by weight percentage: SiO2: 40-45%, ZrO2: 18-22%, CaO: 8-10%, ZnO: 5-6%, B2O3: 4-5%, Al2O3: 10-12%, MgO: 4-5%, and loss on ignition: 0.5-1%.

[0008] The protective glaze layer is prepared by means of a protective glaze, and the protective glaze comprises the following raw materials in parts by weight: 45-50 parts of transparent frit, 1-7 parts of composite antibacterial agent, 8-10 parts of sodium feldspar, 6-10 parts of potassium feldspar, 1-3 parts of zirconium oxide, 6-12 parts of calcite, 4-10 parts of calcined alumina, 10-20 parts of calcined kaolin, 1-7 parts of anionic surfactant, and 1-3 parts of dispersant.

[0009] Further, the preparation method of the composite antibacterial agent is as follows: dispersing silver-loaded silica microspheres in a silane coupling agent solution, heating to 45℃~65℃, stirring at a speed of 50r / min~100r / min for 20min~30min, then adding 2-methacryloyloxyethyltrimethylammonium chloride, stirring at 60℃~75℃ for 30min~60min, then adding a cationic surfactant, and continuing to stir for 15min~30min to obtain the composite antibacterial agent.

[0010] Furthermore, the silver loading in the silver-loaded silica microspheres is 0.01% to 0.03%.

[0011] Further, by weight, the ratio of the silver-loaded silica microspheres, silane coupling agent solution, 2-methacryloyloxyethyltrimethylammonium chloride and cationic surfactant is (1~9):(10~15):(1~5):(1~3).

[0012] Furthermore, the cationic surfactant is hexadecyltrimethylammonium bromide.

[0013] Furthermore, the particle size D50 of the crystalline dry granules is 20μm~50μm, and the particle size D50 of the flocculent white dry granules is 80μm~180μm.

[0014] Furthermore, the transparent frit comprises the following chemical composition by mass percentage: SiO2: 45~60%, Al2O3: 15~20%, CaO: 5~12%, MgO: 1~5%, Na2O: 1~3%, K2O: 2~4%, ZnO: 2~8%, BaO: 1~2%, B2O3: 1~5%, and loss on ignition: 0.5~1%.

[0015] Furthermore, the anionic surfactant is sodium lignosulfonate.

[0016] In addition, the present invention also provides a method for preparing a positioning ceramic tile with a dual superposition effect of ice crystals and flocculent inclusions, the preparation method comprising the following steps:

[0017] S1. Press the green body powder into shape to obtain a green body, send the green body into a drying kiln to dry, apply a surface glaze to the surface of the dried green body, and after drying, form a surface glaze layer.

[0018] S2. A pattern layer is formed on the surface of the glaze layer by inkjet printing;

[0019] S3. The flocculent dry granules are precisely applied to the preset area of ​​the pattern layer using an application device, and then the crystalline dry granules are precisely applied to the preset area of ​​the pattern layer using an application device to form a dual-positioning dry granule layer.

[0020] S4. Prepare a protective glaze, apply the protective glaze to the dry granule layer, and after drying, form a protective glaze layer;

[0021] S5. The material after step S4 is fired at 1180℃~1210℃ for 50min~90min, followed by soft polishing to obtain a positioning tile with a double superposition effect of ice crystals and flocculent particles.

[0022] Furthermore, the preparation method of the protective glaze is as follows: transparent frit, sodium feldspar, potassium feldspar, zirconium oxide, calcite, calcined alumina, calcined kaolin and dispersant are added to a ball mill, an appropriate amount of water is added, and wet ball milling is performed. Then, a composite antibacterial agent and anionic surfactant are added, and ball milling is continued. After sieving, the protective glaze is obtained.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. This invention uses crystalline dry particles of different particle sizes and chemical compositions, as well as flocculent white dry particles, as dry particle layers. Through a dual-positioning application process, they preferentially melt and react in their respective positioning areas during high-temperature firing, resulting in a double superposition effect of crystalline effect zone with sparkling crystals and flocculent texture. Moreover, the two are partially fused at the interface, producing different melting and crystallization states. The double superposition effect of ice crystals and flocculent texture is excellent, and the three-dimensionality and artistic feel of the pattern are excellent.

