A stain-resistant matte ceramic tile and a method of making the same

Abstract

The application belongs to the technical field of building ceramics, and particularly discloses a stain-resistant matte ceramic tile and a preparation method thereof. The stain-resistant matte ceramic tile comprises, from bottom to top, a body, a surface glaze layer, a pattern layer, a dry particle layer and a protective glaze layer. The protective glaze layer is prepared by firing a mixed protective glaze, and the mixed protective glaze comprises a basic protective glaze and a nano suspension. The nano suspension contains nano oxide A and nano oxide B. The nano oxide A comprises silicon oxide and / or aluminum oxide, and the nano oxide B comprises at least one of magnesium oxide, calcium oxide and zinc oxide. The stain-resistant matte ceramic tile of the application is coated with the mixed protective glaze on the dry particle layer, and the mixed protective glaze comprises the basic protective glaze and the nano suspension with specific components. The dry particle layer is composed of matte dry particles with different particle sizes and different initial melting temperatures. On the premise of ensuring the matte surface, the stain-resistant performance of the product is improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of building ceramics, and particularly relates to a stain-resistant matte ceramic tile and a preparation method thereof. BACKGROUND

[0002] In the production and use of building ceramics, the stain resistance of antique ceramic tile is closely related to the glossiness of the surface thereof. The lower the glossiness, the higher the roughness of the surface, and the more easily the pits of the surface hide dirt and stains, and the stain resistance is also reduced. Therefore, how to realize good stain resistance of the ceramic tile under low glossiness is a technical problem to be solved in the industry.

[0003] In actual production, the defects on the surface of the ceramic tile are mainly related to the body, the initial melting temperature and the thermal expansion coefficient of the glaze layer, and the influence relationship mainly shows that the thermal expansion coefficient of the glaze with low initial melting temperature is large; when the glaze with low initial melting temperature is used in combination with the body with high initial melting temperature, the probability of defects such as pinholes in the glaze layer is high.

[0004] At present, the glaze layer of the matte ceramic tile is mainly formed by high initial melting temperature and large dry particles (or raw material particles) to form a suspension under the action of glue, the suspension is applied to the surface of the tile body, and the matte ceramic tile with low glossiness is formed after drying and firing; and the large dry particles of the matte ceramic tile are in contact with each other to form large gaps, which are easy to cause defects such as pinholes in the glaze layer after firing, and these defects will seriously affect the stain resistance of the tile surface. In view of the solution to the defects such as pinholes in the glaze layer of the matte dry particles in the matte ceramic tile after firing, the initial melting temperature is generally increased to accelerate the melting of the dry particles and reduce the pinholes in the glaze layer, but this will lead to the increase of the glossiness of the matte glaze layer, which will affect the final touch and color development effect of the pattern on the tile surface.

[0005] Therefore, it is urgent to develop a ceramic tile which can reduce pinholes in the glaze surface and improve the stain resistance of the product under the premise of ensuring low glossiness (matte) of the glaze surface. SUMMARY

[0006] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides a stain-resistant matte ceramic tile and a preparation method thereof. The ceramic tile is prepared by applying a mixed protective glaze on the dry particle layer, and the mixed protective glaze contains a specific component of nano-oxide, and the dry particle layer is formed by firing matte dry particles with different particle sizes and initial melting temperatures. The stain resistance of the product is improved under the premise of ensuring the matte glaze.

[0007] To solve the above technical problems, the first aspect of the present application provides a stain-resistant matte ceramic tile, which comprises a body, a surface glaze layer, a pattern layer, a dry particle layer and a protective glaze layer from bottom to top.

[0008] The protective glaze layer is fired from a mixed protective glaze, which comprises a basic protective glaze and a nano-suspension;

[0009] The nano-suspension contains nano-oxide A and nano-oxide B, the nano-oxide A comprises silicon oxide and / or aluminum oxide, and the nano-oxide B comprises at least one of magnesium oxide, calcium oxide and zinc oxide.

[0010] Specifically, the present application applies a layer of mixed protective glaze on the surface of the dry particle layer, and the mixed protective glaze contains, in addition to the basic protective glaze, nano-oxide A (silicon oxide and / or aluminum oxide) and nano-oxide B (magnesium oxide, calcium oxide and zinc oxide) as network formers. The nano-oxide A and nano-oxide B are beneficial to reducing the initial melting temperature of the glaze on the one hand, and to accelerating the high-temperature reaction between the glaze and the dry particles on the other hand, thereby reducing the porosity between the dry particles, reducing the number of pinholes in the glaze layer after firing, and improving the stain resistance of the ceramic tile.