[0025] 2. The protective glaze of the present invention incorporates a composite antibacterial agent. The silver-loaded silica microspheres with excellent antibacterial activity are surface-modified with a silane coupling agent and then react with 2-methacryloyloxyethyltrimethylammonium chloride to significantly improve the antibacterial performance. Combined with a cationic surfactant, the composite antibacterial agent can interact with the anionic surfactant in the protective glaze, which helps to improve the uniform dispersion of the composite antibacterial agent and reduce its migration.

[0026] 3. By optimizing the composition of the protective glaze, this invention creates a transparent protective glaze layer that not only does not damage the decorative elements and artistic expression of the ceramic tile, but also provides excellent antibacterial effects, achieving a balance between function and art and meeting market demands. Detailed Implementation

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0028] A positioning ceramic tile with a double superposition effect of ice crystals and flocculent particles in one embodiment of the present invention includes a body, a surface glaze layer, a pattern layer, a dry granule layer and a protective glaze layer arranged in sequence, wherein the dry granule layer includes crystalline dry granules and flocculent white dry granules.

[0029] The crystalline dry granules comprise the following chemical composition by mass percentage: ZrO2: 65~68%, SiO2: 32~35%;

[0030] The flocculated white dry granules comprise the following chemical composition by weight percentage: SiO2: 40-45%, ZrO2: 18-22%, CaO: 8-10%, ZnO: 5-6%, B2O3: 4-5%, Al2O3: 10-12%, MgO: 4-5%, and loss on ignition: 0.5-1%.

[0031] The protective glaze layer is prepared by means of a protective glaze, and the protective glaze comprises the following raw materials in parts by weight: 45-50 parts of transparent frit, 1-7 parts of composite antibacterial agent, 8-10 parts of sodium feldspar, 6-10 parts of potassium feldspar, 1-3 parts of zirconium oxide, 6-12 parts of calcite, 4-10 parts of calcined alumina, 10-20 parts of calcined kaolin, 1-7 parts of anionic surfactant, and 1-3 parts of dispersant.

[0032] In one embodiment, the composite antibacterial agent is prepared by dispersing silver-loaded silica microspheres in a silane coupling agent solution, heating to 45°C~65°C, stirring at 50r / min~100r / min for 20min~30min, then adding 2-methacryloyloxyethyltrimethylammonium chloride, stirring at 60°C~75°C for 30min~60min, then adding a cationic surfactant, and continuing to stir for 15min~30min to obtain the composite antibacterial agent.

[0033] In one embodiment, the silver loading in the silver-loaded silica microspheres is 0.01% to 0.03%.

[0034] In one embodiment, the particle size of the silver-loaded silica microspheres is 50 nm to 200 nm.

[0035] In one embodiment, the ratio of the silver-loaded silica microspheres, silane coupling agent solution, 2-methacryloyloxyethyltrimethylammonium chloride and cationic surfactant by weight is (1~9):(10~15):(1~5):(1~3).

[0036] In one embodiment, the cationic surfactant is hexadecyltrimethylammonium bromide.

[0037] In one embodiment, the silane coupling agent solution comprises at least one of 3-(isobutenoyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and methylvinyldiethoxysilane.

[0038] In one embodiment, the volume ratio of silane coupling agent to ethanol in the silane coupling agent solution is (3~5):(5~7).

[0039] In one embodiment, the particle size D50 of the crystalline dry granules is 20μm~50μm, and the particle size D50 of the flocculent white dry granules is 80μm~180μm.

[0040] In one embodiment, the transparent frit comprises the following chemical composition by mass percentage: SiO2: 45-60%, Al2O3: 15-20%, CaO: 5-12%, MgO: 1-5%, Na2O: 1-3%, K2O: 2-4%, ZnO: 2-8%, BaO: 1-2%, B2O3: 1-5%, and loss on ignition: 0.5-1%.

[0041] In one embodiment, the anionic surfactant is sodium lignosulfonate.

[0042] In one embodiment, the dispersant is at least one of sodium tripolyphosphate and sodium carboxymethyl cellulose.

[0043] In addition, the present invention also provides a method for preparing a positioning ceramic tile with a dual superposition effect of ice crystals and flocculent inclusions, the preparation method comprising the following steps:

[0044] S1. Press the green body powder into shape to obtain a green body, send the green body into a drying kiln to dry, apply a surface glaze to the surface of the dried green body, and after drying, form a surface glaze layer.

[0045] S2. A pattern layer is formed on the surface of the glaze layer by inkjet printing;

[0046] S3. The flocculent dry granules are precisely applied to the preset area of ​​the pattern layer using an application device, and then the crystalline dry granules are precisely applied to the preset area of ​​the pattern layer using an application device to form a dual-positioning dry granule layer.

[0047] S4. Prepare a protective glaze, apply the protective glaze to the dry granule layer, and after drying, form a protective glaze layer;

[0048] S5. The material after step S4 is fired at 1180℃~1210℃ for 50min~90min, followed by soft polishing to obtain a positioning tile with a double superposition effect of ice crystals and flocculent particles.

[0049] In one embodiment, in step S3, the application rate of the dried crystal particles is 50 g / m³. 2 ~200g / m 2 .

[0050] In one embodiment, in step S3, the application rate of the clump dry particles is 120 g / m³. 2 ~200g / m 2 .

[0051] In one embodiment, the protective glaze is prepared by adding transparent frit, sodium feldspar, potassium feldspar, zirconium oxide, calcite, calcined alumina, calcined kaolin and dispersant into a ball mill, adding an appropriate amount of water, performing wet ball milling, then adding a composite antibacterial agent and anionic surfactant, continuing ball milling, and sieving to obtain the protective glaze.

[0052] In one embodiment, the protective glaze is prepared by adding transparent frit, sodium feldspar, potassium feldspar, zirconium oxide, calcite, calcined alumina, calcined kaolin, and a dispersant into a ball mill, adding an appropriate amount of water, and performing wet ball milling at a speed of 50 r / min to 80 r / min for 4 h to 8 h. Then, a composite antibacterial agent and anionic surfactant are added, and the ball milling is continued at 20 r / min to 50 r / min for 10 min to 30 min. The mixture is then passed through a 300 to 350 mesh sieve to obtain the protective glaze.

[0053] In one embodiment, the specific gravity of the protective glaze is 1.60 to 1.65.

[0054] In one embodiment, the application rate of the protective glaze is 300 g / m³. 3 ~400g / m 3 .

[0055] The implementation schemes of the present invention will be described in detail below with reference to specific embodiments. The raw materials, reagents, etc. used in the embodiments that are not described in detail are all commercially available. The processes that are not limited in detail are conventional technical means and will not be described in detail here. Example 1:

[0056] A method for preparing a positioning ceramic tile with a dual superimposed effect of ice crystals and flocculent inclusions includes the following steps:

[0057] S1. Press the green body powder into shape to obtain a green body, send the green body into a drying kiln to dry, apply a surface glaze to the surface of the dried green body, and after drying, form a surface glaze layer.

[0058] S2. A pattern layer is formed on the surface of the glaze layer by inkjet printing;

[0059] S3. Use a distribution device to distribute the clumps of white dry granules at 200g / m³. 2 The application amount is precisely applied to the preset area of ​​the pattern layer, and then the crystalline dry particles are applied at a rate of 150 g / m² using an application device. 2 The amount of material applied is precisely applied to the preset area of ​​the pattern layer to form a dual-positioned dry granule layer.

[0060] The crystalline dry particles comprise the following chemical composition by mass percentage: ZrO2: 66.3%, SiO2: 33.7%;

[0061] The flocculated white dry granules comprise the following chemical composition by weight percentage: SiO2: 43.5%, ZrO2: 19%, CaO: 10%, ZnO: 6%, B2O3: 5%, Al2O3: 11%, MgO: 5%, and loss on ignition: 0.5%.

[0062] The particle size D50 of the crystalline dry granules is 45 μm, and the particle size D50 of the flocculent white dry granules is 150 μm.