[0011] Meanwhile, the nano-oxide A and nano-oxide B are both the constituent oxides of the basic protective glaze, and the reason why only the nano-oxide A and nano-oxide B are nano-sized, but not part of the basic protective glaze or only the nano-oxide A or nano-oxide B is nano-sized, is that, according to the analysis of the components of the glaze and the network structure formed by silicon-oxygen tetrahedron [SiO4], the main component for reducing the temperature and high-temperature viscosity of the glaze is the network-breaking oxide (such as alkali metal oxides K2O and Na2O), and the alkaline earth metal oxides (such as MgO, CaO and ZnO) act as network intermediates, which can significantly control the high-temperature viscosity of the melt on the basis of the network-breaking oxides, and at the same time slow down the high-temperature erosion of the alkali metal to the silicon-oxygen tetrahedron [SiO4]. Therefore, by nano-sizing the network formers and network intermediates, the activity of the network intermediates is improved, and in the process of increasing the firing temperature, the network formers, network intermediates and network-breaking oxides are preferentially involved in the mutual reaction, thereby reducing the residual gas in the glaze layer, reducing the number of pinholes on the glaze surface, and improving the stain resistance of the ceramic tile. If all the raw materials of the mixed basic protective glaze are nano-sized, the activity of the alkali metal oxides will be increased, which will affect the high-temperature viscosity, and the gas discharged upward from the body will be sealed in the glaze layer, forming defects such as bubbles and pinholes.

[0012] Preferably, the mass ratio of the nano-oxide A to the nano-oxide B is (8-12):1, and by controlling the mass ratio of the nano-oxide A to the nano-oxide B, the high-temperature viscosity of the glaze melt is controlled, thereby reducing the generation of pinholes on the glaze surface.

[0013] Preferably, the solid content of the nano-suspension is 20-30wt%.

[0014] Preferably, the particle size range of the nano-oxide A and the nano-oxide B is D50 between 30-50 nm and D90 between 60-100 nm.

[0015] Preferably, the suspending agent of the nano-suspension is selected from sodium acrylate and / or sodium carboxylate.

[0016] Preferably, the raw material components of the base protective enamel include, in parts by weight, transparent clinker 20-25 parts, quartz sand 13-18 parts, sodium feldspar 20-25 parts, calcined kaolin 17-22 parts, alumina 3-7 parts, wollastonite 4-7 parts, and calcined talc 3-6 parts.

[0017] Preferably, the particle size range of the base protective enamel is D50 between 10-20 μm and D90 between 40-80 μm.

[0018] Preferably, the dry weight ratio of the base protective enamel and the nano-suspension is (10-15):1.

[0019] Preferably, the raw material for preparing the dry particle layer includes first, second and third matte dry particles, the first matte dry particle has an initial melting temperature of 1160-1190℃, the second matte dry particle has an initial melting temperature of 1120-1150℃, and the third matte dry particle has an initial melting temperature of 1080-1110℃.

[0020] Preferably, the particle sizes of the first, second and third matte dry particles are 150-300 mesh, 200-400 mesh and 300-500 mesh, respectively.

[0021] Specifically, the dry particle layer of the present application is composed of matte dry particles with different initial melting temperatures and different particle sizes, the matte dry particles with different initial melting temperatures start to appear in glass phase at different temperatures, which can make the pinholes generated by the pores of the green body at a relatively low temperature stage be fused flat by the dry particles with higher initial melting point, forming a gradient melting temperature, which can effectively reduce the generation of pinholes; at the same time, the matte dry particles with different particle sizes are mixed, and the particles will form a close packing, further reducing the porosity between the particles, thereby improving the stain resistance of the product.

[0022] Preferably, the mass ratio of the first, second and third matte dry particles is (3-5):(1-3):1.

[0023] Preferably, the first matt dry granule has a chemical composition, by weight percentage, comprising: 44.70-49.40% Si02, 18.70-20.80% Al203, 0.06-0.15% Ti02, 0.06-0.13% Fe203, 3.50-3.90% MgO, 14.40-16.00% CaO, 1.50-1.70% Na20, 1.20-1.35% K20, 8.65-9.60% BaO, 0.20-0.30% ZnO, 0.70-0.85% SrO, 0.90-1.10% B203, loss on ignition 0.08-0.20%.

[0024] Preferably, the second matt dry granule has a chemical composition, by weight percentage, comprising: 58.40-63.60% Si02, 14.50-17.10% Al203, 0.03-0.10% Ti02, 0.05-0.15% Fe203, 0.85-1.20% MgO, 9.90-11.10% CaO, 0.50-0.75% Na20, 4.20-4.75% K20, 4.20-4.70% ZnO, 0.20-0.30% BaO, 1.40-1.70% SrO, loss on ignition 0.10-0.50%.

[0025] Preferably, the third matt dry granule has a chemical composition, by weight percentage, comprising: 54.20-59.90% Si02, 15.25-16.90% Al203, 0.02-0.10% Ti02, 0.05-0.20% Fe203, 2.50-3.00% MgO, 11.50-13.00% CaO, 4.00-4.50% Na20, 1.75-2.00% K20, 2.30-2.70% ZnO, 1.70-2.00% BaO, 0.70-1.00% SrO, 0.10-0.18% P205, loss on ignition 0.10-0.30%.

[0026] Preferably, the face glaze layer is fired from a face glaze having a chemical composition, by weight percentage, comprising: 52.01-56.37% Si02, 36.05-39.85% Al203, 0.09-0.12% Ti02, 0.03-0.08% Fe203, 0.50-0.58% MgO, 0.49-0.59% CaO, 2.95-3.28% Na20, 1.10-1.25% K20, loss on ignition 1.70-3.00%.

[0027] Preferably, the chemical composition of the body comprises, in percentage by weight: 63.22-69.88% SiO2, 19.73-21.81% Al2O3, 0.15-2.00% TiO2, 0.65-0.80% Fe2O3, 0.90-1.00% MgO, 0.15-2.00% CaO, 3.75-4.15% Na2O, 2.94-3.28% K2O, and a loss on ignition of 1.30-3.80%.