[0063] S4. Prepare a protective glaze at 350 g / m 3 The amount of protective glaze applied is applied to the dry granule layer, and after drying, a protective glaze layer is formed.

[0064] The preparation method of the protective glaze is as follows: 50 parts of transparent frit, 9 parts of albite, 6 parts of potassium feldspar, 2 parts of zirconium oxide, 6 parts of calcite, 5 parts of calcined alumina, 17 parts of calcined kaolin and 2 parts of sodium tripolyphosphate are added to a ball mill by weight, an appropriate amount of water is added, and wet ball milling is performed at 50 r / min for 8 hours. Then, 5 parts of composite antibacterial agent and 6 parts of sodium lignosulfonate are added, and ball milling is continued at 20 r / min for 25 minutes. The mixture is then passed through a 320 mesh sieve to obtain a protective glaze with a specific gravity of 1.62.

[0065] The transparent frit comprises the following chemical composition by mass percentage: SiO2: 57.5%, Al2O3: 18%, CaO: 7%, MgO: 3%, Na2O: 1%, K2O: 3%, ZnO: 5%, BaO: 1%, B2O3: 4%, and loss on ignition: 0.5%.

[0066] The preparation method of the composite antibacterial agent is as follows: 7 parts by weight of silver-loaded silica microspheres with a silver loading of 0.01% are dispersed in 10 parts by weight of a silane coupling agent solution (a mixture of vinyltrimethoxysilane and ethanol in a volume ratio of 4:6). The solution is heated to 60°C and stirred at 50 r / min for 25 min. Then, 4 parts by weight of 2-methacryloyloxyethyltrimethylammonium chloride are added, and the solution is stirred at 65°C for 30 min. Finally, 2 parts by weight of hexadecyltrimethylammonium bromide are added, and the solution is stirred for another 20 min to obtain the composite antibacterial agent.

[0067] The silver-loaded silica microspheres have a particle size of 80 nm.

[0068] S5. The material after step S4 is fired at 1200℃ for 70 minutes, followed by soft polishing to obtain a positioning tile with a double superposition effect of ice crystals and flocculent inclusions. Example 2:

[0069] A method for preparing a positioning ceramic tile with a dual superimposed effect of ice crystals and flocculent inclusions includes the following steps:

[0070] S1. Press the green body powder into shape to obtain a green body, send the green body into a drying kiln to dry, apply a surface glaze to the surface of the dried green body, and after drying, form a surface glaze layer.

[0071] S2. A pattern layer is formed on the surface of the glaze layer by inkjet printing;

[0072] S3. Use a distribution device to distribute the clumps of white dry granules at 200g / m³. 2 The application amount is precisely applied to the preset area of ​​the pattern layer, and then the crystalline dry particles are applied at a rate of 150 g / m² using an application device. 2 The amount of material applied is precisely applied to the preset area of ​​the pattern layer to form a dual-positioned dry granule layer.

[0073] The crystalline dry particles comprise the following chemical composition by mass percentage: ZrO2: 66.8%, SiO2: 33.2%;

[0074] The flocculated white dry granules comprise the following chemical composition by weight percentage: SiO2: 43.5%, ZrO2: 20%, CaO: 10%, ZnO: 5%, B2O3: 5%, Al2O3: 12%, MgO: 4%, and loss on ignition: 0.5%.

[0075] The particle size D50 of the crystalline dry granules is 45 μm, and the particle size D50 of the flocculent white dry granules is 150 μm.

[0076] S4. Prepare a protective glaze at 350 g / m 3 The amount of protective glaze applied is applied to the dry granule layer, and after drying, a protective glaze layer is formed.

[0077] The preparation method of the protective glaze is as follows: 50 parts of transparent frit, 8 parts of albite, 7 parts of potassium feldspar, 2 parts of zirconium oxide, 7 parts of calcite, 5 parts of calcined alumina, 18 parts of calcined kaolin and 3 parts of sodium tripolyphosphate are added to a ball mill by weight, an appropriate amount of water is added, and wet ball milling is performed at a speed of 50 r / min for 8 hours. Then, 6 parts of composite antibacterial agent and 7 parts of sodium lignosulfonate are added, and ball milling is continued at 20 r / min for 30 minutes. The glaze is then passed through a 325 mesh sieve to obtain a protective glaze with a specific gravity of 1.63.

[0078] The transparent frit comprises the following chemical composition by mass percentage: SiO2: 55.5%, Al2O3: 18%, CaO: 8%, MgO: 3%, Na2O: 2%, K2O: 2%, ZnO: 5%, BaO: 1%, B2O3: 5%, and loss on ignition: 0.5%.

[0079] The preparation method of the composite antibacterial agent is as follows: 7 parts by weight of silver-loaded silica microspheres with a silver loading of 0.01% are dispersed in 10 parts by weight of a silane coupling agent solution (a mixture of vinyltrimethoxysilane and ethanol in a volume ratio of 4:6). The solution is heated to 60°C and stirred at 50 r / min for 25 min. Then, 5 parts by weight of 2-methacryloyloxyethyltrimethylammonium chloride are added, and the mixture is stirred at 60°C for 35 min. Finally, 3 parts by weight of hexadecyltrimethylammonium bromide are added, and the mixture is stirred for another 20 min to obtain the composite antibacterial agent.

[0080] The silver-loaded silica microspheres have a particle size of 80 nm.

[0081] S5. The material after step S4 is fired at 1200℃ for 70 minutes, followed by soft polishing to obtain a positioning tile with a double superposition effect of ice crystals and flocculent inclusions. Example 3:

[0082] A method for preparing a positioning ceramic tile with a dual superimposed effect of ice crystals and flocculent inclusions includes the following steps:

[0083] S1. Press the green body powder into shape to obtain a green body, send the green body into a drying kiln to dry, apply a surface glaze to the surface of the dried green body, and after drying, form a surface glaze layer.

[0084] S2. A pattern layer is formed on the surface of the glaze layer by inkjet printing;

[0085] S3. Use a distribution device to distribute the clumps of white dry granules at 200g / m³. 2 The application amount is precisely applied to the preset area of ​​the pattern layer, and then the crystalline dry particles are applied at a rate of 150 g / m² using an application device. 2 The amount of material applied is precisely applied to the preset area of ​​the pattern layer to form a dual-positioned dry granule layer.

[0086] The crystalline dry particles comprise the following chemical composition by mass percentage: ZrO2: 66.5%, SiO2: 33.5%;

[0087] The flocculated white dry granules comprise the following chemical composition by weight percentage: SiO2: 44.5%, ZrO2: 19%, CaO: 10%, ZnO: 6%, B2O3: 5%, Al2O3: 10%, MgO: 5%, and loss on ignition: 0.5%.

[0088] The particle size D50 of the crystalline dry granules is 45 μm, and the particle size D50 of the flocculent white dry granules is 150 μm.

[0089] S4. Prepare a protective glaze at 350 g / m 3 The amount of protective glaze applied is applied to the dry granule layer, and after drying, a protective glaze layer is formed.

[0090] The preparation method of the protective glaze is as follows: 50 parts of transparent frit, 9 parts of albite, 6 parts of potassium feldspar, 2 parts of zirconium oxide, 7 parts of calcite, 6 parts of calcined alumina, 20 parts of calcined kaolin and 3 parts of sodium tripolyphosphate are added to a ball mill by weight, an appropriate amount of water is added, and wet ball milling is performed at a speed of 50 r / min for 8 hours. Then, 7 parts of composite antibacterial agent and 7 parts of sodium lignosulfonate are added, and ball milling is continued at 20 r / min for 30 minutes. The glaze is then passed through a 325 mesh sieve to obtain a protective glaze with a specific gravity of 1.65.

[0091] The transparent frit comprises the following chemical composition by mass percentage: SiO2: 53.5%, Al2O3: 17%, CaO: 9%, MgO: 4%, Na2O: 2%, K2O: 3%, ZnO: 4%, BaO: 2%, B2O3: 5%, and loss on ignition: 0.5%.