[0028] The face glaze of the present application is well adaptable to the chemical composition of the body and dry particles, and does not negatively affect the comprehensive performance of the product.

[0029] The second aspect of the present application provides a method for preparing a stain-resistant matte ceramic tile, comprising the following steps:

[0030] The face glaze, the pattern layer, and the protective glaze layer are formed in sequence by applying the face glaze, spraying and printing the pattern, applying the dry particles, and spraying the mixed protective glaze on the body, respectively, and then drying and firing in a kiln to obtain the stain-resistant matte ceramic tile.

[0031] Preferably, the face glaze is applied to the upper surface of the body to form the face glaze layer by bell jar glazing, and the specific gravity of the glaze paste of the face glaze is 1.83g / cm3-1.87g / cm3. 3 3 .

[0032] Preferably, the application amount of the face glaze is 460g / m2-505g / m2. 2 2 .

[0033] Preferably, the dry particle application process is as follows: first, the dry particles are mixed with glue to form a glue suspension; then, the dry particle layer is formed by bell jar glazing on the surface of the pattern layer.

[0034] Preferably, the specific gravity of the glue suspension is 1.21g / cm3-1.24g / cm3. 3 3 .

[0035] Preferably, the application amount of the glue suspension is 370g / m2-415g / m2. 2 2 .

[0036] Preferably, the mixed protective glaze is applied to the upper surface of the dry particle layer to form the protective glaze layer by spraying cabinet.

[0037] Preferably, the specific gravity of the mixed protective glaze is 1.18g / cm3-1.22g / cm3. 3 3 .

[0038] ​​​​​Preferably, the application amount of the mixed protective glaze is 180g / m 2 -205g / m 2 .

[0039] Preferably, the temperature of the firing is 1100-1180℃, and the period of the firing is 50-70min.

[0040] The above technical solutions of the present application have at least the following technical effects or advantages over the prior art:

[0041] (1) The stain-resistant matte ceramic tile of the present application comprises, from bottom to top, a body, a surface glaze layer, a pattern layer, a dry particle layer and a protective glaze layer, wherein the protective glaze layer is fired from a mixed protective glaze, and the mixed protective glaze contains network-forming nano-oxide A (silicon oxide and / or aluminum oxide) and network intermediate alkali earth metal nano-oxide B (magnesium oxide, calcium oxide, zinc oxide). The nano-sized oxide A and oxide B, due to their small particle size effect, on the one hand, are conducive to reducing the initial melting temperature of the glaze, and on the other hand, can accelerate the high-temperature reaction with the dry particle layer; the two work together to effectively reduce the porosity of the dry particles and reduce the pinhole defects of the glaze surface after high-temperature firing, thereby improving the stain resistance of the ceramic tile.

[0042] (2) The present application improves the activity of the network intermediate by only nanoizing the network-forming nano-oxide A and the alkali earth metal nano-oxide B, and in the process of increasing the firing temperature, preferentially intervenes in the mutual reaction of the network-forming body, the network intermediate and the broken network oxide, thereby effectively reducing the residual gas in the glaze layer, reducing the number of pinholes on the glaze surface, and thereby improving the stain resistance of the ceramic tile.

[0043] (3) The ceramic tile prepared by the present application has a good stain resistance effect with a stain resistance level of 5 when the gloss is matte. DETAILED DESCRIPTION

[0044] The present application will be described in detail below with reference to the examples, so as to facilitate the understanding of the present application by those skilled in the art. It is necessary to point out here that the examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application. Non-essential improvements and adjustments to the present application made by those skilled in the art based on the above description should still fall within the protection scope of the present application. Meanwhile, the raw materials mentioned below are not described in detail, which are all commercially available products; the process steps or preparation methods not mentioned in detail are all known to those skilled in the art.

[0045] The transparent frit used in the following examples and comparative examples has a chemical composition, in terms of weight percentage, including: 48.97% SiO2, 18.96% Al2O3, 0.05% TiO2, 0.11% Fe2O3, 5.13% MgO, 14.54% CaO, 0.38% Na2O, 0.46% K2O, 10.94% BaO, 0.15% P2O5, 0.08% SrO, and a loss on ignition of 0.23%.

[0046] Example 1

[0047] A stain-resistant matte ceramic tile sequentially includes, from bottom to top, a body, a face glaze layer, a pattern layer, a dry particle layer, and a protective glaze layer.

[0048] wherein:

[0049] The preparation raw material of the protective glaze layer is mixed protective glaze including a base protective glaze and a nano-suspension, and the nano-suspension contains nano-silicon oxide (particle size: D50 is 42 nm, D90 is 82 nm), nano-zinc oxide (particle size: D50 is 38 nm, D90 is 75 nm), and a suspending agent sodium acrylate salt, the mass ratio of the nano-silicon oxide and the nano-zinc oxide is 10:1, and the solid content of the nano-suspension is 20%; the dry weight ratio of the base protective glaze and the nano-suspension is 10:1.

[0050] The raw material components of the base protective glaze include, in terms of weight parts: transparent frit 23.5 parts, quartz sand 16.5 parts, sodium feldspar 23.5 parts, calcined kaolin 20.5 parts, aluminum oxide 6.0 parts, wollastonite 6.0 parts, and calcined talc 4.0 parts. The particle size range of the base protective glaze is D50 of 15 μm and D90 of 60 μm.

[0051] The preparation raw material of the dry particle layer includes a first matte dry particle, a second matte dry particle, and a third matte dry particle, and the mass ratio of the first matte dry particle, the second matte dry particle, and the third matte dry particle is 4:2:1.

[0052] The chemical composition of the first matte dry particle includes, in terms of weight percentage: 47.04% SiO2, 19.74% Al2O3, 0.10% TiO2, 0.08% Fe2O3, 3.71% MgO, 15.19% CaO, 1.60% Na2O, 1.29% K2O, 9.14% BaO, 0.25% ZnO, 0.77% SrO, 0.96% B2O3, and a loss on ignition of 0.13%. The first matte dry particle has an initial melting temperature of 1180°C and an average particle size of 200 mesh.

[0053] The chemical composition of the second matt dry granule includes, by weight percentage, 61.50% SiO2, 15.26% Al2O3, 0.05% TiO2, 0.11% Fe2O3, 1.02% MgO, 10.43% CaO, 0.64% Na2O, 4.50% K2O, 0.27% BaO, 4.47% ZnO, 1.54% SrO, and a loss on ignition of 0.21%. The initial melting temperature of the second matt dry granule is 1130°C, and the average particle size is 300 mesh.

[0054] The chemical composition of the third matt dry granule includes, by weight percentage, 57.05% SiO2, 16.07% Al2O3, 0.04% TiO2, 0.10% Fe2O3, 2.81% MgO, 12.34% CaO, 4.26% Na2O, 1.86% K2O, 1.82% BaO, 2.49% ZnO, 0.84% SrO, 0.14% P2O5, and a loss on ignition of 0.18%. The initial melting temperature of the third matt dry granule is 1100°C, and the particle size is 400 mesh.

[0055] The chemical composition of the face glaze layer includes, by weight percentage, 53.69% SiO2, 37.95% Al2O3, 0.10% TiO2, 0.04% Fe2O3, 0.54% MgO, 0.54% CaO, 3.10% Na2O, 1.17% K2O, and a loss on ignition of 2.87%.

[0056] The chemical composition of the body includes, by weight percentage, 66.55% SiO2, 20.77% Al2O3, 0.19% TiO2, 0.72% Fe2O3, 0.96% MgO, 0.17% CaO, 3.95% Na2O, 3.11% K2O, and a loss on ignition of 3.58%.

[0057] A method for preparing a stain-resistant matt ceramic tile, characterized by comprising the following steps:

[0058] (1) The raw materials for preparing the body are weighed according to the mass ratio, ball milled with water (the mass ratio of the materials to water is 100:40), spray dried to obtain body powder, and the body powder is pressed to form the body;

[0059] (2) The raw materials for preparing the face glaze layer are weighed according to the mass ratio, ball milled with water (the mass ratio of the materials to water is 100:40) to obtain face glaze glaze slurry (the specific gravity is 1.84 g / cm 3 ), and the face glaze glaze slurry is applied to the upper surface of the body prepared in step (1) by bell jar glazing (the glaze application amount of the face glaze glaze slurry is 485 g / m 2 ), to form a face glaze layer; then a pattern layer is obtained by inkjet printing a pattern on the surface of the face glaze layer;

[0060] (3) The first matte dry particle, the second matte dry particle and the third matte dry particle are weighed according to the mass ratio, and then glue is added for mixing to form a glue dry particle glaze slurry (the mass ratio of the mixed dry particle to the glue is 3:7, and the specific gravity is 1.22 g / cm 3 ). The glue dry particle glaze slurry is applied to the surface of the pattern layer prepared in step (2) by bell jar glazing (the application amount of the glue dry particle glaze slurry is 395 g / m 2 ), to form a dry particle layer;

[0061] (4) The nano-silicon oxide and the nano-zinc oxide are added into the sodium salt of acrylic acid to obtain a nano-suspension; then the raw materials for preparing the base protective glaze are weighed according to the mass ratio, and water is added for ball milling (the mass ratio of the materials to water is 100:40) to obtain a base protective glaze slurry (the specific gravity is 1.52 g / cm 3 ); the nano-suspension and the base protective glaze slurry are mixed, and water is added for stirring to obtain a mixed protective glaze slurry (the specific gravity is 1.22 g / cm 3 ); and then the mixed protective glaze slurry is sprayed on the surface of the dry particle layer prepared in step (3) by a glaze spraying cabinet (the application amount of the mixed protective glaze slurry is 190 g / m 2 ), to form a protective glaze layer; after drying, the protective glaze layer is fired in a kiln at a maximum temperature of 1180°C for a firing period of 60 min, to obtain the stain-resistant matte ceramic tile of the present embodiment.

[0062] Embodiment 2

[0063] A stain-resistant matte ceramic tile comprises, from bottom to top, a body, a surface glaze layer, a pattern layer, a dry particle layer and a protective glaze layer.