[0092] The preparation method of the composite antibacterial agent is as follows: 7 parts by weight of silver-loaded silica microspheres with a silver loading of 0.01% are dispersed in 10 parts by weight of a silane coupling agent solution (a mixture of vinyltrimethoxysilane and ethanol in a volume ratio of 4:6). The solution is heated to 60°C and stirred at 50 r / min for 30 min. Then, 4 parts by weight of 2-methacryloyloxyethyltrimethylammonium chloride are added, and the mixture is stirred at 60°C for 30 min. Finally, 3 parts by weight of hexadecyltrimethylammonium bromide are added, and the mixture is stirred for another 30 min to obtain the composite antibacterial agent.

[0093] The silver-loaded silica microspheres have a particle size of 80 nm.

[0094] S5. The material after step S4 is fired at 1200℃ for 70 minutes, followed by soft polishing to obtain a positioning tile with a double superposition effect of ice crystals and flocculent inclusions.

[0095] Comparative Example 1:

[0096] The difference between Comparative Example 1 and Example 3 is that step S3 is different in Comparative Example 1, and the gradation of the crystalline dry particles and the flocculent white dry particles is different. The rest is the same as in Example 3.

[0097] Step S3 of Comparative Example 1 is as follows: After mixing the flocculent white dry granules and the crystalline dry granules, at a concentration of 350 g / m³... 2 The amount of material applied is precisely applied to the pattern layer to form a dry granule layer;

[0098] The particle size D50 of both the crystalline dry particles and the flocculent white dry particles in Comparative Example 1 was 150 μm.

[0099] Comparative Example 2:

[0100] The difference between Comparative Example 2 and Example 3 is that Comparative Example 2 did not add flocculent white dry granules, but otherwise it was the same as Example 3.

[0101] Comparative Example 3:

[0102] The difference between Comparative Example 3 and Example 3 is that the composite antibacterial agent in Comparative Example 3 did not contain 2-methacryloyloxyethyltrimethylammonium chloride, while the rest was the same as in Example 3.

[0103] Comparative Example 4:

[0104] The difference between Comparative Example 4 and Example 3 is that the composite antibacterial agent in Comparative Example 4 did not contain cetyltrimethylammonium bromide (a cationic surfactant), while the rest was the same as in Example 3.

[0105] Comparative Example 5:

[0106] The difference between Comparative Example 5 and Example 3 is that no composite antibacterial agent was added to the protective glaze of Comparative Example 5, but otherwise it is the same as Example 3.

[0107] Comparative Example 6:

[0108] The difference between Comparative Example 6 and Example 3 is that sodium lignosulfonate (anionic surfactant) was not added to the protective glaze of Comparative Example 6, but otherwise it was the same as Example 3.

[0109] Comparative Example 7:

[0110] The difference between Comparative Example 7 and Example 3 is that the chemical composition of the transparent frit in the protective glaze of Comparative Example 7 is different, while the rest is the same as Example 3.

[0111] The transparent frit in Comparative Example 7 comprises the following chemical composition by mass percentage: SiO2: 53.5%, Al2O3: 23%, MgO: 5%, Na2O: 5%, K2O: 6%, ZnO: 5%, ZrO2: 2%, and loss on ignition: 0.5%.

[0112] I. The appearance of the samples prepared in Examples 1-3 and the samples prepared in Comparative Examples 1-7 was evaluated. The test method was to observe and record the results with the naked eye by those skilled in the art. If necessary, tools such as magnifying glasses and microscopes could be used. The results are shown in Table 1 below.

[0113] Table 1: Appearance Evaluation

[0114]