[0064] In the present embodiment, the surface glaze layer is prepared by the following steps:

[0065] The raw materials for preparing the protective glaze layer are mixed protective glaze, which comprises a base protective glaze and a nano-suspension, and the nano-suspension contains nano-alumina (particle size: D50 is 38 nm, and D90 is 79 nm), nano-magnesia (particle size: D50 is 43 nm, and D90 is 85 nm) and a suspending agent sodium salt of carboxylic acid, and the mass ratio of the nano-alumina to the nano-magnesia is 12:1, and the solid content of the nano-suspension is 30%; and the dry weight ratio of the base protective glaze to the nano-suspension is 15:1.

[0066] The raw material components of the base protective glaze include, by weight, 22 parts of transparent frit, 17.5 parts of quartz sand, 24 parts of sodium feldspar, 22 parts of calcined kaolin, 5.7 parts of alumina, 6.0 parts of wollastonite and 3.8 parts of calcined talc, and the particle size range of the base protective glaze is D50 of 14 μm and D90 of 58 μm.

[0067] The raw materials for preparing the dry particle layer include the first matte dry particle, the second matte dry particle and the third matte dry particle, and the mass ratio of the first matte dry particle, the second matte dry particle and the third matte dry particle is 3:3:1.

[0068] The chemical composition of the first matt dry granule includes, by weight percentage, 48.19% SiO2, 18.97% Al2O3, 0.11% TiO2, 0.07% Fe2O3, 3.62% MgO, 15.04% CaO, 1.66% Na2O, 1.24% K2O, 8.97% BaO, 0.25% ZnO, 0.77% SrO, 0.92% B2O3, and a loss on ignition of 0.19%. The first matt dry granule has an initial melting temperature of 1175°C and an average particle size of 250 mesh.

[0069] The chemical composition of the second matt dry granule includes, by weight percentage, 60.46% SiO2, 15.96% Al2O3, 0.07% TiO2, 0.12% Fe2O3, 1.12% MgO, 10.66% CaO, 0.68% Na2O, 4.42% K2O, 0.25% BaO, 4.40% ZnO, 1.60% SrO, and a loss on ignition of 0.26%. The second matt dry granule has an initial melting temperature of 1130°C and an average particle size of 350 mesh.

[0070] The chemical composition of the third matt dry granule includes, by weight percentage, 57.05% SiO2, 15.97% Al2O3, 0.06% TiO2, 0.11% Fe2O3, 2.60% MgO, 12.50% CaO, 4.41% Na2O, 1.88% K2O, 1.75% BaO, 2.61% ZnO, 0.76% SrO, 0.16% P2O5, and a loss on ignition of 0.14%. The third matt dry granule has an initial melting temperature of 1095°C and a particle size of 400 mesh.

[0071] The face glaze layer is prepared from a face glaze, which has a chemical composition including, by weight percentage, 53.54% SiO2, 38.05% Al2O3, 0.11% TiO2, 0.05% Fe2O3, 0.56% MgO, 0.52% CaO, 3.18% Na2O, 1.14% K2O, and a loss on ignition of 2.85%.

[0072] The chemical composition of the body includes, by weight percentage, 66.38% SiO2, 20.87% Al2O3, 0.17% TiO2, 0.70% Fe2O3, 0.94% MgO, 0.18% CaO, 4.07% Na2O, 3.09% K2O, and a loss on ignition of 3.60%.

[0073] A method for preparing a stain-resistant matt ceramic tile, characterized by comprising the following steps:

[0074] (1) the raw materials for preparing the body are weighed according to the mass ratio, ball-milling is performed (the mass ratio of the materials to water is 100:40), spray drying is performed, the body powder is obtained, and the body powder is pressed to form a body;

[0075] (2) the raw materials for preparing the surface glaze layer are weighed according to the mass ratio, ball-milling is performed (the mass ratio of the materials to water is 100:40), the surface glaze slurry (the specific gravity is 1.85 g / cm 3 ) is obtained, the surface glaze slurry is applied to the upper surface of the body prepared in step (1) by bell jar glazing (the glazing amount of the surface glaze slurry is 480 g / m 2 ), and the surface glaze layer is formed; then, the pattern layer is obtained by inkjet printing a pattern on the surface of the surface glaze layer;

[0076] (3) the first matte dry particles, the second matte dry particles and the third matte dry particles are weighed according to the mass ratio, and then the glue is added to mix, forming the glue dry particle slurry (the mass ratio of the mixed dry particles to the glue is 3:7, and the specific gravity is 1.21 g / cm 3 ), the surface of the pattern layer prepared in step (2) is coated with the glue dry particle slurry by bell jar glazing (the glazing amount of the glue dry particle slurry is 400 g / m 2 ), and the dry particle layer is formed;

[0077] (4) the nano-silicon oxide and the nano-zinc oxide are added into the sodium salt of acrylic acid to obtain a nano-suspension; then, the raw materials for preparing the base protective glaze are weighed according to the mass ratio, ball-milling is performed (the mass ratio of the materials to water is 100:40), and the base protective glaze slurry (the specific gravity is 1.51 g / cm 3 ) is obtained; the nano-suspension and the base protective glaze slurry are mixed, and water is added to stir, and the mixed protective glaze slurry (the specific gravity is 1.20 g / cm 3 ) is obtained; the mixed protective glaze slurry is sprayed on the surface of the dry particle layer prepared in step (3) by using a spray glazing cabinet (the glazing amount of the mixed protective glaze slurry is 195 g / m 2 ), and the protective glaze layer is formed; after drying, the protective glaze layer is fired in a kiln at a maximum temperature of 1175℃ for 60 min, and the stain-resistant matte ceramic tile of the present embodiment is obtained.

[0078] Example 3

[0079] A stain-resistant matte ceramic tile comprises, from bottom to top, a body, a surface glaze layer, a pattern layer, a dry particle layer and a protective glaze layer.

[0080] In the present embodiment, the surface glaze layer, the pattern layer, the dry particle layer and the protective glaze layer are prepared according to the following steps:

[0081] The preparation raw material of the protective enamel layer is mixed protective enamel including base protective enamel and nano suspension, and the nano suspension contains nano silicon oxide (particle size: D50 is 42 nm, D90 is 82 nm), nano calcium oxide (particle size: D50 is 45 nm, D90 is 95 nm) and suspension agent sodium salt of acrylic acid, the mass ratio of nano silicon oxide and nano zinc oxide is 8:1, and the solid content of the nano suspension is 20%; the dry weight ratio of the base protective enamel and the nano suspension is 14:1.

[0082] The raw material components of the base protective enamel include, in terms of weight parts, 24.0 parts of transparent clinker, 17.0 parts of quartz sand, 24.0 parts of sodium feldspar, 19.5 parts of calcined kaolin, 5.8 parts of aluminum oxide, 5.5 parts of wollastonite and 4.2 parts of calcined talc. The particle size range of the base protective enamel is D50 of 16 μm and D90 of 65 μm.

[0083] The preparation raw material of the dry particle layer includes first, second and third matte dry particles, and the mass ratio of the first, second and third matte dry particles is 4:1:1.

[0084] The chemical composition of the first matte dry particle includes, in terms of weight percentage, 47.49% SiO2, 19.37% Al2O3, 0.11% TiO2, 0.09% Fe2O3, 3.66% MgO, 15.14% CaO, 1.63% Na2O, 1.28% K2O, 9.04% BaO, 0.24% ZnO, 0.79% SrO, 0.98% B2O3 and a loss on ignition of 0.18%. The first matte dry particle has an initial melting temperature of 1180°C and an average particle size of 250 mesh.

[0085] The chemical composition of the second matte dry particle includes, in terms of weight percentage, 61.35% SiO2, 15.84% Al2O3, 0.07% TiO2, 0.08% Fe2O3, 1.13% MgO, 10.17% CaO, 0.66% Na2O, 4.34% K2O, 0.27% BaO, 4.29% ZnO, 1.48% SrO and a loss on ignition of 0.32%. The second matte dry particle has an initial melting temperature of 1130°C and an average particle size of 300 mesh.

[0086] The chemical composition of the third matte dry particle includes, in terms of weight percentage, 56.75% SiO2, 16.47% Al2O3, 0.06% TiO2, 0.12% Fe2O3, 2.85% MgO, 12.24% CaO, 4.21% Na2O, 1.81% K2O, 1.85% BaO, 2.46% ZnO, 0.82% SrO, 0.14% P2O5 and a loss on ignition of 0.22%. The third matte dry particle has an initial melting temperature of 1105°C and a particle size of 400 mesh.

[0087] The preparation raw material of the surface glaze layer is surface glaze, and the chemical composition includes, in percentage by weight, 54.64% SiO2, 36.95% Al2O3, 0.11% TiO2, 0.06% Fe2O3, 0.55% MgO, 0.55% CaO, 3.09% Na2O, 1.19% K2O, and a loss on ignition of 2.86%.

[0088] The chemical composition of the body includes, in percentage by weight, 67.16% SiO2, 20.35% Al2O3, 0.16% TiO2, 0.70% Fe2O3, 0.93% MgO, 0.18% CaO, 3.98% Na2O, 3.15% K2O, and a loss on ignition of 3.39%.

[0089] A preparation method of a stain-resistant matte ceramic tile, characterized in that it comprises the following steps:

[0090] (1) The raw materials for preparing the body are weighed according to the mass ratio, and are ball milled with water (the mass ratio of the materials to water is 100:40), and are spray dried to obtain body powder, which is pressed and formed to obtain the body;

[0091] (2) The raw materials for preparing the surface glaze layer are weighed according to the mass ratio, and are ball milled with water (the mass ratio of the materials to water is 100:40) to obtain surface glaze slip (the specific gravity is 1.84 g / cm 3 ), which is applied to the upper surface of the body prepared in step (1) by bell jar glazing (the glazing amount of the surface glaze slip is 480 g / m 2 ), to form a surface glaze layer; then a pattern layer is obtained by inkjet printing a pattern on the surface of the surface glaze layer;

[0092] (3) The first matte dry particles, the second matte dry particles and the third matte dry particles are weighed according to the mass ratio, and then are mixed with glue to form glue dry particle slip (the mass ratio of the mixed dry particles to glue is 3:7, and the specific gravity is 1.22 g / cm 3 ), which is applied to the surface of the pattern layer prepared in step (2) by bell jar glazing (the glazing amount of the glue dry particle slip is 390 g / m 2 ), to form a dry particle layer;

[0093] (4) Nano-silicon oxide and nano-zinc oxide are added into sodium acrylate to obtain a nano-suspension; then the raw materials for preparing the base protective glaze are weighed according to the mass ratio, and are ball milled with water (the mass ratio of the materials to water is 100:40) to obtain base protective glaze slip (the specific gravity is 1.55 g / cm 3 ); the nano-suspension and the base protective glaze slip are mixed, and are stirred with water to obtain mixed protective glaze slip (the specific gravity is 1.20 g / cm 3); then the mixed protective glaze slurry is sprayed on the surface of the dry particle layer prepared in step (3) by using a spray glaze cabinet (the amount of glaze applied by the mixed protective glaze slurry is 195 g / m 2 ), to form a protective glaze layer; after drying, the sample is fired in a kiln at a maximum temperature of 1175°C for a firing period of 65 min, to obtain the stain-resistant matte ceramic tile of the present example.