[0115] As can be seen from Table 1, the glaze of the ceramic tile of the present invention is delicate and smooth, with a double superposition effect of ice crystals and flocculent inclusions, and has a strong three-dimensional effect. The overall artistic effect is excellent and can meet market demand. Compared with Example 3, Comparative Example 1, which mixed crystalline dry particles with a particle size D50 of 150μm and flocculent white dry particles, resulted in a noticeable graininess, blurred patterns, and an artistic effect inferior to Example 3. Comparative Example 2, which did not use flocculent white dry particles and only retained the shimmering crystalline effect, had a single artistic effect and failed to achieve the dual superposition effect of ice crystals and flocculent particles, thus failing to meet the overall artistic requirements. Comparative Examples 3-5 mainly involved changes in antibacterial components, which had little impact on the short-term appearance quality of the tiles. In Comparative Example 6, sodium lignosulfonate (anionic surfactant) was not added to the protective glaze, resulting in lower uniformity and dispersibility compared to Example 3, which in turn affected the overall effect of the glaze surface. In Comparative Example 7, the different composition of the transparent flocculent reduced the texture of the protective glaze, thus affecting the appearance and artistic effect of the tile layer. This demonstrates that the present invention, through component optimization, can promote the production of tiles with distinct layers of shimmering crystals and matte flocculent backgrounds, strong three-dimensionality, and clear pattern outlines.

[0116] II. Performance tests were conducted on the samples prepared in Examples 1-3 and Comparative Examples 1-7. The antibacterial test method followed JC / T897-2014 "Antibacterial Properties of Antibacterial Ceramic Products," and the results are shown in Table 2.

[0117] Table 2: Performance Test Results

[0118]

[0119] Analysis of the data in Table 2 shows that the ceramic tile of the present invention has a composite glaze with a shimmering crystal effect area and a matte background area with a flocculent texture, forming a positioning tile with a double superposition effect of ice crystals and flocculent texture. In addition, through the optimization of the composition of the composite antibacterial agent and the protective glaze, the composite antibacterial agent is effectively dispersed and fixed in the protective glaze layer, enabling it to exert significant and long-lasting antibacterial properties. Compared to Example 3, in Comparative Example 1, crystalline dry particles with a particle size D50 of 150 μm and flocculent white dry particles were mixed and applied. During firing, the dry particles affected each other. Although the antibacterial performance was comparable to Example 3, the artistic effect was not as good as Example 3. In Comparative Example 2, no flocculent white dry particles were added. The antibacterial performance was comparable to Example 3, but the surface was mainly composed of sparkling crystals with a high gloss, which was not soft enough and failed to achieve the dual superposition effect of ice crystals and flocculent particles. In Comparative Example 3, the composite antibacterial agent did not contain 2-methacryloyloxyethyltrimethylammonium chloride, lacking the synergistic antibacterial effect of 2-methacryloyloxyethyltrimethylammonium chloride, resulting in a lower antibacterial effect than Example 3, and the antibacterial durability was also lower than that of Example 3. This indicates that the addition of 2-methacryloyloxyethyltrimethylammonium chloride has a synergistic antibacterial effect. In Comparative Example 4, the composite antibacterial agent did not contain hexadecyltrimethyl bromide. The presence of ammonium chloride (a cationic surfactant) in the protective glaze resulted in poorer dispersibility of the composite antibacterial agent in the protective glaze compared to Example 3, weakened electrostatic anchoring, and easier migration of antibacterial components, thus affecting the durability of antibacterial performance. In Comparative Example 5, the absence of a composite antibacterial agent in the protective glaze led to a significant decrease in antibacterial performance, indicating that adding a composite antibacterial agent to the protective glaze can significantly improve the antibacterial performance of the ceramic tile. In Comparative Example 6, the absence of sodium lignosulfonate (anionic surfactant) in the protective glaze prevented the formation of electrostatic anchoring with the composite antibacterial agent, resulting in poorer suspension and dispersion of the antibacterial agent in the glaze layer compared to Example 3, thus affecting both antibacterial performance and durability. In Comparative Example 7, the different chemical composition of the transparent frit in the protective glaze resulted in lower glaze density and smoothness during firing compared to Example 3, leading to poorer antibacterial performance and durability. Overall, this invention demonstrates that through synergistic optimization of components and processes, it can obtain positioning tiles with a dual superposition effect of ice crystals and flocculent inclusions. While ensuring its artistic effect, it also improves its antibacterial properties and antibacterial durability, giving it greater application value.