[0094] Comparative Example 1

[0095] The difference between Comparative Example 1 and Example 1 is that the ceramic tile of Comparative Example 1 does not contain a protective glaze layer.

[0096] Comparative Example 2

[0097] The difference between Comparative Example 2 and Example 1 is that the raw materials for preparing the protective glaze layer are different, and the protective glaze layer of Comparative Example 2 contains only the base protective glaze, without the nano-suspension.

[0098] Comparative Example 3

[0099] The difference between Comparative Example 3 and Example 1 is that the raw materials for preparing the protective glaze layer are different, and the nano-suspension in the protective glaze layer of Comparative Example 3 has the same solid raw material components as the base protective glaze.

[0100] Comparative Example 4

[0101] The difference between Comparative Example 4 and Example 1 is that the raw materials for preparing the dry particle layer are different, and the dry particle layer of Comparative Example 4 contains only the second matte dry particle.

[0102] Comparative Example 5

[0103] The difference between Comparative Example 5 and Example 1 is that the raw materials for preparing the dry particle layer are different, and the dry particle layer of Comparative Example 5 contains the first matte dry particle, the second matte dry particle, and the third matte dry particle, and the particle sizes of the first matte dry particle, the second matte dry particle, and the third matte dry particle are all 200-400 mesh.

[0104] Performance Test

[0105] The ceramic tile samples prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to stain absorption, glossiness, and stain resistance grade tests, and the test results are shown in Table 1.

[0106] Among them, the glossiness test was detected by using a glossiness meter; the test method for stain absorption was as follows: ink was applied on the glaze surface of ceramic tile samples of the same size (length x width = 10 cm x 10 cm), and a rubber glove was used to apply the ink for 5 min; after the ink was dried, it was washed with clean water, dried, and the number of stain absorption points was observed; the stain resistance grade was tested according to “GB / T 3810.14-2016 Ceramic Tiles - Test Methods - Part 14: Determination of Stain Resistance”, and the stain resistance performance was divided into grades, with grade 1 indicating the worst stain resistance and grade 5 indicating the best stain resistance.

[0107] Table 1: Comparison table of performance test of ceramic tile samples prepared in Examples 1-3 and Comparative Examples 1-5

[0108] Sample Gloss (GU) Stain Pick-up (number) Stain Resistance Rating Example 1 25 2 5 Example 2 20 3 5 Example 3 20 4 5 Comparative Example 1 8 65 2 Comparative Example 2 20 25 4 Comparative Example 3 25 35 3 Comparative Example 4 30 28 4 Comparative Example 5 35 25 4

[0109] As can be seen from Table 1, the ceramic tile samples prepared in Examples 1-3 have a glossiness of 20-25, which is a matte ceramic glaze, and the stain resistance grade all reaches the highest level of 5, having excellent stain resistance, and realizing good stain resistance of the matte ceramic tile.

[0110] Compared with Example 1, the ceramic tile sample of Comparative Example 1 has no protective glaze layer, the surface of the tile body is a matte dry particle glaze layer, the glossiness is low, and the stain resistance is also significantly reduced.

[0111] Compared with Example 1, the ceramic tile sample of Comparative Example 2 has only a basic protective glaze in the protective glaze layer, without nano-suspension, the high-temperature reaction of the mixed protective glaze and the dry particles is delayed, the voids of the glaze surface cannot be completely fused flat, and therefore the stain resistance of the product is reduced.

[0112] Compared with Example 1, the ceramic tile sample of Comparative Example 2 has the same solid raw material components in the nano-suspension and the basic protective glaze, i.e. the nano-suspension contains a nano-alkali component, which causes the reaction temperature of the mixed protective glaze to be lower, accelerates the filling of the mixed protective glaze to the voids, and at the same time seals the gas between the body or the dry particles, and therefore the stain resistance of the product is also reduced.

[0113] Compared with Example 1, Comparative Example 4 uses a single component matte dry particle, which is greatly affected by the temperature fluctuation in the kiln, and the distribution amount of the void structure also fluctuates significantly under the same temperature system, and therefore the overall stain resistance of the tile surface is also reduced.

[0114] Compared with Example 1, Comparative Example 5 uses a single particle size mixed matte dry particle, and because of the similar particle size, the reaction temperature between the dry particles is reduced, the glossiness of the tile surface is significantly improved, which cannot meet the requirements of the matte ceramic tile, and the stain resistance is also slightly reduced.

[0115] For those skilled in the art to which the present application belongs, without departing from the concept of the present application, a number of simple deductions or substitutions can be made without having to undergo creative labor. Therefore, the simple improvements made by those skilled in the art to the present application according to the disclosure of the present application should be within the protection scope of the present application. The above examples are preferred embodiments of the present application, and any similar processes and equivalent changes made should be within the protection scope of the present application.

Claims

1. A stain resistant matte ceramic tile, characterized by, The blank body, the surface glaze layer, the pattern layer, the dry particle layer and the protective glaze layer are sequentially arranged from bottom to top. The protective glaze layer is fired from a mixed protective glaze, and the mixed protective glaze comprises a basic protective glaze and a nano-suspension; The nano-suspension comprises nano-oxide A and nano-oxide B, the nano-oxide A is aluminum oxide, and the nano-oxide B is magnesium oxide and / or calcium oxide; The mass ratio of the nano-oxide A to the nano-oxide B is (8-12):1, the solid content of the nano-suspension is 20-30wt%, the particle size range of the nano-oxide A and the nano-oxide B is D50 between 30-50nm and D90 between 60-100nm; The raw material components of the basic protective glaze comprise, by weight fraction, 20-25 parts of transparent frit, 13-18 parts of quartz sand, 20-25 parts of sodium feldspar, 17-22 parts of calcined kaolin, 3-7 parts of aluminum oxide, 4-7 parts of wollastonite and 3-6 parts of calcined talc; the particle size range of the basic protective glaze is D50 between 10-20μm and D90 between 40-80μm; and the dry weight ratio of the basic protective glaze to the nano-suspension is (10-15):1; The preparation raw materials of the dry particle layer comprise first, second and third matte dry particles, the first matte dry particle has a starting melting temperature of 1160-1190℃, the second matte dry particle has a starting melting temperature of 1120-1150℃, and the third matte dry particle has a starting melting temperature of 1080-1110℃; the mass ratio of the first, second and third matte dry particles is (3-5):(1-3):1; and the particle sizes of the first, second and third matte dry particles are 150-300 mesh, 200-400 mesh and 300-500 mesh, respectively.

2. The stain resistant matte ceramic tile according to claim 1, wherein, The first matte dry particle has a chemical composition comprising, by weight percentage, 44.70-49.40% SiO2, 18.70-20.80% Al2O3, 0.06-0.15% TiO2, 0.06-0.13% Fe2O3, 3.50-3.90% MgO, 14.40-16.00% CaO, 1.50-1.70% Na2O, 1.20-1.35% K2O, 8.65-9.60% BaO, 0.20-0.30% ZnO, 0.70-0.85% SrO, 0.90-1.10% B2O3, and a loss on ignition of 0.08-0.20%. And / or, the second matte dry particle has a chemical composition including, by weight percentage, 58.40-63.60% SiO2, 14.50-17.10% Al2O3, 0.03-0.10% TiO2, 0.05-0.15% Fe2O3, 0.85-1.20% MgO, 9.90-11.10% CaO, 0.50-0.75% Na2O, 4.20-4.75% K2O, 4.20-4.70% ZnO, 0.20-0.30% BaO, 1.40-1.70% SrO, and a loss on ignition of 0.10-0.50%. And / or, the third matte dry particle has a chemical composition including, by weight percentage, 54.20-59.90% SiO2, 15.25-16.90% Al2O3, 0.02-0.10% TiO2, 0.05-0.20% Fe2O3, 2.50-3.00% MgO, 11.50-13.00% CaO, 4.00-4.50% Na2O, 1.75-2.00% K2O, 2.30-2.70% ZnO, 1.70-2.00% BaO, 0.70-1.00% SrO, 0.10-0.18% P2O5, and a loss on ignition of 0.10-0.30%.

3. The stain resistant matte ceramic tile of claim 1, wherein, The surface glaze layer is fired from a surface glaze, and the surface glaze has a chemical composition including, by weight percentage, 52.01-56.37% SiO2, 36.05-39.85% Al2O3, 0.09-0.12% TiO2, 0.03-0.08% Fe2O3, 0.50-0.58% MgO, 0.49-0.59% CaO, 2.95-3.28% Na2O, 1.10-1.25% K2O, and a loss on ignition of 1.70-3.00%. And / or, the body has a chemical composition including, by weight percentage, 63.22-69.88% SiO2, 19.73-21.81% Al2O3, 0.15-2.00% TiO2, 0.65-0.80% Fe2O3, 0.90-1.00% MgO, 0.15-2.00% CaO, 3.75-4.15% Na2O, 2.94-3.28% K2O, and a loss on ignition of 1.30-3.80%.

4. A method of manufacturing a stain-resistant matte ceramic tile according to any one of claims 1 to 3, characterized in that, The method comprises the following steps: The surface glaze, the pattern layer and the protective glaze layer are formed in sequence by applying the surface glaze, spraying the pattern, applying the dry particles and spraying the protective glaze on the body in sequence, and then dried and fired in a kiln to obtain the stain-resistant matte ceramic tile.

5. The method for preparing stain-resistant matte ceramic tiles according to claim 4, characterized in that, The dry particles are mixed with glue to form a glue suspension, and then applied to the surface of the pattern layer by bell jar glazing to form the dry particle layer.

6. The method for preparing stain-resistant matte ceramic tiles according to claim 4, characterized in that, The firing temperature is 1100-1180°C, and the firing period is 50-70 min.