[0120] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A positioning ceramic tile with a dual superimposed effect of ice crystals and flocculent inclusions, comprising a body, a glaze layer, a pattern layer, a dry granule layer, and a protective glaze layer arranged sequentially, characterized in that, The raw materials for preparing the dry granule layer include crystalline dry granules and flocculent white dry granules; The crystalline dry granules comprise the following chemical composition by mass percentage: ZrO2: 65~68%, SiO2: 32~35%; the particle size D50 of the crystalline dry granules is 20μm~50μm, and the particle size D50 of the flocculent white dry granules is 80μm~180μm; The flocculated white dry granules comprise the following chemical composition by weight percentage: SiO2: 40-45%, ZrO2: 18-22%, CaO: 8-10%, ZnO: 5-6%, B2O3: 4-5%, Al2O3: 10-12%, MgO: 4-5%, and loss on ignition: 0.5-1%. The protective glaze layer is prepared by the protective glaze, and the protective glaze includes the following raw materials in parts by weight: 45-50 parts of transparent frit, 1-7 parts of composite antibacterial agent, 8-10 parts of sodium feldspar, 6-10 parts of potassium feldspar, 1-3 parts of zirconium oxide, 6-12 parts of calcite, 4-10 parts of calcined alumina, 10-20 parts of calcined kaolin, 1-7 parts of anionic surfactant, and 1-3 parts of dispersant; The transparent frit comprises the following chemical composition by mass percentage: SiO2: 45-60%, Al2O3: 15-20%, CaO: 5-12%, MgO: 1-5%, Na2O: 1-3%, K2O: 2-4%, ZnO: 2-8%, BaO: 1-2%, B2O3: 1-5%, and loss on ignition: 0.5-1%. The preparation method of the composite antibacterial agent is as follows: silver-loaded silica microspheres are dispersed in a silane coupling agent solution, heated to 45℃~65℃, and stirred at a speed of 50r / min~100r / min for 20min~30min. Then, 2-methacryloyloxyethyltrimethylammonium chloride is added, and stirred at 60℃~75℃ for 30min~60min. Then, a cationic surfactant is added, and stirring is continued for 15min~30min to obtain the composite antibacterial agent.

2. The positioning tile according to claim 1, characterized in that, By mass percentage, the silver loading in the silver-loaded silica microspheres is 0.01% to 0.03%.

3. The positioning tile according to claim 2, characterized in that, The weight ratio of the silver-loaded silica microspheres, silane coupling agent solution, 2-methacryloyloxyethyltrimethylammonium chloride and cationic surfactant is (1~9):(10~15):(1~5):(1~3).

4. The positioning tile according to claim 3, characterized in that, The cationic surfactant is hexadecyltrimethylammonium bromide.

5. The positioning tile according to claim 1, characterized in that, The anionic surfactant is sodium lignosulfonate.

6. A method for preparing a positioning ceramic tile with a dual superimposed effect of ice crystals and flocculent inclusions, characterized in that, The preparation method is used to prepare the positioning ceramic tile with the dual superposition effect of ice crystals and flocculent clusters as described in any one of claims 1 to 5, and the preparation method includes the following steps: S1. Press the green body powder into shape to obtain a green body, send the green body into a drying kiln to dry, apply a surface glaze to the surface of the dried green body, and after drying, form a surface glaze layer. S2. A pattern layer is formed on the surface of the glaze layer by inkjet printing; S3. The flocculent dry granules are precisely applied to the preset area of ​​the pattern layer using an application device, and then the crystalline dry granules are precisely applied to the preset area of ​​the pattern layer using an application device to form a dual-positioning dry granule layer. S4. Prepare a protective glaze, apply the protective glaze to the dry granule layer, and after drying, form a protective glaze layer; S5. The material after step S4 is fired at 1180℃~1210℃ for 50min~90min, followed by soft polishing to obtain a positioning tile with a double superposition effect of ice crystals and flocculent particles.

7. The preparation method according to claim 6, characterized in that, The protective glaze is prepared by adding transparent frit, sodium feldspar, potassium feldspar, zirconium oxide, calcite, calcined alumina, calcined kaolin and dispersant into a ball mill, adding an appropriate amount of water, and performing wet ball milling. Then, a composite antibacterial agent and anionic surfactant are added, and the ball milling process is continued. After sieving, the protective glaze is obtained.

Images